CN101384425A - Porous film and multilayer assembly using the same - Google Patents

Abstract

To provide a porous-film layered product which has excellent porousness, has flexibility, and is excellent in handleability and formability; and a process for producing the layered product. [MEANS FOR SOLVING PROBLEMS] The porous-film layered product comprises a base and, superposed on at least one side thereof, a porous layer having many fine interconnecting pores having an average pore diameter of 0.01-10 [mu]m, and is characterized by suffering no interfacial separation between the base and the porous layer when examined in a tape peeling test by the following method. Tape peeling test A 24 mm-wide masking tape [Film Masking Tape No. 603(#25)] manufactured by Teraoka Seisakusho Co., Ltd. is applied to the surface of the porous layer of the porous-film layered product and press-bonded thereto with a roller having a diameter of 30 mm and a load of 200 gf. Thereafter, this sample is subjected to a T-peel test with a tensile tester at a peeling rate of 50 mm/min.

Description

Porous film and used the duplexer of porous film

Technical field

The present invention relates to a kind of porous membrane laminated body and its manufacture method and used composite and its manufacture method of this porous membrane laminated body, described porous membrane laminated body is folded at least one surface layer of base material the porous layer that has formed many continuous micropores.The hole characteristic that this porous membrane laminated body directly utilizes porous layer to have, or use the functional material filling pore, thus, can be used as the circuit substrate, heat sink material (radiator, heat sink), electromagnetic waves such as electromagnetic wave baffle plate or electromagnetic wave absorb control material, battery separator, capacitor (paper capacitor, plastic film capacitor, ceramic capacitor, mica condenser, electrolytic capacitor etc.), advanced low-k materials, dividing plate, padded coaming, printing ink video picture sheet material, test paper, insulating materials, heat-barrier material, the cell culture medium material, the baseplate material of catalyst substrate wide regions such as (catalyst carriers).

The invention still further relates to the wiring board of employed wiring board and its manufacture method, particularly distribution close adhesion and distribution illustrative excellence in fields such as electric, electronics, communication and its manufacture method and to manufacture method that obtains the useful printed patterns of printed matter such as in same domain employed printed substrate and the printed matter that obtains by this manufacture method.

Background technology

As the duplexer that constitutes by base material and porous layer, for example, the spy opens 2000-143848 communique and spy and opens and disclose a kind of printing ink video picture sheet material in the 2000-158798 communique, and described printing ink video picture sheet material forms porous layer manufacturing by comprising resin and carrying out the conversion of dry type layer with respect to filming of the good solvent of this resin and poor solvent.This dry type layer transformation approach is the method that makes solvent evaporates contained in above-mentioned the filming and produce microphase-separated, therefore, the problem of its existence is, the resin (macromolecular compound) that constitutes porous layer is defined in the resin that can be dissolved in lower boiling good solvent, can not use molecular weight greatly, the macromolecular compound of slightly solubility in essence.

In addition, there is the unfavorable condition of following several aspects: in order to dissolve macromolecular compound, and solvent is volatilized fast after forming filming, preferably use low viscous coating liquid, but its result is difficult to obtain filming of thickness sufficient; In the constituent of filming,, therefore, be difficult to utilize the additive of fixedness when solvent evaporates because the composition of not removing remains in porous layer; Because the structure of the porous layer that obtains depends on heating condition or manufacturing environment condition in the manufacturing process greatly, therefore, be difficult to carry out stable manufacturing, and aperture, percent opening, porosity, thickness etc. are membranous might disperse etc.

On the other hand, as by base material that utilizes the manufacture method beyond above-mentioned and the duplexer that porous layer constitutes, disclose in the world and to disclose following method in the WO98/25997 brochure, promptly, to curtain coating on base material and filming of obtaining, utilize under high humility, carry out dry wet type phase inversion method with two stages and make duplexer.Utilize this method, can make manufacturing environment conditional stabilityization, but owing to use the method for heat drying basically, therefore, can not solve the problems referred to above in the membranous dry type phase inversion method such as discrete.

But, in recent years,, install in order in printed substrate, also to realize the high density high-performance along with the progress of highly integrated, the miniaturization of electrical/electronic parts such as semiconductor, carrying out fine patterning, the fine pitchization of conductor wirings.

In subtraction as the representative manufacture method of printed substrate, usually obtain wiring board by the following method, promptly, laminated copper foil on insulator, on this Copper Foil, apply resist, form resist film, after by mask this resist film being carried out pattern exposure, develops, implement etching, remove resist film (with reference to patent documentation 1,2) then.At this moment, generally,, the face that is connected side with insulator of Copper Foil is implemented asperities handle in order to improve the close adhesion intensity between insulator and the Copper Foil.But when carrying out the fine pitch of conductor wirings, when Copper Foil being implemented asperities and handle, Copper Foil concavo-convex produces the problem that distribution ruptures or peels off and so on during because of etching.On the other hand, when using the Copper Foil of not implementing the asperities processing, though can successfully carry out etching, the close adhesion intensity step-down of insulator and Copper Foil, distribution integral body is peeled off easily.

In addition, also can produce following problem: when the thickness of Copper Foil was big, the middle body of the thickness direction of Copper Foil was along digging perpendicular to the direction of thickness direction when etching, and the cross section of distribution can not form square; When carrying out fine pitch, fracture takes place or peels off in distribution.Therefore,, need the thickness of attenuate Copper Foil, but when the reduced thickness of Copper Foil, be difficult to carry out the manufacturing and the use of Copper Foil in order carry out fine pitchization.Therefore, in existing subtraction, we can say on the fine pitchization of distribution, to have boundary.

In the manufacturing of wiring board, the method of carrying out printing paste on resin films such as PET (PETG) film, PI (polyimides) film at present and making distribution, but when describing fine distribution, exist because of printing problems such as making the wiring closet connection such as spread and sink in.

Open the spy and to disclose following method in the flat 5-85815 communique: carry out alumina powder, quartz glass powder, calcium borosilicate glass frit end mixing, make the sheet material green compact, behind printed conductor cream on these sheet material green compact, carry out roasting, make glass ceramic baseplate.But though there is following shortcoming in the printing excellence of the fine distribution of the sheet material green compact of mixture of powders: need cost an arm and a leg near the calcining process of the temperature 1000 ℃, in addition, ready-made goods do not have pliability, crisp.

Open the spy and to disclose following method in the 2006-135090 communique: after the surface of substrate forms channel patterns by the laser irradiation, in channel patterns, put into the black liquid that contains conductive material, make fine distribution.But this method has following shortcoming: need the laser irradiation process, productivity is low and cost is high, need put into the high technology of black liquid in channel patterns, the property produced in batches shortcoming etc.

Disclose following technology in the 2001-298253 communique: in order to carry out fine printing on Copper Foil, the porous material of amine compound that will have the population of specified particle diameter carries out film forming, forms the printing counterdie.But, in this technology, because emboliform film is carried out coating, so the tunicle weak strength, be not durable as wiring material.

Patent documentation 1: the spy opens the 2000-143848 communique

Patent documentation 2: the spy opens the 2000-158798 communique

Patent documentation 3: the international WO98/25997 brochure that discloses

Patent documentation 4: the spy opens the 2003-243799 communique

Patent documentation 5: the spy opens the 2004-63575 communique

Patent documentation 6: the spy opens flat 5-85815 communique

Patent documentation 7: the spy opens the 2006-135090 communique

Patent documentation 8: the spy opens the 2001-298253 communique

Summary of the invention

The objective of the invention is to, a kind of porous membrane laminated body and manufacture method thereof are provided, the hole excellent of described porous membrane laminated body has flexibility, and applicability and shaping processability excellence.

Other purposes of the present invention are, a kind of composite and manufacture method thereof of having used the porous membrane laminated body with above-mentioned characteristic is provided.

In addition, the objective of the invention is to, provide a kind of distribution close adhesion and distribution illustrative all excellent wiring board.

Other purposes of the present invention are, a kind of method that can make the wiring board of distribution close adhesion and the equal excellence of distribution illustrative easy and effectively is provided.

And, the objective of the invention is to, a kind of printed matter of fine rule illustrative excellence is provided.

Other purposes of the present invention are, a kind of printed matter is provided, its can be easy and productivity well, make at an easy rate, simultaneously the intensity height, be difficult to ruined fine rule illustrative excellence.

Other purposes of the present invention also are, a kind of printed matter is provided, and described printed matter is except having above-mentioned characteristic, and the repeatability excellence is described in its printing.

The present invention also aims to, the printed matter that a kind of manufacture method of printed patterns is provided and utilizes this manufacture method to obtain, the fine rule illustrative excellence of described printed patterns manufacture method, simultaneously can be easy and productivity make well the intensity of part to be printed and printing close adhesion intensity height, be difficult to ruined printed patterns.

To achieve these goals, the inventor etc. concentrate on studies, and the result obtains following opinion, has finished the present invention.That is,

(1) by on substrate surface to porous layer system film and carry out stackedly simultaneously, can obtain having excellent hole characteristic, have flexibility and because of having the porous membrane laminated body of full intensity applicability and shaping processability excellence;

(2) particularly by having on the substrate surface of many through holes porous layer system film and carrying out stacked simultaneously, can obtain having excellent hole characteristic, have flexibility and because of having the porous membrane laminated body of full intensity applicability and shaping processability excellence, in addition, by on the metallic foil substrates surface to porous layer system film and carry out stackedly simultaneously, can obtain having excellent hole characteristic, have flexibility and because of having the porous membrane laminated body of full intensity applicability and shaping processability excellence;

(3) the polar solvent solution curtain coating on substrate with resin becomes the film shape, remains under the defined terms, then, when it impregnated in the solidification liquid, can obtain being formed uniformly the porous rete in the very little hole of average pore size; When utilizing print process to form conductor wirings at this perforated membrane laminar surface, can obtain to make the distribution width easily and spacing width is very little, the conductor wirings of close adhesion excellence simultaneously; In addition, when when this perforated membrane laminar surface is implemented printing, can obtain fine rule illustrative, printing easily and describe repeatability excellence and intensity height, be difficult to ruined printed matter;

(4) after implementing printing on the porous rete, when implemented the state of the porous rete dissolving of printing through utilizing solvent or solvent and heat to make, when removing this solvent, can be easy and productivity make well and can form compacted zone, fine rule illustrative excellence, the intensity of part to be printed and the high printed patterns of close adhesion intensity of printing simultaneously.

Promptly, the invention provides a kind of porous membrane laminated body, its at least one face at base material is laminated with micropore with many connectednesses and the average pore size of this micropore is the porous layer of 0.01～10 μ m, wherein, by the belt stripping test based on following method, interface peel does not take place in base material and porous layer.

Belt stripping test

The ridge, temple of pasting fabric width 24mm on the porous layer surface of porous membrane laminated body makes the masking tape [film masking tape No.603 (#25)] that company of institute makes, with the roller of diameter 30mm, 200 gram force loadings press sticking after, use cupping machine to carry out the T mould and peel off with peeling rate 50mm/ minute.

Above-mentioned base material is base material or the metallic foil substrates with many through holes.In the material that constitutes above-mentioned base material with many through holes, contain fabric, eyelet fabric, punching film, wire netting, punch metal, expanded metal and etching metal etc.In the material that constitutes above-mentioned metallic foil substrates, contain Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel and stainless steel foil etc.

Porous membrane laminated body of the present invention can form by following operation, that is, Polymer Solution after curtain coating on the base material becomes the film shape, is directed in the solidification liquid, carries out drying then, at the folded porous rete of at least one surface layer of base material.Above-mentioned Polymer Solution is to contain for example mixed solution of macromolecule component 8～25 weight %, water-soluble polymer 5～50 weight %, water 0～10 weight %, water soluble polar solvent 30～82 weight %.

In porous membrane laminated body of the present invention, the macromolecule component that constitutes porous layer can be that to be selected from polyimides be resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, at least a in the acrylic resin, the material that constitutes base material can be that to be selected from polyimides be resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, acrylic resin, the PET series resin, PEN is a resin, polybutylene terephthalate (PBT) is a resin, polyether-ether-ketone is a resin, fluorine resin, the olefin-based resin, polyarylate is at least a in the resin.

For porous membrane laminated body of the present invention, for example, the macromolecule component that constitutes porous layer can be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a in resin and the polyamide-based resin for being selected from polyimides, and the material that constitutes base material can be that resin, polyamidoimide are that resin, PEI are that resin, liquid crystalline polyester are that resin, aromatic polyamides are that resin, PET series resin, PEN are at least a in the resin for being selected from polyimides.

In addition, for porous membrane laminated body of the present invention, the macromolecule component that constitutes porous layer can be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a in resin and the polyamide-based resin for being selected from polyimides, and the material that constitutes the base material with many through holes can be to be selected from least a in fabric, eyelet fabric, punching film, wire netting, punch metal, expanded metal and the etching metal.

And, for porous membrane laminated body of the present invention, the macromolecule component that constitutes porous layer can be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a in resin and the polyamide-based resin for being selected from polyimides, and the material that constitutes metallic foil substrates can be for being selected from least a in Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel, the stainless steel foil.

The porous layer thickness of perforated membrane formed body of the present invention for example is about 0.1～100 μ m, and the porosity of porous layer for example is about 30～80%, and the thickness of base material for example is about 1～300 μ m.

In the present invention, for example, the perforated membrane formed body that is made of the base material with many through holes is preferably used as filter, battery separator, separator for capacitor, electrolyte membrane for fuel cell or catalyst carrier etc., and the perforated membrane formed body that is made of metallic foil substrates is preferably used as electromagnetic wave control material, circuit board or heat sink.

The present invention also provides a kind of manufacture method of porous membrane laminated body, and it obtains the porous membrane laminated body of the invention described above by the following method, promptly, with Polymer Solution after curtain coating on the base material becomes the film shape, import solidification liquid, carry out drying then, at the folded porous layer of at least one surface layer of base material.Above-mentioned Polymer Solution can be the mixed solution that is made of macromolecule component 8～25 weight %, water-soluble polymer 5～50 weight %, water 0～10 weight %, water soluble polar solvent 30～82 weight %.

And, the invention provides a kind of composite, its at least one porous layer surface at the porous membrane laminated body that constitutes the invention described above is laminated with metal-plated coating and/or magnetic coating layer.Composite of the present invention can be used for for example circuit substrate, heat sink material or electromagnetic wave control material.

The present invention also provides a kind of manufacture method of composite, it obtains composite by at least one the stacked metal deposition layer in porous layer surface at the porous membrane laminated body that constitutes the invention described above, and this method comprises following operation: thus the operation of photosensitive layer is set at the photosensitive composite that the compound of porous layer surface applied reaction of formation group by utilizing illumination to penetrate of above-mentioned porous membrane laminated body constitutes; Above-mentioned photosensitive layer is exposed, makes the operation of exposure portion reaction of formation group by mask; And the reactive group that exposure portion is generated combines, forms the operation of conductive pattern with metal.

In addition, the invention provides a kind of manufacture method of composite, it obtains composite by at least one the stacked metal deposition layer in porous layer surface at the porous membrane laminated body that constitutes the invention described above, and this method comprises following operation: the photosensitive composite that the compound that reactive group is disappeared in the porous layer surface applied of above-mentioned porous membrane laminated body constitutes, the operation that photosensitive layer is set; Above-mentioned photosensitive layer is exposed, makes in exposure portion the operation of reactive group disappearance by mask; And make the reactive group that remains in unexposed portion combine, form the operation of conductive pattern with metal.

The manufacture method of composite of the present invention can be to obtain for example method of circuit substrate, heat sink material or the employed composite of electromagnetic wave control material.

And, the invention provides a kind of composite, described composite utilizes printing technology to form electric conductor at least one porous layer surface of the porous membrane laminated body that constitutes the invention described above.As above-mentioned composite, for example can enumerate: circuit substrate, heat sink, electromagnetic wave control material, battery with assembly and capacitor with assembly etc.As above-mentioned printing technology, for example can enumerate: ink jet printing, screen painting, distributor printing (デ イ ス ペ Application サ printing), letterpress (aniline printing), subliming type printing, hectographic printing, laser printing printing (toner printing), intaglio printing (photogravure), contact print and micro-contact printing etc.As above-mentioned electric conductor, for example can enumerate: silver, gold, copper, nickel, tin indium oxide, carbon, CNT etc.

Composite of the present invention also utilizes printing technology to use the printing ink that contains the electric conductor particle to be formed with electric conductor at porous surface, wherein, and when the average perforate with the porous layer top layer directly is set at R ₁, the average grain diameter of electric conductor particle is set at R ₂The time, preferably it satisfies formula: 0.0001 ≦ R ₂/ R ₁≦ 1000.Above-mentioned electric conductor can be the electric conductor of the formation that for example covers with coating or insulating materials, more preferably enumerates electric conductor and is silver, the formation that covers with coating or insulating materials on the surface of silver.As above-mentioned coating, for example can enumerate: copper coating, gold plate, nickel coating etc.

In composite of the present invention, comprise in the hole of composite, porous layer of the hole of residual the porous layer that remains untouched and be filled with the composite of resin, handle the composite of the pore structure that loses porous layer etc. by solvent.As the resin in the hole that is filled in above-mentioned porous layer, for example can enumerate: epoxy resin, oxetane resin, acrylic resin, vinyl ether resin, polyimide resin, mylar, polyamide-imide resin etc.Above-mentioned composite can also be at porous layer upper strata superimposition cap rock.

In addition, the invention provides a kind of wiring board, it is to exist many at least one masks with porous rete of connective micropore that the wiring board of conductor wirings is arranged, and it is not by producing the disappearance of distribution in the disbonded test that utilizes cellophane tape [nichiban (strain) manufacturing, trade name " fabric strip (registration mark) No.405 ", fabric width 24mm] to carry out (180 ° peel off, peeling rate 50mm/ minute).

The present invention also provides a kind of wiring board, it is to exist many at least one masks with porous rete of connective micropore that the wiring board of conductor wirings is arranged, and its disbonded test by utilizing paper self-adhesive tape [nichiban (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] to carry out (180 ° peel off, peeling rate 50mm/ minute) does not produce the disappearance of distribution.

In above-mentioned each wiring board, the average grain diameter of porous rete for example is 0.01～10 μ m.

The present invention also provides a kind of wiring board, and it exists many at least one masks with porous rete of connective micropore that conductor wirings is arranged, and wherein, the average pore size of porous rete is 0.01～10 μ m, and conductor wirings utilizes print process to form.

In above-mentioned each wiring board, the porosity of porous rete for example is 30～80%.The thickness of porous rete for example is 0.1～100 μ m.The porous rete is preferably the layer that is formed by resin.In the porous rete, comprise by being that resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are that resin and polyimides are the layer that the material of at least a resin in the resin constitutes to be selected from polyamidoimide.In addition, in the porous rete, comprise the porous resin thin layer that utilizes phase inversion method to form.

The porous rete is preferably the layer that is made of perforated membrane, the following making of described perforated membrane: will in polar solvent, be dissolved with the material of this porous rete of formation and solution curtain coating on substrate of water-soluble polymer and become the film shape, under the atmosphere of relative humidity 70～100%, kept 0.2～15 minute, after impregnated in the solidification liquid that the non-solvent by above-mentioned material constitutes, carry out drying, desolventizing.

The one or both sides that the porous rete can substantially not have the compacted zone in hole form.Conductor wirings can utilize print process to form.

The present invention also provides a kind of manufacture method of wiring board, and it is the method that is used to make above-mentioned wiring board, and wherein, the one side at least that has many micropores of connectedness and the porous rete that average pore size is 0.01～10 μ m in existence forms conductor wirings.

In this manufacture method, the porous rete can be the resin bed that utilizes phase inversion method to form.In addition, can substantially not having the formed average pore size of one or both sides of the compacted zone in hole is the surface formation conductor wirings of the porous rete of 0.01～10 μ m.Can utilize print process to form conductor wirings on the surface of porous rete.For example: (1) uses electrically conductive ink on the surface of porous rete with ink-jetting style, can form conductor wirings thus; (2) formed coating electrically conductive printing ink on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete, can forms conductor wirings thus; (3),, can form conductor wirings by extruding conductor paste from syringe and describing on the surface of porous rete; (4) utilize screen painting to describe conductor paste on the surface of porous rete, can form conductor wirings thus.On the conductor wirings that forms like this, can further implement plating.

Also have, (5) on the surface of porous rete, utilize ink-jetting style with Wiring pattern shape printing plating catalyst after, implement plating, can form conductor wirings thus; (6) forming coating plating catalyst on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete after, implement plating, can form conductor wirings thus; (7) on the surface of porous rete, after extruding the plating catalyst from syringe and depicting the Wiring pattern shape as, implement plating, can form conductor wirings; (8) on the surface of porous rete, utilize screen painting to depict the plating catalyst as the Wiring pattern shape after, implement plating, can form conductor wirings thus.

And, the invention provides a kind of printed matter (below, be sometimes referred to as " printed matter 1 of the present invention "), it is a printed matter of having implemented to have with average live width 10～1000 μ m the printing of the straight line portion more than the long 500 μ m on the surface of porous rete at least, wherein, the change value F of the live width of following formula (1) expression is below 30%.

F＝(LMax-LMin)/LAve×100 (1)

(in the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m).

In addition, the present invention also provide a kind of printed matter (below, be sometimes referred to as " printed matter 2 of the present invention "), it is a printed matter of having implemented to have with average live width 10～1000 μ m the printing of the straight line portion more than the long 500 μ m on the surface of porous rete at least, wherein, the standard deviation ∑ of the live width of following formula (2) expression is below 7.

$\mathrm{\Σ}=\sqrt{(({(\mathrm{LAve}-\mathrm{LMax})}^2+{(\mathrm{LAve}-\mathrm{LMin})}^2)/2)}---\left(2\right)$

(in the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m).

In addition, the invention provides a kind of printed matter (below, be sometimes referred to as " printed matter 3 of the present invention "), it is a printed matter of having implemented printing on the surface of porous rete with version, wherein, and the aperture widths L of version ₁With the corresponding printing width L in printing back ₂Ratio (L ₂/ L ₁) be 0.8～1.2.

In above-mentioned each printed matter, comprise following printed matter: (i) use and contain following liquid as the printing-ink of main solvent or stick with paste and implement the printed matter that printing forms, the characteristics of described liquid are as follows: after the perforated membrane laminar surface drips, contact angle 300 microseconds of this perforated membrane laminar surface with interior be below 60 °; (ii) use and contain following liquid as the printing-ink of main solvent or stick with paste and implement the printed matter that printing forms, the characteristics of described liquid are as follows: drip the drop of 1 μ l at the perforated membrane laminar surface after, contact angle 300 microseconds of this perforated membrane laminar surface with interior be below 60 °, and the droplet radius during through 300 microseconds is below the 1600 μ m; (iii) using viscosity is the printing-ink of 0.05～1Pas or the printed matter that paste enforcement printing forms.These printed matters can be extruded to stick with paste to implement to print and form by screen cloth or metal mask.

The average pore size of porous rete for example is 0.01～10 μ m, and the porosity of porous rete for example is 30～80%, and the thickness of porous rete for example is 0.1～100 μ m.

The porous rete can be the layer that is formed by resin.At this moment, the resin of formation porous rete is preferably heat-resistant resin.As heat-resistant resin, can use and be selected from polyamidoimide is that resin, PEI are that resin, polycarbonate-based resin and polyether sulfone are the resin in the resin.

The porous rete is preferably the porous resin thin layer that utilizes phase inversion method to form.For example, the porous rete can be the layer that is made of perforated membrane, the following making of described perforated membrane: will in polar solvent, be dissolved with the material of this porous rete of formation and solution curtain coating on substrate of water-soluble polymer and become the film shape, under the atmosphere of relative humidity 70～100%, kept 0.2～15 minute, after in the solidification liquid that the non-solvent that impregnated in by above-mentioned material constitutes, carry out drying, desolventizing.

In printed matter, contain printed substrate.

And, the invention provides a kind of printed patterns manufacture method (below, be sometimes referred to as " manufacture method 1 of printed patterns of the present invention "), it comprises: operation, (2A) that implements printing through (1) on the porous rete makes operation that the porous rete of having implemented printing contacts with solvent, reaches the operation that the operation that (3A) makes solvent seasoning forms compacted zone.

The present invention also provide a kind of printed patterns manufacture method (below, be sometimes referred to as " manufacture method 2 of printed patterns of the present invention "), wherein, it comprises: (1) implements printing on the porous rete operation, (2B) make the porous rete of having implemented printing carry out heat fusing operation, and (3B) carry out the operation that cooling curing forms compacted zone.The ratio F2/F1 of the hot strength F1 of the porous rete that carries out the hot strength F2 of the compacted zone that cooling curing forms and use in operation (1) in above-mentioned operation (3B) is the value greater than 1.

In this manufacture method, the contact angle θ A when preferably the surface of the porous rete that uses in operation (1) drips behind the water through 1000 microseconds ₁₀₀₀With in operation (3A), make solvent seasoning after carry out the compacted zone that cooling curing forms in the compacted zone that forms or the operation (3B) the contact angle θ B of surface when dripping behind the water through 1000 μ sec ₁₀₀₀Than θ A ₁₀₀₀/ θ B ₁₀₀₀Preferably less than 1.

In addition, when porous rete that in measuring operation (1), uses and the contact angle between the water, the preferred contact angle θ A during through 1000 microseconds behind the surface of porous rete dropping water ₁₀₀₀Contact angle θ A with through 100 microseconds the time ₁₀₀Than θ A ₁₀₀₀/ A ₁₀₀Preferably less than 0.6, when carrying out the contact angle of compacted zone that cooling curing forms and water in compacted zone that forms after in measuring operation (3A), making solvent seasoning or the operation (3B), the preferred contact angle θ B during through 1000 microseconds behind the surface of compacted zone dropping water ₁₀₀₀Contact angle θ B with through 100 microseconds the time ₁₀₀Than θ B ₁₀₀₀/ θ B ₁₀₀For greater than 0.6 value.

As printing process, for example can enumerate: ink-jetting style, screen painting, hectographic printing, distillation mode, temperature-sensitive mode, photogravure, laser printing, paste printing or nano contact printing.

The average pore size of porous rete for example is 0.01～10 μ m, and the porosity of porous rete for example is 30～80%, and the thickness of porous rete for example is 0.1～100 μ m.

The porous rete can be the layer that is formed by resin.At this moment, the resin of formation porous rete is preferably heat-resistant resin.As heat-resistant resin, can use and be selected from polyamidoimide is that resin, PEI are that resin, polycarbonate-based resin and polyether sulfone are the resin in the resin.

The porous rete is preferably the porous resin thin layer that utilizes phase inversion method to form.For example, the porous rete is the layer that is made of perforated membrane, the following making of described perforated membrane: will in polar solvent, be dissolved with the material of this porous rete of formation and solution curtain coating on substrate of water-soluble polymer and become the film shape, under the atmosphere of relative humidity 70～100%, kept 0.2～15 minute, after in the solidification liquid that the non-solvent that impregnated in by above-mentioned material constitutes, carry out drying, desolventizing.

The present invention also provides a kind of manufacture method of utilizing above-mentioned printed patterns to form the printed matter of printed patterns.

This printed matter comprises printed substrate.

Because porous membrane laminated body of the present invention has the porous layer that is made of many micropores, therefore, the flexibility excellence, has excellent hole characteristic simultaneously, and since this porous layer lining cutting on base material, therefore, even for having the situation of voidage, also can bring into play full intensity, bending resistance, applicability are very excellent.According to the present invention, can stably make with easy method have above-mentioned characteristic, membranous uniform porous membrane laminated body.Because the porous membrane laminated body that obtains like this has above-mentioned characteristic, therefore, can be used for advanced low-k materials, filter, dividing plate, electrolyte membrane for fuel cell, catalyst substrate (catalyst carrier), padded coaming, printing ink video picture sheet material, test paper, insulating materials, heat-barrier material etc., in addition, hole by with the filling porous layer of functional material can be widely used as the circuit substrate, heat sink material (radiator, heat sink), electromagnetic waves such as electromagnetic wave baffle plate and electromagnetic wave absorb control material, battery separator, capacitor (paper capacitor, plastic film capacitor, ceramic capacitor, mica condenser, electrolytic capacitor etc.), the cell culture medium material, catalyst substrate (catalyst carrier) etc.

In addition, wiring board of the present invention is to exist many at least one masks with porous rete of connective micropore (micropore continuously) that the wiring board of conductor wirings is arranged equably, has following characteristic: for for example conductor wirings of fabric width 50～200 μ m, when the disbonded test that utilizes cellophane tape [nichiban (strain) manufacturing, trade name " fabric strip (registration mark) No.405 ", fabric width 24mm] (180 ° peel off, peeling rate 50mm/ minute), do not produce the disappearance of distribution.In above-mentioned belt stripping test,, also can use the cellophane tape that has equal bonding force (4.00N/10mm) with it to replace above-mentioned " fabric strip (registration mark) No.405 " as cellophane tape.

And, the method according to this invention, owing to be on the porous rete, to implement printing, therefore, solvent in printing-ink or the paste is quickly absorbed in the hole, the viscosity of printing ink rises and loses flowability, and therefore, can carry out the printing of fine rule illustrative excellence, and, owing to remove this solvent on the basis that is temporarily utilizing solvent or solvent and heat that the porous rete is dissolved after the printing, therefore, it is fine and close that the porous rete has become, being printed the intensity of part and the close adhesion intensity of printing thus improves, can also prevent the absorption of liquid such as sealing, so, can be easy and productivity make the ruined printed patterns that is not easy of having implemented accurate printing well.In addition, because the porous rete becomes fine and close, therefore, also improve gas shield and wear-resisting wiping.Therefore, can improve reliability based on the printed matter of wiring board.

The specific embodiment

Porous membrane laminated body of the present invention has following structure: at least one surface layer at base material is folded porous layer, and by belt stripping test base material and porous layer interface peel does not take place.Above-mentioned belt stripping test is as follows: the ridge, temple of pasting fabric width 24mm on the porous layer surface of porous membrane laminated body makes the masking tape [film masking tape No.603 (#25)] that company of institute makes, with the roller of diameter 30mm, 200 gram force loadings press sticking after, use cupping machine to carry out the T mould and peel off with peeling rate 50mm/ minute.That is, refer to interlayer close adhesion intensity laminated substrate and porous layer in above-mentioned belt stripping test with the degree that interface peel does not take place.

Porous membrane laminated body of the present invention has following advantage, as mentioned above, because it has the formation that directly is laminated with base material and porous layer with specific interlayer close adhesion intensity, therefore have flexibility and excellent hole characteristic, on the other hand, because of it has appropriate rigidity, so applicability improves.And, owing to can broadly select to constitute the macromolecule component of porous layer, therefore, can be suitable as the material in multiple field.The interlayer close adhesion intensity of base material and porous layer can constitute the raw-material kind of each layer and the physical characteristic at interface is adjusted by suitable setting.

Material as constituting base material so long as can form the base material that interface peel does not take place by above-mentioned belt stripping test and porous layer, does not just have particular determination, can suitably select according to the material that constitutes porous layer.As the material that constitutes base material, for example can enumerate: polyimides is a resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, acrylic resin, the PET series resin, PEN is a resin, polybutylene terephthalate (PBT) is a resin, polyether-ether-ketone is a resin, fluorine resin, olefin-based resin (comprising annular ethylene series resin etc.), polyarylate is plastics such as resin etc.These materials can be used alone or mixed use of two or more, and in addition, also can be used alone or in combination the copolymer (graft polymers, block copolymer, random copolymer etc.) of above-mentioned resin.And, also can use the polymer of the skeleton (polymer chain) that contains above-mentioned resin on main chain or the side chain.As the concrete example of this polymer, can enumerate contain polysiloxane and polyimides skeleton on the main chain contain polysiloxanes polyimides etc.

As the base material among the present invention, also can use the film of following illustrative commercially available product etc.As the polyimides based resin film, commercially available have: " APICAL " that " Kapton " that Toray Dupont Co., Ltd. makes, the Kaneka of Co., Ltd. make, " UPILEX " of Ube Industries, Ltd etc.As pet film, commercially available have: " Supreme Being people Tetoron film ", " Melinex " that Supreme Being people dupont film Co., Ltd. makes, " Mylar " etc.As the PEN film, commercially available have: " Teonex " that Supreme Being people dupont film Co., Ltd. makes etc.

As liquid crystalline polyester is film, and " Vectra " that Polyplastics Co., Ltd. (JP) 30, Azuchimachi 2-chome, Higashi-ku, Osaka-shi, Osak can be made, " the シ べ ラ ス " that toray Co., Ltd. makes, the commercially available resins such as " SUMIKASUPER LCP " that Sumitomo Chemical Company Ltd makes are made film and used.

Polyacrylic film can be enumerated as the most normally used film of olefin-based resin film, commercially available polypropylene film can be easily obtained.In addition, also can use the film of annular ethylene series resin manufacturing with circulus, for example, " TPX " that Mitsui Chemicals, Inc can be made, " ZEONOR " that Japanese zeon Co., Ltd. makes, commercially available resins such as " TOPAS " that Polyplastics Co., Ltd. (JP) 30, Azuchimachi 2-chome, Higashi-ku, Osaka-shi, Osak makes are made film and are used.

As previously described, also can use the base material that has formed adhesive phase in the one side of base material.As this base material, for example can enumerate: the ridge, temple makes the commercially available electric and electronic adhesive tape of company of institute.Can use " Kapton adhesive tape ", " PPS film adhesive adhesive tape ", " PEI film adhesive adhesive tape ", " PEN film adhesive adhesive tape ", " polyester film adhesive tape " etc.

In the present invention, also can use base material with many through holes or metallic foil substrates etc. as base material.

At this, so-called " base material with through hole " is meant at the base material that has the hole of perforation with respect to substrate plane approximate vertical direction.As base material,, just there is not particular determination so long as can form many through holes and not produce interface peel by above-mentioned belt stripping test and porous layer with many through holes.As constituting this material, for example can enumerate: plastic sheeting or sheet materials such as fabric, nonwoven, eyelet fabric, punching film with base material of many through holes; Metal forming such as wire netting, punch metal, expanded metal and etching metal or sheet material etc. can suitably be selected to utilize according to characteristics such as resistance to water, hear resistance, resistances to chemical reagents.Wherein, preferably use fine and have the eyelet fabric of regular texture.In addition, because the cost of nonwoven is quite low, therefore also preferably use.

As fabric, can utilize be selected from the following fiber one or both combination and the fabric that forms, described fiber for example has: natural fibers such as cotton fiber, silk flock; Glass fibre, PEEK fiber, aramid fibre, polybenzoxazole fibers resin fibres such as (wood-fibreds etc.), carbon fiber etc.

As nonwoven, can utilize be selected from the following fiber one or both combination and the nonwoven that forms, described fiber for example has: natural fibers such as cotton, wool, fiber crops, paper pulp, silk, mineral fibres for example; Artificial silk, nylon, polyester, polypropylene, acrylic fiber, vinylon, aramid fibre, liquid crystalline polyester chemical fibres such as (LCP); Glass fibre etc.The kind of the resin of the base material of formation nonwoven can be according to selections such as hear resistance, resistance to chemical reagents, intensity, costs.

In eyelet fabric, because of there are a plurality of kinds in its mesh (micron number of the size in the slit between yarn and the yarn), yarn diameter (micron number of the rugosity of yarn), sieve aperture (radical of the yarn between 1 inch), mesh rate (with respect to the ratio of the aperture portion of whole sieve aperture), thickness differences such as (micron numbers of the thickness of sieve aperture).The weave of eyelet fabric is also various, and ASTM (U.S.'s commercial size), DIN (Deutsche Industrie Normen (DIN)), HD, XX, GG, HC﹠amp are arranged; P, シ ユ リ Application ガ-etc. kind.Can from these eyelet fabrics, suitably select to use the eyelet fabric that possesses the rerum natura of wanting.

As the punching film, can enumerate by the film of PET, polyimides etc. being implemented the punching film that stamping-out processing etc. is washed into holes such as circle, square, rectangle, ellipse.

As wire netting, can utilize commercially available plain weave wire netting, twill wire netting, seat type plain weave wire netting, seat type twill wire netting etc.As material, can enumerate iron, stainless steel, copper, nickel etc.

As punch metal, can enumerate by the paper tinsel of metal or sheet material being implemented the punching film that stamping-out processing etc. is washed into holes such as circle, square, rectangle, ellipse.As material, can enumerate iron, aluminium, stainless steel, copper, titanium etc.

As expanded metal, can enumerate the expanded metal of the shape of JIS specification.XS63, XS42 cover plate etc. are for example arranged.As material, can enumerate iron, aluminium, stainless steel etc.

Above-mentioned base material with many through holes can be made corresponding to the conventional process of material by processing methods such as etching and processing, stamping-out processing, laser irradiation etc.It has following advantage: utilize this base material with many through holes, by to this surface applied Polymer Solution and stacked porous layer, can carry out stacked with the interlayer close adhesion intensity of excellence.In addition, can obtain following effect: have flexibility and excellent hole characteristic, on the other hand, because of it has the rigidity of appropriateness, so improved applicability.

When the base material with many through holes is eyelet fabric, the average pore size of substrate surface (mesh: for example be 30～1000 μ m the size in the slit between wire rod and the wire rod), be preferably about 40～200 μ m that surperficial percent opening (mesh rate: with respect to the ratio of the aperture portion of whole sieve aperture) is 20～70% for example, is preferably about 25～60%.Cross when low when each numerical value of above-mentioned mesh and mesh rate, make easily that the interlayer close adhesion is insufficient, the flexibility step-down, when above-mentioned each numerical value is too high, the rigidity of mechanical strength aspect is reduced, poor for applicability, not preferred.

When the base material with many through holes was punching film or punch metal, its surperficial percent opening was about 20～80%, is preferably about 30～70%.Cross when low when the numerical value of surperficial percent opening, make the permeability variation of gas or liquid easily, when numerical value is too high, make easily intensity reduce, poor for applicability, not preferred.

When the base material with many through holes was wire netting, surperficial percent opening was about 20～80%, is preferably about 25～70%.Cross when low when the numerical value of surperficial percent opening, make the permeability variation of gas or liquid easily, when numerical value is too high, make easily intensity reduce, poor for applicability, not preferred.

When the base material with many through holes was expanded metal, surperficial percent opening was about 20～80%, is preferably about 25～70%.Cross when low when the numerical value of surperficial percent opening, make the permeability variation of gas or liquid easily, when numerical value is too high, make easily intensity reduce, poor for applicability, not preferred.

Base material can be a single thin film, also can be by comprising the laminated film that identical or different raw-material multilayer constitutes.Laminated film can be to use bonding agent etc. to be laminated with the laminate film of a plurality of films as required, also can be to implement processing such as coating, evaporation, sputter and the film that obtains.

In addition, when the one side of base material forms porous layer, can on the face of the face of stacked porous layer and opposition side, form adhesive phase, and can on adhesive phase, paste diaphragm (demoulding film) so that its easy operation.Adhesive phase also can form on the opposing face at base material after forming porous layer, also can form porous layer on the opposing face of the base material that has simultaneously formed adhesive phase.Adhesive phase can form by coating, also can paste adhesive films.It perhaps also can be the method for pasting double faced adhesive tape.

Base material among the present invention is preferred: when coating is used to form the Polymer Solution (coating liquid) of porous layer, film does not take place or the base material of membranous variations such as rare dissolving or strong deformation.

The base material with many through holes among the present invention can utilize commercially available product.For example, as nonwoven, commercially available have: PP type nonwoven (trade name " FC-310 "), polyesters nonwoven (trade name " MF-80K ") that Japanese Vilene company makes; The aramid nonwoven fabric (trade name " Nomex paper " 410 types, 411 types, 414 types, 418 types etc.) that dupont Supreme Being people ア De バ Application ス De ペ-パ-company makes; Liquid crystalline polyester (LCP) nonwoven (trade name " ベ Network Le ス " MBBK-CKJ type, MBBK-KJ type etc.) that kuraray company makes etc.In addition, the eyelet fabric that SEFAR company makes is according to having numerous species as raw-material resin, particularly, commercially available have: polyester eyelet fabric (trade name " PETEX "), nylon eyelet fabric (trade name " NYTAL "), carbon eyelet fabric (trade name " CARBOTEX "), special teflon (registration mark) eyelet fabric (trade name " FLUORTEX "), polypropylene mesh cloth (trade name " PROPYLTEX "), silk eyelet fabric (trade name " SILK ") etc. and polyethylene mesh cloth etc.The kind of the resin of the base material of formation eyelet fabric etc. can be according to selections such as hear resistance, resistances to chemical reagents.

Can implement surface treatments such as roughening processing, easy bonding processing, antistatic treatment, blasting treatment (sandblast delustring processing), Corona discharge Treatment, plasma treatment, chemical etching processing, water delustring processing, flame treatment, acid treatment, alkali treatment, oxidation processes, ultraviolet treatment with irradiation, silane coupler processing to base material, also can use and implement this surface-treated commercially available product.As this base material, for example can enumerate: coating carbon and the nylon that forms or the eyelet fabric of polyester etc.

In addition, also above-mentioned kinds of surface treatment combination can be carried out.For example, can utilize and base material is at first implemented Corona discharge Treatment, plasma treatment, flame treatment, acid treatment, alkali treatment, oxidation processes, ultraviolet treatment with irradiation etc. any carries out method that silane coupler handles etc. after handling.According to the kind of base material, but compare often intensive treatment, particularly polyimides with the independent processing of silane coupler be that base material etc. can be expected high effect to said method.As silane coupler, can enumerate the product that chemical industrial company of SHIN-ETSU HANTOTAI makes or Japanese energy companies is made.

Material as constituting metallic foil substrates as long as can form the base material that does not produce interface peel by belt stripping test and porous layer, does not just have particular determination, can suitably select according to the material that constitutes porous layer.As the material that constitutes metallic foil substrates, for example can enumerate: Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel, stainless steel foil etc.These materials can be used alone or mixed use of two or more.

Metallic foil substrates can be that individual layer also can be by comprising the laminated film that identical or different raw-material multilayer constitutes.Composite metallic material can be to use bonding agent etc. to be laminated with the laminate film of a plurality of metal formings as required, also can be to implement processing such as coating, evaporation, sputter and the composite metallic material that obtains.In addition, form the situation of porous layer, can on the face of the face of stacked porous layer and opposition side, form adhesive phase, can also on adhesive phase, paste diaphragm (demoulding film), so that its easy operation in the one side of metallic foil substrates.

Metallic foil substrates among the present invention is preferred: when coating is used to form the Polymer Solution (coating liquid) of porous layer, film does not take place or the metallic foil substrates of membranous variations such as rare dissolving or strong deformation.

As the metallic foil substrates among the present invention, also can use the metal forming of the film shape of following illustrative commercially available product.

Copper Foil is commercially available to be had: the rolled copper foil that the electrolytic copper foil (kind: HTE, VLP) that the electrolytic copper foil (kind: HTE, VP, HS, SV) that Fukuda Metal Foil ﹠ POwder Co., Ltd. makes, rolled copper foil (kind: RCF, RCF-AN), Mitsu Mining ﹠ Smelting Co., Ltd make, Japanese foliation Co., Ltd. make etc.

Aluminium foil is commercially available to be had: the aluminium foil that the aluminium foil that Fukuda Metal Foil ﹠ POwder Co., Ltd. makes, Japanese foliation Co., Ltd. make, live the aluminium foil that light aluminium foil Co., Ltd. makes.

Iron foil is commercially available to be had: the iron foil that zinc Co., Ltd. of eastern nation makes.

In addition, also can use the metal forming that is coated with adhesive in the one side of metal forming, as commercially available product, can obtain Copper Foil adhesive tape, aluminum foil tape, stainless steel foil adhesive tape, electric conductivity Copper Foil adhesive tape, electric conductivity aluminum foil tape, the shielding adhesive tape (electric conductivity cloth adhesive tape) of K. K. Teraoka Seisakusho etc. with above-mentioned formation.In addition, also can use the commercially available products such as stainless steel adhesive tape of the nitoms of Co., Ltd..

Also can implement surface treatments such as roughening processing, easy bonding processing, antistatic treatment, blasting treatment (sandblast delustring processing), Corona discharge Treatment, plasma treatment, chemical etching processing, water delustring processing, flame treatment, acid treatment, alkali treatment, oxidation processes to metallic foil substrates, also can use and implement this surface-treated commercially available product.This metallic foil substrates for example can be enumerated: implemented the Copper Foil of roughening processing etc.

The thickness of metallic foil substrates for example is 1～300 μ m, is preferably 5～200 μ m, more preferably 5～100 μ m.Cross when thin when thickness, be difficult to operation, on the other hand, when it was blocked up, often flexibility reduced.In above-mentioned illustrative commercially available base material, it is the base material of 9 μ m, 12 μ m, 18 μ m, 35 μ m, 70 μ m etc. that thickness is arranged, and can use.

The main component of porous layer is made of for example macromolecule component.Macromolecule component as constituting porous layer as long as can form the metallic foil substrates that does not produce interface peel by above-mentioned belt stripping test and porous layer, does not just have particular determination, can suitably select according to the material that constitutes metallic foil substrates.As above-mentioned macromolecule component, for example can enumerate: polyimides is that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, polyphenylene sulfide are that resin, liquid crystalline polyester are that resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polybenzothiozole are that resin, polysulfones are plastics such as resin, cellulose-based resin, acrylic resin etc.These macromolecule components can be used alone or mixed use of two or more, and in addition, also can be used alone or in combination the copolymer (graft polymers, block copolymer, random copolymer etc.) of above-mentioned resin.And, also can use the polymer of the skeleton (polymer chain) that contains above-mentioned resin on main chain and the side chain.As the concrete example of this polymer, that can enumerate the skeleton that contains polysiloxane and polyimides on the main chain contains polysiloxanes polyimides etc.

Wherein, as the preferred embodiment of the macromolecule component that constitutes porous layer, can enumerate and to have hear resistance, can carry out hot forming, mechanical strength and resistance to chemical reagents and all excellent polyamide-based resin, the polyamidoimide of electrical characteristics is that resin or polyimides are the macromolecule component of resin as main component.Polyamidoimide is that resin can be made by carrying out imidizate after carrying out polymerization in the reaction of the reaction that utilizes trimellitic anhydride and vulcabond or trimellitic anhydride acyl chlorides and diamines usually.Polyimides is that resin can obtain polyamic acid by the reaction that for example utilizes tetrabasic carboxylic acid composition and two amine components and it further carried out imidizate make.By polyimides be resin when constituting porous layer since when it carries out imidizate the dissolubility variation, therefore, at first behind the stage of polyamic acid formation perforated membrane, carry out imidizate (hot-imide, chemical imidizate etc.) more mostly.

Base material can be that individual layer also can be by comprising the laminated film that identical or different raw-material multilayer constitutes.Laminated film can be to use bonding agent etc. to be laminated with the laminate film of a plurality of films as required, also can be to implement processing such as coating, evaporation, sputter and the laminated film that obtains.

Base material among the present invention is preferred: when coating is used to form the Polymer Solution (coating liquid) of porous layer, film does not take place or the base material of membranous variations such as rare dissolving or strong deformation.

Can implement surface treatments such as easy bonding processing, antistatic treatment, blasting treatment (sandblast delustring processing), Corona discharge Treatment, plasma treatment, chemical etching processing, water delustring processing, flame treatment, acid treatment, alkali treatment, oxidation processes, ultraviolet treatment with irradiation, silane coupler processing to base material, also can use and implement this surface-treated commercially available product.As this base material, for example can enumerate: implemented the PET film of easy bonding processing or antistatic treatment, the Kapton that plasma treatment is crossed etc.

In addition, also above-mentioned kinds of surface treatment combination can be carried out.For example, can utilize and base material is at first implemented Corona discharge Treatment, plasma treatment, flame treatment, acid treatment, alkali treatment, oxidation processes, ultraviolet treatment with irradiation etc. any carries out method that silane coupler handles etc. after handling.According to the kind of base material, but compare often intensive treatment, particularly polyimides with the independent processing of silane coupler be that base material etc. can be expected high effect to said method.As silane coupler, can enumerate the product that chemical industrial company of SHIN-ETSU HANTOTAI makes or Japanese energy companies is made.

The thickness of base material for example is 1～300 μ m, is preferably 5～200 μ m, more preferably 5～100 μ m.Cross when thin when thickness, be difficult to operation, on the other hand, when it was blocked up, often flexibility reduced.In above-mentioned illustrative commercially available base material, it is the base material of 12 μ m, 12.5 μ m, 25 μ m, 50 μ m, 75 μ m, 125 μ m etc. that thickness is arranged, and can use.

Particularly when use had the base material of many through holes, the thickness with base material of many through holes for example was 1～1000 μ m, is preferably 5～200 μ m, more preferably 5～100 μ m.Cross when thin when the thickness of the base material with many through holes, be difficult to operation, on the other hand, when it was blocked up, often flexibility reduced.

The main component of porous layer is made of for example macromolecule component.Macromolecule component as constituting porous layer as long as can form the base material that does not produce interface peel by above-mentioned belt stripping test and porous layer, does not just have particular determination, can suitably select according to the material that constitutes base material.As above-mentioned macromolecule component, for example can enumerate: polyimides is that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, polyphenylene sulfide are that resin, liquid crystalline polyester are that resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polybenzothiozole are that resin, polysulfones are plastics such as resin, cellulose-based resin, acrylic resin etc.These macromolecule components can be used alone or mixed use of two or more, and in addition, also can be used alone or in combination the copolymer (graft polymers, block copolymer, random copolymer etc.) of above-mentioned resin.And, also can use the polymer of the skeleton (polymer chain) that contains above-mentioned resin on main chain and the side chain.As the concrete example of this polymer, that can enumerate the skeleton that contains polysiloxane and polyimides on the main chain contains polysiloxanes polyimides etc.

Wherein, as the preferred embodiment of the macromolecule component that constitutes porous layer, can enumerate and to have hear resistance, can carry out hot forming, mechanical strength and resistance to chemical reagents and all excellent polyamidoimide of electrical characteristics is that resin or polyimides are the macromolecule component of resin as main component.Polyamidoimide is that resin can be made by carrying out imidizate after carrying out polymerization in the reaction of the reaction that utilizes trimellitic anhydride and vulcabond or trimellitic anhydride acyl chlorides and diamines usually.Polyimides is that resin can obtain polyamic acid by the reaction that for example utilizes tetrabasic carboxylic acid composition and two amine components and it further carried out imidizate make.By polyimides be resin when constituting porous layer since when it carries out imidizate the dissolubility variation, therefore, at first behind the stage of polyamic acid formation perforated membrane, carry out imidizate (hot-imide, chemical imidizate etc.) more mostly.

Porous layer thickness for example is 0.1～100 μ m, is preferably 0.5～70 μ m, more preferably 1～50 μ m.Cross when thin when thickness, be difficult to stably make, on the other hand, when it is blocked up, be difficult to control equably pore-size distribution.

Particularly when use had the base material of many through holes, porous layer thickness for example was 0.1～1000 μ m, was preferably 0.5～500 μ m, more preferably 1～200 μ m.Cross when thin when thickness, be difficult to stably make, on the other hand, when it is blocked up, be difficult to control equably pore-size distribution.

Do not accompany other layers between the base material of porous membrane laminated body of the present invention and the porous layer, carry out stacked with the interlayer close adhesion intensity of degree that interface peel does not take place in above-mentioned belt stripping test.As the method for the close adhesion that improves base material and porous layer, for example can enumerate: suitable surface-treated methods such as blasting treatment (sandblast delustring processing), Corona discharge Treatment, acid treatment, alkali treatment, oxidation processes, ultraviolet treatment with irradiation, plasma treatment, chemical etching processing, water delustring processing, flame treatment, silane coupler processing are implemented on the surface of stacked porous layer one side in base material; Be used in combination the material that to bring into play good close adhesion (compatibility, compatibility) as the method for the composition that constitutes base material and porous layer etc.As silane coupler, can use above-mentioned illustrative silane coupler.Above-mentioned surface treatment can multiple combination and implement, and according to base material, preferred compositions is implemented silane coupler and handled and other processing.

Consider from the angle of the close adhesion of base material and porous layer, porous membrane laminated body of the present invention preferably has following structure: for example, the macromolecule component that constitutes porous layer is a resin for being selected from polyimides, polyamidoimide is a resin, PEI is a resin, aromatic polyamides is at least a in resin and the polyamide-based resin, and it is resin that the material that constitutes base material is selected from polyimides, polyamidoimide is a resin, PEI is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, the PET series resin, PEN is at least a in the resin.Consider from same angle, as the optimal way of porous membrane laminated body, can enumerate: at least a portion of monomeric unit that each component portion that constitutes base material and porous layer is identical or all identical, for example constitute two-layer macromolecular compound is identical.This porous membrane laminated body comprises: for example constitute the duplexer that the material of base material/porous layer is constituted by polyimides/polyimides, polyamidoimide/polyimides, polyimide/polyamide acid imide, PEI/polyimides, polyimide/polyetherimide, polyamidoimide/PEI, PEI/polyamidoimide etc.

In addition, consider from the angle of the close adhesion of base material with many through holes and porous layer, porous membrane laminated body of the present invention preferably has following structure: for example, the macromolecule component that constitutes porous layer is that to be selected from polyimides be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a in resin and the polyamide-based resin, and the material that constitutes the base material with many through holes is selected from least a in fabric, nonwoven, eyelet fabric, punching film, wire netting, punch metal, expanded metal, the etching metal.

And, consider from the angle of the close adhesion of metallic foil substrates and porous layer, porous membrane laminated body of the present invention preferably has following structure: for example, the macromolecule component that constitutes porous layer is that to be selected from polyimides be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a in resin and the polyamide-based resin, and the material that constitutes metallic foil substrates is selected from least a in Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel, the stainless steel foil.

There are many connective micropores that have in porous layer among the present invention, and the average pore size of this micropore (average pore size of=film inside) is 0.01～10 μ m.The average pore size of micropore is preferably 0.05～5 μ m.In the time of outside average pore size is above-mentioned scope, be difficult to obtain according to aspect the desirable effect of purposes, the hole characteristic is poor, for example, when undersized, tend to cause that shock-absorbing capacity reduces, impregnability reduction, insulating properties or the thermal insulation reduction etc. of printing ink, when it is excessive, ink diffusion or be difficult to form fine distribution sometimes.

The mean porosities of the inside of porous film is 30～80% for example, is preferably 40～80%, more preferably 45～80%.In the time of outside porosity is above-mentioned scope, be difficult to obtain according to the desirable hole characteristic of purposes, for example cross when low when porosity, sometimes dielectric constant rises, or the shock-absorbing capacity reduction, or printing ink can not soak into, or thermal insulation reduces, can not obtain desirable effect even fill functional material, when porosity is too high, intensity, bending resistance possible deviation.In addition, as the percent opening (surperficial percent opening) on the surface of porous film, for example be (for example 48～80%) more than 48%, be preferably about 60～80%.Cross when low when surperficial percent opening, remove and take place the inadequate situation of through performance, even the filling functional material often can not be given full play to its function in hole, when it was too high, bending resistance reduced easily.

Porous layer gets final product in the formation of one side at least of base material, also can form on the two sides.Form porous layer by two sides, can effectively utilize its hole characteristic, obtain giving the porous membrane laminated body of low-k, resiliency, printing ink video picture, thermal insulation etc. on the two sides at base material.And, by fill the hole on two sides with functional material, can be as the baseplate material of circuit with electromagnetic waves such as substrate, heat sink material (radiator, heat sink), electromagnetic wave dividing plate or electromagnetic wave absorb control material, battery separator, capacitor (paper capacitor, plastic film capacitor, ceramic capacitor, mica condenser, electrolytic capacitor etc.), advanced low-k materials, dividing plate, padded coaming, printing ink video picture sheet material, test paper, insulating materials, heat-barrier material, cell culture medium material, catalyst substrate wide regions such as (catalyst carriers).Also can give multiple function by in the hole on two sides, filling different functional materials.Certainly, also can one side still fill functional material and use for hole, another side.

Also can implement to give the processing of resistance to chemical reagents to the porous layer of porous membrane laminated body of the present invention.By giving resistance to chemical reagents to porous membrane laminated body, utilize in the mode the multiple of porous membrane laminated body, it is favourable can avoiding on splitting, swelling, dissolving, the unfavorable condition this point such as rotten when it contacts with solvent, acid, alkali etc.As the processing of giving resistance to chemical reagents, can enumerate: the physical treatment that utilizes heat, ultraviolet ray, visible light, electron beam, radioactive ray etc. to carry out; On porous layer, cover the chemical treatment of resistance to chemical reagents macromolecule etc. etc.

For example, the porous layer of porous membrane laminated body of the present invention can cover with the resistance to chemical reagents macromolecule.The tunicle that this porous membrane laminated body can form resistance to chemical reagents at the surface or the inner micropore surface of for example porous layer can constitute the duplexer with resistance to chemical reagents.At this, so-called medicine, be that the known resin of existing formation porous film that makes dissolves, swelling, shrink, decompose, reduction is as the medicine of the function of porous film, because of the kind of the formation resin of porous layer and base material different, cannot treat different things as the same, concrete example as this medicine, can enumerate: dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), 2-Pyrrolidone, cyclohexanone, acetone, methyl acetate, ethyl acetate, ethyl lactate, acrylonitrile, carrene, chloroform, tetrachloroethanes, oxolane intensive polar solvents such as (THF); Inorganic salts such as NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, potash; Amines such as triethylamine; Be dissolved with aqueous slkalis such as the aqueous solution of alkali such as ammonia or organic solvent; Inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid; Be dissolved with acetate, phthalic acid etc. and have acid solutions such as the aqueous acid such as organic acid of carboxylic acid or organic solvent; And their mixture etc.

As the resistance to chemical reagents macromolecular compound, as long as medicines such as intensive polar solvent, alkali, acid are had excellent patience, just do not have particular restriction, for example can enumerate: phenol resin, diformazan benzene series resin, urea are that resin, melamine are that resin, benzoguanamine are that resin, benzoxazine are that resin, alkyd are that resin, triazine resin, furans are that resin, unsaturated polyester (UP), epoxy are that resin, silicon are that resin, polyurethane series resin, polyimides are thermosetting resin or photo-curable resins such as resin; Polyvinyl alcohol, acetate fiber prime system resin, polypropylene-based resin, fluorine resin, phthalic acid are that resin, maleic acid are thermoplastic resins such as resin, saturated polyester, ethylene-vinyl alcohol copolymer, chitin, shitosan etc.These macromolecular compounds can use a kind of or mixing is used two or more.In addition, macromolecular compound can be that copolymer also can be a graft polymers.

The porous membrane laminated body that constitutes by the porous layer that covers with this resistance to chemical reagents macromolecule, even when contacting with medicines such as above-mentioned intensive polar solvent, alkali, acid, dissolving or swelling set iso-metamorphism do not take place in porous layer fully yet, and maybe can suppress does not have the rotten of effect to application target and purposes.For example, in the purposes of the time weak point that porous layer contacts with medicine, as long as give the resistance to chemical reagents of stay-in-grade degree in this time.

Need to prove because above-mentioned resistance to chemical reagents macromolecular compound has hear resistance mostly simultaneously, therefore, with cover porous layer with the resistance to chemical reagents macromolecular compound before compare, the possibility of hear resistance reduction is few.

In addition, in the present invention, also can be the formation that in the micropore that constitutes porous layer, is filled with functional material.As functional material, for example can enumerate: ferrite particles, metal particle (comprising containing metal particulates such as metal oxide microparticle), carbon black, CNT, fullerene, titanium oxide, barium titanate etc.The filling condition of functional material does not have particular determination, by filling with the resolution of sub-micron～micron unit, can suppress the loss of the hole characteristic that porous layer had originally, and can improve applicability, the operability of the loading etc. of easy adjustment functional material, so preferred.When filling functional material, when the micropore of porous layer is too small, be difficult to fill functional material, when it is excessive, be difficult to the filling of functional material is controlled to be sub-micron～micron unit, therefore, the average pore size of micropore is preferably in the above-mentioned number range, and the maximum diameter of hole of film surface is preferably below the 15 μ m.

The porosity that porous membrane laminated body of the present invention tends to take place porous layer improves or forms loose structure when the aperture is reduced and cause the weakened of porous layer part or reduce with the close adhesion intensity of base material.By utilizing method described later that loose structure is disappeared, can strengthen the intensity of porous layer part, or the close adhesion intensity of raising and base material.In addition, disappear, can suppress the diffuse reflection of visible light, make it become transparent, therefore can be applied to purposes widely by making loose structure.

Because therefore porous membrane laminated body of the present invention, has the hole characteristic of aforesaid excellence for be laminated with the formation of base material on the perforated membrane of softness, has sufficient bending resistance simultaneously.Bending resistance is, carrying out repeatedly based on the bend test of following condition to the number of times of tested material fracture is to be evaluated as more than 10 times the time to have bending resistance.In addition, basis for estimation is: the number of bends to fracture is high more, and its bending resistance that has is excellent more, for example, requires in the purposes of alternating bending at electronic material etc., preferably have to the number of times of fracture be the bending resistance of degree more than 100 times.Bend test uses the smart mechanism of Japan to make the MIT anti-fatigue test machine MIT-D of manufacturing, under the condition of radius of curvature (R) 0.38mm of sample shape 15 * 110mm, 135 ° of angle of bend, flexure plane, rate of bending 175cpm, tension force 4.9N, carry out according to the counter-bending test of JIS C 5016.

According to porous membrane laminated body of the present invention, be also not rupture, have very excellent resistant to bending porous membrane laminated body for 20000 times even also comprise number of bends.Therefore, excellent processability, formability can be brought into play, purposes widely can be applied in many ways.

In addition, the porous membrane laminated body that is made of the base material with many through holes because it is to have the base material of many through holes and high-molecular porous layer with the integrated structure that forms of the close adhesion of excellence, therefore, possesses high mechanical strength.Therefore, be favourable even under the gross thickness at porous membrane laminated body for example is lower than the very thin situation about 100 μ m, also can bring into play aspect the full intensity.

Optimal way of the present invention is the porous membrane laminated body with porous layer, described porous layer covers the one or both sides of base material, have and have connective many micropores, and the average grain diameter of this micropore is 0.01～10 μ m, and this porous layer thickness is that 0.1～100 μ m, porosity are 30～80%, the thickness of base material is 1～300 μ m.This porous membrane laminated body can by suitable setting constitute porous layer and base material material, thickness, create conditions to wait and make.

In addition, optimal way when base material is made of the base material with many through holes is the porous membrane laminated body with porous layer, described porous layer covers the one or both sides of base material, have and have connective many micropores, and the average grain diameter of this micropore is 0.01～10 μ m, and this porous layer thickness is that 0.1～1000 μ m, porosity are 30～80%, the thickness of base material is 1～1000 μ m.This porous membrane laminated body can by suitable setting constitute porous layer and base material material, thickness, create conditions to wait and make.

This porous membrane laminated body can be made by the following method, for example, with Polymer Solution to curtain coating on the base material become the film shape, make its contact with solidification liquid implement porous and handle after, directly carry out drying, obtain the method for the duplexer of substrate and porous layer; After having implemented above-mentioned porous and having handled, be needed on the surface of support etc., carry out drying, obtain on support, being laminated with the method for the duplexer of porous film thus.In the present invention, as detailed in the following, preferably use the former method.Carry out the method for porous as it is contacted with solidification liquid, for example can use: utilize the wet type phase inversion method to obtain the method (for example opening the 2001-145826 communique), dry type phase inversion method (for example with reference to international open communique WO98/25997 brochure etc.) of film with reference to the spy and use solvent exchange speed adjust the method for material (for example with reference to the spy open the 2000-319442 communique, the spy opens the 2001-67643 communique) etc. known method.

The manufacture method of porous membrane laminated body of the present invention is characterised in that, with Polymer Solution after curtain coating on the base material becomes the film shape, import solidification liquid, carry out drying then, at the folded porous layer of at least one surface layer of base material, obtain porous membrane laminated body thus.According to this method owing to be to use the wet type phase inversion method after forming porous layer on the base material, directly carrying out drying, therefore, porous layer can be when forming close adhesion in substrate surface and carry out stacked, so can improve manufacturing efficient.In addition, owing to have the porous layer softness of many micropores, therefore, the film monomer that constitutes porous layer is difficult to use, be difficult to carry out stacked operation, but according in the system film, carrying out stacked manufacture method of the present invention, can avoid this problem, can easily directly be laminated with the porous layer of hole characteristic and the porous membrane laminated body of base material with excellence.

As base material, preferably use the base material that when contacting, is not easy deterioration with solidification liquid, can enumerate for example conduct and form the material of the base material that constitutes porous membrane laminated body in above-mentioned illustrative base material.

In said method, when base material is made of the base material with many through holes that comprises nonwoven, punching film, punch metal or etching metal, because the structure of substrate surface is made of the plane except that through hole portion, therefore preferred porous layer forms in the plane.On the other hand, at base material with many through holes by eyelet fabric, wire netting, when expanded metal constitutes, because the structure of substrate surface is not for having the plane basically, having and weave into fibrous formation, therefore, in most cases Polymer Solution enters its space easily, becomes the incorporate state of porous layer covering substrates.

As base material with many through holes, preferably use the base material that when contacting, is not easy deterioration with solidification liquid, can enumerate for example conduct and form the material of the base material that constitutes porous membrane laminated body in above-mentioned illustrative base material.

As the Polymer Solution that carries out curtain coating, can use to comprise the raw-material macromolecule component that for example constitutes porous layer, water-soluble polymer, water soluble polar solvent, mixed solution that comprises water as required etc.

As the raw-material macromolecule component that constitutes porous layer, preferably in water soluble polar solvent, have dissolubility and can utilize the film forming macromolecule component of phase inversion method, can use a kind of or the two or more above-mentioned illustrative macromolecule components of mixing use.In addition, can use the macromolecule component of the replacement formation porous layers such as precursor before such as monomer component (raw material), its oligomer, inferior amidatioon or cyclisation of this macromolecule component.

For membrane structure being made the spongy of porous, be effective to the Polymer Solution interpolation water-soluble polymer or the water that carry out curtain coating.As water-soluble polymer, for example can enumerate: or derivatives thereof such as polyethylene glycol, PVP, PEO, polyvinyl alcohol, polyacrylic acid, polysaccharide and their mixture etc.Wherein, the formation in the space in suppressing film inside, can improve aspect the mechanical strength of film preferably polyethylene base pyrrolidones.These water-soluble polymers can use separately or be used in combination.Consider that from the angle of porous for porous, the molecular weight of water-soluble polymer is to be advisable more than 200, is preferably more than 300, be preferably more than 400 (for example about 400～200,000) especially, particularly molecular weight can be for more than 1000.Can adjust aperture diameter by adding water, for example,, can increase aperture diameter when increasing when polymer solution adds the amount of water.

Water-soluble polymer is spongy very effective to membrane structure is made, and kind and amount by the change water-soluble polymer can obtain multiple structure.Therefore, in order to give desirable hole characteristic, water-soluble polymer very preferably is used as the additive when forming porous layer.On the other hand, water-soluble polymer is the final inessential composition that does not constitute porous layer and should remove.In utilizing the method for the present invention of wet type phase inversion method, water-soluble polymer is in impregnated in solidification liquids such as water and carry out being cleaned in the operation of phase transformation and remove.Relative therewith, in the dry type phase inversion method, the composition (inessential composition) that does not constitute porous layer is removed by heating, removes because water-soluble polymer is not suitable for heating usually, therefore, is very difficult to as additive.As mentioned above, utilize dry type layer transformation approach to be difficult to form multiple pore structure, relative therewith, manufacture method of the present invention is favourable can easily making aspect the porous membrane laminated body with desirable hole characteristic.

As water soluble polar solvent, for example can enumerate: dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), 2-Pyrrolidone and their mixture etc. can use according to the chemical skeleton of the resin that is used as above-mentioned macromolecule component to have deliquescent water soluble polar solvent (good solvent of macromolecule component).

As the polymer solution that carries out curtain coating, preferably comprise as raw-material macromolecule component 8～25 weight %, water-soluble polymer 5～50 weight % that constitute porous film, the mixed solution of water 0～10 weight %, water soluble polar solvent 30～82 weight % etc.At this moment, cross when low when the concentration of macromolecule component, porous layer thickness is insufficient, is difficult to obtain desirable hole characteristic, in addition, when it is too high, the tendency that exists porosity to diminish.Water-soluble polymer adds for the spongiform loose structure of film inside being made homogeneous, at this moment, crosses when low when concentration, surpasses the such huge space of 10 μ m inner generation of film, and homogenieity reduces.In addition, when the excessive concentration of water-soluble polymer, the dissolubility variation in addition, when it surpasses 50 weight %, is easy to generate unfavorable conditions such as film strength dies down.The addition of water can be used for the adjustment of aperture diameter, can increase diameter by increasing addition.

When the Polymer Solution curtain coating is become the film shape, wish after this film is kept 0.2～15 minute under by relative humidity 70%～100%, 15～90 ℃ of atmosphere that constitute of temperature, to import the solidification liquid that the non-solvent by macromolecule component constitutes.By the tympan after the curtain coating is placed under these conditions, can make porous layer become homogeneous and connective high state.It has been generally acknowledged that its reason is, by being placed under the humidified condition, moisture is immersed in inside from film surface, promotes being separated of Polymer Solution effectively.Particularly preferred condition is: relative humidity is 90～100%, temperature is 30～80 ℃, and relative humidity is about 100%, and (for example 95～100%), temperature are 40～70 ℃.When airborne water content than it after a little while, produce the inadequate unfavorable condition of percent opening on surface sometimes.

Utilize said method, can easily be shaped has connective many micropores and the average pore size of this micropore is the porous layer of 0.01～10 μ m.Constitute micro-pore diameter, porosity, the percent opening of the porous layer of the porous membrane laminated body among the present invention, humidity when the consumption of the kind of constituent that as mentioned above, can be by suitable selection Polymer Solution and amount, water, curtain coating, temperature and time etc. are adjusted to desirable value.

As the solidification liquid that is used for phase inversion method, so long as the solvent that macromolecule component is solidified gets final product, can suitably select according to high molecular kind, for example as macromolecule component, so long as make polyamidoimide is that the solvent that resin or polyamic acid solidify gets final product, and for example can use: water; Monohydric alcohol such as methyl alcohol, ethanol; Alcohol such as polyalcohol such as glycerine; Water soluble polymers such as polyethylene glycol; Water-soluble solidification liquids such as their mixture etc.

In manufacture method of the present invention, the importing solidification liquid directly carries out drying behind substrate surface shaping porous layer, can make thus to have the porous membrane laminated body that directly is laminated with the structure of porous layer on the surface of base material.Drying means does not have particular determination, gets final product so long as can remove the method for solidification liquid equal solvent composition, can be that heating is dry down, can be to utilize natural drying at room temperature yet.Methods of heating treatment does not have particular determination, can be the method in hot blast processing, hot-rolling processing or input thermostat and the baking oven etc., gets final product so long as porous membrane laminated body can be controlled at the method for temperature of defined.Heating-up temperature can be selected from the wide region about for example room temperature～600 ℃.Atmosphere during heat treated can be an air, also can be nitrogen or non-active gas.It is the most cheap using the situation of air, but might be with oxidation reaction.Avoid this situation can use nitrogen or non-active gas, consider preferred nitrogen from the cost aspect.Heating condition can be considered suitably settings such as the rerum natura of productivity, porous layer and base material.By carrying out drying, can obtain having the porous membrane laminated body of porous layer in the substrate surface direct forming.

To the porous membrane laminated body that obtains like this, can further use heat, visible light, ultraviolet ray, electron beam, radioactive ray etc. to implement crosslinking Treatment.By above-mentioned processing, the precursor that constitutes porous layer carries out polymerization, crosslinked, curing etc., form macromolecular compound, time carry out crosslinked, curing etc. constituting high-molecular porous layer by macromolecular compound, can obtain having the porous membrane laminated body of the porous layer that characteristics such as rigidity, resistance to chemical reagents have further improved.For example, be in the good porous layer of forming precursor using polyimides, by further enforcement hot-imide or chemical imidizate etc., can obtain the polyimides porous layer.Using polyamidoimide is can implement heat cross-linking in the good porous layer of ester moulding.Need to prove that heat cross-linking can and be used to carry out dry heat treated after importing solidification liquid to be implemented simultaneously.

Cross-linking reaction often according to circumstances takes place in above-mentioned crosslinking Treatment between high-molecular porous layer and base film.Improve the close adhesion of base film and porous layer thus.For example, when being the Kapton of the porous layer of precursor when heat-treating to having formed polyimides, precursor when becoming polyimides close adhesion on Kapton.In addition, when being the Kapton of the porous layer of resin when heat-treating to having formed polyamidoimide, the porous layer close adhesion is on Kapton.

Manufacturing method according to the invention, the one or both sides that can easily obtain base film by high-molecular porous layer cover, high-molecular porous layer have have connective many micropores, the average pore size of this micropore is the film with porous layer of 0.01～10 μ m.

For porous membrane laminated body of the present invention, as long as, also can have porous layer on the two sides of base material at the folded porous layer of at least one surface layer of base material.In addition, in porous layer, functional material can be filled, when having a plurality of porous layer, the functional material of identical or different kind can be filled.And, in order to give desirable characteristic, can implement heat treatment or tunicle as required and form processing porous membrane laminated body.

Because porous membrane laminated body of the present invention has above-mentioned formation, therefore, can be applied to multiple use in extensive fields.Particularly, the hole characteristic of directly utilizing porous layer to have can be as for example advanced low-k materials, dividing plate, padded coaming, printing ink display material, test paper, insulating materials, heat-barrier material etc.And, as the composite that on porous membrane laminated body, is laminated with other layers (metal-plated coating, magnetic coating layer etc.), in addition, use by the form that is filled with functional material in the hole with porous layer, can control material, battery separator, capacitor (paper capacitor, plastic film capacitor, ceramic capacitor, mica condenser, electrolytic capacitor etc.), cell culture medium material, catalyst substrate (catalyst carrier) etc. with electromagnetic waves such as substrate, heat sink material (heat sink), electromagnetic wave baffle plate or electromagnetic wave absorbs as for example circuit.

In addition, porous membrane laminated body of the present invention also can be used as test paper.Test paper experiment with, be widely used in medical etc., for example can enumerate: pH test paper (for example litmus paper), water quality detection test paper (for example ion test paper), oily test paper, moisture test paper, tetra paper, urine test paper, blood test paper etc.Above-mentioned ion test paper can detect metal ion and anion qualitative or quantitatively.Urine test paper can detect glucose in urine, urine albumen, occult blood etc. quantitatively.The blood test paper can detect blood glucose value etc. quantitatively.Because the assay method of these test paper is simple, therefore, use chance to increase year by year.

Porous membrane laminated body of the present invention is because the porous layer close adhesion in base material, therefore, can be guaranteed full intensity in the use.In addition, because porous layer can adsorb employed indicator in the judgement, be preferred medium therefore.In addition, owing to can keep samples such as water equal solvent, urine, blood, therefore be preferred for these purposes.

Wherein, the porous membrane laminated body that constitutes with the base material with many through holes can be suitable as filter.Because form porous layer having on the base material of many through holes, therefore, base material can be guaranteed full intensity.Since the porosity height of porous film, therefore, also might be to the inadequate purposes expansion of the intensity of single porous film.As the filter that has used porous membrane laminated body of the present invention, for example can enumerate: the filter for filtration of gases such as the filtration of the aqueous solution such as water and air; Can remove the use in waste water treatment filter of the above impurity of sub-micron; Filter for filtration such as blood such as erythrocytic separation; Filter for air condition that corpse of dust, pollen, fungi, mite etc. is separated from air etc.Porous membrane laminated body of the present invention can also be used as the base material that employed oxygen coalescence film is used in the air-conditioning.

Porous membrane laminated body of the present invention also is preferably used as battery separator.Battery separator needs retentivity excellence, the ionic conductivity of electrolyte good when separating both positive and negative polarity.In addition, require to possess various characteristicses such as hear resistance, flexibility, intensity.According to porous membrane laminated body of the present invention, can balancedly bring into play these characteristics, therefore, be very useful as various battery separators.

Porous membrane laminated body of the present invention also can be as the base material of electrolyte membrane for fuel cell.In recent years, as the portable equipment power supply, carrying out the directly exploitation of methanol fuel cell (DMFC) always.DMFC directly imports the fuel cell that acts as a fuel in the battery with methyl alcohol.At present, DMFC is that the poly-perfluoro alkyl sulfonic acid of representative is the investigation example of dielectric film (fluorine is a dielectric film) with E.I.Du Pont Company " Nafion " mostly, but because of the compatibility height of these films and methyl alcohol causes dielectric film because of methyl alcohol generation swelling, intersect (methyl alcohol penetrate dielectric film) thereby methyl alcohol takes place, the problem of energy loss is extremely urgent.According to porous membrane laminated body of the present invention, can provide the electrolyte membrane for fuel cell that can address the above problem.

Porous membrane laminated body of the present invention can also be as the skeleton of dielectric film.Because therefore porous membrane laminated body can, can prevent the swelling of base material with the indefatigable eyelet fabric of methyl alcohol equal solvent (for example eyelet fabrics such as nylon, polyester, polypropylene, TFE) is used as base material.And, since porous layer portion connective excellent, be formed with fine hole, therefore,, can make electrolyte membrane for fuel cell by in the hole, filling electrolyte.

The act as a fuel kind of battery also has the polymer electrolyte fuel cell (PEFC) that is used as automotive battery etc. in addition.It is to be the fuel cell that fuel uses with hydrogen, but is the problem that still exists hydrogen to intersect in the dielectric film at fluorine.In order to ensure the electric conductivity of proton, need make under the moistening state of dielectric film at water and use, fluorine is that the swelling that caused by water still takes place dielectric film, hydrogen intersects becomes problem.

Because porous membrane laminated body can use the eyelet fabric (for example eyelet fabrics such as nylon, polyester, polypropylene, TFE) with resistance to water as base material, therefore, can prevent the swelling of base material.And, since porous layer portion connective excellent, be formed with fine hole, therefore,, can make the PEFC electrolyte membrane for fuel cell by in the hole, filling electrolyte.

Composite of the present invention is characterised in that, is laminated with metal-plated coating and/or magnetic coating layer on the surface of at least one porous layer of the porous membrane laminated body that constitutes the invention described above.

The metal-plated coating can form as very thin metal casing on surface of porous layer for example and inner micropore surface, also can be to have used the mode of hole metal filled.As the metal that constitutes the metal-plated coating, for example can enumerate: copper, nickel, silver, gold, tin, bismuth, zinc, aluminium, lead, chromium, iron, indium, cobalt, rhodium, platinum, palladium and their alloy etc.And, also can enumerate the multiple alloy tunicle that contains metal element in addition such as nickel-phosphorus, nickel-copper-phosphorus, Ni-Fe-phosphorus, nickel-tungsten-phosphorus, nickel-molybdenum-phosphorus, nickel-chromium-phosphorus, nickel-boron-phosphorus.The metal-plated coating can use above-mentioned metal separately or multiple being used in combination, and can be individual layer, also can stacked multilayer.

Material as constituting the magnetic coating layer does not just have particular determination so long as have the compound of magnetic, can be any of ferromagnetism body and normal magnetic, can illustration for example: nickel-cobalt, cobalt-iron-phosphorus, cobalt-tungsten-phosphorus, cobalt-nickel-alloys such as manganese; Has in metal complex based compounds such as the compound at the position that can produce free radical, the charge transfer complex of decamethyl ferrocene, the graphitization way organic magnetic body that the compounds such as polyacrylonitrile as material with carbon element constitute etc. by methoxyacetonitrile polymer etc.

This composite can utilize the known method manufacturing, and described known method is with metal or the cambial method of organic compound on the porous layer surface of the porous membrane laminated body of the invention described above.

In the formation of metal-plated coating, can utilize that for example electroless plating covers and known method such as electrolytic coating.In porous membrane laminated body of the present invention, preferably using electroless plating described later to cover aspect the porous layer constituting with macromolecule component, can be used in combination also that electroless plating covers and electrolytic coating.

The plating liquid that is used to form the metal-plated coating is known to the various plating liquids of forming, and also can obtain the plating liquid that manufactory sells.The composition of plating liquid does not have particular determination, as long as select to meet the plating liquid of various requirement (attractive in appearance, hardness, mar proof, discoloration-resistant, corrosion resistance, electrical conductivity, heat conductivity, hear resistance, sliding, hydrophobicity, wetting quality, paste wetting quality, sealing, electromagnetic wave shielding characteristic, reflection characteristic etc.).

The manufacture method of composite of the present invention is carried out by the following method, and described method comprises: the photosensitive composite that constitutes at the compound of at least one porous layer surface applied reaction of formation group by utilizing illumination to penetrate of the porous membrane laminated body that constitutes the invention described above, the operation that photosensitive layer is set; By mask to above-mentioned photosensitive layer expose, in the operation of exposure portion reaction of formation group; And the reactive group that exposure portion is generated combines, forms the method for the operation of conductive pattern with metal; Or comprise: in the manufacture method of the composite of the invention described above, use the compound that utilizes illumination to penetrate reactive group is disappeared to replace utilizing illumination to penetrate and the compound of reaction of formation group, the operation that reactive group is disappeared in exposure portion; And make the reactive group that remains in unexposed portion combine, form the operation of conductive pattern with metal.

The compound of reaction of formation group as utilizing illumination to penetrate, so long as in molecule, generate the compound that can form the reactive group of key with metal (containing metal ion), just do not have particular determination, for example can enumerate: contain photosensitive compounds that is selected from least a kind of derivative in salt derivative, sulfonium salt derivative, carboxylic acid derivates and naphthoquinones two azido derivants etc.These photosensitive compounds are imbued with versatility, utilize illumination to penetrate and can easily generate the reactive group that can combine with metal, therefore, can make the precision of the conductive part with fine pattern good.

As the compound that utilizes illumination to penetrate to make reactive group to disappear, for example can enumerate: it has the compound that can form the reactive group of key with metal (containing metal ion), utilize illumination to penetrate this reactive group and generate hydrophobic functional groups, become and in water, be difficult to dissolve or the compound of swelling etc.

The above-mentioned reactive group that utilizes illumination to penetrate and generate or disappear, so long as can form the reactive group of key with above-mentioned metal (containing metal ion), just do not have particular determination, can illustration for example: can carry out functional group of ion-exchange etc. with metal ion, preferably enumerate the cation exchange group.The cation exchange group for example comprises-the COOX group ,-SO ₃The X group or-PO ₃X ₂Acidic-groups such as group (wherein, X is hydrogen atom, alkali metal or alkaline-earth metal and belongs to periodic table I, the typical metal of II family, ammonium) etc.Wherein, utilizing the pKa value is cation exchange group below 7.2, can form key with the metal of per unit area abundance, therefore, can easily obtain desirable electric conductivity, preferred.This reactive group carries out metal ion exchanged in subsequent processing, can bring into play the stable energy of adsorption that is formed by metallic reducing body and metal particle.

As irradiates light, as long as can promote the generation or the disappearance of reactive group, just there is not particular determination, can use for example light of the wavelength more than the 280nm, but because of deterioration takes place in exposure, preferably use wavelength to be preferably the above light of above (about 300～600nm), the particularly 350nm of 300nm for fear of porous membrane laminated body.

After carrying out illumination by mask and penetrating, clean as required, thus can be at exposure portion or unexposed the pattern that formation is made of reactive group.The reactive group and the metal bonding that utilize method shown below to make to be arranged on the porous layer surface like this can form conductive pattern.

In the present invention, as method with reactive group and metal bonding, the preferred method of utilizing electroless plating to cover of using.It is useful that known electroless plating covers general conduct method of laminated metal on the resin bed of formation such as plastics.In order to improve the close adhesion with metal, the porous film surface of porous membrane laminated body also can be implemented processing such as degreasing, cleaning, neutralization, catalytic treatment in advance.As above-mentioned catalytic treatment, can use and for example on processed, make catalyst metals karyomorphism established law that the catalyst metals that can promote metal to separate out adheres to etc.Catalyst metals karyomorphism established law can be enumerated: after making it and the colloidal solution that contains catalyst metals (salt) contacts, contact with acid or aqueous slkali or reducing agent, promote the method (catalyst (catalyst)-accelerator (promoter) method) of chemical plating; After making it and the colloidal solution that contains the catalyst metals particulate contact, wait to remove by heating and to desolvate or additive etc., form the method (metal particle method) of catalyst metals nuclear; After making it and acid that contains reducing agent or aqueous slkali contact, contact with the acid or the aqueous slkali of catalyst metals, and contact activation (activation) liquid, make method (photosensitive processing (sensitization)-activation (activation) method) that catalyst metals separates out etc.

As containing catalyst metals (salt) solution in catalyst-accelerator method, can use solution of containing metals (salt) such as tin-palladium mixed solution, copper sulphate for example etc.For catalyst-accelerator method, for example, after impregnated in porous membrane laminated body in the copper sulfate solution, clean as required and remove excessive copper sulphate, impregnated in then in the aqueous solution of sodium borohydride, can form the catalyst core that constitutes by the copper particulate on the porous layer surface of porous membrane laminated body thus.For the metal particle method, for example, after the colloidal solution that is dispersed with Nano silver grain is contacted with porous layer is surperficial, heat additives such as removing surfactant or adhesive, can make the porous layer surface separate out the catalyst core that constitutes by silver particles thus.For photosensitive processing-activation method, for example, after making it and the hydrochloric acid solution of stannic chloride contacts, contact with the hydrochloric acid solution of palladium bichloride, separate out the catalyst core that constitutes by palladium thus.As making these treatment fluids contact the method for porous membrane laminated body, can use in the method that the folded layer by layer porous layer surface of metal deposition is applied, make porous membrane laminated body impregnated in method in the treatment fluid etc.

In above-mentioned catalyst metals karyomorphism method becomes, be porous membrane laminated body that base material, another surface constitute for porous layer when impregnated in the treatment fluid making a surface, preferred substrates layer is made of homogeneous.When the porous membrane laminated body that one side is had the base material of homogeneous impregnated in the treatment fluid, not only form catalyst core on the porous layer surface of porous membrane laminated body, and also form catalyst core at substrate surface, on the big porous layer surface of surface area, a large amount of catalyst core are adhered to, and keep easily, relative therewith, on the base material of homogeneous, because the base film surface smoothing, therefore catalyst core is difficult to separate out, and comes off easily.On the porous layer surface of the catalyst core that has formed q.s like this, can continue to utilize electroless plating to cover and optionally form the metal-plated coating.

Employed main metal in covering as electroless plating can be enumerated for example copper, nickel, silver, gold, nickel-phosphorus etc.Be used for plating liquid that electroless plating covers except containing for example above-mentioned metal or its salt, also contain complexing agents such as reducing agents such as formaldehyde, hydrazine, sodium hypophosphite, sodium borohydride, ascorbic acid, glyoxalic acid, sodium acetate, EDTA, tartaric acid, malic acid, citric acid, glycine or separate out controlling agent etc., these have commercially available product mostly and can obtain simply.Can carry out electroless plating by the porous membrane laminated body that dipping in above-mentioned plating liquid has been implemented above-mentioned processing covers.Need to prove, be pasted with by one side and implement electroless plating under the state of screening glass and cover, can only implement electroless plating and cover, therefore, for example can prevent that metal separates out on base material etc. at another side at porous membrane laminated body.

The thickness of metal-plated coating does not have particular determination, can suitably select according to purposes, for example is about 0.01～20 μ m, is preferably about 0.1～10 μ m.In order to increase the thickness of metal-plated coating effectively, often embodiment covers the method that forms the metal-plated coating with the electrolytic coating combination as making electroless plating.That is,, therefore,, can obtain thick metal-plated coating at short notice by next implementing more effective electrolytic coating owing to utilize electroless plating to cover to have formed the porous layer surface of metal tunicle to be endowed electric conductivity.

Said method is preferred especially as obtaining being used for the method that circuit substrate, heat sink material or electromagnetic wave are controlled the composite of material.

Circuit substrate is made by the following method: generally making with glass epoxy resin or polyimides etc. is raw-material substrate surface applying Copper Foil, utilizes etching to remove the unwanted part of Copper Foil, forms distribution thus.But this existing method is difficult to form can be corresponding to the fine distribution of the circuit substrate of densification.In order to make the distribution miniaturization, need make extremely thin Copper Foil securely close adhesion with glass epoxy resin or polyimides etc. on the raw-material substrate, but the thin non-constant of Copper Foil applicability is difficult to carry out to the stacked operation of substrate.In addition, itself difficulty of the manufacturing of thin Copper Foil costs an arm and a leg, and, the close adhesion power of employed glass epoxy resin or polyimides and Copper Foil is original just little in the raw material of base material, and therefore there are the following problems: when carrying out miniaturization, distribution is from strippable substrate.

Under this background, owing to utilize composite of the present invention, porous membrane laminated body has above-mentioned formation, therefore, can guarantee the sufficient close adhesion power of itself and metal-plated coating, is suitable for having the circuit board use material of fine distribution.In addition, for composite of the present invention, because the metal-plated coating is filled in the hole that the top layer part of porous layer exists, metal can be shaped in the mode that interweaves on porous layer, therefore, even fine distribution also can be brought into play strong close adhesion power.When the forming circuit material for substrate, the metal-plated coating preferably is made of copper, nickel, silver etc.

The circuit substrate that porous membrane laminated body of the present invention is made as the method that is used in the fine distribution of the direct formation in porous layer surface is very useful.As the method for making the sort circuit substrate, can utilize the method for putting down in writing as the manufacture method of the composite of the invention described above.According to this method, owing to use porous membrane laminated body of the present invention, therefore, can on porous layer, form the fine distribution that interweaves securely, and use the exposure technique can high accuracy and form distribution simply.The film that one side has porous layer can form a distribution, and the film that the two sides has porous layer can form double-sided printed.Connect at needs under the situation of path distribution on two sides, can utilize present employed rig or laser boring, utilize the filling of conductive paste or coating to form.Up to now, known have on porous body use electroless plating to cover the method that method forms distribution, but the problem that exists is because existing porous body weak strength is therefore poor for applicability, breakage etc. in manufacturing process.Relative therewith, when using porous membrane laminated body of the present invention,, can provide the circuit substrate of applicability excellence because the porous layer close adhesion on base material and be formed, therefore, can be guaranteed full intensity.

Heat sink material (heat sink etc.) can be used for being arranged in the cabinet of many equipment such as notebook computer, compact disc device, projector, portable phone.In recent years, along with the height output of high-density installation development of technology and equipment, the progress of high speed, the caloric value of part increases, this from now on trend also can further develop, therefore, the importance of heat radiation cooling technology strengthens, and the use chance of the heat sink material that spreads or dispel the heat (thermoreceptor, heat sink) increases to some extent.According to composite of the present invention, utilize the porous layer that has excellent hole characteristic as mentioned above, area of dissipation is wide, the radiating efficiency excellence can be carried out miniaturization, and utilizes the metal-plated coating can give excellent heat conduction, therefore, can be as excellent heat sink material.Can improve aspect the above-mentioned effect, the metal-plated coating that constitutes heat sink material is preferably formed by the high metal of hot conductivity, and preference is as copper, silver, gold, cobalt, chromium, nickel, tin, zinc etc.

As blocking (shielding) or absorb electromagnetic material, electromagnetic wave control material for alleviate or suppresses around the influence that produces of electromagnetic environment or the influence that is subjected to of equipment itself from electromagnetic environment on every side utilize.The popularizing of digital electronic device, notebook computer or portable phone etc. produce source at our the many electromagnetic waves such as electric/electronic device or wireless device, system etc. that exist at one's side, and they radiate various electromagnetic waves.Bring influence might for electromagnetic environment on every side by the electromagnetic wave of these equipment radiation, in addition, equipment itself also is subjected to the influence from electromagnetic environment on every side.As its countermeasure, electromagnetic waves such as electromagnetic shielding material, electromagnetic wave absorb material control material becomes more and more important.For composite of the present invention, for example, by giving the electric conductivity blocking that produces by metal-plated coating electromagnetic wave, can give electromagnetic wave shielding performance, in addition, in the hole that constitutes porous layer, fill electromagnetic wave absorbent material, can give electromagnetic wave absorbability, therefore, the electromagnetic wave control material as excellence is very useful.

The metal-plated coating that constitutes electromagnetic wave control material preferably can be given the metal-plated coating of electric conductivity, and it is effective for example being formed by nickel, copper, silver etc.In addition, having at composite and to overlay on the porous layer shaping surface by electroless plating and be magnetic the layer of coating layer when constituting, is useful as the electromagnetic wave absorb material.As the material that when utilizing electroless plating to cover formation magnetic coating layer, uses, for example can enumerate: the magnetic material of alloys such as nickel, nickel-cobalt, cobalt-iron-phosphorus, cobalt-tungsten-phosphorus, cobalt-nickel-manganese etc.Composite of the present invention can obtain material extremely thin and that flexibility is high, owing to utilize formed metal of coating or magnetic to interweave on porous layer, therefore, coating layer is difficult for peeling off, and can improve resistance to bend(ing) (counter-bending).This composite can be provided with or stick on the place arbitrarily of electronic equipment and use.

Porous membrane laminated body of the present invention also is useful as advanced low-k materials.Because the arrival of broadband era need be with the high-speed transfer bulky information.Therefore, the frequency of using in the electronic equipment also raises gradually, and use therein electronic component also need be corresponding to high-frequency signal.When present wiring board (mainly being glass epoxy resin) when being used for high-frequency circuit, is produced following problem: the transmission signal that (1) is caused by high dielectric constant slow; (2) the signal interference that causes by high dielectric loss, the generation of decay, the increase of power consumption, the heating in the circuit etc.Be considered to useful as the high frequency that is used to address these problems with the porous material of wiring board material.This is because low with respect to the ratio dielectric constant of air is 1, so long as porous material just can be realized low ratio dielectric constant.Therefore, need the porous baseplate material at present, in order to make low-k, need to improve porosity, its result exists the intensity as substrate to reduce such problem.The porous layer of porous membrane laminated body of the present invention is layered on the base material, not only has the low-k characteristic, and because the porous layer close adhesion on base material, therefore, can be guaranteed full intensity in the use, is preferred medium as advanced low-k materials.

Printing ink video picture sheet material is also referred to as printed medium, is often used in printing technology.On the other hand, many print processes are practical, are utilized, as this printing technology, for example can enumerate: ink jet printing, screen painting, some offset printing brush, letterpress (aniline printing), subliming type printing, hectographic printing, laser printing printing (toner printing), intaglio printing (photogravure), contact print, micro-contact printing etc.Constituent as employed printing ink does not have particular determination, for example can enumerate: electric conductor, dielectric, semiconductor, insulator, resistance, pigment etc.

The advantage of being made electronic material by print process has: (1) can be by simple technology manufacturing; (2) be the few low environmental load technology of discarded object; (3) can make at short notice by low-yield consumption; (4) can reduce initial investment volume etc. significantly, still, on the other hand, the high meticulous printing that its requirement does not have at present, technical difficulty also is true.Therefore, particularly about being used to make the printing of electronic material, not only the performance of printing equipment has a significant impact print result, and the characteristic of printing ink or printing ink video picture sheet material also has a significant impact print result.Because the porous layer close adhesion of porous membrane laminated body of the present invention is on substrate, the fine loose structure of porous layer can absorb printing ink or fixing printing ink accurately, therefore, can realize the high meticulous printing that do not have at present, very preferably use.In addition,, for example, also can print continuously, can enhance productivity significantly with Scroll because the porous layer close adhesion on substrate, therefore can be guaranteed full intensity in the use.

When utilizing print process to make electronic material, can utilize said method as print process.As the concrete example of the electronic material that utilizes print process to make, can enumerate: LCD, OLED display, field-emitter display (FED), IC-card, IC tag, solar cell, LED element, organic transistor, capacitor (capacitor), Electronic Paper, flexible batteries, flexible transducer, membrane switch, touch panel, EMI shielding etc.

Make the method for above-mentioned electronic material, comprise and to contain the operation of the ink printing of electronic materials such as electric conductor, dielectric, semiconductor, insulator, resistance for example on porous layer surface (substrate) surface.By for example printing with containing dielectric printing ink, can form capacitor (capacitor) on porous layer (substrate) surface.As this dielectric, can enumerate barium titanate, strontium titanates etc.In addition, by printing, can form transistor etc. with containing semi-conductive printing ink.As semiconductor, can enumerate: pentacene, liquid silicon, fluorenes-di-thiophene copolymers (F8T2), poly-(3-hexyl thiophene) are (P3HT) etc.

By printing with the printing ink that contains electric conductor, can form distribution, therefore, can make flexible base plate or TAB substrate, antenna etc.As above-mentioned electric conductor, can enumerate: silver, gold, copper, nickel, tin indium oxide, carbon, CNT etc. have the inorganic particulate of electric conductivity; Has the particle that the organic polymer of electric conductivity constitutes by polyaniline, polythiophene, polyacetylene, polypyrrole etc.As above-mentioned polythiophene, can enumerate poly-(ethene dioxythiophene) (PEDOT) etc.These can be as the printing ink of solution or colloid shape.Wherein, preferably the conducting particles that is made of inorganic particulate is particularly considered from the balance aspect of electrical characteristics and cost, especially preferably uses silver particles and copper particle.As the shape of particle, can enumerate spherical, flakey (laminar) etc.Particle size does not have particular determination, for example, from average grain diameter count about μ m, to the number nm so-called nano particle can use.It is multiple that these particles also can mix use.As the printing ink of electric conductivity, below illustrational be the silver-colored printing ink that can easily obtain (silver is stuck with paste), but be not limited thereto, also can use the printing ink of other kinds.

For silver-colored printing ink, as its constituent, generally contain silver particles, surfactant, adhesive, solvent etc., in addition, as other examples, the character of utilizing silver oxide to be reduced by heating is also arranged, the printing ink that will contain the particle of silver oxide prints, add thermal reduction then, make silver-colored distribution.Further,, also there is the printing ink that to contain organic silver compound to print, adds thermal decomposition then, make silver-colored distribution as other examples.In organic silver compound, also can utilize the organic silver compound that is dissolved in solvent.As the particle that constitutes silver-colored printing ink, silver particles, silver oxide, organic silver compound etc. can independent or multiple being used in combination, and in addition, also can mix the particle that uses different-grain diameter.After using silver-colored printing ink to print, the temperature when making ink solidification (sintering temperature) can suitably be selected according to the composition of printing ink, particle diameter etc., but is generally mostly in the scope about 100～300 ℃.Because porous membrane laminated body of the present invention is an organic material, therefore, for fear of deterioration, preferred sintering temperature is lower temperature, but in order to reduce the resistance of distribution, general preferred roasting, the printing ink that needs the selection use to have suitable solidification temperature of at high temperature carrying out.As the commercially available product of this silver-colored printing ink, known trade name " NANODOTITEXA9053 ", the Harima that has the trade name " CA-2503 ", the Teng Cang that grind chemical industry (strain) manufacturing greatly to change into (strain) manufacturing changes into the trade name " NPS " of (strain) manufacturing, the trade name " thin ball SVW102 " (the about 30nm of average grain diameter) that " NPS-J " (the about 5nm of average grain diameter), Japanese paint (strain) make etc.

The printing ink that Fig. 1 represents to contain the electric conductor particle prints and has formed on porous layer (substrate) surface the generalized section of the wiring board of distribution.Wherein, Fig. 1 (A)～(C) expression uses full-bodied printing ink to form the distributing frame of distribution 2 on porous layer 1 surface, and Fig. 1 (D)～(F) expression uses low viscous printing ink to form the distributing frame of distribution 2 on porous layer 1 surface.The distribution that forms like this make an addition to according to the perforate footpath (for example average perforate footpath) on for example porous layer surface, electric conductor particle etc. printing ink particle size and distribute (for example particle diameter, size distribution), the ratio of above-mentioned perforate footpath and particle diameter etc. has different shape.

Fig. 1 (A) reaches (D), and expression directly is an example of the formed distributing frame of printing ink of the little particle of particle diameter with containing many average perforates with respect to the porous layer top layer.At this moment, distribution 2 mainly forms in porous layer 1.Therefore, because the distribution 2 that interweaves on the porous layer 1, so the close adhesion raising of distribution, but, therefore the relative tendency that raises of resistance is arranged owing to contain the resin that constitutes porous layer 1 at distribution 2.

Fig. 1 (C) reaches (F), and expression directly is an example of the formed distributing frame of printing ink of the big particle of particle diameter with containing many average perforates with respect to the porous layer top layer.At this moment, distribution 2 mainly forms on porous layer 1.Therefore, owing to be substantially devoid of the resin that constitutes porous layer 1 in the distribution 2, thus the resistance step-down, but the tendency that exists the distribution close adhesion to reduce relatively.

Fig. 1 (B) and (E) expression with an example of the formed distributing frame of printing ink of the particle of the particle diameter that contains many average perforate footpaths of approaching the porous layer top layer.At this moment, distribution 2 forms with the state that a part enters in the porous layer 1, a part is exposed on porous layer 1.Therefore, have certain substrate close adhesion, the resistance of distribution 2 raises a little, and substrate close adhesion and preceding two examples are in a ratio of moderate.

Consider from above angle, preferably consider the balance of desired resistance of wiring board and distribution close adhesion, select to make an addition to the size of particle diameter of electric conductor etc. of printing ink or size distribution, blending ratio.

More specifically, directly be set at R when average perforate with the porous layer top layer ₁, the average grain diameter of the electric conductor particle that contained in the printing ink is set at R ₂The time, preferred R ₁Be about 0.01～10 μ m, R ₂Be in the scope about 0.001～10 μ m.That is, preferably satisfy formula: 0.0001 ≦ R ₂/ R ₁≦ 1000 relation.Particularly utilize the printing technology of having used the printing ink that contains the electric conductor particle to be formed with in the example of composite of electric conductor, when the average perforate with the porous layer top layer directly is set at R on porous layer surface ₁, the average grain diameter of electric conductor particle is set at R ₂The time, preferably satisfy formula: 0.0001 ≦ R ₂/ R ₁≦ 1000 relation.

Under the situation of ink jet printing, in nozzle, the low and particle that make an addition to printing ink of the viscosity of preferred printing ink is the particle of small particle diameter for fear of clogged with ink.Therefore, preferred R ₁Be about 0.01～5 μ m, R ₂Be about 0.001～0.2 μ m.That is, preferably satisfy formula: 0.0002 ≦ R ₂/ R ₁≦ 20 relation.

Under the situation of screen painting, cross when low when viscosity, in half tone, be difficult to keep printing ink, therefore, preferred viscosities is up to a certain degree printing ink, even the particle diameter of contained particle is greatly also no problem in the printing ink without hesitation, in addition, under the little situation of particle diameter, preferably reduce quantity of solvent.Therefore, preferred R ₁Be about 0.01～10 μ m, R ₂Be about 0.001～10 μ m.That is, preferably satisfy formula: 0.0001 ≦ R ₂/ R ₁≦ 1000 relation.

Distribution can also can form on the two sides only in the one side formation of porous layer.Form on the two sides under the situation of distribution, also can form the path of the distribution that connects the two sides as required.Via hole can form with rig, also can form with laser.Electric conductor in the via hole can be stuck with paste with conduction and form, and also can form with coating.

In addition, it is surperficial and use to coat the distribution that is formed by conductive ink with coating or insulator.Particularly have report to point out, silver-colored distribution and copper wiring be relatively the time, electron transfer or particle takes place easily move (Nikkei electron technology 2002.6.17 number 75 pages).Therefore, in order to improve the reliability of distribution, it is effective coating the distribution surface that is formed by silver-colored printing ink with coating.As coating, can enumerate copper coating, gold plate, nickel coating etc.Plating can carry out with known method.

And, the also distribution surface that can form by the printing ink of electric conductivity with resin-coating and using.Above-mentioned formation goes for the protection of distribution, the insulation of distribution, the oxidation that prevents distribution or purposes such as migration, raising bendability.For example, silver-colored distribution is by being oxidized into silver oxide, and copper wiring becomes cupric oxide, and electric conductivity might reduce, but by with above-mentioned resin-coating distribution surface, can avoid distribution to contact with oxygen or moisture, can suppress the reduction of electric conductivity.As the method for the distribution surface optionally being carried out resin-coating, can enumerate for example to use has gel-type resin described later or soluble resin as methods such as the location that is filled in the resin of hole, some glue, screen painting, ink-jets.

Formed original state that the porous portion behind the distribution can keep hole, also can be in hole potting resin etc., can suitably select according to the purposes of wiring board.Under the situation of the original state that keeps hole,, therefore, be preferably used as the high frequency wiring board because porous portion is a low-k.In hole, be filled with under the situation of resin etc., owing to, therefore, have distribution and be difficult to fracture, or insulating reliability also increases such advantage with protection distributions such as resins.When loose structure is disappeared, can strengthen the intensity of porous portion, or the close adhesion intensity of raising and base material.In addition, disappear, can suppress the diffuse reflection of visible light, make it transparent by making loose structure.

In the present invention, constitute as the layer of composite, residual the hole of porous layer that for example can remain untouched, also can be in the hole of porous layer potting resin, also can be the formation of the pore structure forfeiture that utilizes solvent to handle to make porous layer.

Resin as the hole that is filled in porous layer does not have particular determination, for example can enumerate: under solvent-free situation employed curable resin, be dissolved in solvent and soluble resin of being utilized etc.When using soluble resin, the volume when needing to consider solvent evaporates reduces part and fills.As mentioned above, soluble resin might produce the hole that does not have potting resin because of volume reduces part when filling.Therefore, for resin complete filling hole, more preferably use solvent-free curable resin.

As curable resin, for example can enumerate: epoxy resin, oxetane resin, acrylic resin, vinyl ethers are resin etc.

In epoxy resin, comprising glycidol ethers such as novolaks system such as bis-phenol systems such as bisphenol A-type or Bisphenol F type, phenolic varnish type or cresols phenolic varnish type is epoxy resin; Alicyclic epoxy resin and their various kinds of resin such as modified resin.As the commercially available product of epoxy resin, can use Hensel to step " my younger brother's glue ", " デ Na コ-Le ", " the セ ロ キ サ イ De " of Daicel chemical industrial company of nagasechemtex company of advanced material company, " the エ Port ト-ト " that Dongdu changes into company etc.Epoxy resin cured product can cause curing reaction and promote the method for reaction to obtain by heating by utilizing the hardening resin composition that for example mixed curing agent obtains in epoxy resin.In above-mentioned curing agent for epoxy resin, can use organic polyamine, organic acid, organic acid anhydride, phenols, polyamide, isocyanates, dicyandiamide etc.

Epoxy resin cured product can also obtain by the following method,, for mix the hardening resin composition that is called as the curing catalysts of potentiality curing agent and obtains in epoxy resin, penetrates initiation reaction by illumination such as heating or ultraviolet rays that is.As above-mentioned potentiality curing agent, can use the commercially available products such as " サ Application エ イ De SI " of three new chemical industrial companies.

As epoxy resin cured product,, just can make the such substrate of flexible substrate with flexibility as long as use the high epoxy resin cured product of pliability.In addition, under the situation that requires hear resistance and high dimensional stability,, also can be used as rigid substrates (hard substrate) by using hardness raises after curing composition as hardening resin composition.

For epoxy resin is filled in hole, the hardening resin composition during filling is preferably low viscosity.As hardening resin composition, can enumerate the composition of Bisphenol F system, the composition of aliphatic poly glycidol ether system with this feature.

As oxetane resin, can enumerate " ア ロ Application oxetane resin " of East Asia Synesis Company etc.The oxetane resin solidfied material can obtain by the following method, for example, mixes the cationic photopolymerization initator " IRGACURE250 " of Ciba company manufacturing etc. in oxetane resin, causes curing reaction by carrying out the ultraviolet ray irradiation.

As soluble resin, low-dielectric resin " low polyphenylene ether " Japan that can use aerochemistry company of Mitsubishi to make polyamide-imide resin " バ イ ロ マ Star Network ス " that company makes of twisting flax fibers and weaving, the polyimide ink " ユ ピ コ-ト " that emerging product company of space portion makes, the polyimide ink " エ バ-レ Star Network " that Dongdu chemical industry is made, the polyimide ink " ULIN COAT " that NI Materials Co., Ltd makes, the polyimide ink " Q-PILON " of PI technical research manufacturing, the saturated polyester resin " ニ チ go-Port リ エ ス -" that Japan synthetic chemistry company makes, acrylic acid solvent type adhesive " コ-Port ニ-Le ", ultraviolet ray/electronic beam solidified resin commercially available products such as " purple lights ".

The solvent of employed soluble resin when filling as dissolving can suitably be selected to use from known organic solvent according to the kind of resin.Typical example as the resin solution that is dissolved with soluble resin in the solvent (soluble resin solution) for example can use: the resin solution that is dissolved with " low polyphenylene ether " in general solvents such as methyl ethyl ketone or toluene; In the ethanol/toluene mixed solvent, be dissolved with the resin solution (trade name " HR15ET ") of " バ イ ロ マ Star Network ス "; In the triethylene-glycol dimethyl ether, be dissolved with the resin solution of " ユ ピ コ-ト " etc.

As method to the hole potting resin of porous layer, there is not particular determination, can make with the following method: use methods such as location, spoon, some glue, screen painting, ink-jet, above-mentioned hardening resin composition or soluble resin solution to porous layer unfolded surface (coating), are removed unnecessary resin with scraper etc. as required.As above-mentioned scraper, can use for example metal scrapers such as resin systems such as rubber, polyphenylene sulfide, stainless steel such as polypropylene, teflon fluorine resins such as (registration marks), silicon rubber.Wherein, aspect not easy damaged distribution or porous layer, preferably use resinous scraper.In addition, also can not use scraper etc., use can be controlled the method for the discharge-amount of location, some glue, screen painting, ink-jet etc., drips an amount of method on the porous layer surface.

For potting resin successfully in the hole of porous layer, preferably use the low resin of viscosity as uncured resin.In addition, the high resin of viscosity reduces viscosity and uses by using method such as being fit to heat under the temperature, can improve fillibility.But when using curable resin, in order to improve curing reaction speed by heating, excessive heat can make operability or fillibility worsen, and is therefore not preferred.

Make above-mentioned resinous principle to the porous layer unfolded surface and after being filled in hole,, preferably implement heat treated in order to promote resin solidification or solvent flashing.Heating means do not have particular determination, because violent heating can make resin or curing agent volatilization, or volatilizees solvent tempestuously, might form inequality thus, therefore, and the preferred method that heats up reposefully.Intensification can be continuously, progressively any.Temperature and time in curing or the drying is preferably suitably adjusted according to resin or solvent types.

In general, the porous layer before resin is filled has following structure: visible light carries out diffuse reflection in the hole in layer, present opaque because the transparency reduces, therefore can not be from side perspective opposition side.Relative therewith, the porous layer that is filled with resin in hole mostly is transparent greatly because of diffuse reflection does not take place.Transparent porous layer has the advantage of applicability excellence, for example, can easily carry out the distribution inspection when being used for wiring board, when being installed in wiring board on the equipment, discerns the position relation of part etc. easily in addition.And when constituting porous membrane laminated body by water white base materials such as PET, PEN, the transparency in the zone beyond the wiring part is very high.Utilize this porous membrane laminated body, can form distribution or circuit, therefore, can omit circuit substrate and make the slimming of display own, in addition, can reduce by expected cost because of simple in structure at display picture itself.

Hole potting resin by the porous layer in porous membrane laminated body carries out transparence, the possibility to aforesaid purposes expansion occurs.In order to obtain the excellent porous membrane laminated body of the transparency, porous layer preferably uses the porous layer of thin thickness light, layer of the resin of formation itself, and in addition, the resin of filling also preferably uses light, the transparent high resin of resin itself.

On the other hand, generate electromagnetic waves, surrounding devices is produced harmful effect (noise) by displays such as PDP.In order to prevent (shielding) this electromagnetic wave, need give electromagnetic wave to the filter that is configured in the PDP front and block function, as this filter, can use the filter of the distribution that is provided with clathrate or cellular (hexagonal configuration) etc.

The electromagnetic shielded film of such use generally has the formation that is laminated with metal level on the film of high transparent (high transparent membrane) having.This film can form by the following method, for example, the method for metal level is set by sputter on high transparent membrane; After pasting Copper Foil etc. on the high transparent membrane, carry out etching, the method for screening etc. is set.As an example of this electromagnetic shielded film, can enumerate the film of the clathrate pattern of live width 20～30 μ m, about 200～400 μ m of spacing (recurrence interval).

According to the present invention,, can provide the electromagnetic shielded film of above-mentioned formation by potting resin behind the distribution that forms clathrate or cellular (hexagonal configuration) etc. on the porous membrane laminated body.At this moment, it has been generally acknowledged that, give making simply such as distribution, can expect that cost reduces by using print processes such as screen painting.

And, print by ITO (tin indium oxide) printing ink of use as the electric conductor of transparent (transmitance of visible light is about 90%), can also further improve the transparency of wiring part.Can use CI to change into the tin indium oxide printing ink of company's manufacturing or the tin indium oxide printing ink " nano metal printing ink " of ULVAC Materials Co., Ltd manufacturing etc.By using transparent electric conductor, might be able to be used for the touch panel of flat-panel displays such as liquid crystal panel or organic EL, solar cell, resistive film mode etc.Also can enumerate use forms distribution as the zinc oxide printing ink of other transparent conductive bodies method.

Composite of the present invention can be the formation of hole of residual porous layer of remaining untouched.The remain untouched composite of hole of residual porous layer of what is called is meant that porous layer has the characteristic as porous body, and particularly, the porous layer when being meant composite for example and utilizing printing technology to form electric conductor is keeping the pore structure of equal extent.This composite can be can keep scope inner stacks as the characteristic of porous body that other layers are arranged or implemented the formation of various processing at porous layer.In addition, this composite does not comprise the forfeit composite of pore structure that is filled with the composite of resin in the hole of porous layer or causes porous layer by solvent processing etc.

For example, when the hole of the residual porous layer that remains untouched, do not carry out resin and fill in order to reduce dielectric constant etc.But the purpose for the protection of distribution, the insulation of distribution, the oxidation that prevents distribution, raising bendability also can only coat wiring part with resin by above-mentioned illustrative method.

For composite of the present invention,, can also be to handle the forfeit formation of pore structure that causes porous layer by solvent as the formation beyond above-mentioned.Particularly, after forming wiring diagram on the porous layer, porous layer is soaked with solvent, make its swelling, softening after, carry out drying, loose structure is disappeared.

For porous membrane laminated body of the present invention, when the porosity that improves porous layer or when making the aperture microminiaturization, because loose structure, the weakened of porous layer portion sometimes, or reduce with the close adhesion intensity of base material.By utilizing said method that loose structure is disappeared, can strengthen the intensity of porous layer portion, or the close adhesion intensity of raising and base material.In addition, disappear, can suppress the diffuse reflection of visible light, make it transparent by making loose structure.

Owing to, also still can expect expansion under this situation, promptly to following purposes with the identical reason of narrating when the porous portion potting resin, check easily, or discern the position of part easily, or form the distribution that display is used, or form the electromagnetic wave shielding film.

The transparence of porous layer can realize by the following method, for example, soaks by making the porous membrane laminated body and function solvent that has formed distribution, and swelling, softening takes place in porous layer portion, and by making its drying thereafter, the pore structure of porous portion is disappeared.As the method that porous membrane laminated body and function solvent is soaked, can be dipping, also can be the spraying that utilizes sprayer.Drying after soaking with solvent can be air dry, also can be the drying by heating.As long as consider the selections such as boiling point of solvent.In order to carry out transparence in heterogeneity, preferably make its drying lentamente.

The solvent that is suitable for making loose structure to disappear is different because of the resin of porous layer, cannot treat different things as the same, so long as can make the resin swelling of porous layer, softening solvent just unrestricted.But the resin of liquidation is not preferred because the resin of porous layer is dissolved fully, therefore must avoid.This is because the reason of formed Wiring pattern disintegration on porous.Solvent not necessarily must be single solvent, also can be the mixed solvent that is mixed with two or more solvents.Preferably, can make its swelling, softening with proper level by solvent is mixed.

As concrete example, for example, the many relatively solvents of polyamidoimide that can be used for porous layer are indissolubles, but are soluble in several polar solvents (NMP, DMF, DMSO, DMAc etc.).When these polar solvents of porous membrane laminated body and function itself are soaked, the porous layer dissolving, the Wiring pattern disintegration, but can mix with these polar solvents and do not dissolve the solvent (water, acetone, THF, methyl alcohol, ethanol, IPA, methyl ethyl ketone etc.) of porous layer by mixing, can make the porous layer swelling, soften.

This mixed solvent system also can carry out drying by two stages.For example, it has been generally acknowledged that, make (water, acetone, THF, methyl alcohol, ethanol, IPA, the methyl ethyl ketone etc.) air dry of lower boiling solvent or after making its drying under the low relatively temperature, at high temperature making high boiling solvent (NMP, DMF, DMSO, DMAc etc.) drying with drying machine etc.As long as final baking temperature and time are the condition of selecting high boiling solvent fully to volatilize.As additive method, can enumerate the method that heats up lentamente from room temperature.During the demanding transparency, the preferred high resin of the more colourless selection transparency of porous layer preferably selects porous layer thickness also extremely thin in display applications etc.And base material is also preferably selected such high base materials of transparency such as PET or PEN.

When making the porous layer swelling with solvent, soften and making loose structure to disappear, the base material of porous membrane laminated body is the base material of insoluble or indissoluble with respect to the solvent that uses preferably.This be because, when base material and porous layer swelling takes place equally, when softening, base material deforms, and makes the dimensional stability reduction as wiring board.Unaccommodated solvent is different because of base material, cannot treat different things as the same, because PET or PEN, polyimides are insoluble with respect to many solvents or indissoluble, be preferred solvent therefore.

As described when the porous portion potting resin, form distribution if use as the tin indium oxide of transparent electric conductor or the printing ink of zinc oxide, then can also further enhance the transparency, can expect to the purposes direction expansion that requires this specific character.Can make the loose structure disappearance and carry out transparence with said method, but distribution might be exposed state this moment.The such resin narrated before preferably utilizing or anisotropic conductive material (anisotropic conducting film or anisotropic conductive are stuck with paste) coat, or the formation cover layer also insulate without exception.

Generally, moving in order to make electric current, wiring board engages with other parts or substrate by scolding tin or connector etc.Therefore, this contact portions must carried out potting resin under the state of sheltering, or avoids contact portions and cover with resin.As this resin, can use above-mentioned illustrative curable resin or soluble resin as the resin in the hole that is filled in porous layer.

In addition, wiring board not only can only be formed by distribution, and can by scolding tin or electric wire binding etc. semiconductor chip, capacitor, resistance etc. be engaged in the circuit board as TAB or COF etc.And distribution forms or part is installed and not only can be carried out in the one side of porous membrane laminated body, also can carry out on the two sides, also can stacked a plurality of substrates and carry out multiple stratification.

Composite of the present invention also can be at porous layer upper strata superimposition cap rock.For example, under the situation of flexible substrate, generally speaking, for the purpose of the protection of distribution, the insulation of distribution, the oxidation that prevents distribution, raising bendability, distribution uses the cover layer that is made of resin films such as Kapton or PET films to cover mostly.As this cover layer film, can enumerate " ニ カ Off レ Star Network ス " or the product that pool making manufacturing is arranged that daily magazine industrial group makes.

As stacked tectal method, for example can enumerate: in tectal methods such as direct at once covering Kaptons behind the porous layer potting resin; To the porous layer potting resin, solidify after, will add the method for thermocompression bonded etc. at the cover layer that tectal one sides such as Kapton or PET film are coated with bonding agent with film.As the bonding agent of cover layer with film, can use known bonding agent, for easy operation, mostly be the state of semi-solid preparation (B level) greatly.

To the porous layer potting resin or only just can fully guarantee anti-oxidant, the bendability of insulation, distribution of protection, the distribution of distribution the time with the resin-coating distribution, not necessarily need cover layer, also can omit.

In addition, also gusset plate can be installed in the circuit board.Because wiring board of the present invention has flexibility, therefore can be used as flexible substrate, but can the strengthening with external bonding plate in the part that requires mechanical strength or hardness.Particularly, preferably carrying part or pasting the gusset plate of suitable material sometimes in the such part of insertion connector.As the material of gusset plate, as long as can achieve the goal, any material can, in general, can use the material of using with same film of the base material of substrate or hard printed base plate mostly.As gusset plate, for example can enumerate: polyester film, Kapton, glass epoxy substrate, phenolic group plate, paper phenolic group plate, metallic plate (aluminium sheet, corrosion resistant plate etc.) etc.As polyester film, Kapton, often use the film about 10～300 μ m.As glass epoxy substrate, phenolic group plate, paper phenolic group plate, often use the substrate about 0.1～3mm.Metallic plate can be not particularly limited thickness ground and use.Wiring board and gusset plate can carry out bonding with any method, can use the bonding agent of film shape, as bonding agent, adhesive type and heat cure sexual type are arranged.In addition, also the gusset plate that is coated with bonding agent on the gusset plate can be pasted use in the circuit board.

As mentioned above, owing to can therefore, also can be used as a kind of rigidity/curved substrate and use according to purpose independent assortment rigid portion (hard portion) and bend (bendable portion).

Wiring board of the present invention is to exist many at least one masks with porous rete of connective micropore (micropore continuously) that the wiring board of conductor wirings is arranged equably, for for example conductor wirings of fabric width 50～200 μ m, when the disbonded test that utilizes cellophane tape [NICHIBAN (strain) manufacturing, trade name " fabric strip (registration mark) No.405 ", fabric width 24mm] (180 ° peel off, peeling rate 50mm/ minute), has the such characteristic of disappearance that does not produce distribution.In above-mentioned adhesive tape disbonded test, as cellophane tape, replace above-mentioned " fabric strip (registration mark) No.405 ", also can use the cellophane tape that has equal bonding force (4.00N/10mm) with it.

The present invention also comprises a kind of wiring board, described wiring board is to exist many at least one masks with porous rete of connective micropore that the wiring board of conductor wirings is arranged, wherein, for for example conductor wirings of fabric width 50～200 μ m, when the disbonded test that utilizes paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " paper self-adhesive tape (registration mark) No.208 ", fabric width 24mm] (180 ° peel off, peeling rate 50mm/ minute), has the such characteristic of disappearance that does not produce distribution.In above-mentioned adhesive tape disbonded test, as paper self-adhesive tape, replace above-mentioned " paper self-adhesive tape No.208 ", also can use the paper self-adhesive tape that has equal bonding force (1.7N/10mm) with it.

Because wiring board of the present invention forms conductor wirings on the surface of the porous rete that has many continuous micropores, therefore, utilizes many micropores can improve the anchoring of conductor wirings, can obtain high distribution close adhesion intensity.In addition,, therefore, the distribution fabric width is narrowed down, can form fine Wiring pattern owing to can suppress the diffusion (line is not swum) of printing ink etc. when utilizing many micropores to form conductor wirings.That is, high distribution close adhesion intensity and high distribution illustrative equilibrium can be made, fine pitchization can be realized.For example, in above-mentioned adhesive tape disbonded test, do not produce the disappearance of distribution, and the resistance change after the adhesive tape disbonded test is also very little.More specifically, for wiring board of the present invention, when the resistance before the adhesive tape disbonded test being set at R1, when the resistance after the adhesive tape disbonded test is set at R2, being generally R2/R1＜5, preferred R2/R1＜3, more preferably R2/R1＜1.5.In addition, wiring board of the present invention is when using that for example the electrically conductive ink of 30pl utilizes ink-jetting style to print, and spot size is generally below the 200 μ m.

The average pore size of porous rete (average pore size of film surface) is preferably 0.01～10 μ m, and more preferably 0.05～5 μ m is preferably 0.1～2 μ m especially.When hole undersized, when utilizing that for example print process forms conductor wirings, the impregnability of printing ink etc. reduces, and the distribution close adhesion reduces easily.In addition, when hole oversize, when utilizing that for example print process forms conductor wirings, the anchoring of printing ink etc. reduces, and the distribution illustrative also reduces easily, or ink diffusion and cause line to be swum, the distribution illustrative reduces easily, and mechanical strength reduces simultaneously, easy deformation.When the average pore size of porous rete was above-mentioned scope, printing ink etc. were successfully absorbed by the porous rete, simultaneously can obtain high anchoring effect, and therefore, distribution close adhesion intensity is very high, can suppress the diffusion of printing ink etc. simultaneously, can obtain excellent distribution illustrative.Thus, the present invention also provides a kind of wiring board, described wiring board is to exist many at least one masks with porous rete of connective micropore that the wiring board of conductor wirings is arranged, and the average pore size of porous rete is 0.01～10 μ m, utilizes print process to form conductor wirings.

Need to prove, when on the base material of densification that is not porous, utilizing print process to form conductor wirings, because printing ink etc. is not absorbed by base material, therefore, close adhesion intensity between this base material and the distribution is low, in addition, because printing ink etc. spread at substrate surface, therefore line is swum easily, is difficult to form fine distribution.In addition, when utilizing print process to form conductor wirings on hydrophobic base material, printing ink etc. can't be stained with on substrate surface, paint thereby can not carry out line drawing.

The porosity of porous rete (voidage) is 30～80% for example, is preferably 40～80%, more preferably 50～80%.Under the low excessively situation of porosity, when utilizing print process to form conductor wirings, the impregnability of printing ink etc. reduces, and the distribution close adhesion reduces easily.On the other hand, under the too high situation of porosity, bad mechanical strength sometimes.In addition, as the percent opening (surperficial percent opening) on the surface of porous rete, for example be (for example 48～80%) more than 48%, be preferably about 60～80%.Under the low excessively situation of surperficial percent opening, when utilizing print process to form conductor wirings, the impregnability of printing ink etc. reduces, and the distribution close adhesion reduces easily.On the other hand, when surperficial percent opening was too high, mechanical strength reduced easily.

The thickness of porous rete for example is 0.1～100 μ m.When the base material of wiring board was independent porous rete, the thickness of porous rete for example was 5～100 μ m, more preferably 25～70 μ m.In addition, when the base material of wiring board was the duplexer of compacted zone and porous rete, the thickness of porous rete for example was 0.1～100 μ m, was preferably 0.5～70 μ m, more preferably 1～50 μ m.Cross when thin when the thickness of porous rete, be difficult to stably make, on the other hand, when it was blocked up, becoming easily was difficult to control equably pore-size distribution.The thickness of porous rete is preferably more than 2 times of average pore size, is preferably especially more than 10 times.

The average pore size of the micropore on two surfaces of porous rete, therefore the build environment difference of the micropore when forming owing to the porous rete, has different hole characteristic mutually sometimes.The average grain diameter A2 of the average grain diameter A1 of the micropore of a face of porous rete and the micropore of another face considers from the viewpoint of its balance, preferably satisfies the relation of 0.1 ≦ A1/A2 ≦ 10 (particularly 0.2 ≦ A1/A2 ≦ 5).

The connectedness that is present in the micropore of porous rete can be set at index with expression grignard value of air permeability and pure water penetration speed etc.The grignard value of porous rete is 0.2～2000 second/100cc for example, is preferably 1～1000 second/100cc, more preferably 1～500 second/100cc.When numerical value was excessive, the through performance in the practicality was insufficient, or can not bring into play its function sometimes because of not filling functional material fully.On the other hand, when numerical value is too small, might bad mechanical strength.

Relation as the fabric width W of the average pore size A of the face of the conductor wirings side that forms the porous rete and conductor wirings is preferably W/A 〉=5, and more preferably W/A 〉=10 are preferably W/A 〉=50 especially.When W/A was lower than 5, when for example utilizing print process to form conductor wirings, the anchoring of printing ink etc. reduced, the reduction of distribution close adhesion, or ink diffusion, and line is spread and sunk in, and the distribution illustrative reduces easily.

As the fabric width W of conductor wirings, for example be 200 μ m following (they for example being 10～200 μ m), be preferably 150 μ m following (for example being 10～150 μ m), more preferably 100 μ m following (for example being 10～100 μ m).The distribution illustrative excellence of wiring board of the present invention when using that for example the electrically conductive ink of 30pl utilizes ink-jetting style to print, can be set at spot size below the 200 μ m, therefore, can be the conductor wirings of aforesaid narrow distribution fabric width.In addition, even the distribution fabric width is narrow, distribution close adhesion intensity is also high, therefore is difficult to peel off.

Material (raw material) as constituting the porous rete so long as have the material of insulating properties, does not just have particular determination, preferred resin.As resin, for example can enumerate: polyimides is that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, polyphenylene sulfide are that resin, liquid crystalline polyester are that resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polybenzothiozole are that resin, polysulfones are resin, cellulose-based resin, acrylic resin etc.Wherein, consider from having the excellent such angle of hear resistance, mechanical strength, resistance to chemical reagents, electrical characteristics, preferred polyimides is that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polysulfones are resin, cellulose-based resin etc., and special preferred polyamide imide series resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are resin.Resin can be a copolymer, also can be graft polymers.These materials can be used alone or in combination of two or more.In addition, the inner surface in the laminar surface of porous rete and hole can coat with the resistance to chemical reagents macromolecular compound.

The porous rete can be used alone as the base material of conductor wirings, and the duplexer that also the porous rete can be formed on the one or both sides of the compacted zone that does not have the hole in fact is used as the base material of conductor wirings.By using this duplexer, can improve the mechanical strength of base material.

In addition, for the porous rete among the present invention, when utilizing print process to form conductor wirings on its surface, when printing ink etc. was absorbed easily, with the close adhesion excellence of distribution, and printing ink etc. was in diffusion into the surface, line is difficult to spread and sink in, form fine distribution easily, therefore, preferably have specific surface characteristic.Consider that from above-mentioned angle preferred porous rete is made of layer as described below, that is, behind the solution 1 μ l of this laminar surface dropping viscosity 0.00001～1Pas, 1000 μ sec are below 30 ° with interior contact angle θ.This porous rete is preferred: drip the solution 1 μ l of viscosity 0.00001～1Pas at this laminar surface after, and the contact angle θ during through 100 microseconds ₁₀₀Contact angle θ with through 1000 microseconds the time ₁₀₀₀Ratio θ ₁₀₀₀/ θ ₁₀₀Less than 0.9, especially preferably use except having above-mentioned characteristic, above-mentioned θ ₁₀₀₀It is the layer below 60 °.As the solution of above-mentioned viscosity 0.00001～1Pas, can enumerate as printing-ink described later or the illustrative solution of solvent in sticking with paste.

As the form of wiring board of the present invention, can enumerate for example Fig. 2～form shown in Figure 6.Fig. 2～Fig. 6 is respectively the generalized section of the example of expression wiring board of the present invention.In each figure, 1 expression porous rete, 2 expression conductor wirings, 3 expression compacted zones.Fig. 2 is the wiring board that has formed conductor wirings 2 in the one side of porous rete 1, Fig. 3 is the wiring board that has formed conductor wirings 2 on the two sides of porous rete 1, Fig. 4 is the wiring board that is laminated with porous rete 1 and forms conductor wirings 2 on the surface of this porous rete 1 on compacted zone 3, Fig. 5 is the wiring board that is laminated with porous rete 1 on the two sides of compacted zone 3 and has formed conductor wirings 2 on a surface of this porous rete 1, and Fig. 6 is the wiring board that is laminated with porous rete 1 on the two sides of compacted zone 3 and has formed conductor wirings 2 on two surfaces of this porous rete 1.On wiring board of the present invention, also can form path.

When the surface of porous rete 1 forms conductor wirings 2, in general, has following several situation: the situation that as Fig. 1 (A) or (D), conductor wirings 2 is absorbed in the porous rete 1, conductor wirings 2 almost all is embedded in the state (burying state underground) in the porous rete 1; As Fig. 1 (B) or (E), conductor wirings 2 parts are absorbed in the porous rete 1, conductor wirings 2 half about be embedded in the situation of the state (partly burying state underground) of porous rete 1; And as Fig. 1 (C) or (F), conductor wirings 2 is not absorbed in the porous rete 1, be laminated in the situation of the state (stacking states) on the surface of porous rete 1.Wherein, consider the state of preferred Fig. 1 (A) and Fig. 1 (B) from distribution close adhesion intensity aspect.When requiring the low conductor of resistance, preferred Fig. 1 (C) or state (F).In the present invention, owing on the porous rete, there are many connective micropores that have, therefore, when utilizing the print process of for example using ink-jetting style to form conductor wirings, mostly be Fig. 1 (A) or state (D) greatly.When print process that utilize to use the screen painting mode forms conductor wirings, mostly be (C) (E) state of (F) representing of Fig. 1 (B) greatly.

More specifically, directly be set at R when average perforate with the porous layer top layer ₁, the average grain diameter of particle contained in the printing ink is set at R ₂The time, preferred R ₁Be about 0.01～10 μ m, R ₂Be in the scope about 0.001～10 μ m.That is, preferably satisfy formula: 0.0001 ≦ R ₂/ R ₁≦ 1000 relation.

Under the situation of ink jet printing, in nozzle, the viscosity particle low, that make an addition to printing ink of preferred printing ink is the particle of small particle diameter for fear of clogged with ink.Therefore, preferred R ₁Be about 0.01～5 μ m, R ₂Be about 0.001～0.2 μ m.That is, preferably satisfy formula: 0.0002 ≦ R ₂/ R ₁≦ 20 relation.

Under the situation of screen painting, cross when low when viscosity, in half tone, be difficult to keep printing ink, therefore, preferred viscosities is up to a certain degree printing ink, even the particle diameter of contained particle is greatly also no problem in the printing ink without hesitation, in addition, under the little situation of particle diameter, preferably reduce quantity of solvent.Therefore, preferred R ₁Be about 0.01～10 μ m, R ₂Be about 0.001～10 μ m.That is, preferably satisfy formula: 0.0001 ≦ R ₂/ R ₁≦ 1000 relation.

As the material (raw material) that constitutes compacted zone, the material so long as not dissolving when forming the porous rete or generation drastic deformation does not just have particular restriction, preferably has the resin of insulating properties.As above-mentioned resin, for example can enumerate: polyimides is a resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyarylate is a resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, acrylic resin, the PET series resin, PEN is a resin, polybutylene terephthalate (PBT) is a resin, polyether-ether-ketone is a resin, fluorine resin, the olefin-based resin, phenylethylene resin series, resins such as vinyl chloride-based resin.Resin can be a copolymer, also can be graft polymers.These materials can use separately or be used in combination.

The thickness of compacted zone for example is 1～300 μ μ m, is preferably 5～100 μ m, more preferably 5～50 μ m.Cross when thin when thickness, be difficult to use, on the other hand, when it was blocked up, flexibility reduced sometimes.

In wiring board of the present invention, the porous rete can utilize phase inversion method to form.For example, to comprise the raw material (resinous principle), water-soluble polymer, polar solvent and the mixed solution curtain coating that comprises water as required that constitute the porous rete after on the substrate of homogeneous, import in the solidification liquid, utilize the wet type phase inversion method can form the porous rete.As the raw material (resinous principle) that constitute the porous rete, be preferably dissolved in water miscible polar solvent and utilize the phase inversion method can film forming material, particularly, can use the above-mentioned resin of crossing as the resin illustration that constitutes the porous rete.Need to prove, replace this resin, also can use precursors such as the monomer component (raw material) of this resin or its oligomer.For example, obtain by polyimides be resin constitute the porous rete time, use as polyimides be the polyamic acid profit of the precursor (polyimides is a precursor) of resin use the same method obtain the porous rete after, utilizing hot-imide, chemical imidizate can obtain by desirable polyimides is the perforated membrane that resin constitutes.

For membrane structure being made the spongy of porous, be effective to the polymer solution interpolation water-soluble polymer or the water that carry out curtain coating.As water-soluble polymer, for example can enumerate: or derivatives thereof such as polyethylene glycol, PVP, PEO, polyvinyl alcohol, polyacrylic acid, polysaccharide and their mixture etc.Wherein, the formation in the space in suppressing film inside, can improve aspect the mechanical strength of film preferably polyethylene base pyrrolidones.These water-soluble polymers can use separately or be used in combination.Consider that from the angle of porous the molecular weight of water-soluble polymer for example is more than 200, to be preferably more than 300, more preferably more than 400 (for example about 400～200,000) is preferably more than 1000 (for example about 1000～200,000) especially.

Water-soluble polymer is an important additive, and is particularly spongy very effective to membrane structure is made, and kind and amount by the change water-soluble polymer can obtain multiple structure.But,, therefore, be cleaned when in impregnated in water etc., porous layer being solidified and remove because water-soluble polymer is inessential composition finally.On the other hand, when forming loose structure,, therefore, can not add water-soluble polymer because insoluble composition must heat basically and remove with the dry type phase inversion method.So, we can say with the dry type phase inversion method to be difficult to form multiple cellular structure.

As above-mentioned polar solvent, can use according to the chemical skeleton of the resin that uses to have deliquescent polar solvent (good solvent).As polyamidoimide is that resin, polyamic acid, PEI are the good solvent of resin, polycarbonate-based resin etc., for example can enumerate: dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), N, dinethylformamide, NMP/ dimethylbenzene, NMP/ dimethylbenzene/methyl ethyl ketone, ethanol/toluene, dimethyl sulfoxide (DMSO), 2-Pyrrolidone etc.Polar solvent can use separately or be used in combination.

As the polymer solution that carries out curtain coating, for example, preferably by the mixed solution that constitutes as raw-material macromolecule component 8～25 weight %, water-soluble polymer 10～50 weight %, water 0～10 weight %, water soluble polar solvent 30～82 weight % that constitute porous film layer etc.

With regard to above-mentioned polymer solution, when the concentration of the polymer (macromolecule component) of the main body that becomes the perforated membrane layer is crossed when low, the weakened of film, in addition, when it was too high, porosity diminished.The water-soluble polymer that constitutes this polymer solution adds for the spongiform loose structure of film inside being made homogeneous, at this moment, crosses when low when concentration, surpasses 10 μ m huge space like that inner generation of film, and homogenieity reduces.In addition, when excessive concentration, the dissolubility variation.The addition of water can be used to regulate aperture diameter, can increase diameter by increasing addition.

As the baseplate material (raw material) of the homogeneous that uses when the curtain coating polymer solution, as the illustrative resin of material (raw material) that constitutes compacted zone, can enumerate glass etc. except that above-mentioned.As the substrate of homogeneous, also can use combination that surperficial raw material multiple raw-material laminated film or the sheet material different with inner raw material are arranged.Laminated film or sheet material can form by fitting, and also can be laminated film or the sheet materials that obtains by surface treatments such as coating, evaporation, sputters.In addition, also can use laminated film or the sheet material of the surface being implemented easy bonding processing, antistatic treatment, blasting treatment, Corona discharge Treatment etc.With the substrate of homogeneous as used herein during directly as this compacted zone of the wiring board with compacted zone, preferred select to use the raw material (for example having the resin of monomeric unit of the same race etc.) or the resin that have a compatibility with the material that constitutes the porous rete were implemented surface-treated substrates such as easy bonding processing or Corona discharge Treatment.

Optimum condition when above-mentioned polymer solution curtain coating is become the film shape is, relative humidity is that 70～100% (being preferably 90～100%), temperature are 15～90 ℃ (being preferably 30～80 ℃), particularly preferred condition is, relative humidity is about 100% (for example being 95～100%), and temperature is 40～70 ℃.When airborne water content than it after a little while, produce the inadequate unfavorable condition of percent opening on surface sometimes.When the polymer solution curtain coating is become the film shape, wish after this film is kept 0.2～15 minute under by relative humidity 70～100%, 15～90 ℃ of atmosphere that constitute of temperature, to be directed into the solidification liquid of making by the non-solvent of macromolecule component.By the tympan after the curtain coating is placed under these conditions, can make porous layer become homogeneous and connective high state.It has been generally acknowledged that its reason is, by being placed under the humidified condition, moisture is immersed in inside from film surface, promotes being separated of Polymer Solution effectively.

As the solidification liquid that is used for phase inversion method, so long as the solvent that component of polymer is solidified gets final product, can suitably select according to the kind of the resin that is used as macromolecule component, for example, as making polyamidoimide is that resin, polyamic acid, PEI are the solvent that resin, polycarbonate-based resin etc. solidify, and for example can use: water; Monohydric alcohol such as methyl alcohol, ethanol; Alcohol such as polyalcohol such as glycerine; Water soluble polymers such as polyethylene glycol; Water-soluble solidification liquids such as their mixture etc.

The perforated membrane that is imported into solidification liquid and separates out when the base material with homogeneous is used as compacted zone, by directly carrying out drying, can obtain the duplexer (base material of wiring board) of compacted zone and porous rete.The duplexer that has the porous rete on the two sides of compacted zone can be made by carry out aforesaid operations once more behind the one side formation porous rete of compacted zone.In addition, be needed on the supporter and carry out drying from the base material of homogeneous, can obtain independent porous rete by being imported into perforated membrane that solidification liquid separates out.This independent porous rete can be as the base material of wiring board.As above-mentioned supporter, preferably constitute and have many supporters that are used to accelerate the micropore of rate of drying on surface, especially preferably have the supporter that can see through the permeability of the degree of solidifying solvent with suitable speed with the film contact side by the material that solidification liquid is had patience.This supporter for example is: air permeability be lower than 1000 seconds/100cc (preferably be lower than 100 seconds/100cc), thickness is 5～1000 μ m (preferred 50～500 μ m), runs through the film cross-wise direction is dispersed with 0.01～10 μ m (preferred 0.03～1 μ m) with sufficient density hole.Particularly, can use with polyolefin such as polyester, polyamide, polyethylene, polypropylene, cellulose, teflon (registration mark) etc. and be the nonwoven of material or perforated membrane etc.Need to prove, also can on the compacted zone of preparing separately, utilize and for example use the stacked independent perforated membrane that obtains like this of pellicular cascade method commonly used that bonding agent etc. is arranged, obtain having the duplexer (base material of wiring board) of porous rete at the one or both sides of above-mentioned compacted zone.

For the perforated membrane (layer) that utilizes said method to form, in order further to improve the polymerization or the resistance to chemical reagents of precursor, also can use heat, visible light, ultraviolet ray, electron beam, radioactive ray etc. to make it carry out polymerization, or implement crosslinked (curing) and handle.For example, as mentioned above, be the film of forming precursor for using polyimides, by further enforcement hot-imide or chemical imidizate etc., can obtain by polyimides is the porous rete that resin constitutes.In addition, using polyimides is that the film that resin etc. has formed the porous rete can be implemented heat cross-linking.In addition, the perforated membrane (layer) that obtains be impregnated in the solution of the polymer with resistance to chemical reagents, and carry out drying, can form the resistance to chemical reagents tunicle at the inner surface in film surface and hole.As the polymer with resistance to chemical reagents, for example can enumerate: phenol resin, urea are that resin, melamine are that resin, benzoguanamine are that resin, polyimides are that resin, epoxy resin, benzoxazine are that resin, polypropylene-based resin, polyurethane series resin, fluorine resin, alkyd are that resin, acetate fiber prime system resin, phthalic acid are that resin, maleic acid are that resin, silicon are that resin, triazine resin, furans are resin, polyester based resin, diformazan benzene series resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, chitin, shitosan etc.

Utilize said method, can obtain perforated membrane as described below (layer), it is to be that resin, PEI are the porous rete that resins such as resin, polycarbonate-based resin constitute by for example there being many polyamidoimides with connective micropore equably, the average pore size of the micropore of this porous rete is 0.01～10 μ m, porosity is 30～80%, and thickness is 0.1～100 μ m.

As mentioned above, humidity, the temperature and time when use amount of the kind of the constituent by suitable selective polymer solution and amount, water, curtain coating, the kind that is used for the homogeneous base material of curtain coating, post processing etc., the micro-pore diameter, porosity, percent opening that can regulate the porous rete are to desirable value.

Wiring board of the present invention can be by forming conductor wirings manufacturing in the many one sides at least with the micropore of connectedness and porous rete that average pore size is 0.01～10 μ m that exist that for example obtain as described above.The resin bed that this porous rete preferably utilizes phase inversion method, particularly aforesaid wet type phase inversion method to form.As mentioned above, above-mentioned independent porous rete can become wiring board, is the base material that the duplexer of the porous rete of 0.01～10 μ m also becomes wiring board but the one or both sides that substantially do not have a compacted zone in hole are laminated with average pore size.

Method as form conductor wirings on the surface of porous rete does not have particular determination, preferably utilizes print process to form conductor wirings.Not having particular determination as print process, for example can be: letterpress (aniline printing), ink-jetting style, screen painting, hectographic printing, distillation (fusion) mode, temperature-sensitive mode, photogravure, laser printing, paste are described, nano contact printing etc. any.These print processes can be carried out with method known or commonly used.

As using print process to form the representative method of conductor wirings, can be set forth in the method for printing conductive inks on the porous rete or conductor paste, for example: (1) uses the method that electrically conductive ink forms conductor wirings on the surface of porous rete with ink-jetting style; (2) formed coating electrically conductive printing ink on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete, forms the method for conductor wirings; (3) on the surface of porous rete, by extruding conductor paste from syringe and describing to form the method for conductor wirings; (4), form method of conductor wirings etc. by utilizing screen painting to describe conductor paste on the surface of porous rete.

Do not have particular determination as electrically conductive ink, for example can use: bronze ink, silver-colored printing ink, silver nano-metal printing ink, copper printing ink, carbon printing ink, silver-carbon printing ink etc.In addition, do not have particular determination, for example can use: silver conductor cream, copper conductor cream, golden conductor paste, palladium conductor paste, palladium-silver conductor cream, platinum conductor paste, platinum-silver conductor cream, nickel conductor paste etc. as conductor paste.Need to prove, in said method, also can on the conductor wirings that forms, further implement plating with method commonly used.

In addition, as using print process to form other representative method of conductor wirings, can be set forth in the method for implementing plating on the porous rete behind the printing plating catalyst, for example: (5) are after the surface of porous rete has been printed the plating catalyst with the Wiring pattern shape with ink-jetting style, implement plating, form the method for conductor wirings; (6) forming coating plating catalyst on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete after, implement plating, form the method for conductor wirings; (7) on the surface of porous rete, after extruding the plating catalyst and depict the Wiring pattern shape as from syringe, implement plating, form the method for conductor wirings; (8) on the surface of porous rete, utilize screen painting to depict the plating catalyst as the Wiring pattern shape after, implement plating, form the method for conductor wirings etc.

As the plating catalyst, can use the salt that covers the metal that the catalyst of processing works as electroless plating.Particularly, for example can enumerate: be selected from the hydroxyl carboxylate (citrate, tartrate etc.) of the metal in the iron family elements such as platinum family elements such as the copper family elements, palladium and the platinum that comprise gold, silver and copper and nickel or inorganic metal salt (sulfate, hydrochloride etc.) etc.The printing of plating catalyst can be undertaken by following operation, and for example, the printing ink that preparation contains plating catalyst, suitable vehicle and additive as required etc. prints it with suitable print process.Behind printing plating catalyst, the plating catalyst reduced handle and after making metal, implementing electroless plating covers processing, further implement electrolytic coating as required to handle, can form conductor wirings thus.In the reduction of plating catalyst is handled, for example can use reducing agents such as hypophosphorous acid or its salt, hydrazine or its salt, boron hydrogen based compound, amino borane based compound, glucose, formaldehyde.Reduction is handled the aqueous solution for example can use the reducing agent of 0.5～10 weight %, is carried out under the temperature about room temperature～50 ℃.Electroless plating covers processing for example can carry out with the known method that uses electrolytic copper free plating liquid, no electrolytic nickel plating liquid etc.In addition, electrolytic coating is for example handled also and can be carried out with the known method that uses copper sulphate etc.

As printing-ink that is used to print or paste, can use the printing ink or the paste that constitute by solid (solid constituent) and solvent at least, preferably containing following liquid is the printing-ink or the paste of main solvent (solvents that content is maximum), the characteristics of described liquid are as follows: the drop that drips 1 μ l at the perforated membrane laminar surface, the contact angle of this perforated membrane laminar surface 300 microseconds with interior be below 60 ° (more preferably below 50 °, more preferably below 40 °), particularly drip the drop of 1 μ l at the perforated membrane laminar surface, 300 microseconds with interior be below 60 ° (more preferably below 50 °, more preferably below 40 °), and the droplet radius during through 300 microseconds is (more preferably below the 1500 μ m, more preferably 1400 μ m are following) below the 1600 μ m.When using this printing-ink or sticking with paste, solvent in printing-ink or the paste is absorbed the hole of porous rete apace, the viscosity of printing ink or paste rises, the flowability forfeiture of printing ink or paste, solid constituent in printing ink or the paste remains in the perforated membrane laminar surface, therefore, can not spread and sink in, the printed matter of fine rule illustrative excellence.

As the solid (solid constituent) in printing ink or the paste, can select according to the purpose of distribution or inductor, illuminator, resistance, capacitor or semiconductor formation, can use known inorganic matter, organic matter etc.As the example of inorganic matter, can use metal (gold, silver, copper, nickel, aluminium etc.) or glass, inorganic EL material (ZnS, Mn/CdSSe, ZnS:TbOF, ZnS:Tb, SrS:Ce, (SrS:CeZnS) _n, CaCa ₂S ₄: Ce, SrGa ₂S ₄: Ce, SrS:Ce/ZnS:Mn etc.), carbon, other inorganic material (ceramic materials such as silica, zirconia etc.).As organic matter, can use organic pigment, electroconductive polymer, organic semiconducting materials (pentacene class or thiophene-based etc.).The shape of solid constituent does not have particular determination, does not get final product so long as do not hinder the shape of printing, can use the solid constituent of particle shape, different shapes such as flakey, hollow-particle, hollow fiber such as laminar, fibrous.

As the solvent in printing-ink or the paste, can for example can use: hydrocarbon system solvent, halogenated hydrocarbons series solvent, pure series solvent, phenol series solvent, ketone series solvent, aliphatic acid acid anhydrides, ester series solvent, nitrogenous sulfur-bearing polar solvent, water etc. according to the suitably selections such as kind of the resin in printing-ink or the paste.Particularly, for example can enumerate: toluene, terpineol, decane, the tetradecane, decyl alcohol, diglycol list ether, diethylene glycol monobutyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, the diglycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, DPG list propyl ether, the glycol monomethyl isopropyl ether, the diglycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, the triethylene-glycol monobutyl ether, propylene glycol monobutyl ether, the DPG monobutyl ether, the glycol monomethyl isobutyl ether, diglycol list isobutyl ether, ethylene glycol ether, the diglycol monohexyl ether, ethylene glycol single 2-ethyl hexyl ether, ethylene glycol monoallyl ether, ethyleneglycol monophenylether, glycol dimethyl ether, the diglycol dimethyl ether, the diglycol diethyl ether, the diglycol butyl oxide, the triethylene-glycol dimethyl ether, acetate of butyl carbitol, terpineol, acetate of butyl carbitol, butanols, propane diols, butanediol, pentanediol, ethylene glycol, glycerine, water etc.These solvents can use a kind separately, and it is two or more also can to mix use.Need to prove, about printing ink solvent, open by technology in TOHKEMY 2004-319281 communique, TOHKEMY 2004-111057 communique, TOHKEMY 2006-059669 communique, TOHKEMY 2004-143325 communique etc.Wherein, absorbing well aspect the porous rete, preferably using viscosity is the solvent of 0.00001～1Pas.

In addition, as printing-ink that is used to print or paste, preferred viscosities is printing-ink or the paste of 0.05～1Pas.When using this printing-ink or sticking with paste, printing-ink or stick with paste in solvent be quickly absorbed into the hole of porous rete, solid constituent remains in the perforated membrane laminar surface, therefore, can not swim, the printed matter of fine rule illustrative excellence.Need to prove, printing-ink or stick with paste in viscosity can be by changing solid constituent kind and the kind of additives such as concentration, resin and concentration, solvent types wait and regulate.

Utilize the manufacture method of wiring board of the present invention, the one side at least that has many micropores of connectedness and the porous rete that average pore size is 0.01～10 μ m in existence forms conductor wirings, therefore, utilize the effect of many micropores, can make distribution close adhesion intensity height and the high wiring board of distribution illustrative easy and effectively.

Printed matter 1 of the present invention is a printed matter of having implemented to have with average live width 10～1000 μ m the printing of the straight line portion more than the long 500 μ m on the surface of porous rete at least, and it has following feature: the change value F of the live width of following formula (1) expression is below 30%.

F＝(LMax-LMin)/LAve×100 (1)

(in the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m).

In addition, printed matter 2 of the present invention is printed matters of having implemented to have with average live width 10～1000 μ m the printing of the straight line portion more than the long 500 μ m on the surface of porous rete at least, and it has following feature: the standard deviation ∑ of the live width of following formula (2) expression is below 7.

$\mathrm{\Σ}=\sqrt{(({(\mathrm{LAve}-\mathrm{LMax})}^2+{(\mathrm{LAve}-\mathrm{LMin})}^2)/2)}---\left(2\right)$

(in the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m).

In the present invention, the change value F of live width and standard deviation ∑ are the values of the above straight line portion of average live width 10～1000 μ m, long 500 μ m, the value of the straight line portion that more preferably average live width 10～500 μ m, long 500 μ m are above is preferably the value of the above straight line portion of average live width 15～100 μ m, long 500 μ m especially.When average live width is lower than 10 μ m, the printing difficulty, when average live width surpasses 1000 μ m, the distribution chap, circuit is whole to become big, impracticable.

Maximum line width LMax, minimum feature LMin can followingly measure, and average live width 10～1000 μ m of printed matter, long 500 μ m straight line portioies are carried out macrophotography, measure (with reference to Figure 11) by this photo.Average live width LAve can calculate by the following method, that is, setting-out on transparent membrane is converted by its weight.As long as F is 30% below, ∑ is below 7, just can be judged to be the good printing (distribution) of fine rule illustrative (linearity) excellence.F is preferably below 20%, more preferably below 10%.∑ is preferably below 5, more preferably below 3.In addition, the preferred especially F numerical value that is afore mentioned rules is following and ∑ is below the numerical value of afore mentioned rules.When on the porous rete, implementing printing, printing-ink (paste) is with when perforated membrane (perforated membrane) contacts, main solvent in the printing ink is absorbed by perforated membrane, the viscosity of printing ink rises, mobile forfeiture, on perforated membrane, do not spread and sink in, therefore, can utilize the excellent straight line of fine rule illustrative (linearity) of various printing ink (paste) to describe.On the other hand, on common PET film or PI film etc., when implementing printing, printing-ink (paste) therefore, is difficult to carry out the good straight line of fine rule illustrative (linearity) and describes around spreading and sinking in and being diffused into.

Printed matter 3 of the present invention is to use version to implement the printed matter of printing on the surface of porous rete, wherein, and the aperture widths L of version ₁With the corresponding printing width L in printing back ₂Ratio (L ₂/ L ₁) be 0.8～1.2.

The aperture widths L of so-called version ₁, for example be meant the live width of this straight line in the shape of the peristome of version for the situation of straight line, for example be meant diameter of a circle in the shape of the peristome of version for the situation of circle.Need to prove that the shape of the aperture portion of version is not limited to straight line or circle, also can be any of polygonals such as curve, triangle or quadrangle, star etc.The corresponding printing width L in printing back ₂Can obtain by the macrophotography that utilizes electron microscope.The average live width that can adopt the straight line of growing 500 μ m when straight line is described is as L ₂, convert and obtain printing width L owing under the concavo-convex grade situation that is difficult to measure, on transparent membrane, draw profile in the profile of printing by weight ₂The last figure of Fig. 4 is that the peristome of expression version is the L of the situation of straight line ₁And L ₂The key diagram of relation, figure below of Fig. 4 is the L of the peristome of expression version for the situation of circle ₁And L ₂The key diagram of relation.As long as L ₂/ L ₁Be 0.8～1.2 scope, just be judged to be the good printing (distribution) that the repeatability excellence is described in printing.The aperture widths L of version ₁Scope for example be 10～1000 μ m (being preferably 10～500 μ m, more preferably 15～100 μ m).L ₂/ L ₁Value be preferably 0.9～1.1 scope.When on the porous rete, using version to implement printing, printing-ink (paste) is with when perforated membrane (perforated membrane) contacts, main solvent in the printing ink is absorbed by perforated membrane, the viscosity of printing ink rises, mobile forfeiture, therefore indiffusion on perforated membrane, can utilize the printing of various printing ink (paste) to describe the printing of repeatability excellence.On the other hand, on common PET film or PI film etc., when using version to implement printing, printing-ink (paste) therefore, is difficult to print and describes the good printing of repeatability around film surface is diffused into.

In the present invention, as the porous rete, preferably there are many perforated membranes equably with connective micropore (micropore continuously).As the porous rete, the most surperficial at least 10 μ m of preferred distance Printing Department are the porous of homogeneous, and more preferably the most surperficial at least 20 μ m apart from Printing Department are the porous of homogeneous.Preferred especially porous rete integral body is the porous of homogeneous.

The average pore size of porous rete (average pore size of film surface) is preferably 0.01～20 μ μ m (for example 0.01～10 μ m), and more preferably 0.5～15 μ m is preferably 1～10 μ m especially.When hole undersized, the impregnability of printing-ink reduces, and the close adhesion of printing reduces easily.In addition, when hole oversize, the anchoring of printing ink reduces, and the close adhesion of printing also reduces easily, or ink diffusion and cause line to be spread and sunk in, and the straight line illustrative reduces easily, and mechanical strength reduces and easy deformation simultaneously.When the average pore size of porous rete was above-mentioned scope, printing ink was successfully absorbed by the porous rete, can obtain high anchoring effect simultaneously, and therefore, the close adhesion intensity of printing is very high, can suppress the diffusion of printing ink simultaneously, obtained excellent fine rule illustrative.

The porosity of perforated membrane (voidage) is about 30～80% for example, is preferably about 40～80% more preferably 50～80%.Cross when low when porosity, the impregnability of printing-ink reduces, and the close adhesion of printing reduces easily.On the other hand, when porosity is too high, bad mechanical strength sometimes.In addition, as the percent opening (surperficial percent opening) of perforated membrane laminar surface, for example be (for example 30～80%) more than 30%, be preferably about 50～80%.Cross when low when surperficial percent opening, the impregnability of printing-ink reduces, and the close adhesion of printing reduces easily.On the other hand, when surperficial percent opening was too high, mechanical strength reduced easily.

The thickness of porous rete for example is 0.1～100 μ m.During for independent porous rete, the thickness of porous rete is preferably 5～100 μ μ m, more preferably 25～70 μ m at the matrix (being printed body) of printed matter.In addition, when the matrix (being printed body) of printed matter during for the duplexer of supporter such as compacted zone and porous rete, the thickness of porous rete is preferably 0.1～25 μ m, more preferably 1～10 μ m.Cross when thin when the thickness of porous rete, the absorbability of the main solvent of printing-ink (paste) is poor, and on the other hand, when it was blocked up, becoming easily was difficult to control equably pore-size distribution.The thickness of porous rete is preferably more than 2 times of average pore size, is preferably especially more than 10 times.

The average pore size of the micropore on two surfaces of porous rete, therefore the build environment difference of the micropore when forming owing to the porous rete, has different hole characteristic mutually sometimes.For example, utilizing with the polymer solution that will be dissolved with the resin that constitutes perforated membrane after base material (substrate) is gone up curtain coating and formed the film shape, when making its phase inversion method that is solidified as the basis make perforated membrane, the perforated membrane that obtains not with the surface (air side surface) of base material contact side and with the surface (base material side surface) of base material contact side in, micropore forms the environment difference, therefore, has different respectively hole characteristics mostly.In the present invention, the average pore size φ B of the micropore of the average pore size φ A of the micropore of a face of preferred porous rete and another face satisfies the relation of 0.1 ≦ φ A/ φ B ≦ 10.When φ A/ φ B is lower than 0.1 or when surpassing 10, be arranged on the inadequate balance of the micropore on film two sides, the fine rule illustrative reduces easily.In addition, when the average pore size of the micropore of the air side surface that φ A is set at perforated membrane, when φ B being set at the average pore size of micropore of base material side surface, preferred 0.15 ≦ φ A/ φ B ≦ 8, further preferred 0.2 ≦ φ A/ φ B ≦ 5.Need to prove that the value of φ A/ φ B can be regulated by creating conditions of suitable setting perforated membrane.Particularly, can the atmosphere (humidity, temperature etc.) when for example suitably setting will contain surface characteristic, the micropore formation of kind that the raw-material polymer solution that constitutes perforated membrane carries out the base material of curtain coating, this base material control.

The connectedness that is present in the micropore of porous rete can be set at index with expression grignard value of air permeability and pure water penetration speed etc.The grignard value of porous rete is preferably 0.2～100 second/100cc, more preferably 1～50 second/100cc.When numerical value was excessive, the absorbability of the solvent of printing-ink reduced easily, on the other hand, when numerical value is too small, might bad mechanical strength.

Relation as the fabric width W of the line part of the average pore size A of the face of the enforcement printed side of porous rete and printing is preferably W/A 〉=5, more preferably W/A 〉=10.When W/A was lower than 5, anchorings such as printing-ink reduced, the close adhesion reduction of printing, or ink diffusion and cause line to be spread and sunk in, and the fine rule illustrative reduces easily.

Printed matter of the present invention has the above line part of the long 500 μ m of average live width 10～1000 μ m at least, can also have width than its narrow line part or width than its wide line part, non-rectilinear portion etc.

As the material (raw material) that constitutes the porous rete, the material that preferably has insulating properties, preferred resin.As resin, for example can enumerate: polyimides is a resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyarylate is a resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, acrylic resin, epoxy resin, (polymethylpentene is a resin to polyolefin-based resins, cyclic polyolefin hydrocarbon system resin etc.), fluorine resin (Kynoar is a resin etc.) etc.Wherein, consider from having the excellent such angle of hear resistance, mechanical strength, resistance to chemical reagents, electrical characteristics, preferred polyimides is that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polysulfones are resin, cellulose-based resin etc., and special preferred polyamide imide series resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are resin.Resin can be a copolymer, also can be graft polymers.These materials can use separately or be used in combination.In addition, the inner surface in the laminar surface of porous rete and hole can coat with the resistance to chemical reagents macromolecular compound.

The porous rete can be used alone as the matrix (being printed body) of printed matter, and the duplexer that also the porous rete can be formed on the one or both sides of the supporters such as compacted zone that do not have the hole in fact is used as the base material of printed matter.By using this duplexer, can improve the mechanical strength of base material.Under the situation of matrix (being printed body) for independent porous rete of printed matter, can print at the one or both sides of porous rete, therefore, can form circuit etc. at one or both sides.In addition, for by supporter with when being arranged on the duplexer that the porous rete of its one or both sides constitutes, can print, therefore, can form circuit etc. at one or both sides at the one or both sides of this matrix at the matrix (being printed body) of printed matter.

Material (raw material) as constituting above-mentioned supporter does not have particular restriction, can use various materials such as resin, fiber, metal, pottery.Supporter can be film shape, any shape such as fibrous, tabular.As the typical example of the material that constitutes supporter, but illustration for example: polyimides is a resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyarylate is a resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, mylar, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, polyolefin-based resins, cellulose-based resin, acrylic resin, fluorine resin, polyurethane series resin, silicones, plastics such as epoxy resin; Metals such as iron, aluminium, copper, titanium, tin, zinc; Inorganic matters such as glass, pottery, concrete, rock; Timber, bamboo etc.These raw material can use separately or be used in combination.As supporter, consider preferred Kapton, PETG or films such as PEN, aromatic polyamides, glass epoxy substrate etc. from the aspects such as easiness, intensity, hear resistance of operation.

The thickness of supporter for example is 1～300 μ m, is preferably 5～100 μ m.Cross when thin when thickness, be difficult to operation, on the other hand, when it was blocked up, flexibility reduced sometimes.

In printed matter of the present invention, the porous rete can utilize phase inversion method to form.For example, to comprise the raw material (resinous principle), water-soluble polymer, polar solvent and the mixed solution curtain coating that comprises water as required that constitute the porous rete after on the substrate of homogeneous, import in the solidification liquid, utilize the wet type phase inversion method can form the porous rete.As the raw material (resinous principle) that constitute the porous rete, be preferably dissolved in water miscible polar solvent and utilize the phase inversion method can film forming material, particularly, can use the above-mentioned resin of crossing as the resin illustration that constitutes the porous rete.Need to prove, replace this resin, also can use precursors such as the monomer component (raw material) of this resin or its oligomer.For example, obtain by polyimides be resin constitute the porous rete time, use as polyimides be the polyamic acid profit of the precursor (polyimides is a precursor) of resin use the same method obtain the porous rete after, utilizing hot-imide, chemical imidizate can obtain by desirable polyimides is the perforated membrane that resin constitutes.

For membrane structure being made the spongy of porous, be effective to the polymer solution interpolation water-soluble polymer or the water that carry out curtain coating.As water-soluble polymer, for example can enumerate: or derivatives thereof such as polyethylene glycol, PVP, PEO, polyvinyl alcohol, polyacrylic acid, polysaccharide and their mixture etc.Wherein, the formation in the space in suppressing film inside, can improve aspect the mechanical strength of film preferably polyethylene base pyrrolidones.These water-soluble polymers can use separately or be used in combination.Consider that from the angle of porous the molecular weight of water-soluble polymer for example is more than 200, to be preferably more than 300, more preferably more than 400 (for example about 400～200,000) is preferably more than 1000 (for example about 1000～200,000) especially.

Water-soluble polymer is an important additive, and is particularly spongy very effective to membrane structure is made, and kind and amount by the change water-soluble polymer can obtain multiple structure.But,, therefore, be cleaned in impregnated in water etc. and when porous layer is solidified and remove because water-soluble polymer is inessential composition finally.On the other hand,, but consider, preferably utilize the wet type phase inversion method to form cellular structure from above-mentioned aspect even utilize any method of dry type phase inversion method and wet type phase inversion method can form cellular structure.

As above-mentioned polar solvent, can use according to the chemical skeleton of the resin that uses to have deliquescent polar solvent (good solvent).As polyamidoimide is that resin, polyamic acid, PEI are the good solvent of resin, polycarbonate-based resin etc., for example can enumerate: dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), N, dinethylformamide, NMP/ dimethylbenzene, NMP/ dimethylbenzene/methyl ethyl ketone, ethanol/toluene, dimethyl sulfoxide (DMSO), 2-Pyrrolidone etc.Polar solvent can use separately or be used in combination.

As the polymer solution that carries out curtain coating, for example, preferably by the mixed solution that constitutes as raw-material macromolecule component 8～25 weight %, water-soluble polymer 10～50 weight %, water 0～10 weight %, water soluble polar solvent 30～82 weight % that constitute porous film etc.

With regard to above-mentioned polymer solution, when the concentration of the polymer (macromolecule component) of the main body that becomes the perforated membrane layer is crossed when low, the weakened of film, in addition, when it was too high, porosity diminished.The water-soluble polymer that constitutes this polymer solution adds for the spongiform loose structure of film inside being made homogeneous, at this moment, crosses when low when concentration, surpasses 10 μ m huge space like that inner generation of film, and homogenieity reduces.In addition, when excessive concentration, the dissolubility variation.The addition of water can be used to regulate aperture diameter, can increase diameter by increasing addition.

As the material (raw material) of the substrate of the homogeneous that uses when the curtain coating polymer solution, can enumerate above-mentioned as the illustrative material of material (raw material) that constitutes the supporter in the duplexer etc.As the substrate of homogeneous, also can use combination that surperficial raw material multiple raw-material laminated film or the sheet material different with inner raw material are arranged.Laminated film or sheet material can form by fitting, and also can be laminated film or the sheet materials that obtains by surface treatments such as coating, evaporation, sputters.In addition, also can use laminated film or the sheet material of the surface being implemented easy bonding processing, antistatic treatment, blasting treatment, Corona discharge Treatment etc.With the substrate of homogeneous as used herein during directly as the supporter in the above-mentioned duplexer, preferred select to use the raw material (for example having the resin of monomeric unit of the same race etc.) or the resin that have a compatibility with the material that constitutes the porous rete were implemented surface-treated substrates such as easy bonding processing or Corona discharge Treatment.

Optimum condition when above-mentioned polymer solution curtain coating is become the film shape is, relative humidity is that 70～100% (being preferably 90～100%), temperature are 15～90 ℃ (being preferably 30～80 ℃), particularly preferred condition is, relative humidity is about 100% (for example being 95～100%), and temperature is 40～70 ℃.When airborne water content than it after a little while, produce the inadequate unfavorable condition of percent opening on surface sometimes.When the polymer solution curtain coating is become the film shape, wish after this film is kept 0.2～15 minute under by relative humidity 70～100%, 15～90 ℃ of atmosphere that constitute of temperature, to import the solidification liquid that the non-solvent by macromolecule component constitutes.By the tympan after the curtain coating is placed under these conditions, can make porous layer become homogeneous and connective high state.It has been generally acknowledged that its reason is, by being placed under the humidified condition, moisture is immersed in inside from film surface, promotes being separated of Polymer Solution effectively.

As the solidification liquid that is used for phase inversion method, so long as the solvent that component of polymer is solidified gets final product, can suitably select according to the kind of the resin that is used as macromolecule component, be that resin, polyamic acid, PEI are the solvent that resin, polycarbonate-based resin etc. solidify for example, for example can use: water as making polyamidoimide; Monohydric alcohol such as methyl alcohol, ethanol; Alcohol such as polyalcohol such as glycerine; Water soluble polymers such as polyethylene glycol; Water-soluble solidification liquids such as their mixture etc.

The perforated membrane that is imported into solidification liquid and separates out, with the base material of homogeneous during as the supporter in the above-mentioned duplexer, by directly carrying out drying, the duplexer (being printed body) of can be supported body and porous rete.The duplexer that has the porous rete on the two sides of supporter can be made by carry out aforesaid operations once more behind the one side formation porous rete of supporter.In addition, be needed on the supporter and carry out drying from the base material of homogeneous, can obtain independent porous rete by being imported into perforated membrane that solidification liquid separates out.This independent porous rete is as the base material of wiring board.As above-mentioned supporter, preferably constitute and have many supporters that are used to accelerate the micropore of rate of drying on surface, especially preferably have the supporter that can see through the permeability of the degree of solidifying solvent with suitable speed with the film contact side by the material that solidification liquid is had patience.This supporter for example is: air permeability be lower than 1000 seconds/100cc (preferably be lower than 100 seconds/100cc), thickness is 5～1000 μ m (preferred 50～500 μ m), runs through the film cross-wise direction is dispersed with 0.01～10 μ m (preferred 0.03～1 μ m) with sufficient density hole.Particularly, can use with polyolefin such as polyester, polyamide, polyethylene, polypropylene, cellulose, teflon (registration mark) etc. and be the nonwoven of material or perforated membrane etc.Need to prove, also can go up to utilize and for example use the stacked perforated membrane monomer that obtains like this of pellicular cascade method commonly used that bonding agent etc. is arranged, obtain having the duplexer (being printed body) of porous rete at the one or both sides of above-mentioned supporter at the supporter of preparing separately (compacted zone etc.).

For the perforated membrane (layer) that utilizes said method to form, in order further to improve the polymerization or the resistance to chemical reagents of precursor, also can use heat, visible light, ultraviolet ray, electron beam, radioactive ray etc. to make it carry out polymerization, or implement crosslinked (curing) and handle.For example, as mentioned above, be the film of forming precursor for using polyimides, by further enforcement hot-imide or chemical imidizate etc., can obtain by polyimides is the porous rete that resin constitutes.In addition, using polyimides is that the film that resin etc. has formed the porous rete can be implemented heat cross-linking.In addition, the perforated membrane (layer) that obtains be impregnated in the solution of the polymer with resistance to chemical reagents, and carry out drying, can form the resistance to chemical reagents tunicle at the inner surface in film surface and hole.As the polymer with resistance to chemical reagents, for example can enumerate: phenol resin, urea are that resin, melamine are that resin, benzoguanamine are that resin, polyimides are that resin, epoxy resin, benzoxazine are that resin, polypropylene-based resin, polyurethane series resin, fluorine resin, alkyd are that resin, acetate fiber prime system resin, phthalic acid are that resin, maleic acid are that resin, silicon are that resin, triazine resin, furans are resin, polyester based resin, diformazan benzene series resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, chitin, shitosan etc.

Utilize said method, can obtain perforated membrane as described below (layer), it is to be that resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are the porous rete that resin such as resin constitutes by for example there being many polyamidoimides with connective micropore equably, the average pore size of the micropore of this porous rete is 0.01～10 μ m, porosity is 30～80%, and thickness is 0.1～100 μ m.

As mentioned above, humidity, the temperature and time when use amount of the kind of the constituent by suitable selective polymer solution and amount, water, curtain coating, the kind that is used for the homogeneous base material of curtain coating, post processing etc., the micro-pore diameter, porosity, percent opening that can regulate the porous rete are to desirable value.

Printed matter 1,2 of the present invention can be made by the following method: for example, in the many one sides at least that exist that obtain as described above, implement to have the printing of the straight line portion more than the long 500 μ m at least with average live width 10～1000 μ m with the micropore of connectedness and porous rete that average pore size is 0.01～10 μ m.The resin bed that this porous rete preferably utilizes phase inversion method, particularly aforesaid wet type phase inversion method to form.As mentioned above, above-mentioned independent porous rete becomes the matrix of printed matter, and it is the matrix that the duplexer of the porous rete of 0.01～20 μ m also becomes printed matter that the one or both sides that substantially do not have supporters such as compacted zone in hole are laminated with average pore size.

Implement method of printing as surface at the porous rete, do not have particular determination, can be that for example ink-jetting style, screen painting, hectographic printing, distillation (fusion) mode, temperature-sensitive mode, photogravure, laser printing, paste are described, nano contact printing etc. any.These print processes can be carried out with method known or commonly used.Wherein, preferably extrude paste and implement method of printing by half tone screen cloth or metal mask.

Printed matter 3 of the present invention can be made by the following method: for example, in the many one sides at least with the micropore of connectedness and porous rete that average pore size is 0.01～10 μ m that exist that obtain as described above, use version to implement to print.The resin bed that this porous rete preferably utilizes phase inversion method, particularly aforesaid wet type phase inversion method to form.As mentioned above, above-mentioned independent porous rete becomes the matrix of printed matter, and it is the matrix that the duplexer of the porous rete of 0.01～10 μ m also becomes printed matter that the one or both sides that substantially do not have supporters such as compacted zone in hole are laminated with average pore size.

As using version to implement method of printing on the surface of porous rete, there is not particular determination, can be any of for example screen painting, hectographic printing, photogravure etc.These print processes can be carried out with method known or commonly used.Wherein, preferably extrude paste and implement method of printing by half tone screen cloth or metal mask.

Below, as the representative instance of making printed matter by printing, come process of making printed circuit board to describe to forming conductive wires (circuit) at the surface printing electrically conductive ink of porous rete or conductor paste.As the concrete method that forms this conductive wires, for example can enumerate: (1) uses the method that electrically conductive ink forms conductor wirings on the surface of porous rete with ink-jetting style; (2) formed coating electrically conductive printing ink on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete, forms the method for conductor wirings; (3) on the surface of porous rete, by extruding conductor paste from syringe and describing to form the method for conductor wirings; (4), form method of conductor wirings etc. by utilizing screen painting to describe conductor paste on the surface of porous rete.

Do not have particular determination as electrically conductive ink, for example can use: bronze ink, silver-colored printing ink, silver nano-metal printing ink, copper printing ink, carbon printing ink, silver-carbon printing ink etc.In addition, do not have particular determination, for example can use: silver conductor cream, copper conductor cream, golden conductor paste, palladium conductor paste, palladium-silver conductor cream, platinum conductor paste, platinum-silver conductor cream, nickel conductor paste etc. as conductor paste.Need to prove, in said method, also can on the conductor wirings that forms, further implement plating with method commonly used.

In addition, as utilizing printing to form other representative method of conductor wirings, can be set forth in the method for implementing plating on the porous rete behind the printing plating catalyst, for example: (5) are after the surface of porous rete has been printed the plating catalyst with the Wiring pattern shape with ink-jetting style, implement plating, form the method for conductor wirings; (6) forming coating plating catalyst on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete after, implement plating, form the method for conductor wirings; (7) the surface of porous rete is extruded the plating catalyst and is depicted the Wiring pattern shape as from syringe after, implement plating, form the method for conductor wirings; (8) after the surface of porous rete utilizes screen painting to depict the plating catalyst as the Wiring pattern shape, implement plating, form the method for conductor wirings etc.

As the plating catalyst, can use the salt that covers the metal that the catalyst of processing works as electroless plating.Particularly, for example can enumerate: be selected from the hydroxyl carboxylate (citrate, tartrate etc.) of the metal in the iron family elements such as platinum family elements such as the copper family elements, palladium and the platinum that constitute by gold, silver and copper and nickel or inorganic metal salt (sulfate, hydrochloride etc.) etc.The printing of plating catalyst can be undertaken by following operation, and for example, the printing ink that preparation contains plating catalyst, suitable vehicle (び ヒ Network Le) and additive as required etc. prints it with suitable print process.Behind printing plating catalyst, the plating catalyst reduced handle and after making metal, implementing electroless plating covers processing, further implement electrolytic coating as required to handle, can form conductor wirings thus.In the reduction of plating catalyst is handled, for example can use reducing agents such as hypophosphorous acid or its salt, hydrazine or its salt, boron hydrogen based compound, amino borane based compound, glucose, formaldehyde.Reduction is handled the aqueous solution for example can use the reducing agent of 0.5～10 weight %, is carried out under the temperature about room temperature～50 ℃.Electroless plating covers processing for example can carry out with the known method that uses electrolytic copper free plating liquid, no electrolytic nickel plating liquid etc.In addition, electrolytic coating is for example handled also and can be carried out with the known method that uses copper sulphate etc.

As printing-ink that is used to print or paste, can use the printing ink or the paste that constitute by solid (solid constituent) and solvent at least, preferably containing following liquid is the printing-ink or the paste of main solvent (solvents that content is maximum), the characteristics of described liquid are as follows: the drop that drips 1 μ l at the perforated membrane laminar surface, the contact angle of this perforated membrane laminar surface 300 microseconds with interior be below 60 ° (more preferably below 50 °, more preferably below 40 °), particularly drip the drop of 1 μ l at the perforated membrane laminar surface, 300 microseconds with interior be below 60 ° (more preferably below 50 °, more preferably below 40 °), and the droplet radius during through 300 microseconds is (more preferably below the 1500 μ m, more preferably 1400 μ m are following) below the 1600 μ m.When using this printing-ink or sticking with paste, solvent in printing-ink or the paste is absorbed the hole of porous rete apace, the viscosity of printing ink or paste rises, the flowability forfeiture of printing ink or paste, solid constituent in printing ink or the paste remains in the perforated membrane laminar surface, therefore, can not spread and sink in, the printed matter of fine rule illustrative excellence.

As the solid (solid constituent) in printing ink or the paste, can select according to the purpose of distribution or inductor, illuminator, resistance, capacitor or semiconductor formation, can use known inorganic matter, organic matter etc.As the example of inorganic matter, can use metal (gold, silver, copper, nickel, aluminium etc.) or glass, inorganic EL material (ZnS, Mn/CdSSe, ZnS:TbOF, ZnS:Tb, SrS:Ce, (SrS:CeZnS) _n, CaCa ₂S ₄: Ce, SrGa ₂S ₄: Ce, SrS:Ce/ZnS:Mn etc.), carbon, other inorganic material (ceramic materials such as silica, zirconia etc.).As organic matter, can use organic pigment, electroconductive polymer, organic semiconducting materials (pentacene class or thiophene-based etc.).The shape of solid constituent does not have particular determination, does not get final product so long as do not hinder the shape of printing, can use the solid constituent of particle shape, different shapes such as flakey, hollow-particle, hollow fiber such as laminar, fibrous.

As the solvent in printing-ink or the paste, can for example can use: hydrocarbon system solvent, halogenated hydrocarbons series solvent, pure series solvent, phenol series solvent, ketone series solvent, aliphatic acid acid anhydrides, ester series solvent, nitrogenous sulfur-bearing polar solvent, water etc. according to the suitably selections such as kind of the resin in printing-ink or the paste.Particularly, for example can enumerate: toluene, terpineol, decane, the tetradecane, decyl alcohol, diglycol list ether, diethylene glycol monobutyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, the diglycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, DPG list propyl ether, the glycol monomethyl isopropyl ether, the diglycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, the triethylene-glycol monobutyl ether, propylene glycol monobutyl ether, the DPG monobutyl ether, the glycol monomethyl isobutyl ether, diglycol list isobutyl ether, ethylene glycol ether, the diglycol monohexyl ether, ethylene glycol single 2-ethyl hexyl ether, ethylene glycol monoallyl ether, ethyleneglycol monophenylether, glycol dimethyl ether, the diglycol dimethyl ether, the diglycol diethyl ether, the diglycol butyl oxide, the triethylene-glycol dimethyl ether, acetate of butyl carbitol, terpineol, acetate of butyl carbitol, butanols, propane diols, butanediol, pentanediol, ethylene glycol, glycerine, water etc.These solvents can use a kind separately, and it is two or more also can to mix use.Need to prove, about printing ink solvent, open by technology in TOHKEMY 2004-319281 communique, TOHKEMY 2004-111057 communique, TOHKEMY 2006-059669 communique, TOHKEMY 2004-143325 communique etc.

In addition, as printing-ink that is used to print or paste, preferred viscosities is printing-ink or the paste of 0.05～1Pas.When using this printing-ink or sticking with paste, printing-ink or stick with paste in solvent be quickly absorbed into the hole of porous rete, solid constituent remains in the perforated membrane laminar surface, therefore, can not swim, the printed matter of fine rule illustrative excellence.Need to prove, printing-ink or stick with paste in viscosity can be by changing solid constituent kind and the kind of additives such as concentration, resin and concentration, solvent types wait and regulate.

The manufacture method of printed patterns of the present invention comprises: operation, (2A) that implements printing through (1) on the porous rete makes operation that the porous rete of having implemented printing contacts with solvent, reaches the operation that the operation that (3A) makes solvent seasoning forms compacted zone.Figure 27 is the key diagram (utilizing profile) of each operation of an example of the manufacture method of expression printed patterns of the present invention.1 expression porous rete, 6 expression supporters, 7 expression printings, 8 expression solvents, the porous rete of solvent has been infiltrated in 9 expressions, 11 expression compacted zones.

[operation (1)]

In operation (1), on porous rete 1, implement printing 7.As the porous rete, preferably there are many porous retes equably with connective micropore (micropore continuously).As the porous rete, the most surperficial at least 10% (with respect to the integral thickness) of preferred distance Printing Department is the porous of homogeneous, and more preferably the most surperficial at least 20% (with respect to the integral thickness) apart from Printing Department is the porous of homogeneous.Preferred especially porous rete integral body is the porous of homogeneous.

The average pore size of porous rete (average pore size of film surface) is preferably 0.01～20 μ m (for example 0.01～10 μ m), and more preferably 0.5～15 μ m is preferably 1～10 μ m especially.When hole undersized, the impregnability of printing-ink reduces, and the close adhesion of printing reduces easily.In addition, when hole oversize, the anchoring of printing ink reduces, and the close adhesion of printing also reduces easily, or ink diffusion and cause line to be spread and sunk in, and the straight line illustrative reduces easily, and mechanical strength reduces and easy deformation simultaneously.When the average pore size of porous rete was above-mentioned scope, printing ink was successfully absorbed by the porous rete, can obtain high anchoring effect simultaneously, and therefore, the close adhesion intensity of printing is very high, can suppress the diffusion of printing ink simultaneously, obtained excellent fine rule illustrative.

The porosity of perforated membrane (voidage) is about 30～80% for example, is preferably about 40～80% more preferably 50～80%.Cross when low when porosity, the impregnability of printing-ink reduces, and the close adhesion of printing reduces easily.On the other hand, when porosity is too high, bad mechanical strength sometimes.In addition, as the percent opening (surperficial percent opening) of perforated membrane laminar surface, for example be (for example 30～80%) more than 30%, be preferably about 50～80%.Cross when low when surperficial percent opening, the impregnability of printing-ink reduces, and the close adhesion of printing reduces easily.On the other hand, when surperficial percent opening was too high, mechanical strength reduced easily.

The thickness of porous rete for example is 0.1～100 μ m.When the matrix (being printed body) of printed matter was porous rete monomer, the thickness of porous rete was preferably 5～100 μ m, more preferably 25～70 μ m.In addition, when the matrix (being printed body) of printed matter during for the duplexer of supporter such as compacted zone and porous rete, the thickness of porous rete is preferably 0.1～25 μ m, more preferably 1～10 μ m.Cross when thin when the thickness of porous rete, the absorbability of the main solvent of printing-ink (paste) is poor, and on the other hand, when it was blocked up, becoming easily was difficult to control equably pore-size distribution.The thickness of porous rete is preferably more than 2 times of average pore size, is preferably especially more than 10 times.

The average pore size of the micropore on two surfaces of porous rete, therefore the build environment difference of the micropore when forming owing to the porous rete, has different hole characteristic mutually sometimes.For example, utilizing with the polymer solution that will be dissolved with the resin that constitutes perforated membrane after base material (substrate) is gone up curtain coating and formed the film shape, when making its phase inversion method that is solidified as the basis make perforated membrane, the perforated membrane that obtains not with the surface (air side surface) of base material contact side and with the surface (base material side surface) of base material contact side in, micropore forms the environment difference, therefore, has different respectively hole characteristics mostly.In the present invention, the average pore size φ B of the micropore of the average pore size φ A of the micropore of a face of preferred porous rete and another face satisfies the relation of 0.1 ≦ φ A/ φ B ≦ 10.When φ A/ φ B is lower than 0.1 or when surpassing 10, be arranged on the inadequate balance of the micropore on film two sides, the fine rule illustrative reduces easily.In addition, when the average pore size of the micropore of the air side surface that φ A is set at perforated membrane, when φ B being set at the average pore size of micropore of base material side surface, preferred 0.15 ≦ φ A/ φ B ≦ 8, further preferred 0.2 ≦ φ A/ φ B ≦ 5.Need to prove that the value of φ A/ φ B can be regulated by creating conditions of suitable setting perforated membrane.Particularly, can the atmosphere (humidity, temperature etc.) when for example suitably setting will contain surface characteristic, the micropore formation of kind that the raw-material polymer solution that constitutes perforated membrane carries out the base material of curtain coating, this base material control.

The connectedness that is present in the micropore of porous rete can wait by expression grignard value of air permeability and pure water penetration speed and characterize.The grignard value of porous rete is preferably 0.2～100 second/100cc, and more preferably 1～50 second/100cc is preferably 1～10 second/100cc especially.When numerical value was excessive, the absorbability of the solvent of printing-ink reduced easily, on the other hand, when numerical value is too small, might bad mechanical strength.

As the material (raw material) that constitutes the porous rete, the material that preferably has insulating properties, preferred resin.As resin, for example can enumerate: polyimides is a resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyarylate is a resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, acrylic resin, epoxy resin, (polymethylpentene is a resin to polyolefin-based resins, cyclic polyolefin hydrocarbon system resin etc.), fluorine resin (Kynoar is a resin etc.) etc.Wherein, consider from having the excellent such angle of hear resistance, mechanical strength, resistance to chemical reagents, electrical characteristics, preferred polyimides is that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polysulfones are resin, cellulose-based resin etc., and special preferred polyamide imide series resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are resin.Resin can be a copolymer, also can be graft polymers.These materials can use separately or be used in combination.In addition, the inner surface in the laminar surface of porous rete and hole can coat with the resistance to chemical reagents macromolecular compound.

Porous rete 1 can be used alone as the matrix (being printed body) of printed matter, also the porous rete can be formed on the base material of the formed duplexer of one or both sides of the supporters such as compacted zone 6 that do not have the hole in fact as printed matter.By using this duplexer, can improve the mechanical strength of base material.Matrix (being printed body) at printed matter is under the situation of porous rete monomer, can print at the one or both sides of porous rete, therefore, can form circuit etc. at one or both sides.In addition, for by supporter with when being arranged on the duplexer that the porous rete of its one or both sides constitutes, can print, therefore, can form circuit etc. at one or both sides at the one or both sides of this matrix at the matrix (being printed body) of printed matter.

Material (raw material) as constituting above-mentioned supporter does not have particular restriction, can use various materials such as resin, fiber, metal, pottery.Supporter can be any shapes such as film shape, fibrous, tabular, paper tinsel shape.In addition, supporter can be fine and close supporter, supporter etc. with many through holes any.

As the typical example of the material that constitutes supporter, but illustration for example: polyimides is a resin, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyarylate is a resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, mylar, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, polyolefin-based resins, cellulose-based resin, acrylic resin, fluorine resin, polyurethane series resin, silicones, plastics such as epoxy resin; Metals such as iron, aluminium, copper, titanium, tin, zinc; Inorganic matters such as glass, pottery, concrete, rock; Timber, bamboo etc.These raw material may be used singly or in combination of two or more.As supporter, consider preferred Kapton, PETG or films such as PEN, aromatic polyamides, glass epoxy substrate etc. from the aspects such as easiness, intensity, hear resistance of operation.

Need to prove, when supporter is metal forming,, can use Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel, stainless steel foil etc. as this metal forming.Metal forming can be an individual layer, also can be by comprising the composite metallic material that identical or different raw-material multilayer constitutes.Can be in the two sides of metal forming with face porous rete opposition side on adhesive phase is set, or further at its arranged outside diaphragm (mould release film).

In addition, at supporter is when having the supporter of many through holes, as the example, can enumerate: fabric is (by natural fibers such as cotton fibers, glass fibre, the PEEK fiber, aramid fibre, the fabric that resin fibres such as polybenzoxazole fibers etc. form etc.), eyelet fabric (polyester eyelet fabric, the nylon eyelet fabric, the carbon eyelet fabric, teflon (registration mark) eyelet fabric, polypropylene mesh cloth, the silk eyelet fabric, polyethylene mesh cloth etc.), the punching film is (to PET, films such as polyimides are implemented stamping-out processing and the film that forms etc.) etc. have the plastic sheeting or a sheet material of many through holes; Wire netting (plain weave wire netting, twill wire netting, seat type plain weave wire netting, seat type twill wire netting), punch metal (paper tinsel of metal or sheet material are implemented stamping-out processing etc. and formed), expanded metal, etching metal etc. have the metal forming of many through holes or sheet material etc.Wherein, the preferred eyelet fabric that uses with resistance to water.

The thickness of supporter for example is 1～300 μ m, is preferably 5～100 μ m.Cross when thin when thickness, be difficult to operation, on the other hand, when it was blocked up, flexibility reduced sometimes.

The porous rete can utilize phase inversion method to form.For example, to comprise the raw material (resinous principle), water-soluble polymer, polar solvent and the mixed solution curtain coating that comprises water as required that constitute the porous rete after on the substrate of homogeneous, import in the solidification liquid, utilize the wet type phase inversion method can form the porous rete.As the raw material (resinous principle) that constitute the porous rete, be preferably dissolved in water miscible polar solvent and utilize the phase inversion method can film forming material, particularly, can use the above-mentioned resin of crossing as the resin illustration that constitutes the porous rete.Need to prove, replace this resin, also can use precursors such as the monomer component (raw material) of this resin or its oligomer.For example, obtain by polyimides be resin constitute the porous rete time, use as polyimides be the polyamic acid profit of the precursor (polyimides is a precursor) of resin use the same method obtain the porous rete after, utilizing hot-imide, chemical imidizate can obtain by desirable polyimides is the perforated membrane that resin constitutes.

For membrane structure being made the spongy of porous, be effective to the polymer solution interpolation water-soluble polymer or the water that carry out curtain coating.As water-soluble polymer, for example can enumerate: or derivatives thereof such as polyethylene glycol, PVP, PEO, polyvinyl alcohol, polyacrylic acid, polysaccharide and their mixture etc.Wherein, the formation in the space in suppressing film inside, can improve aspect the mechanical strength of film preferably polyethylene base pyrrolidones.These water-soluble polymers can use separately or be used in combination.Consider that from the angle of porous the weight average molecular weight of water-soluble polymer for example is more than 200, to be preferably more than 300, more preferably more than 400 (for example about 400～200,000) is preferably more than 1000 (for example about 1000～200,000) especially.

Water-soluble polymer is an important additive, and is particularly spongy very effective to membrane structure is made, and kind and amount by the change water-soluble polymer can obtain multiple structure.But,, therefore, be cleaned in impregnated in water etc. and when porous layer is solidified and remove because water-soluble polymer is inessential composition finally.On the other hand,, but consider, preferably utilize the wet type phase inversion method to form cellular structure from above-mentioned aspect even utilize any method of dry type phase inversion method and wet type phase inversion method can form cellular structure.

As above-mentioned polar solvent, can use according to the chemical skeleton of the resin that uses to have deliquescent polar solvent (good solvent).As polyamidoimide is that resin, polyamic acid, PEI are the good solvent of resin, polycarbonate-based resin etc., for example can enumerate: dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), N, dinethylformamide, NMP/ dimethylbenzene, NMP/ dimethylbenzene/methyl ethyl ketone, ethanol/toluene, dimethyl sulfoxide (DMSO), 2-Pyrrolidone etc.Polar solvent can use separately or be used in combination.

As the polymer solution that carries out curtain coating, for example, preferably by the mixed solution that constitutes as raw-material macromolecule component 8～25 weight %, water-soluble polymer 10～50 weight %, water 0～10 weight %, water soluble polar solvent 30～82 weight % that constitute porous film etc.

With regard to above-mentioned polymer solution, when the concentration of the polymer (macromolecule component) of the main body that becomes the perforated membrane layer is crossed when low, the weakened of film, in addition, when it was too high, porosity diminished.The water-soluble polymer that constitutes this polymer solution adds for the spongiform loose structure of film inside being made homogeneous, at this moment, crosses when low when concentration, surpasses 10 μ m huge space like that inner generation of film, and homogenieity reduces.In addition, when excessive concentration, the dissolubility variation.The addition of water can be used to regulate aperture diameter, can increase diameter by increasing addition.

As the material (raw material) of the substrate of the homogeneous that uses when the curtain coating polymer solution, can enumerate above-mentioned as the illustrative material of material (raw material) that constitutes the supporter in the duplexer etc.As the substrate of homogeneous, also can use combination that surperficial raw material multiple raw-material laminated film or the sheet material different with inner raw material are arranged.Laminated film or sheet material can form by fitting, and also can be laminated film or the sheet materials that obtains by surface treatments such as coating, evaporation, sputters.In addition, also can use laminated film or the sheet material of the surface being implemented easy bonding processing, antistatic treatment, blasting treatment, Corona discharge Treatment etc.With the substrate of homogeneous as used herein during directly as the supporter in the above-mentioned duplexer, preferred select to use the raw material (for example having the resin of monomeric unit of the same race etc.) or the resin that have a compatibility with the material that constitutes the porous rete were implemented surface-treated substrates such as easy bonding processing or Corona discharge Treatment.

Optimum condition when above-mentioned polymer solution curtain coating is become the film shape is, relative humidity is that 70～100% (being preferably 90～100%), temperature are 15～90 ℃ (being preferably 30～80 ℃), particularly preferred condition is, relative humidity is about 100% (for example being 95～100%), and temperature is 40～70 ℃.When airborne water content than it after a little while, produce the inadequate unfavorable condition of percent opening on surface sometimes.When the polymer solution curtain coating is become the film shape, wish after this film is kept 0.2～15 minute under by relative humidity 70～100%, 15～90 ℃ of atmosphere that constitute of temperature, to import the solidification liquid that the non-solvent by macromolecule component constitutes.By the tympan after the curtain coating is placed under these conditions, can make porous layer become homogeneous and connective high state.It has been generally acknowledged that its reason is, by being placed under the humidified condition, moisture is immersed in inside from film surface, promotes being separated of Polymer Solution effectively.

As the solidification liquid that is used for phase inversion method, so long as the solvent that component of polymer is solidified gets final product, can suitably select according to the kind of the resin that is used as macromolecule component, be that resin, polyamic acid, PEI are the solvent that resin, polycarbonate-based resin etc. solidify for example, for example can use: water as making polyamidoimide; Monohydric alcohol such as methyl alcohol, ethanol; Alcohol such as polyalcohol such as glycerine; Water soluble polymers such as polyethylene glycol; Water-soluble solidification liquids such as their mixture etc.

The perforated membrane that is imported into solidification liquid and separates out, with the base material of homogeneous during as the supporter in the above-mentioned duplexer, by directly carrying out drying, the duplexer (being printed body) of can be supported body and porous rete.The duplexer that has the porous rete on the two sides of supporter can be made by carry out aforesaid operations once more behind the one side formation porous rete of supporter.In addition, be needed on the supporter and carry out drying from the base material of homogeneous, can obtain the porous rete in the mode of monomer by being imported into perforated membrane that solidification liquid separates out.This independent porous rete is as the base material of wiring board.As above-mentioned supporter, preferably constitute and have many supporters that are used to accelerate the micropore of rate of drying on surface, especially preferably have the supporter that can see through the permeability of the degree of solidifying solvent with suitable speed with the film contact side by the material that solidification liquid is had patience.This supporter for example is: air permeability be lower than 1000 μ sec/100cc (preferably be lower than 100 seconds/100cc), thickness is 5～1000 μ m (preferred 50～500 μ m), runs through the film cross-wise direction is dispersed with 0.01～10 μ m (preferred 0.03～1 μ m) with sufficient density hole.Particularly, can use with polyolefin such as polyester, polyamide, polyethylene, polypropylene, cellulose, teflon (registration mark) etc. and be the nonwoven of material or perforated membrane etc.Need to prove, also can go up to utilize and for example use the stacked perforated membrane monomer that obtains like this of pellicular cascade method commonly used that bonding agent etc. is arranged, obtain having the duplexer (being printed body) of porous rete at the one or both sides of above-mentioned supporter at the supporter of preparing separately (compacted zone etc.).

For the perforated membrane (layer) that utilizes said method to form, in order further to improve the polymerization or the resistance to chemical reagents of precursor, also can use heat, visible light, ultraviolet ray, electron beam, radioactive ray etc. to make it carry out polymerization, or implement crosslinked (curing) and handle.For example, as mentioned above, be the film of forming precursor for using polyimides, by further enforcement hot-imide or chemical imidizate etc., can obtain by polyimides is the porous rete that resin constitutes.In addition, using polyimides is that the film that resin etc. has formed the porous rete can be implemented heat cross-linking.In addition, the perforated membrane (layer) that obtains be impregnated in the solution of the polymer with resistance to chemical reagents, and carry out drying, can form the resistance to chemical reagents tunicle at the inner surface in film surface and hole.As the polymer with resistance to chemical reagents, for example can enumerate: phenol resin, urea are that resin, melamine are that resin, benzoguanamine are that resin, polyimides are that resin, epoxy resin, benzoxazine are that resin, polypropylene-based resin, polyurethane series resin, fluorine resin, alkyd are that resin, acetate fiber prime system resin, phthalic acid are that resin, maleic acid are that resin, silicon are that resin, triazine resin, furans are resin, polyester based resin, diformazan benzene series resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, chitin, shitosan etc.

Utilize said method, can obtain perforated membrane as described below (layer), it is to be that resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are the porous rete that resin such as resin constitutes by for example there being many polyamidoimides with connective micropore equably, the average pore size of the micropore of this porous rete is 0.01～10 μ m, porosity is 30～80%, and thickness is 0.1～100 μ m.

As mentioned above, humidity, the temperature and time when use amount of the kind of the constituent by suitable selective polymer solution and amount, water, curtain coating, the kind that is used for the homogeneous base material of curtain coating, post processing etc., the micro-pore diameter, porosity, percent opening that can regulate the porous rete are to desirable value.

Implement method of printing as surface at the porous rete, do not have particular determination, can be that for example ink-jetting style, screen painting, hectographic printing, distillation (fusion) mode, temperature-sensitive mode, photogravure, laser printing, paste are described, nano contact printing etc. any.These print processes can be carried out with method known or commonly used.Wherein, preferred especially ink-jetting style, screen painting.

Below, as the representative instance of making printed matter by printing, come process of making printed circuit board to describe to forming conductive wires (circuit) at the surface printing electrically conductive ink of porous rete or conductor paste.As the concrete method that forms this conductive wires, for example can enumerate: (1) uses the method that electrically conductive ink forms conductor wirings on the surface of porous rete with ink-jetting style; (2) formed coating electrically conductive printing ink on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete, forms the method for conductor wirings; (3) on the surface of porous rete, by extruding conductor paste from syringe and describing to form the method for conductor wirings; (4), form method of conductor wirings etc. by utilizing screen painting to describe conductor paste on the surface of porous rete.

Do not have particular determination as electrically conductive ink, can use for example bronze ink, silver-colored printing ink, silver nano-metal printing ink, copper printing ink, carbon printing ink, silver-carbon printing ink etc.In addition, do not have particular determination, can use for example silver conductor cream, copper conductor cream, golden conductor paste, palladium conductor paste, palladium-silver conductor cream, platinum conductor paste, platinum-silver conductor cream, nickel conductor paste etc. as conductor paste.Need to prove, in said method, also can on the conductor wirings that forms, further implement plating with method commonly used.The time point that carries out plating does not have particular determination, for example, can in operation (1), implement to implement plating behind printing, process operation (2), (3) formation compacted zone, in addition, also can in operation (1), implement to carry out plating after the printing, pass through operation (2), (3) formation compacted zone then.

In addition, as utilizing printing to form other representative method of conductor wirings, can be set forth in the method for implementing plating on the porous rete behind the printing plating catalyst, for example: (5) are after the surface of porous rete has been printed the plating catalyst with the Wiring pattern shape with ink-jetting style, implement plating, form the method for conductor wirings; (6) forming coating plating catalyst on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete after, implement plating, form the method for conductor wirings; (7) the surface of porous rete is extruded the plating catalyst and is depicted the Wiring pattern shape as from syringe after, implement plating, form the method for conductor wirings; (8) after the surface of porous rete utilizes screen painting to depict the plating catalyst as the Wiring pattern shape, implement plating, form the method for conductor wirings etc.

As the plating catalyst, can use the salt that covers the metal that the catalyst of processing works as electroless plating.Particularly, for example can enumerate: be selected from the hydroxyl carboxylate (citrate, tartrate etc.) of the metal in the iron family elements such as platinum family element such as copper family elements, palladium and platinum that gold, silver and copper constitutes and nickel or inorganic metal salt (sulfate, hydrochloride etc.) etc.The printing of plating catalyst can be undertaken by following operation, and for example, the printing ink that preparation contains plating catalyst, suitable vehicle and additive as required etc. prints it with suitable print process.Behind printing plating catalyst, the plating catalyst reduced handle and after making metal, implementing electroless plating covers processing, further implement electrolytic coating as required to handle, can form conductor wirings thus.In the reduction of plating catalyst is handled, for example can use reducing agents such as hypophosphorous acid or its salt, hydrazine or its salt, boron hydrogen based compound, amino borane based compound, glucose, formaldehyde.Reduction is handled the aqueous solution for example can use the reducing agent of 0.5～10 weight %, is carried out under the temperature about room temperature～50 ℃.Electroless plating covers processing for example can carry out with the known method that uses electrolytic copper free plating liquid, no electrolytic nickel plating liquid etc.In addition, electrolytic coating is for example handled also and can be carried out with the known method that uses copper sulphate etc.

As printing-ink that is used to print or paste, can use the printing ink or the paste that constitute by solid (solid constituent) and solvent at least, preferably containing following liquid is the printing-ink or the paste of main solvent (solvents that content is maximum), the characteristics of described liquid are as follows: the drop that drips 1 μ l at the perforated membrane laminar surface, the contact angle of this perforated membrane laminar surface 300 microseconds with interior be below 60 ° (more preferably below 50 °, more preferably below 40 °), particularly drip the drop of 1 μ l at the perforated membrane laminar surface, 300 microseconds with interior be below 60 ° (more preferably below 50 °, more preferably below 40 °), and the droplet radius during through 300 microseconds is (more preferably below the 1500 μ m, more preferably 1400 μ m are following) below the 1600 μ m.When using this printing-ink or sticking with paste, solvent in printing-ink or the paste is absorbed the hole of porous rete apace, the viscosity of printing ink or paste rises, the flowability forfeiture of printing ink or paste, solid constituent in printing ink or the paste remains in the perforated membrane laminar surface, therefore, can not spread and sink in, the printed matter of fine rule illustrative excellence.

As the solid (solid constituent) in printing ink or the paste, can select according to the purpose of distribution or inductor, illuminator, resistance, capacitor or semiconductor formation, can use known inorganic matter, organic matter etc.As the example of inorganic matter, can use metal (gold, silver, copper, nickel, aluminium etc.) or glass, inorganic EL material (ZnS, Mn/CdSSe, ZnS:TbOF, ZnS:Tb, SrS:Ce, (SrS:CeZnS) _n, CaCa ₂S ₄: Ce, SrGa ₂S ₄: Ce, SrS:Ce/ZnS:Mn etc.), carbon, other inorganic material (ceramic materials such as silica, zirconia etc.).As organic matter, can use organic pigment, electroconductive polymer, organic semiconducting materials (pentacene class or thiophene-based etc.).The shape of solid constituent does not have particular determination, does not get final product so long as do not hinder the shape of printing, can use the solid constituent of particle shape, different shapes such as flakey, hollow-particle, hollow fiber such as laminar, fibrous.

As the solvent in printing-ink or the paste, can for example can use: hydrocarbon system solvent, halogenated hydrocarbons series solvent, pure series solvent, phenol series solvent, ketone series solvent, aliphatic acid acid anhydrides, ester series solvent, nitrogenous sulfur-bearing polar solvent, water etc. according to the suitably selections such as kind of the resin in printing-ink or the paste.Particularly, for example can enumerate: toluene, terpineol, decane, the tetradecane, decyl alcohol, diglycol list ether, diethylene glycol monobutyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, the diglycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, DPG list propyl ether, the glycol monomethyl isopropyl ether, the diglycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, the triethylene-glycol monobutyl ether, propylene glycol monobutyl ether, the DPG monobutyl ether, the glycol monomethyl isobutyl ether, diglycol list isobutyl ether, ethylene glycol ether, the diglycol monohexyl ether, ethylene glycol single 2-ethyl hexyl ether, ethylene glycol monoallyl ether, ethyleneglycol monophenylether, glycol dimethyl ether, the diglycol dimethyl ether, the diglycol diethyl ether, the diglycol butyl oxide, the triethylene-glycol dimethyl ether, acetate of butyl carbitol, terpineol, acetate of butyl carbitol, butanols, propane diols, butanediol, pentanediol, ethylene glycol, glycerine, water etc.These solvents can use a kind separately, and it is two or more also can to mix use.Need to prove, about printing ink solvent, open by technology in TOHKEMY 2004-319281 communique, TOHKEMY 2004-111057 communique, TOHKEMY 2006-059669 communique, TOHKEMY 2004-143325 communique etc.

In addition, as printing-ink that is used to print or paste, preferred viscosities is printing-ink or the paste of 0.05～1Pas.When using this printing-ink or sticking with paste, printing-ink or stick with paste in solvent be quickly absorbed into the hole of porous rete, solid constituent remains in the perforated membrane laminar surface, therefore, can not spread and sink in, the printed matter of fine rule illustrative excellence.Need to prove, printing-ink or stick with paste in viscosity can be by changing solid constituent kind and the kind of additives such as concentration, resin and concentration, solvent types wait and regulate.

By operation (1), can obtain the printing of fine rule illustrative excellence.For example, when having implemented to have the printing of the straight line portion more than the long 500 μ m with average live width 10～1000 μ m on the surface of porous rete, the change value F that can carry out the live width of following formula (1) expression is the printing below 30%.

F＝(LMax-LMin)/LAve×100 (1)

(in the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m).

In addition, when having implemented at least to have the printing of the straight line portion more than the long 500 μ m with average live width 10～1000 μ m on the surface of porous rete, the standard deviation ∑ that can carry out the live width of following formula (2) expression is the printing below 7.

$\mathrm{\Σ}=\sqrt{(({(\mathrm{LAve}-\mathrm{LMax})}^2+{(\mathrm{LAve}-\mathrm{LMin})}^2)/2)}---\left(2\right)$

(in the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m).

Need to prove, the change value F of above-mentioned live width and standard deviation ∑ are the values with the straight line portion more than the long 500 μ m of average live width 10～1000 μ m, more preferably, be preferably value especially with the straight line portion more than the long 500 μ m of average live width 15～100 μ m with the value of the straight line portion more than the long 500 μ m of average live width 10～500 μ m.When average live width is lower than 10 μ m, the printing difficulty, when average live width surpasses 1000 μ m, the distribution chap, circuit is whole to become big, impracticable.

Maximum line width LMax, minimum feature LMin can followingly measure, and average live width 10～1000 μ m of printed matter, long 500 μ m straight line portioies are carried out macrophotography, measure (with reference to Figure 13) by this photo.Average live width LAve can calculate by the following method, that is, setting-out on transparent membrane is converted by its weight.As long as F is below 30% or ∑ is below 7, just can be judged to be the excellent good printing (distribution) of fine rule illustrative (linearity).F is preferably below 20%, more preferably below 10%.∑ is preferably below 5, more preferably below 3.In addition, the preferred especially F numerical value that is afore mentioned rules is following and ∑ is below the numerical value of afore mentioned rules.When on the porous rete, implementing printing, printing-ink (paste) is with when perforated membrane (perforated membrane) contacts, main solvent in the printing ink is absorbed by perforated membrane, the viscosity of printing ink rises, mobile forfeiture, on perforated membrane, do not spread and sink in, therefore, can utilize the excellent straight line of fine rule illustrative (linearity) of various printing ink (paste) to describe.On the other hand, on common PET film or PI film etc., when implementing printing, printing-ink (paste) therefore, is difficult to carry out the good straight line of fine rule illustrative (linearity) and describes around spreading and sinking in and being diffused into.

[operation (2A)]

In operation (2A), make and implemented to print 7 porous rete 1 and contact with solvent 8, make solvent 8 infiltrate porous retes 1, the porous rete is dissolved in the solvent.Among Figure 27 9 is porous retes that solvent has infiltrated.Need to prove that the porous rete can not necessarily be dissolved in the solvent in the stage of operation (2A), also can operation (3A) below in order to make it dry and be dissolved in the solvent the earliest under the situation about heating.In addition, the porous rete also can be dissolved in the solvent in operation (2A) and this two-step of operation (3A).The operation that the porous rete is dissolved in solvent changes according to solvent types of using and baking temperature etc.For example, when using, in operation (2A), after the dissolving, in operation (3A), solvent is carried out drying, the formation compacted zone with respect to the high solvent of porous rete dissolubility.In addition, when using, in operation (3A), utilize the hot porous rete when dry to be dissolved in the solvent, carry out drying simultaneously, form compacted zone with respect to the low solvent of porous rete dissolubility.

As above-mentioned solvent, so long as do not make the solvent that printing is dissolved and dissolving constitutes the raw material (resin etc.) of porous rete under room temperature or heating, just there is not particular restriction, can be used alone or mixed use of two or more all kinds of solvents.In addition, also can use with respect to the porous rete and show separately not showing the mixed liquor more than a kind or 2 kinds of deliquescent non-solvent (alcohol, hydrocarbon etc.) or water etc. separately, dissolve the solvent of porous rete in fact more than a kind or 2 kinds and with respect to the porous rete of deliquescent solvent.By showing that with respect to the porous rete mixing does not show deliquescent non-solvent or water separately with respect to the porous rete in the high deliquescent solvent, can control the dissolubility or the drying time of porous rete.For example, when the solvent that the use dissolubility is high separately, worry that the porous rete dissolves rapidly, the printing of implementing before transferring to drying process is flowed with lysed porous rete.Relative therewith, when adding non-solvent or water in the high solvent of dissolubility, the dissolubility of porous rete reduces, and therefore, can prevent that the printing of implementing is mobile with lysed porous rete.In addition, when in the high solvent of dissolubility, adding than high non-solvent of this solvent volatility or water, non-solvent exists before carrying out drying, therefore, can keep dissolubility lower, the solvent that non-solvent and dissolubility are high when drying volatilizees lentamente, can prevent the outflow of the printing implemented, forms compacted zone simultaneously.

As operable solvent, can suitably select according to the raw-material kind that constitutes the porous rete, for example can enumerate: dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), oxolane (THF), 1,3-two oxa-s penta ring, 1,3-diox, 1, one or more of the mixture of 4-diox, gamma-butyrolacton (GBL), these solvents, these solvents and the independent solvent of perforated membrane layer or the mixture of water etc. of not dissolving.State in the use illustrative these solvents one or more and do not dissolve separately the solvent of perforated membrane layer or during the mixture of water, the former (one or more of above-mentioned illustrative solvent) and latter's (not dissolving the solvent or the water of perforated membrane layer separately) ratio (weight ratio of the former total amount and the latter's total amount) for example for the former/latter=10/90～99/1, be preferably the former/latter=20/80～95/5, more preferably the former/latter=30/70～90/10, be preferably especially the former/latter=40/60～80/20.

For example, at the raw material that constitute the porous rete is that polyamidoimide is when being resin, as above-mentioned solvent, can use dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N, the mixture of N-dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), oxolane (THF), gamma-butyrolacton (GBL), these solvents, these solvents and the independent solvent of perforated membrane layer or the mixture of water etc. of not dissolving.In addition, at the raw material that constitute the porous rete is that PEI is when being resin, as above-mentioned solvent, can use dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), 1,3-two oxa-s penta ring, 1, one or more of the mixture of 4-diox, gamma-butyrolacton (GBL), these solvents, these solvents and the independent solvent of perforated membrane layer or the mixture of water etc. of not dissolving.

With solvent that the porous rete contacts in, can add additive, resin, inorganic matter etc. as required.By in solvent, adding these compositions, can control viscosity, and can improve the screening characteristics of solvent.In addition, when nonvolatile component such as interpolation resin in solvent, have in the residual advantage of protecting the printing of implementing of this nonvolatile component of print surface.And when nonvolatile component such as interpolation additive or inorganic matter in solvent, this nonvolatile component is residual on compacted zone, and when carrying out the second impression on compacted zone, printing improves.

Method as the porous rete of having implemented printing is contacted with solvent does not have particular determination, and for example can enumerate: the porous rete that will implement to print impregnated in the method in the solvent; Utilize die head coating machine or roll coater, rod to be coated with the method that coating methods such as machine, intaglio plate coating machine, spin coater are coated on solvent the perforated membrane laminar surface; With sprayer etc. with the method for ejection of solvent in perforated membrane laminar surface (spraying); Drip the method for solvent at the perforated membrane laminar surface; Solvent is heated the method for the steam contact perforated membrane laminar surface of the solvent that makes volatilization; After making absorber impregnation solvents such as nonwoven or sponge, contact and the method for transfer printing solvent with the porous rete; Ink jet printing method; Half-tone screen printing method; Offset printing method; The photogravure method; Letterpress method etc.Can make whole dissolving of perforated membrane layer,, it is partly dissolved for purposes such as further other printings of enforcement.At this moment, the print process of using at present, for example ink jet printing method, half-tone screen printing method, offset printing method, photogravure method, letterpress method etc. are effective.

When the porous rete of having implemented printing contact with solvent, it is contacted, also in porous rete and the solvent at least one can be heated, the raising dissolubility makes its contact.

Make the degree of porous rete dissolving, so long as the degree that printing does not deform gets final product.For example, the porous rete beyond the printing position all can be dissolved, also can only dissolve the top layer part of printing position porous rete in addition.In addition, also can be the dissolving that to guarantee after drying, can to prevent the degree of the compactness that liquid absorbs.

[operation (3A)]

(3A) makes solvent seasoning in operation.As mentioned above, the porous rete is dissolved in the solvent in operation (2A) and/or operation (3A).By making this solvent seasoning, form compacted zone 10 then.After making the dissolving of porous rete, when making solvent seasoning, break and cause printing surface by densified in the hole of porous.Therefore, the close adhesion intensity that is printed the intensity of portion and printing improves, and simultaneously, when being printed body and being the duplexer of supporter and porous rete, the close adhesion intensity of its interlayer also improves.In addition, densified by the top layer part that makes printed matter, the problems such as swelling that the absorption by liquid such as water that the situation in porous of also can eliminating is easy to generate causes, and improve gas shield or marresistance.And the intensity of the printed matter that obtains also improves.

The drying of solvent is undertaken by heating usually.Heating-up temperature or heat time heating time can suitably be set according to the solvent types of using.For example, when using the low high boiling solvent of volatility (for example NMP etc.),, can dryly remove and desolvate by about 200 ℃ * 10 minutes heat treated.In addition, when using the high solvent of volatility (for example THF etc.),, can dryly remove and desolvate by about 100 ℃ * 10 minutes heat treated.Can under higher temperature, handle.

In the present invention, when the porous rete that in measuring operation (1), uses and the contact angle (25 ℃ of temperature, humidity 60%) of water, drip water (1 μ 1), the contact angle θ A during through 1000 microseconds on the surface of porous rete ₁₀₀₀Contact angle θ A with through 100 microseconds the time ₁₀₀Than θ A ₁₀₀₀/ θ A ₁₀₀Preferably less than 0.6 (θ A ₁₀₀₀/ θ A ₁₀₀＜0.6), in addition, the compacted zone that forms make solvent seasoning in measuring operation (3A) after is during with the contact angle of water, at the surface of compacted zone dropping water, the contact angle θ B during through 1000 microseconds ₁₀₀₀Contact angle θ B with through 100 microseconds the time ₁₀₀Than θ B ₁₀₀₀/ θ B ₁₀₀Be preferably more than 0.6 value (θ B ₁₀₀₀/ θ B ₁₀₀0.6).

θ A ₁₀₀₀/ θ A ₁₀₀Situation less than 0.6 is meant that water droplet is absorbed (when water droplet was absorbed, contact angle diminished) by the hole of porous rete rapidly.Can wait by average pore size, porosity, thickness, the air permeability of regulating the porous rete and satisfy θ A ₁₀₀₀/ θ A ₁₀₀＜0.6 relational expression.Satisfying under the situation of this relational expression, generally speaking, solvent when printing in printing-ink or the paste is absorbed by the hole of porous rete rapidly, the viscosity of printing ink or paste rises, the flowability forfeiture of printing ink or paste, printing ink or stick with paste in solid constituent remain in porous surface, therefore, can not spread and sink in, the printed patterns of fine rule illustrative excellence.θ A ₁₀₀₀/ θ A ₁₀₀Value less than 0.6, be preferably below 0.55, more preferably below 0.5.θ A ₁₀₀₀/ θ A ₁₀₀The lower limit of value be 0.1 for example, be preferably 0.2.Need to prove θ A ₁₀₀Value be preferably 10 °～80 °, more preferably 20 °～60 °.

θ B ₁₀₀₀/ θ B ₁₀₀Situation greater than 0.6 is meant that water droplet is slow by the speed that compacted zone absorbs, that is, break and cause printing surface by densified in the hole of porous.Contact method, solvent types and use amount that can be by regulating porous rete in the operation (2A) and solvent, with the contacting temperature and wait time of contact and satisfy θ B of solvent ₁₀₀₀/ θ B ₁₀₀0.6 relational expression.Satisfying under the situation of this relational expression, because the surface of printed matter after the printing is by densified, therefore, the close adhesion intensity height of printing or top layer (being printed the situation that body is a duplexer).θ B ₁₀₀₀/ θ B ₁₀₀Value greater than 0.6, be preferably more than 0.65.θ B ₁₀₀₀/ θ B ₁₀₀Value on be limited to 1.Need to prove θ B ₁₀₀Value be preferably 10 °～80 °, more preferably 20 °～60 °.

When liquid such as porous rete absorption water, problems such as swelling take place sometimes.The method according to this invention breaks the hole owing to the porous rete is carried out heat fusing, makes surface densification, therefore, can prevent the swelling that the absorption by liquid causes.The porous rete utilizes the dry densified degree of handling of the dissolving-utilization of solvent, can be by θ A ₁₀₀₀With θ B ₁₀₀₀Than θ A ₁₀₀₀/ θ B ₁₀₀₀Judge.In the present invention, θ A ₁₀₀₀/ θ B ₁₀₀₀Less than 1, be preferably less than 0.85, more preferably less than 0.7.θ A ₁₀₀₀/ θ B ₁₀₀₀Lower limit be 0.02 for example, be preferably 0.05.

The manufacture method 2 of printed patterns of the present invention comprises: (1) implements printing on the porous rete operation, (2B) make the porous rete of having implemented printing carry out heat fusing operation, and (3B) carry out the operation that cooling curing forms compacted zone.Figure 28 is the key diagram (utilizing profile) of each operation of other examples of the manufacture method of expression printed patterns of the present invention.1 expression porous rete, 6 expression supporters, 7 expression printings, 10 expression fusions the porous rete, 11 expression compacted zones.

[operation (1)]

Except that the thickness of porous rete, the operation (1) in the manufacture method 1 of operation (1) and above-mentioned printed patterns is identical.

The thickness of porous rete for example is 0.1～1000 μ m.When the matrix (being printed body) of printed matter was porous rete monomer, the thickness of porous rete was preferably 5～100 μ m, more preferably 25～70 μ m.In addition, during for the duplexer of the supporter that is made of compacted zone and porous rete, the thickness of porous rete is generally 0.1～100 μ m, is preferably 0.1～25 μ m, more preferably 1～10 μ m at the matrix (being printed body) of printed matter.In addition, at the matrix (being printed body) of printed matter during for the duplexer of supporter with many through holes (for example eyelet fabric etc.) and porous rete, the thickness of porous rete is generally 0.5～1000 μ m, is preferably 1～1000 μ m, more preferably 5～500 μ m.Cross when thin when the thickness of porous rete, the absorbability of the main solvent of printing-ink (paste) is poor, and on the other hand, when it was blocked up, becoming easily was difficult to control equably pore-size distribution.The thickness of porous rete is preferably more than 2 times of average pore size, is preferably especially more than 10 times.

[operation (2B)]

In operation (2B), make and implemented to print 3 porous rete 1 and carry out heat fusing.Among Figure 28 10 be by the heat fusing fusion the porous rete.As making the porous rete carry out the method for heat fusing, there is not particular restriction, for example can enumerate: the mode that the porous rete is heated with infrared heater or make its method that contacts with warm-up mill, put into the medium method of heated oven.As the degree of the heat fusing of porous rete, the fusion fully of porous rete, also can be for example top layer partial melting only, the part of a part of porous is residual.The heat fusing of porous rete can be waited by the disappearance of the liquid-absorbent on the surface behind the cooling curing to be confirmed.The heat fusing degree of porous rete also can be the degree that can guarantee to prevent the compactness of liquid absorption behind cooling curing.

Temperature or time when making the porous rete carry out heat fusing, because of the raw-material fusing point vitrification point that constitutes the porous rete different, and can in the scope that printing does not deform, suitably select, but generally speaking, temperature when making its heat fusing is 180～450 ℃, be preferably 200～420 ℃, the time is 1 minute～5 hours, be preferably 10 minutes～and about 1 hour.For example, 30 minutes method of heating in heated oven, when the porous rete is Merlon, heating-up temperature is preferably 220 ℃～270 ℃, when the porous rete was PEI, heating-up temperature was preferably 270 ℃～400 ℃, in addition, when the porous rete was polyether sulfone, heating-up temperature was preferably 250 ℃～360 ℃.

[operation (3B)]

In operation (3B), with fusion porous rete 10 carry out cooling curing, form compacted zone 11.When carrying out cooling curing after making the porous rete carry out heat fusing, break and cause printing surface by densified in the hole of porous.Therefore, the close adhesion intensity that is printed the intensity of portion and printing improves, and simultaneously, when being printed body and being the duplexer of supporter and porous rete, the close adhesion intensity of its interlayer also improves.In addition, densified by the top layer part that makes printed matter, the problems such as swelling that the absorption by liquid such as water that the situation in porous of also can eliminating is easy to generate causes, and improve gas shield or marresistance.And the intensity of the printed matter that obtains also improves.

The method of cooling curing does not have particular restriction, can be undertaken by cooling off naturally, can force cooling yet.

In the present invention, when the porous rete that in measuring operation (1), uses and the contact angle (25 ℃ of temperature, humidity 60%) of water, drip water (1 μ l), the contact angle θ A during through 1000 microseconds on the surface of porous rete ₁₀₀₀Contact angle θ A with through 100 microseconds the time ₁₀₀Than θ A ₁₀₀₀/ θ A ₁₀₀Preferably less than 0.6 (θ A ₁₀₀₀/ θ A ₁₀₀＜0.6), in addition, in measuring operation (3), carry out cooling curing and during the contact angle of the compacted zone that obtains and water, at the surface of compacted zone dropping water, the contact angle θ B during through 1000 microseconds ₁₀₀₀Contact angle θ B with through 100 microseconds the time ₁₀₀Than θ B ₁₀₀₀/ θ B ₁₀₀Be preferably more than 0.6 value (θ B ₁₀₀₀/ θ B ₁₀₀0.6).

θ A ₁₀₀₀/ θ A ₁₀₀Situation less than 0.6 is meant that water droplet is absorbed (when water droplet was absorbed, contact angle diminished) by the hole of porous rete rapidly.Can wait by average pore size, porosity, thickness, the air permeability of regulating the porous rete and satisfy θ A ₁₀₀₀/ θ A ₁₀₀＜0.6 relational expression.Satisfying under the situation of this relational expression, generally speaking, solvent when printing in printing-ink or the paste is absorbed by the hole of porous rete rapidly, the viscosity of printing ink or paste rises, the flowability forfeiture of printing ink or paste, printing ink or stick with paste in solid constituent remain in porous surface, therefore, can not spread and sink in, the printed patterns of fine rule illustrative excellence.θ A ₁₀₀₀/ θ A ₁₀₀Value be preferably below 0.55, more preferably below 0.5.θ A ₁₀₀₀/ θ A ₁₀₀The lower limit of value be 0.1 for example, be preferably 0.2.Need to prove θ A ₁₀₀Value be preferably 10 °～80 °, more preferably 20 °～60 °.

θ B ₁₀₀₀/ θ B ₁₀₀Situation greater than 0.6 is meant that water droplet is slow by the speed that compacted zone absorbs, that is, break and cause printing surface by densified in the hole of porous.Temperature that can be by regulating the heat fusing in the operation (2B) or time are waited and satisfy θ B ₁₀₀₀/ θ B ₁₀₀0.6 relational expression.Satisfying under the situation of this relational expression, because the surface of printed matter after the printing is by densified, therefore, the close adhesion intensity height of printing or top layer (being printed the situation that body is a duplexer).θ B ₁₀₀₀/ θ B ₁₀₀Value be preferably more than 0.65.θ B ₁₀₀₀/ θ B ₁₀₀Value on be limited to 1.Need to prove θ B ₁₀₀Value be preferably 10 °～80 °, more preferably 20 °～60 °.

When liquid such as porous rete absorption water, problems such as swelling take place sometimes.The method according to this invention breaks the hole owing to the porous rete is carried out heat fusing, makes surface densification, therefore, can prevent the swelling that the absorption by liquid causes.The porous rete utilizes the dry densified degree of handling of the dissolving-utilization of solvent, can be by θ A ₁₀₀₀With θ B ₁₀₀₀Than θ A ₁₀₀₀/ θ B ₁₀₀₀Judge.In the present invention, θ A ₁₀₀₀/ θ B ₁₀₀₀Less than 1, be preferably less than 0.85, more preferably less than 0.7.θ A ₁₀₀₀/ θ B ₁₀₀₀Lower limit be 0.02 for example, be preferably 0.05.

In the present invention, by the heat fusing-cooling curing of porous rete, make porous densified, therefore, the hot strength of layer improves.That is, in operation (3B), carry out cooling curing and the ratio F2/F1 of the hot strength F1 of the porous rete that uses in the hot strength F2 of the compacted zone that obtains and the operation (1) for greater than 1 value.The value of F2/F1 also becomes the index of densification degree, is preferably more than 1.5, more preferably more than 2.The upper limit of the value of F2/F1 for example is 100.

The printed matter that utilizes the manufacture method of printed patterns of the present invention to form printed patterns has following characteristics: the fine rule illustrative excellence of not spreading and sinking in etc., simultaneously, the close adhesion intensity height of printing and top layer (being printed the situation that body is a duplexer), be difficult for destroyed, as this printed matter, except that printed substrate (tellite), also can enumerate part (electrical/electronic part), electromagnetic shielded film of the illuminator, resistor-capacitor transistor etc. of inductor, EL etc. etc.

Embodiment

Below, illustrate in greater detail the present invention based on embodiment, but the present invention is not limited to these embodiment.Adhesive tape disbonded test, average pore size, porosity are calculated or are measured in order to following method.These average pore sizes and porosity are only obtained as object with the micropore that the foremost of electron micrograph is seen, the micropore that photo inside is seen is set at outside the object.

(assay method)

The adhesive tape disbonded test

(i) on porous layer, paste above-mentioned adhesive tape, describe bonding portion with roller.

(ii) use universal tensile testing machine [manufacturing of (strain) OLINTEC company, trade name " TENSILONRTA-500 "], under 50mm/ minute condition, carry out the T mould and peel off.

(iii) observe the having or not of interface peel of porous layer and base material.

Adhesive tape: the ridge, temple makes the made membrane masking tape No.603 of institute (#25), wide 24mm.

Roller: the loading of φ 30mm, 200 gram forces.

Average pore size

By electron micrograph its area is measured on the surface of duplexer or any hole more than 30 in cross section, its mean value is set at average hole area Save.Suppose the Kong Weizheng circle, will use following formula to be set at average pore size by the value that average hole area is scaled the aperture.Represent pi at this π.

Surperficial or inner average pore size [μ m]=2 * (Save/ π) ^1/2

Porosity

The porosity of porous layer inside utilizes following formula to calculate.V represents the volume [cm of film ³], W represents the weight [g] of porous layer, ρ represents the raw-material density [g/cm of porous layer ³].The density of polyamidoimide is set at 1.45[g/cm ³], the density of polyimides is set at 1.42[g/cm ³].

Porosity [%]=100-100 * W/ (ρ V)

The porosity of the porous layer that changes into the base material one that has formed through hole

Because it is integrated that porous layer and the base material that has formed through hole carry out, and therefore, directly measures the porosity difficulty of porous layer inside.Therefore, as base material, use PET film (manufacturing of Teijin DuPont company, goods name " S type ") to replace eyelet fabric, with the stoste curtain coating after on the PET film, impregnated in it is solidified, peel off by the PET film then, make its drying, the porous film that use obtains is measured, and calculates inner porosity by following formula.

V represents the volume [cm of film ³], W represents the weight [g] of porous layer, ρ represents the raw-material density [g/cm of porous layer ³].The density of polyamidoimide is set at 1.45[g/cm ³], the density of polyimides is set at 1.42[g/cm ³].

Porosity [%]=100-100 * W/ (ρ V)

Embodiment 1

At polyamidoimide is the resin solution (trade name " バ イ ロ マ Star Network ス HR11NN " that Japan company of twisting flax fibers and weaving makes; Solid component concentration 15 weight %, solvent NMP, solution viscosity 20dPas/25 ℃) in 100 weight portions, add PVP (molecular weight 50,000) 30 weight portions as water-soluble polymer, make the stoste that film is used.This stoste being set at 25 ℃, going up and use membrane applicator making PET film (S type, thickness 100 μ m) as the Teijin DuPont company of base material, is to carry out curtain coating under the condition of 127 μ m in the gap of membrane applicator and base material.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 50 μ m, and the gross thickness of duplexer is about 150 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and PET film close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1.0 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 1.0 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 2

Using water-soluble polymer 33.3 weight portions, is to carry out curtain coating under the condition of 102 μ m in the gap of membrane applicator and PET film substrate, in addition, carries out operation similarly to Example 1, obtains at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 35 μ m, and the gross thickness of duplexer is about 135 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 3

Using water-soluble polymer 40 weight portions, is to carry out curtain coating under the condition of 51 μ m in the gap of membrane applicator and PET film substrate, in addition, carries out operation similarly to Example 1, obtains at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 15 μ m, and the gross thickness of duplexer is about 115 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 4

At polyamidoimide is the resin solution (trade name " バ イ ロ マ Star Network ス HR11NN " that Japan company of twisting flax fibers and weaving makes; Solid component concentration 15 weight %, solvent NMP, solution viscosity 20dPas/25 ℃) add PVP (molecular weight 50,000) 40 weight portions in 100 weight portions as water-soluble polymer, make the stoste that film is used.This stoste being set at 25 ℃, going up and use membrane applicator making PET film (G2 type, thickness 50 μ m) as the Teijin DuPont company of base material, is to carry out curtain coating under the condition of 51 μ m in the gap of membrane applicator and base material.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 15 μ m, and the gross thickness of duplexer is about 65 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.Membrane structure with the observable porous layer of electron microscope, porous layer and PET film close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 5

As base material, use Teijin DuPont company to make PET film (HS type, antistatic treatment, thickness 100 μ m) replace the G2 type PET film of embodiment 4, in addition, carry out operation similarly to Example 4, obtain at the folded duplexer that porous layer is arranged of layers on substrates.The porous layer thickness that obtains is about 15 μ m, and the gross thickness of duplexer is about 115 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and PET film close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 6

Use water-soluble polymer 30 weight portions, as the PET film of base material, in addition, carry out operation similarly to Example 4 among use polypropylene film (thickness 50 μ m) the replacement embodiment 4, obtain at the folded duplexer that porous layer is arranged of layers on substrates.The porous layer thickness that obtains is about 15 μ m, and the gross thickness of duplexer is about 65 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and PET film close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 7

At polyamidoimide is the resin solution (trade name " バ イ ロ マ Star Network ス HR11NN " that Japan company of twisting flax fibers and weaving makes; Solid component concentration 15 weight %, solvent NMP, solution viscosity 20dPas/25 ℃) add PVP (molecular weight 50,000) 40 weight portions in 100 weight portions as water-soluble polymer, make the stoste that film is used.This stoste is set at 25 ℃, in the Kapton (trade name " Kapton100H " that TorayDuPont company makes as base material, thickness 25 μ m) go up using membrane applicator, is to carry out curtain coating under the condition of 51 μ m in the gap of membrane applicator and base material.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 20 μ m, and the gross thickness of duplexer is about 45 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Comparative example 1

As base material, (Teijin DuPont company makes to use the PET film, trade name " S type ") Kapton of replacement embodiment 7, after curtain coating stoste on the PET film, impregnated in it is solidified, then, in the Kapton (trade name " Kapton100H " that TorayDuPont company makes, thickness 25 μ m) go up the transfer printing porous layer, carry out drying then, obtain porous membrane thus.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result had the part of Kapton and porous layer generation interface peel before peel off at the interface of adhesive tape and porous layer.This be because, when porous layer is needed on Kapton, in the process of using thin porous layer, produce gauffer, produced the space is contained in many places at the interlayer of porous layer and Kapton position.With this duplexer of electron microscope observation, the result see the many places porous layer not with the part of Kapton close adhesion.The average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 8

The polyamic acid solution (trade name " U-ワ ニ ス-A " that emerging product company of space portion makes with polyimide precursor; Solid component concentration 18 weight %, solvent NMP, solution viscosity 5dPas/30 ℃), mix with the ratio of the weight ratio 15/85/33.3 of polyamic acid/NMP/ PVP as the PVP (molecular weight 50,000) of water-soluble polymer and as the NMP of solvent, make the stoste that film is used.This stoste being set at 25 ℃, going up at the Kapton of making as the TorayDuPont company of base material (Kapton 100H, thickness 25 μ m) and use membrane applicator, is to carry out curtain coating under the condition of 25 μ m in the gap of membrane applicator and base material.Kept 8 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and the temperature groove of 30 ℃ of temperature, carry out drying from base material, then, heating is 30 minutes in 270 ℃ temperature groove, and the polyamic acid that constitutes porous layer is carried out imidizate, obtains thus at the folded duplexer that the porous layer that is made of polyimides is arranged of layers on substrates.Porous layer thickness is about 20 μ m, and the gross thickness of duplexer is about 45 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 9

As water-soluble polymer, use polyethylene glycol (molecular weight 400) to replace the PVP of embodiment 8, ratio with the weight ratio 15/85/20 of polyamic acid/NMP/ polypropylene glycol is mixed, as making the stoste that film is used, in addition, carry out operation similarly to Example 8, obtain at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 4 μ m, and the gross thickness of duplexer is about 29 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.1 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the micropore of the connectedness with the about 0.1 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 10

By the duplexer (base material/porous layer polyimide/polyamide acid imide) that is obtained by embodiment 7 is implemented 30 minutes heat treated in 270 ℃ temperature groove, make the polyamidoimide that constitutes porous layer carry out heat cross-linking, it is not dissolved, give the porous layer resistance to chemical reagents.Given the duplexer with porous layer of solvent resistance by heat treated, relative therewith even also do not dissolve after 10 minutes in impregnated in NMP, the duplexer (before the heat treated) that is obtained by embodiment 7 impregnated in the NMP several seconds with interior dissolving.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and the new porous layer that is shaped, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, new porous layer and the base material close adhesion that is shaped of result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of the new porous layer inside that is shaped is 70%.

Embodiment 11

Not forming on the porous aspect of base material in the duplexer that obtains by embodiment 7 (base material/porous layer is Kapton (25 μ m)/polyamidoimide (20 μ m)), operate similarly to Example 7, form the porous layer that constitutes by polyamidoimide with the about 20 μ m of thickness, obtain having porous layer/base material/the porous membrane laminated body in two sides that layer that porous layer is made of polyamidoimide (20 μ m)/polyimides (25 μ m)/polyamidoimide (20 μ m) constitutes with gross thickness 65 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.3 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 12

PEI at 100 weight portions is that resin solution (make, trade name " ウ Le テ system 1000 " by Japanese GE plastics; Solid component concentration 15 weight %, solvent NMP) in, add PVP (molecular weight 50,000) 45 weight portions as water-soluble polymer, make film stoste.This stoste is set at 25 ℃, be to use membrane applicator under the condition of 51 μ m in the gap of membrane applicator and Kapton base material, on the Kapton (Kapton100H, thickness 25 μ m) that the TorayDuPont company as base material makes, carry out curtain coating.Kept for 30 seconds in the container that about 80% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 20 μ m, and the gross thickness of duplexer is about 45 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the micropore of the connectedness with the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 80%.

Embodiment 13

Dilute phenolic resin varnish type epoxy resin (Toto Kasei KK's manufacturing, trade name " YDCN-701 ") with dimethylbenzene, preparation phenolic resin varnish type epoxy resin/solvent is that the resistance to chemical reagents of 5 weight portions/100 weight portions is improved treatment fluid.Improve duplexer (base material/porous layer Kapton/polyamidoimide) dipping that will obtain by embodiment 7 in the treatment fluid after 3 minutes in this resistance to chemical reagents, take out, make its air dry from coating liquid.With the fixing dried duplexer of polyimides band, heating is 30 minutes in 220 ℃ temperature groove, and phenolic resin varnish type epoxy resin is solidified on the plate of teflon (registration mark) system.With the result of the observable duplexer of electron microscope, same with the duplexer that is obtained by embodiment 7, porous layer is inner to be homogeneous substantially, constitutes by having connective micropore in the whole film.

Embodiment 14

Make coating fluororesin (trade name " Le ミ Off ロ Application LF-200 ") and polyisocyanate compounds (Japanese polyurethane industrial group manufacturing with dimethylbenzene dilution Asahi Glass Co., Ltd, trade name " コ ロ ネ-ト HK "), preparation fluororesin/polyisocyanate compounds/solvent is the coating liquid of 0.86 weight portion/0.14 weight portion/100 weight portions.

Film (the porous layer that will have the porous layer that is made into by embodiment 7; Polyamidoimide, base film; Polyimides) dipping took out from coating liquid after 3 minutes in above-mentioned coating liquid, made its air dry.With the fixing dry good film with porous layer of polyimides band, heating is 30 minutes in 270 ℃ temperature groove, and fluororesin/polyisocyanate compounds is solidified on the plate of teflon (registration mark) system.With the result of the observable duplexer of electron microscope, same with the duplexer that is obtained by embodiment 7, porous layer is inner to be homogeneous substantially, constitutes by having connective micropore in the whole film.

Embodiment 15

Use utilizes following method to make wiring board by the duplexer that embodiment 13 is made into.

To contain diazo naphthoquinone phenolic resin (diazo naphthoquinone content: 33mol equivalent %) be dissolved in acetone, the photosensitive polymer combination solution of the concentration of preparation 1wt%.Use resulting solution, carry out coating on the two sides of the duplexer that is made into by embodiment 13 by infusion process.By this operation, with containing the internal void surface that the diazo naphthoquinone phenolic resin covers porous layer.And, at room temperature make its dry 30 minutes, formed the photosensitive composite cover layer.

By the mask of live width 1mm, line-spacing 1mm at light exposure 500mJ/cm ²Under the condition of (wavelength 436nm), the porous layer side that is provided with the tectal duplexer of photosensitive composite is exposed, form the sub-image that constitutes by the indene carboxylic acid.The duplexer that has formed the pattern sub-image is implemented to utilize the catalytic treatment of catalyst-accelerator method.Particularly, dipping utilized distilled water to carry out 3 times repeatedly and cleans after 5 minutes in being adjusted into the copper sulfate solution of 0.5M.The pH of the copper sulfate solution that uses is 4.1.With thin film dipped after cleaning in the sodium borohydride aqueous solution of 0.01M 30 minutes, clean with distilled water then.By above-mentioned catalytic treatment, be produced on pattern sub-image portion and have the assembly of going back native copper.The wiring board that obtains with material on, form the pattern of live width 1mm, line-spacing 1mm.The wiring board that obtains like this be impregnated in the electrolytic copper free plating liquid 30 minutes again with material, implement copper coating, make the wiring board of Wiring pattern thus with live width 1mm, line-spacing 1mm in exposing patterns portion.

Embodiment 16

The duplexer that use is made into by embodiment 8, in addition, the utilization exposing patterns portion that operates in similarly to Example 15 makes the wiring board of the copper wiring pattern with live width 1mm, line-spacing 1mm.

Embodiment 17

As duplexer, use the duplexer [base material/porous layer is Kapton (25 μ m)/polyamidoimide (20 μ m)] that obtains by embodiment 7, use photosensitive processing-activation method to make the wiring board material as catalytic treatment.Particularly, photosensitive processing-activation method is undertaken by following method.

Preparation is by 0.89mol/m ³SnCl ₂, 2.4mol/m ³The stannous chloride solution that HCl constitutes is as photosensitive treatment fluid.In addition, preparation is by 0.56mol/m ³PbCl ₂, 12.0mol/m ³The palladium chloride solution that HCl constitutes is as activating liquid.

For duplexer, dipping cleaned with ion exchange water after 120 seconds in photosensitive treatment fluid.Then, dipping cleaned with ion exchange water after 60 seconds in activating liquid, thus, implemented catalytic treatment (utilizing the activation processing that forms catalyst core) on the surface of duplexer.

Dissolving 3g NiSO in the 100ml ion exchange water ₄6H ₂Behind the O, add 1g two hydration natrium citricums and dissolve, then, will add that 1g one hydration sodium hypophosphite dissolves and the solution that obtains as the nickel plating liquid.

After impregnated in the porous membrane laminated body after the catalytic treatment in the nickel plating liquid that is heated to 90 ℃, produce bubble at once, form the tunicle of nickel on the porous layer surface.Take out porous membrane laminated body after 10 minutes, after cleaning with ion exchange water, carry out air dry.Separate out to the porous layer surface selectivity of the tunicle of nickel in porous membrane laminated body.Can see that on base material (polyimide layer of homogeneous) tunicle of nickel separates out a little, next by having used the cleaning of ion exchange water, nickel flashing comes off fully.It has been generally acknowledged that this is because duplexer for obtaining like this, by catalytic treatment, catalyst attached on the big porous layer of surface area, quickens separating out of nickel in large quantities thus, and interweaves on porous layer and firmly fixed by the nickel of separating out.Nickel flashing it has been generally acknowledged that,, constitute, so nickel can't interweave, so can't form by homogeneous surfaces because substrate surface is obviously few at the adhesion amount of catalyst.

Embodiment 18

As duplexer, use the duplexer [base material/porous layer is Kapton (25 μ m)/polyimides (20 μ m)] that obtains by embodiment 8, in addition, utilize method similarly to Example 17 to make the wiring board material.

Embodiment 19

As duplexer, go up with electrically conductive ink [Fujikura Kasei Co., Ltd makes silver and sticks with paste NANODOTITEXA9053] under the condition of print speed printing speed 30mm/sec, squeegee pressure 0.1MPa at the duplexer that obtains by embodiment 7 [base material/porous layer is Kapton (25 μ m)/polyamidoimide (20 μ m)], use the live width of 20 μ m and the Wiring pattern of line-spacing (L/S=20 μ m/20 μ m), print with the screen painting mode.The screen printer that uses is the LS-25TVA of the accurate Industrial Co., Ltd of ニ ユ-ロ Application グ system.After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 180 ℃.The printing ink that uses is the printing ink that silver oxide is reduced into the type of silver by heating, and has just printed the back and has been black, shows the gloss of argent after heating.Observe with electron microscope, the result forms the Wiring pattern of L/S=20 μ m/20 μ μ m.

Embodiment 20

At polyamidoimide is the resin solution (trade name " バ イ ロ マ Star Network ス N-100H " that Japan company of twisting flax fibers and weaving makes; Solid component concentration 15 weight %, solvent NMP, solution viscosity 60dPas/25 ℃) add PVP (molecular weight 50,000) 15 weight portions in 100 weight portions as water-soluble polymer, make the stoste that film is used.This stoste is remained on 25 ℃, in the Kapton (trade name " Kapton100H " that Toray DuPont company makes as base material, thickness 25 μ m) go up using membrane applicator to carry out curtain coating, at this moment, is to carry out under the condition of 89 μ m in the gap of membrane applicator and base material.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 14 μ m, and the gross thickness of duplexer is about 39 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the micropore of the connectedness with the about 1 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 21

In addition use, carries out operation similarly to Example 7 as PVP (molecular weight 50,000) 30 weight portions of water-soluble polymer, obtains at the folded duplexer that porous layer is arranged of layers on substrates.The porous layer thickness that obtains is about 23 μ m, and the gross thickness of duplexer is about 48 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the micropore of the connectedness with the about 1 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 22

In embodiment 1, as base material, use Teijin DuPont company to make PET film (trade name " HS74AS " thickness 100 μ m), carry out curtain coating will making on the AS of this film face (antistatic treatment face) under the condition that stoste that film uses is 13 μ m in the gap of membrane applicator and base material, in addition, carry out operation similarly to Example 1, obtain at the folded duplexer that porous layer is arranged of layers on substrates.The porous layer thickness that obtains is 7 μ m, and the gross thickness of duplexer is about 107 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, porous layer and PET film close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the micropore of the connectedness with the about 1 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment 23

As duplexer, use the duplexer [base material/porous layer is Kapton (25 μ m)/polyamidoimide (23 μ m)] that obtains by embodiment 21, in addition, carry out operation similarly to Example 19, use the Wiring pattern of L/S=20 μ m/20 μ m to implement printing, make wiring board with the screen painting mode.With the observable wiring board of electron microscope, the result forms the Wiring pattern of L/S=20 μ m/20 μ m.

Embodiment 24

As duplexer, use the duplexer [base material/porous layer is PET film (100 μ m)/polyamidoimide (7 μ m)] that obtains by embodiment 22, in addition, carry out operation similarly to Example 19, use the Wiring pattern of L/S=20 μ m/20 μ m to implement printing, make wiring board with the screen painting mode.Behind the observable wiring board of electron microscope, form the Wiring pattern of L/S=20 μ m/20 μ m.

Embodiment 25

To the wiring board that obtains by embodiment 23, potting resin in the hole of polyamidoimide porous layer in accordance with the following methods.

With the polyimides band above-mentioned wiring board is fixed on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes, is warming up to 60 ℃.Hensel is stepped A liquid/B liquid that advanced material company makes epoxy resin (trade name " ア ラ Le ダ イ ト 2020 ", two one-pack-type epoxy resins) mix by weight 100/30, the curable resin (uncured epoxy resin) that obtains is loaded on the porous layer side surface of wiring board.Curable resin is carried out integral extension with the scraper of fluororesin system, at the uncured epoxy resin of hole part complete filling of porous layer.After remaining used for epoxy resin scraper and paper rag are removed, directly continue down heating 1.5 hours, make epoxy resin cure, be manufactured on the wiring board that is filled with resin in the hole of porous layer at 60 ℃.

Embodiment 26

As epoxy resin, A liquid/B liquid that use steps Hensel the trade name " ア ラ Le ダ イ ト 2011 " (two one-pack-type epoxy resins) that advanced material company makes mixes and the curable resin that obtains replaces in embodiment 25 " ア ラ Le ダ イ ト 2020 " by weight 100/80, in addition, carry out operation similarly to Example 25, be manufactured on the wiring board that is filled with resin in the hole of porous layer.

Embodiment 27

To the wiring board that obtains by embodiment 23 potting resin in the hole of polyamidoimide porous layer in accordance with the following methods.

With the polyimides band above-mentioned wiring board is fixed on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes, is warming up to 60 ℃.Hensel is stepped A liquid/B liquid that advanced material company makes epoxy resin (trade name " ア ラ Le ダ イ ト 2020 ", two one-pack-type epoxy resins) mix by weight 100/30, the curable resin (uncured epoxy resin) that obtains is loaded on the porous layer side surface of wiring board.Curable resin is carried out integral extension with the scraper of fluororesin system, at the uncured epoxy resin of hole part complete filling of porous layer.Remaining used for epoxy resin scraper and paper rag are removed.

And, load carefully on the porous layer surface that is filled with resin of wiring board as tectal Kapton (trade name " Kapton 100H " thickness 25 μ m) with said method, so that do not enter bubble, further make its close adhesion with scraper at interlayer.Directly continue down heating 1.5 hours, make epoxy resin cure, be manufactured on potting resin in the hole of porous layer thus at 60 ℃, and the tectal pliability wiring board of the polyimides system of being laminated with.

Embodiment 28

The wiring board polyimides band that is filled with resin in the hole of porous layer that will be obtained by embodiment 25 is that the mode on surface is fixed on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes with the porous layer side.At this Kapton base material cover layer film made from the overlapping ニ Star of the mode カ Application Industrial Co., Ltd that contacts the bond layer surface above wiring board [trade name " CISV-2525DB ", layer constitute (thickness)=Kapton base material (25 μ m)/heat-curing resin bond layer (25 μ m)], remove the bubble of interlayer with scraper.Weight (floor space 100cm made of iron with 1.5kg ²) be loaded in cover layer with on the film, be warming up to 150 ℃, heated 1.5 hours, under original state, stop heating, at room temperature carry out the nature cooling, cover layer is solidified with the bond layer of film, be manufactured on potting resin in the hole of porous layer, and the tectal pliability wiring board of the polyimides system of being laminated with.

Embodiment 29

Kapton (trade name " ミ De Off イ Le NS ", thickness 50 μ m that the Cangfu company of twisting flax fibers and weaving makes) be impregnated in the 0.1NaOH aqueous solution 60 minutes, carry out the surface treatment (alkali treatment) of Kapton.

Then, be the resin solution (trade name " バ イ ロ マ Star Network ス HR11NN " that Japan company of twisting flax fibers and weaving makes at polyamidoimide; Solid component concentration 15 weight %, solvent NMP, solution viscosity 20dPas/25 ℃) add PVP (molecular weight 50,000) 30 weight portions in 100 weight portions as water-soluble polymer, make the stoste that film is used.This stoste being set at 25 ℃, using membrane applicator on the face of the surface-treated side of having implemented above-mentioned Kapton (ミ De Off イ Le NS), is to carry out curtain coating under the condition of 51 μ m in the gap of membrane applicator and base material.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 25 μ m, and the gross thickness of duplexer is about 75 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of paper tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the micropore of the connectedness with the about 1 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Reference example 1

As Kapton, use the Kapton that does not carry out surface treatment (alkali treatment), in addition, carry out operation similarly to Example 29.But when it impregnated in the water in the near future, porous layer is peeled off from Kapton, can not obtain duplexer.

Embodiment 30

To the wiring board that obtains by embodiment 23, potting resin in the hole of polyamidoimide porous layer in accordance with the following methods.

Above-mentioned wiring board is fixed on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes with the polyimides band.As the resin solution that in solvent, is dissolved with soluble resin, (resinous principle: polyamidoimide is a resin to use Japan company of twisting flax fibers and weaving to make バ イ ロ マ Star Network ス HR15ET, solvent: alcohol solvent 50 weight %/toluene 50 weight %, solid component concentration 25 weight %, solution viscosity 7dPas/25 ℃), this resin combination is loaded on the porous layer of wiring board, scraper with fluororesin system carries out integral extension, at the partially filled resin solution of the hole of porous layer, rest solution is removed with scraper and paper rag.Then, continue down heating 1.5 hours at 60 ℃, solvent evaporates obtains being filled with the duplexer of resin.

Reference example 2

After will impregnated in the nmp solvent in the glass system culture dish by the wiring board that embodiment 23 obtains, pull out immediately, remove the NMP that is clamped in the surplus between rag.But the porous layer of wiring board is dissolved among the NMP immediately, and the distribution that is depicted on the porous layer flows out, and pattern crumbles fully.

Reference example 3

To the wiring board that obtains by embodiment 23, implement solvent in accordance with the following methods and handle, but in the pore structure of porous layer, do not see variation.

After in the acetone solvent that above-mentioned wiring board be impregnated in the glass system culture dish, pull out immediately, remove the acetone that is clamped in the surplus between rag.Then, make its air dry, be fixed on the polyimides band on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes.Heated 20 minutes down at 150 ℃.With compare before solvent is handled, the porous layer of the wiring board that obtains is not seen variation basically.

Embodiment 31～44 and reference example 4,5

The wiring board that use is obtained by embodiment 23, the mixed solvent that uses each shown in the table 1 to form is implemented solvent in order to following method and is handled, and makes the wiring board of the pore structure that has lost porous layer.

After impregnated in above-mentioned wiring board in the mixed solvent in the glass system culture dish, pull out immediately, remove the mixed solvent that is clamped in the surplus between rag.Then, make its air dry, be fixed on the polyimides band on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes.Heated 20 minutes down at 150 ℃.Based on evaluation criterion described later the transparency of porous layer and the retentivity of Wiring pattern are estimated.It is the results are shown in table 1.

Embodiment 45

The wiring board that use is obtained by embodiment 24 in order to method enforcement solvent processing down, is made the wiring board of the pore structure that has lost porous layer.

After impregnated in above-mentioned wiring board in the mixed solvent (NMP/ water (weight ratio)=1/2) in the glass system culture dish, pull out immediately, remove the mixed solvent that is clipped in the surplus between rag.Then, make its air dry, be fixed on the polyimides band on the baking tray of the electric hot plate (trade name " MODELHP-19U300 ") that KPI company makes.Heated 20 minutes down at 150 ℃.Handle by above-mentioned solvent, the polyamidoimide porous layer is by transparence, and the wiring board that obtains obtains with the form that has formed distribution on the transparent membrane that turns to be yellow a little in integral body.

Embodiment 46

As duplexer, go up with electrically conductive ink [the silver paste that Fujikura Kasei Co., Ltd makes at the duplexer that obtains by embodiment 22 [base material/porous layer is PET film (100 μ m)/polyamidoimide (7 μ m)], NANODOTITEXA9053] under the condition of print speed printing speed 10mm/sec, squeegee pressure 0.2MPa, use the half tone of the grid pattern of live width 20 μ m, line-spacing (recurrence interval) 300 μ m to print with the screen painting mode.The screen printer that uses is made LS-150TVA as the accurate Industrial Co., Ltd of ニ ユ-ロ Application グ.After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 150 ℃.The printing ink that uses is the printing ink that silver oxide is reduced into the type of silver by heating, and has just printed the back and has been black, shows the gloss of argent after heating.Observe with electron microscope, the result forms the grid pattern of live width 20 μ m, line-spacing (recurrence interval) 300 μ m.Can be used as electromagnetic wave baffle plate film uses.

Embodiment 47

To the grid pattern printed matter that obtains by embodiment 46, potting resin in the hole of polyamidoimide porous layer in accordance with the following methods.

Above-mentioned wiring board is fixed on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes with the polyimides band, is warming up to 60 ℃.Hensel is stepped A liquid/B liquid that advanced material company makes epoxy resin (trade name " ア ラ Le ダ イ ト 2020 ", two one-pack-type epoxy resins) mix by weight 100/30, the curable resin (uncured epoxy resin) that obtains is loaded on the porous layer side surface of grid pattern printed matter.Curable resin is carried out integral extension with the scraper of fluororesin system, at the uncured epoxy resin of hole part complete filling of porous layer.After remaining used for epoxy resin scraper and paper rag are removed, remain untouched under about 30 ℃ room temperature and to place 10 hours, make epoxy resin cure, be manufactured on the grid pattern printed matter that is filled with resin in the hole of porous layer.Can be used as electromagnetic wave baffle plate film uses.

Embodiment 48

The grid pattern printed matter that use is obtained by embodiment 46 in order to method enforcement solvent processing down, is made the grid pattern printed matter of the pore structure that loses porous layer.

Sprayer (trade name " ダ イ ヤ ス プ レ-エ Network セ レ Application ト NO.3530 ") the spraying mixed solvent made from Off Le プ ラ company on above-mentioned grid pattern printed matter [NMP/ acetone (weight ratio)=1/4] soaks integral body in heterogeneity.Then, make its air dry, be fixed on the polyimides band on the baking tray of the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes, 60 ℃ of heating 60 minutes down.Handle by above-mentioned solvent, the polyamidoimide porous layer is by transparence, and the clathrate pattern printed matter that obtains obtains with the form that has formed distribution on the transparent membrane that turns to be yellow a little in integral body.Can be used as electromagnetic wave baffle plate film uses.

Embodiment 49

As base material, use Kapton adhesive tape (ridge, temple makes the manufacturing of company of institute, trade name " 650R#25 (band mould release film) ", Kapton thickness 25 μ m, adhesive thickness 25 μ m) to replace the PET film, be to carry out curtain coating under the condition of 51 μ m in the gap of membrane applicator and Kapton adhesive band base, in addition, carry out operation similarly to Example 1, obtain at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 20 μ m, and the gross thickness of duplexer is about 45 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1.0 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 1.0 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment A 1

At polyamidoimide is the resin solution (trade name " バ イ ロ マ Star Network ス HR11NN " that Japan company of twisting flax fibers and weaving makes; Solid component concentration 15 weight %, solvent NMP, solution viscosity 20dPas/25 ℃) add PVP (molecular weight 50,000) 30 weight portions in 100 weight portions as water-soluble polymer, make the stoste that film is used.Place the eyelet fabric (thickness 50 μ m, trade name " PETEX PET 64HC ") that SEFAR company makes on glass plate, the stoste of using membrane applicator will remain on 25 ℃ on this eyelet fabric is carried out curtain coating.The membrane applicator when carrying out curtain coating and the gap of eyelet fabric are 51 μ m.Remain on apace after the curtain coating that humidity is about 100%, in the container of 50 ℃ of temperature 4 minutes.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain the duplexer that eyelet fabric and porous layer one change into thus from eyelet fabric.The gross thickness of duplexer is about 62 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in eyelet fabric and porous layer as a result.With this duplexer of electron microscope observation, porous layer and eyelet fabric close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1.0 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 1.0 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment A 2

As eyelet fabric, use the eyelet fabric (thickness 61 μ m) of the trade name " NYTAL NY90HC " that SEFAR company makes, in addition, carry out the operation same with embodiment A 1, obtain the duplexer that eyelet fabric and porous layer one change into.The gross thickness of duplexer is about 70 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in eyelet fabric and porous layer as a result.With this duplexer of electron microscope observation, porous layer and eyelet fabric close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1.0 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 1.0 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment A 3

As eyelet fabric, use the eyelet fabric (thickness 90 μ m) of the trade name " NYTAL PACF130-49 " that SEFAR company makes, in addition, carry out the operation same with embodiment A 1, obtain the duplexer that eyelet fabric and porous layer one change into.The gross thickness of duplexer is about 97 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in eyelet fabric and porous layer as a result.With this duplexer of electron microscope observation, porous layer and eyelet fabric close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1.0 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 1.0 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment A 4

As duplexer, use the duplexer [gross thickness is about 62 μ m: eyelet fabric (PETEX PET 64HC)/porous layer is the polyamidoimide film] that obtains by embodiment A 1, as catalytic treatment, use photosensitive processing-activation method to make electromagnetic wave control material.Particularly, photosensitive processing-activation method is undertaken by following method.

Preparation is by 0.89mol/m ³SnCl ₂, 2.4mol/m ³The stannous chloride solution that HCl constitutes is as photosensitive treatment fluid.In addition, preparation 0.56mol/m ³PdCl ₂, 12.0mol/m ³The palladium chloride solution that HCl constitutes is as activating liquid.

Duplexer flooded for 120 seconds in photosensitive treatment fluid after, clean with ion exchange water.Then, dipping cleaned with ion exchange water after 60 seconds in activating liquid, thus catalytic treatment (utilizing the activation processing that forms catalyst core) was implemented on the surface of duplexer.

Dissolving 3g NiSO in the 100ml ion exchange water ₄6H ₂Behind the O, add 1g two hydration natrium citricums and dissolve, then, will add that 1g one hydration sodium hypophosphite dissolves and the solution that obtains as the nickel plating liquid.

Porous membrane laminated body after the catalytic treatment be impregnated in the nickel plating liquid that is heated to 90 ℃, and the result produces bubble at once, forms the tunicle of nickel on the porous layer surface.Take out porous membrane laminated body after 10 minutes, after cleaning with ion exchange water, carry out air dry.The tunicle of nickel is optionally separated out the porous layer surface in porous membrane laminated body.It has been generally acknowledged that this is because duplexer for obtaining like this, by catalytic treatment, catalyst attached on the big porous layer of surface area, quickens separating out of nickel in large quantities thus, and interweaves on porous layer and firmly fixing by the nickel of separating out.

Embodiment A 5

Using the polyester of the trade name " MF-80K " that Japanese Vilene company makes is the nonwoven that nonwoven (the about 100 μ m of thickness) replaces embodiment A 1, in addition, carry out the operation same, obtain the duplexer that eyelet fabric and porous layer one change into embodiment A 1.The gross thickness of duplexer is about 127 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in nonwoven and porous layer as a result.With this duplexer of electron microscope observation, porous layer and nonwoven close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 1.0 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 1.0 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment A 6

Is that 15/85/30 ratio is mixed with polyether sulfone (sumitomo chemical company make trade name " ス ミ カ エ Network セ Le PES 5200P "), as the PVP (molecular weight 50,000) of water-soluble polymer and as the NMP of solvent in the weight ratio of polyether sulfone/NMP/ PVP, makes the stoste that film is used.This stoste is set at 25 ℃, the polyester of the trade name of making in the Japanese Vilene company as base material " MF-80K " is that nonwoven (the about 100 μ m of thickness) is gone up and used membrane applicator, in the gap of membrane applicator and base material is to carry out curtain coating under the condition of 102 μ m.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.The gross thickness of porous layer is about 122 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in nonwoven and porous layer as a result.With this duplexer of electron microscope observation, porous layer and nonwoven close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 3.0 μ m, and porous layer inside is roughly homogeneous, spreads all over the connective micropore that has that there are the about 3.0 μ m of average pore size in whole film.In addition, the porosity of porous layer inside is 70%.

Embodiment A 7

As duplexer, [base material/porous layer is that polyester is nonwoven (about 100 μ m)/polyamidoimide at the duplexer that is obtained by embodiment A 5, the about 127 μ m of gross thickness] go up with electrically conductive ink [Fujikura Kasei Co., Ltd's manufacturing silver paste, NANODOTITEXA9053] under the condition of print speed printing speed 30mm/sec, squeegee pressure 0.1MPa, use the live width of 20 μ m and the half tone of line-spacing (L/S=20 μ m/20 μ m) to print with the screen painting mode.The screen printer that uses is the system LS-25TVA of the accurate Industrial Co., Ltd of ニ ユ-ロ Application グ.After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 180 ℃.The printing ink that uses is the printing ink that silver oxide is reduced into the type of silver by heating, and has just printed the back and has been black, shows the gloss of argent after heating.Observe with electron microscope, the result forms the Wiring pattern of L/S=20 μ m/20 μ m.

Embodiment A 8

To the wiring board that obtains by embodiment A 7, potting resin in the hole of polyamidoimide porous layer in accordance with the following methods.

Above-mentioned wiring board is fixed on teflon (registration mark) sheet material (thickness 50 μ m) on the baking tray that is positioned over the electric hot plate (trade name " MODEL HP-19U300 ") that KPI company makes with the polyimides band, is warming up to 60 ℃.Hensel is stepped A liquid/B liquid that advanced material company makes epoxy resin (trade name " ア ラ Le ダ イ ト 2020 ", two one-pack-type epoxy resins) mix by weight 100/30, the curable resin (uncured epoxy resin) that obtains is loaded on the porous layer side surface of wiring board.Curable resin is carried out integral extension with the scraper of fluororesin system, at the uncured epoxy resin of hole part complete filling of porous layer.After remaining used for epoxy resin scraper and paper rag are removed, directly under 30 ℃ room temperature, continue heating 10 hours, make epoxy resin cure, be manufactured on the wiring board that is filled with resin in the hole of porous layer.

Embodiment A 9

To carry out shaping by the duplexer that embodiment A 1 obtains, the length of making each limit is sample scope, that have 3 the aperture on the summit that the forms right angled triangle (30mm * 20mm) of 8～30mm, the distance of a, b, c between measuring at 3, the variation of the shape of assess sample thus.At first, measure the initial stage apart from a1, b1, c1.Then, in the culture dish of the about 100mm of diameter, put into about 50cc methanol solvate, wherein drop into sample.Take out sample at dipping after 10 minutes, moist and after clamping with slide, measure in order to make it apart from a2, b2, c2.Use following formula to calculate a, b, c rate of change separately.

The rate of change of a behind the dipping (%)={ [a2-a1]/a1} * 100

The rate of change of b and c also uses the same method and calculates.

Its result, the rate of change behind the dipping, a, b, c all are 0%, do not see the variation of the shape that duplexer is caused by methyl alcohol.Find that eyelet fabric is very effective to keeping of shape.

Embodiment A 10

Use ion exchange water as solvent, in addition, carry out the operation same, the variation of the shape of assess sample with embodiment A 9.

Its result, the rate of change behind the dipping, a, b, c all are 0%, do not see the variation of the shape that duplexer is caused by ion exchange water.Find that eyelet fabric is very effective to keeping of shape.

Embodiment B 1

At polyamidoimide is the resin solution (trade name " バ イ ロ マ Star Network ス HR11NN " that Japan company of twisting flax fibers and weaving makes; Solid component concentration 15 weight %, solvent NMP, solution viscosity 20dPas/25 ℃) add PVP (molecular weight 50,000) 30 weight portions in 100 weight portions as water-soluble polymer, make the stoste that film is used.This stoste being set at 25 ℃, using membrane applicator on as the Mitsu Mining ﹠ Smelting Co., Ltd of base material system Copper Foil (trade name " 3EC-THE ", thickness 18 μ m) asperities, is to carry out curtain coating under the condition of 51 μ m in the gap of membrane applicator and base material.Kept 4 minutes in the container that about 100% in humidity apace after the curtain coating, temperature is 50 ℃.Then, impregnated in it is solidified, then, do not make it peel off and at room temperature carry out air dry, obtain thus at the folded duplexer that porous layer is arranged of layers on substrates from base material.Porous layer thickness is about 15 μ m, and the gross thickness of duplexer is about 33 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and PET film close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

Embodiment B 2

Using water-soluble polymer 10 weight portions, is to carry out curtain coating under the condition of 152 μ m in the gap of membrane applicator and base material, in addition, carries out the operation same with Embodiment B 1, obtains at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 37 μ m, and the gross thickness of duplexer is about 55 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 7 μ m, and porous layer is inner be homogeneous substantially, and whole thin-film memory is at the micropore with connectedness of the about 7 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

Embodiment B 3

As base material, use Japanese foliation Co., Ltd.'s system aluminium foil (trade name " ニ Star パ Network ホ イ Le ", thickness 12 μ m) to replace the Copper Foil of Embodiment B 1, on the asperities of this aluminium foil, be to carry out curtain coating under the condition of 89 μ m in the gap of membrane applicator and aluminium foil base material, in addition, carry out the operation same, obtain at the folded duplexer that porous layer is arranged of layers on substrates with Embodiment B 1.Porous layer thickness is about 23 μ m, and the gross thickness of duplexer is about 35 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

Embodiment B 4

In Embodiment B 3, in addition curtain coating stoste on as the glassy surface of the aluminium foil of base material, carry out the operation same with Embodiment B 3, obtains at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 18 μ m, and the gross thickness of duplexer is about 30 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

Comparative example B1

As base material, use PET film (manufacturing of Teijin DuPont company, trade name " S type ") to replace the Copper Foil of Embodiment B 1, with the stoste curtain coating after on the PET film, impregnated in it is solidified, then, transfer printing porous layer on Copper Foil (trade name of Mitsu Mining ﹠ Smelting Co., Ltd's system " 3EC-THE " thickness 18 μ m) asperities carries out drying then, obtains porous membrane thus.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result has before the interface peel of adhesive tape and perforated membrane, the part of copper foil base material and porous layer generation interface peel.This be because, when porous layer is needed on copper foil base material, in the process of using thin porous layer, produce gauffer, produced the space is contained in many places at the interlayer of porous layer and copper foil base material position.With this duplexer of electron microscope observation, the result see the many places porous layer not with the part of copper foil base material close adhesion.The average pore size in hole that is present in the surface of porous layer is about 0.3 μ m, and porous layer is inner be homogeneous substantially, and whole thin-film memory is at the micropore with connectedness of the about 0.3 μ m of average pore size.In addition, the porosity of porous layer inside is 70%.

Embodiment B 5

To in 270 ℃ temperature groove, implement 30 minutes heat treated by the duplexer (base material/porous layer is Copper Foil/polyamidoimide) that Embodiment B 1 obtains, thus, make the polyamidoimide that constitutes porous layer carry out heat cross-linking and it is not dissolved, give the porous layer resistance to chemical reagents.Given the duplexer with porous layer of solvent resistance by heat treated, even impregnated in also not dissolving after 10 minutes among the NMP, relative therewith, the duplexer (before the heat treated) that is obtained by Embodiment B 1 impregnated in the NMP several seconds with interior dissolving.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and the result peels off at the interface of adhesive tape and porous layer, and peel off at the interface of base material and porous layer, still mutual close adhesion.With this duplexer of electron microscope observation, new porous layer and the base material close adhesion that is shaped of result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of the new porous layer inside that is shaped is 60%.

Embodiment B 6

Carry out the operation same on the face that does not form porous layer of the copper foil base material in the duplexer that obtains by Embodiment B 1 [base material/porous layer is Copper Foil (18 μ m)/polyamidoimide (15 μ m)] with Embodiment B 1, form the porous layer that constitutes by polyamidoimide with the about 15 μ m of thickness, obtain having porous layer/base material/the porous membrane laminated body in two sides that layer that porous layer is made of polyamidoimide (15 μ m)/Copper Foil (18 μ m)/polyamidoimide (15 μ m) constitutes with the about 48 μ m of gross thickness.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and Kapton close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

Embodiment B 7

Phenolic resin varnish type epoxy resin (Toto Kasei KK's system, trade name " YDCN-701 ") is diluted with dimethylbenzene, and preparation phenolic resin varnish type epoxy resin/solvent is that the resistance to chemical reagents of 5 weight portions/100 weight portions is improved treatment fluid.Improve in the treatment fluid in this resistance to chemical reagents, duplexer (base material/porous layer the is Copper Foil/polyamidoimide) dipping that will be obtained by Embodiment B 1 took out from coating liquid after 3 minutes, made its air dry.Dried duplexer is fixed on the polyimides band on the plate of teflon (registration mark) system, and heating is 30 minutes in 220 ℃ temperature groove, and phenolic resin varnish type epoxy resin is solidified.With this duplexer of electron microscope observation, the result is same with the duplexer that is obtained by Embodiment B 1, and porous layer is inner to be homogeneous substantially, constitutes by having connective micropore in the whole film.

Embodiment B 8

Asahi Glass Co., Ltd is made coating fluororesin (trade name " Le ミ Off ロ Application LF-200 ") and polyisocyanate compounds (Japanese polyurethane industrial group manufacturing, trade name " コ ロ ネ-ト HX ") with the dimethylbenzene dilution, preparation fluororesin/polyisocyanate compounds/solvent is the coating liquid of 0.86 weight portion/0.14 weight portion/100 weight portions.

To have the film with porous layer [base material/porous layer is Copper Foil/polyamidoimide] that is made into by Embodiment B 1 and impregnated in the above-mentioned coating liquid after 3 minutes, take out, make its air dry from coating liquid.Then, the film with porous layer that drying is good is fixed on the polyimides band on the plate of teflon (registration mark) system, and heating is 30 minutes in 270 ℃ temperature groove, and fluororesin/polyisocyanate compounds is solidified.With the observable duplexer of electron microscope, the result is same with the duplexer that is obtained by Embodiment B 1, and porous layer is inner to be homogeneous substantially, constitutes by having connective micropore in the whole film.

Embodiment B 9

As copper foil base material, use Fukuda Metal Foil ﹠ POwder Co., Ltd.'s system Copper Foil (trade name " RCF-T5B-18 ", thickness 18 μ m) to replace the Mitsu Mining ﹠ Smelting Co., Ltd in the Embodiment B 1 to make Copper Foil, in addition, carry out the operation same, obtain at the folded duplexer that porous layer is arranged of layers on substrates with Embodiment B 1.Porous layer thickness is about 21 μ m, and the gross thickness of duplexer is about 39 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

Embodiment B 10

In addition curtain coating stoste on as the asperities of the aluminium foil of base material, carry out the operation same with Embodiment B 9, obtains at the folded duplexer that porous layer is arranged of layers on substrates.Porous layer thickness is about 19 μ m, and the gross thickness of duplexer is about 37 μ m.

The duplexer that obtains has been carried out the adhesive tape disbonded test, and interface peel does not take place in base material and porous layer as a result.With this duplexer of electron microscope observation, porous layer and base material close adhesion as a result, the average pore size that is present in the hole on porous layer surface is about 0.5 μ m, and porous layer is inner to be homogeneous substantially, and whole thin-film memory is at the connective micropore that has of the about 0.5 μ m of average pore size.In addition, the porosity of porous layer inside is 60%.

(evaluation test)

Bending resistance

To the duplexer [base material/porous layer is Kapton (25 μ m)/polyamidoimide (20 μ m)] that obtains by embodiment 7 and the duplexer [base material/porous layer is Copper Foil/polyamidoimide] that obtains by Embodiment B 1, use the smart mechanism of Japan to do that made MIT is anti-to rub the counter-bending test that fatigue tester MIT-D carries out JISC 5016.Experimental condition is set at radius of curvature (R) 0.38mm, rate of bending 175cpm, the tension force 4.9N of sample shape 15 * 110mm, 135 ° of angle of bend, flexure plane.This result of the test is, even any duplexer number of bends is 20000 also not fractures, only can find out the vestige of porous layer slight curvature, shows high bending resistance, possesses excellent flexibility.

The transparency

The Wiring pattern of the wiring board that visualization is obtained by embodiment 31～44 and reference example 4,5 and the transparency of porous layer are estimated with following standard.It is the results are shown in table 1.

The evaluation of the retentivity of Wiring pattern

*: distribution flows because of the dissolving of porous layer, the Wiring pattern complete obiteration.

Zero: Wiring pattern is maintained state.

The evaluation of the transparency of porous layer

-: the porous layer dissolving, can not estimate

*: porous layer does not dissolve, but opaque basically

△: opaque part is arranged in the part of porous layer

Zero: the porous layer whole clearing

Table 1

To following embodiment, average pore size, measurement method of porosity, the disbonded test that utilizes cellophane tape and the measurement of contact angle on the air permeability of perforated membrane, surface utilize following method to carry out.Show the result in table C1～table C4.

[air permeability]

Gurley ' the s Densometer that uses YOSHIMITSU company to make measures according to JIS P8117.But,, therefore, obtain according to the grignard value that JIS P8117 appendix 1 is converted into standard owing to measure 1/10 the device that area uses standard.

[average pore size on surface]

By electron micrograph its area is measured in any hole more than 30 of film surface, at first, its mean value is set at average hole area Save.Then, be converted into the aperture of supposing this Kong Weizheng bowlder, this value is set at average pore size by following formula.At this, π represents pi.

Average pore size=2 * (the Save/ π) 1/2 on surface

[porosity]

The porosity of film utilizes following formula to obtain.At this, V is the volume (cm of film ³), W is the weight (g) of film, D is the raw-material density (g/cm of film ³), for example, the density of the Merlon that uses among the Production Example C3 is set at 1.2 (g/cm ³).

Porosity (%)=100-100 * W/ (VD)

[utilizing the disbonded test of cellophane tape]

At the two sides sticking glass paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " fabric strip (registration mark) No.405 ", fabric width 24mm] of the perforated membrane of having made distribution (base material of wiring board), describe bonding portion with roller (φ 300mm, 200 gram force loadings).Then, use universal testing machine [(strain) OLINTEC, trade name " TENSILON RTA-500 "], carry out 180 degree with 50mm/ minute draw speed and peel off.Need to prove that this method uses cellophane tape to peel off in the method for JIS K6854-2, peel off to replace smearing bonding agent.

[measurement of contact angle]

In measurement of contact angle, use the measurement of contact angle device [DropMaster700] of consonance interface science (strain) system.Drip the experimental liquid of 1 μ l at film surface, measure the contact angle and the droplet radius (with reference to Fig. 9) of drop.Figure 10 is illustrated on the PAI perforated membrane (air side surface) that is obtained by Production Example C1 and has dripped (i) distilled water (surface tension 73dune/cm) respectively, (ii) toluene (surface tension 28.4dune/cm), (iii) acetate of butyl carbitol (surface tension 29.9dune/cm/20 ℃), (iv) high viscosity water solution A [in distilled water, being added with the aqueous solution of the earnest natural gum (DAICEL chemical industry (strain) system carboxymethyl cellulose resin) of 0.5 weight %], (v) elapsed time after the dropping during high viscosity water solution B [in distilled water, dripping the aqueous solution of the earnest natural gum (the carboxymethyl cellulose resin of DAICEL chemical industry (strain) system) that 2.0 weight % are arranged respectively] and the relation of contact angle θ.And, table 5 expression above-mentioned (i)～(rerum natura of liquid v) and drip after contact angle during through 100 microseconds and 1000 microseconds.

Production Example C1

Use the twist flax fibers and weave trade name " バ イ ロ マ Star Network ス HR11NN " [polyamidoimide be resin (PAI) solution, solid component concentration 15 weight %, solvent N-N-methyl-2-2-pyrrolidone N-(NMP), solution viscosity 20dPas/25 ℃] of (strain) system of Japan, with respect to these solution 100 weight portions, adding is made the stoste that film is used as PVP (molecular weight 5.5 ten thousand) 30 weight portions of water-soluble polymer.This stoste is set at 25 ℃, uses membrane applicator to carry out the gap adjustment,, on Teijin DuPont (strain) system PET film (S type, thickness 100 μ m), carry out curtain coating as base material (substrate of homogeneous) so that the thickness of perforated membrane is 50 μ m.Move on to apace after the curtain coating that relative humidity is about 100%, keep after 3 minutes in the container of 40 ℃ of temperature, impregnated in it is solidified.Then, use polypropylene system nonwoven (supporter: air permeability is lower than 1 second/100cc, thickness 260 μ m), transfer film on this supporter carries out drying together with supporter, obtains perforated membrane (perforated membrane A) thus.

Membrane structure with the observable perforated membrane of electron microscope (SEM), the average pore size A1 on the surface that the result contacts with air side when curtain coating is about 1.1 μ m, be about 0.9 μ m with the average pore size A2 on the surface of base material side contacts, A1/A2=1.22, film is inner to be homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 80%, and when having measured through performance, the sharp air permeability of lattice is 9.5 seconds.

The result of contact angle has been measured in table 5 expression to the perforated membrane that obtains.As shown in table 5, this perforated membrane to (i) distilled water, (ii) toluene, (iii) acetate of butyl carbitol, (iv) the high viscosity water solution A, (v) any of high viscosity water solution B can be brought into play good absorbability.

Production Example C2

PEI (PEI) [Japanese GE plastics (strain) system, " ウ Le テ system 1000 " and PVP (molecular weight 5.5 ten thousand)] is dissolved among the solvent NMP, makes concentration reach 17 weight % respectively, make film stoste.This stoste is set at 25 ℃, uses membrane applicator, the thickness that the gap is adjusted into perforated membrane is 50 μ m, carries out curtain coating on Teijin DuPont (strain) the system PET film (S type, thickness 100 μ m) as base material (substrate of homogeneous).After the curtain coating, keep after 3 minutes in the atmosphere that, temperature about 100% in relative humidity is 25 ℃, impregnated in it is solidified.Then, use polypropylene system nonwoven (supporter: air permeability is lower than 1 second/100cc, thickness 260 μ m), transfer film on this supporter carries out drying together with supporter, obtains perforated membrane (perforated membrane B) thus.

Membrane structure with the observable perforated membrane of electron microscope (SEM), the average pore size A1 on the surface that the result contacts with air side when curtain coating is about 3.2 μ m, be about 3.5 μ m with the average pore size A2 on the surface of base material side contacts, A1/A2=0.91, film is inner to be homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 70%, and through performance is measured, and the sharp air permeability of result case is 7.2 seconds.

Production Example C3

Merlon (PC) [Sumitomo DOW (strain) system, trade name " カ リ バ-200-3 "] is dissolved in N-N-methyl-2-2-pyrrolidone N-(NMP), obtains the solution that polycarbonate-based resin concentration is 20 weight %.Add 20 weight account polyethylene base pyrrolidones (molecular weight 5.5 ten thousand) with respect to these solution 100 weight portions and dissolve, make the stoste that film is used.Use membrane applicator, this stoste of curtain coating so that dried thickness is 50 μ m, is carried out in the adjusting play on Teijin DuPont (strain) the system PET film (S type, thickness 100 μ m) as base material (substrate of homogeneous).Keep after 3 minutes in the atmosphere that about 100% in relative humidity after the curtain coating, temperature is 25 ℃, impregnated in it is solidified.Then, use polypropylene system nonwoven (supporter: air permeability is lower than 1 second/100cc, thickness 260 μ m), transfer film on this supporter carries out drying together with supporter, obtains perforated membrane (perforated membrane C) thus.

Membrane structure with the observable perforated membrane of electron microscope (SEM), the average pore size A1 on the surface that the result contacts with air side when curtain coating is about 2.4 μ m, be about 3.3 μ m with the average pore size A2 on the surface of base material side contacts, A1/A2=0.73, film is inner to be homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 70%, and through performance is measured, and the sharp air permeability of result case is 11.2 seconds.

Production Example C4

The use amount of PVP is set at 40 weight portions, in addition, uses with Production Example C1 and obtain the perforated membrane that dried thickness is 50 μ m (perforated membrane D) with quadrat method.

With the membrane structure of the observable perforated membrane of electron microscope (SEM), the average pore size A1 on the surface that the result contacts with air side when curtain coating is about 0.2 μ m, and film is inner to be homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 80%.

Production Example C5

The use amount of PVP is set at 25 weight %, in addition, uses with Production Example C2 and obtain the perforated membrane that dried thickness is 50 μ m (perforated membrane E) with quadrat method.

With the membrane structure of the observable perforated membrane of electron microscope (SEM), the average pore size A1 on the surface that the result contacts with air side when curtain coating is about 2 μ m, and film is inner to be homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 70%.

Production Example C6

The use amount of PVP is set at 12 weight %, in addition, uses with Production Example C2 and obtain the perforated membrane that dried thickness is 50 μ m (perforated membrane F) with quadrat method.

With the membrane structure of the observable perforated membrane of electron microscope (SEM), the average pore size A1 on the surface that the result contacts with air side when curtain coating is about 6 μ m, and film is inner to be homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 70%.

Embodiment C 1

On the perforated membrane A that obtains by Production Example C1, use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jet (IJ) mode.At first, print 1 point (30pl), obtain average diameter (oval situation is the mean value of major axis, minor axis), the result is 120 μ m.Then, print according to shape shown in Figure 7 [square (liner) 4 of Pei Zhi 2 5mm abreast, the shape that links between the mid point of line 5 with long 10mm] the relative limit of square (liner) 4.Need to prove that line partly is to describe 1 row in the mode that point is spaced apart half (60 μ m) of average diameter.Live width is 130 μ m.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Measure the electric conductivity of distribution as described below.

Close adhesion conductive adhesive Cu line applies the voltage of 2V at this on the liner 4 at the two ends in Fig. 7, detects the electric current that flows, and calculates resistance value (Ω) by this electric current.

Its result, the electric conductivity of distribution are 45 Ω.Then, this distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.Measure the electric conductivity of distribution after disbonded test once more, the result is 47 Ω.

Embodiment C 2

On the perforated membrane B that obtains by Embodiment C 2, use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jetting style.At first, print 1 point (30pl), obtain average diameter (oval situation is the mean value of major axis minor axis), the result is 85 μ m.Then, print according to shape shown in Figure 7.Need to prove that line partly is to describe 1 row in the mode that point is spaced apart half (43 μ m) of average diameter.Live width is 90 μ m.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Similarly measured the electric conductivity of distribution with Embodiment C 1, the result is 50 Ω.Then, this distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.Measured the electric conductivity of distribution after disbonded test once more, the result is 54 Ω.

Embodiment C 3

On the perforated membrane C that obtains by Production Example C3, use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jetting style.At first, print 1 point (30pl), obtain average diameter (oval situation is the mean value of major axis, minor axis), the result is 140 μ m.Then, print according to shape shown in Figure 7.Need to prove that line partly is to describe 1 row in the mode that point is spaced apart half (70 μ m) of average diameter.Live width is 140 μ m.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Similarly measured the electric conductivity of distribution with Embodiment C 1, the result is 42 Ω.Then, this distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.Measured the electric conductivity of distribution after disbonded test once more, the result is 51 Ω.

Comparative example C1

Going up use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] at Kapton (PI film) [TorayDuPont (strain) system, trade name " KaptonH ", thickness 50 μ m] prints with ink-jetting style.At first, print 1 point (30pl), obtain average diameter (oval situation is the mean value of major axis minor axis), the result is 170 μ m.Then, print according to shape shown in Figure 7.Need to prove that line partly is to describe 1 row in the mode that point is spaced apart half (85 μ m) of average diameter.Live width is 230 μ m.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Similarly measured the electric conductivity of distribution with Embodiment C 1, the result is 40 Ω.Then, this distribution is utilized the disbonded test of cellophane tape, distribution and adhesive tape cling and peel off from Kapton as a result.Measured the electric conductivity of distribution after the disbonded test once more, but current value can not be measured (resistance value ∞) for detecting below the lower limit.Need to prove, paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] a little less than using bonding force than cellophane tape replaces cellophane tape, when similarly carrying out disbonded test, distribution also clings with adhesive tape and peels off from Kapton.

Comparative example C2

At fluororesin is that film (etfe film) [ダ イ キ Application industry (strain) system, trade name " ネ オ Off ロ Application ETFE EF-0050 ", thickness 50 μ m] upward uses electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jetting style.At first, print 1 point (30pl), obtain average diameter (oval situation is the mean value of major axis minor axis), the result is 80 μ m.Secondly, print according to shape shown in Figure 7.Need to prove that line partly is to describe 1 row in the mode that point is spaced apart half (40 μ m) of average diameter.Live width is 110 μ m, but sees depression in online, and the place of broken string is arranged.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Similarly measured the electric conductivity of distribution with Embodiment C 1, but current value can not be measured (resistance value ∞) for detecting below the lower limit.Then, this distribution is utilized the disbonded test of cellophane tape, distribution and adhesive tape cling and are that film strips down from fluororesin as a result.Measured the electric conductivity of distribution after the disbonded test once more, but current value can not be measured (resistance value ∞) for detecting below the lower limit.Need to prove, paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] a little less than using bonding force than cellophane tape replaces cellophane tape, when similarly carrying out disbonded test, distribution also clings with adhesive tape and peels off from Kapton.

Table 2

Embodiment C 4

On the perforated membrane D that obtains by Production Example C4, use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jetting style.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Then, this distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.

Embodiment C 5

On the perforated membrane E that obtains by Production Example C5, use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jetting style.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Then, this distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.

Embodiment C 6

On the perforated membrane F that obtains by Production Example C6, use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] to print with ink-jetting style.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Then, this distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.

Comparative example C3

Going up use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] at polyamidoimide (PAI) [dense film of thickness 25 μ m: average pore size 0.001 μ m, porosity 50%] prints with ink-jetting style.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Then, this distribution is utilized the disbonded test of cellophane tape, distribution and adhesive tape cling and strip down from the polyamidoimide film as a result.Measured the electric conductivity of distribution after the disbonded test, but current value can not be measured (resistance value ∞) for detecting below the lower limit.Need to prove, paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] a little less than using bonding force than cellophane tape replaces cellophane tape, when similarly carrying out disbonded test, distribution also clings with adhesive tape and strips down from the polyamidoimide film.

Comparative example C4

Going up use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] at Kapton (PI film) [dense film of thickness 100 μ m: average pore size 0.005 μ m, porosity 60%] prints with ink-jetting style.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Then, this distribution is utilized the disbonded test of cellophane tape, distribution and adhesive tape cling and peel off from the polyamidoimide film as a result.Measured the electric conductivity of distribution after the disbonded test, but current value can not be measured (resistance value ∞) for detecting below the lower limit.Need to prove, paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] a little less than using bonding force than cellophane tape replaces cellophane tape, when similarly carrying out disbonded test, distribution also clings with adhesive tape and peels off from Kapton.

Comparative example C5

Going up use electrically conductive ink [ア Le バ Star Network マ テ リ ア Le (strain) system, trade name " Ag nano metal printing ink Ag1TeH "] at pet film (PET film) [dense film of thickness 25 μ m: average pore size 0.008 μ m, porosity 60%] prints with ink-jetting style.

After the printing, kept 30 minutes down, electrically conductive ink is solidified and the formation distribution at 200 ℃.Then, this distribution is utilized the disbonded test of cellophane tape, distribution and adhesive tape cling and strip down from the polyamidoimide film as a result.Measured the electric conductivity of distribution after the disbonded test, but current value can not be measured (resistance value ∞) for detecting below the lower limit.Need to prove, paper self-adhesive tape [NICHIBAN (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] a little less than using bonding force than cellophane tape replaces cellophane tape, when similarly carrying out disbonded test, distribution also clings with adhesive tape and peels off from the polyamidoimide film.

Table 3

Embodiment C 7

On the perforated membrane A that obtains by Production Example C1, use electrically conductive ink [Ag sticks with paste: grind chemical industry (strain) system, trade name " CA-2503 " greatly] to print with the silk screen mode.

Use has the version of the straight line portion of live width 50 μ m (L1) and carries out screen painting as pattern.Use electron microscope that straight line portion is carried out the macrophotography of 200 times of multiplying powers, measure the average live width (L2) of long 500 μ m, the result is 100 μ m.

In addition, use the version of the straight line portion with live width 20 μ m (L1) to carry out screen painting as pattern 2, similarly measure average live width, the result is 40 μ m.Fig. 8 (a) expression will use the printing surface of edition printed matter that obtains of pattern 2 to be amplified to the electron micrograph of taking after 200 times.By Fig. 8 (a) as can be known, can obtain printing the printing of describing the repeatability excellence.And Fig. 8 (b) expression is amplified to 1000 times electron micrograph with A-A ' the line cross section of Fig. 8 (a).By Fig. 8 (b) as can be known, can obtain the printing of the excellent in stability of electrically conductive ink and porous film surface close adhesion.

After the printing, after 100 ℃ maintenance made solvent seasoning in 30 minutes down, kept 30 minutes down, make electrically conductive ink curing and form distribution at 200 ℃.This distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.

Embodiment C 8

The perforated membrane B that use is obtained by Production Example C2 is as perforated membrane, in addition, according to carrying out screen painting with the same method of Embodiment C 7, use the version of pattern 1 to obtain the printed matter of average live width 100 μ m, use the version of pattern 2 to obtain the printed matter of average live width 40 μ m.This distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.

Embodiment C 9

The perforated membrane C that use is obtained by Production Example C3 is as perforated membrane, in addition, according to carrying out screen painting with the same method of Embodiment C 7, use the version of pattern 1 to obtain the printed matter of average live width 100 μ m, use the version of pattern 2 to obtain the printed matter of average live width 40 μ m.This distribution is utilized the disbonded test of cellophane tape, tape stripping as a result, distribution is disappearance not.

Table 4

Table 5

To following embodiment, on the basis of above-mentioned evaluation, utilize following method to carry out the evaluation that repeatability is described in the mensuration of contact angle and droplet radius, fine rule illustrative and printing.

[mensuration of contact angle and droplet radius]

In measurement of contact angle, the contact angle determination device " DropMaster700 " that uses consonance interface science (strain) to make.The experimental liquid of 1 μ l is dripped at film surface, measure the contact angle and the droplet radius (with reference to Fig. 9) of drop.Each film surface of the PI film that uses in PET film that uses in the PEI perforated membrane (air side surface) that Figure 11 is illustrated in the PAI perforated membrane (air side surface) that obtained by Production Example D1, obtained by Production Example D2, the Comparative Example D 1 and the Comparative Example D 2 drips the elapsed time after dropping when acetate of butyl carbitol is arranged and the relation of contact angle.In addition, each film surface of the PI film that uses in PET film that Figure 12 is illustrated in the PAI perforated membrane (air side surface) that obtained by Production Example D1, use in the PEI perforated membrane (air side surface) that obtained by Production Example D2, Comparative Example D 1 and the Comparative Example D 2 drips the elapsed time after dropping when acetate of butyl carbitol is arranged and the relation of droplet radius.

[evaluation of fine rule illustrative]

Use electron microscope that wide 10～1000 μ m, straight line portion more than the length 500 μ m are carried out macrophotography (200 times).Measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, utilize following formula (1) to calculate change value F, utilize following formula (2) to calculate standard deviation ∑ (with reference to Figure 13).

F＝(LMax-LMin)/LAve×100 (1)

$\mathrm{\Σ}=\sqrt{(({(\mathrm{LAve}-\mathrm{LMax})}^2+{(\mathrm{LAve}-\mathrm{LMin})}^2)/2)}---\left(2\right)$

Need to prove that with regard to average live width (LAve), setting-out on transparent membrane is converted and calculated average live width by its weight.

[evaluation of repeatability is described in printing]

Using electron microscope is that straight line portion more than the 500 μ m carries out macrophotography (200 times) to wide 10～1000 μ m, length.On transparent membrane, describe the straight line portion of long 500 μ m, convert and calculate average live width (L2) by its weight.By using the aperture widths (L1) of this average live width (L2), obtain the value (with reference to Figure 14) of L2/L1 divided by the straight line portion of the version of half tone.

Production Example D1

With polyamidoimide (PAI) be resin solution [Japan twist flax fibers and weave (strain) system, trade name " バ イ ロ マ Star Network ス HR11NN "] 100 weight portions and PVP (molecular weight 5.5 ten thousand, water-soluble polymer) 35 weight portions mix, dissolve, and make the polymer solution that film is used.Use membrane applicator and adjusting play, at polyimides (PI) made membrane (base material of homogeneous; Thickness 25 μ m) carry out this polymer solution of curtain coating on, so that dried thickness is about 30 μ m.After the curtain coating, film was kept 3 minutes in 25 ℃, the atmosphere of 100%RH, impregnated in it is solidified, carry out drying then, obtain perforated membrane.

Membrane structure to the perforated membrane that obtains is observed, found that, the average pore size A1 of the micropore on the surface that contacts with air side when curtain coating is 0.2 μ m, the average pore size A2 of the micropore on the surface that contacts with substrate-side is 0.2 μ m, A1/A2=1, it is all films in aperture uniformly of positive and reverse side.And with the surface and the cross section of electron microscope (SEM) viewing film, the air side surface of film and base material side surface all are the micropores with uniform pore size as a result, and inner is homogeneous substantially, and whole thin-film memory has connective micropore.In addition, the porosity of film is 80%, and grignard value is below 10 seconds.Need to prove that A2, grignard value are measured after peeling off the PAI perforated membrane from the PI film substrate.

Production Example D2

With PEI (PEI) [Japanese GE plastics (strain) system, trade name " ULTEM1000 "] and PVP (molecular weight 5.5 ten thousand; Water-soluble polymer) is dissolved in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP), makes the film polymer solution with what show that concentration is respectively 17 weight %.Use the membrane applicator crack adjustment in the ranks of going forward side by side, at PETG (PET) made membrane (base material of homogeneous; Thickness 100 μ m) carry out this polymer solution of curtain coating on, so that dried thickness is about 30 μ m.After the curtain coating, film was kept for 10 seconds in 25 ℃, the atmosphere of 100%RH, impregnated in it is solidified, carry out drying then, obtain perforated membrane.

Membrane structure to the perforated membrane that obtains is observed, found that, the average pore size A1 of the micropore on the surface that contacts with air side when curtain coating is 3.2 μ m, the average pore size A2 of the micropore on the surface that contacts with substrate-side is 3.5 μ m, A1/A2=0.91, it is all films in aperture uniformly of positive and reverse side.And with the surface and the cross section of electron microscope (SEM) viewing film, the air side surface of film and base material side surface have all disperseed to have the micropore in uniform aperture as a result, and inner is homogeneous substantially, and whole thin-film memory has connective micropore.In addition, the porosity of film is 60%, and grignard value is below 10 seconds.Need to prove that A2, grignard value are measured after peeling off the PAI perforated membrane from the PET film substrate.

Embodiment D1

Use pattern figure (straight line on the surface of the PAI perforated membrane that obtains by Production Example D1 (air side surface); The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 47.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 3%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 1.1.Figure 15 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain the excellent printing of linearity (fine rule illustrative).

Need to prove that drip acetate of butyl carbitol on the surface of the PAI perforated membrane that is obtained by Production Example D1 (air side surface) and measure contact angle, the contact angle the when result drips back 300 microseconds is 19.5 °, the droplet radius of this moment is 1290 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measure contact angle on the surface of perforated membrane, the contact angle when dripping back 300 microseconds is respectively 17.2 °, 13.7 °, 25.2 °.Even use, also obtain the printed matter of fine rule illustrative excellence with the printing ink of these solvents as main solvent.

Embodiment D2

Use pattern figure (straight line on the surface of the PAI perforated membrane that obtains by Production Example D1 (air side surface); The setting value of linear width is 20 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 21.2 μ m, 24.2 μ m, 23.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 6%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 2.5.Figure 16 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain the excellent printing of linearity (fine rule illustrative).

Embodiment D3

Use pattern figure (straight line on the surface of the PEI perforated membrane that obtains by Production Example D2 (air side surface); The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 47.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 3%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 1.1.Figure 17 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain the excellent printing of linearity (fine rule illustrative).

Need to prove that drip acetate of butyl carbitol on the surface of the PEI perforated membrane that is obtained by Production Example D2 (air side surface) and measure contact angle, the contact angle the when result drips back 300 microseconds is 20.8 °, the droplet radius of this moment is 1340 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measured contact angle on the surface of perforated membrane, the contact angle the when result drips back 300 microseconds is respectively 17 °, 12 °, 29.5 °.Even use, also obtain the printed matter of fine rule illustrative excellence with the printing ink of these solvents as main solvent.

Embodiment D4

Use pattern figure (straight line on the surface of the PEI perforated membrane that obtains by Production Example D2 (air side surface); The setting value of linear width is 20 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 23.3 μ m, 24.2 μ m, 18.2 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 26%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 3.7.Figure 18 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain the excellent printing of linearity (fine rule illustrative).

Comparative Example D 1

Go up use pattern figure (straight line at PETG (PET) film [Teijin DuPont film (strain) system, trade name " are washed special human relations S100 ", thickness 100 μ m]; The setting value of linear width is 20 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 43.9 μ m, 48.5 μ m, 33.3 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 34%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 8.2.Figure 19 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, only obtain the not good printing of linearity (fine rule illustrative).

Need to prove that drip acetate of butyl carbitol and measure contact angle on the surface of above-mentioned PETG (PET) film, the contact angle the when result drips back 300 microseconds is 14.7 °, the droplet radius of this moment is 1690 μ m.

Comparative Example D 2

Go up use pattern figure (straight line at Kapton (PI film) [TorayDuPont (strain) system, trade name " Kapton100H ", thickness 25 μ m]; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 65.9 μ m, 83.3 μ m, 50.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 51%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 16.7.Figure 20 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, only obtain the printing that linearity (fine rule illustrative) lacks.

Need to prove that drip acetate of butyl carbitol and measured contact angle on the surface of above-mentioned Kapton (PI film), the contact angle the when result drips back 300 microseconds is 12.8 °, the droplet radius of this moment is 1630 μ m.

Embodiment E 1

Use the version of straight line portion to carry out screen painting on the surface of the PAI perforated membrane that obtains by Production Example D1 (air side surface) with live width 50 μ m (L1).The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measured the average live width (L2) of long 500 μ m, the result is 47.0 μ m, L2/L1=0.94.Figure 21 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain printing the printing of describing the repeatability excellence.

Need to prove that drip acetate of butyl carbitol on the surface of the PAI perforated membrane that is obtained by Production Example D1 (air side surface) and measured contact angle, the contact angle the when result drips back 300 microseconds is 19.5 °, the droplet radius of this moment is 1290 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measured contact angle on the surface of perforated membrane, the contact angle the when result drips back 300 microseconds is respectively 17.2 °, 13.7 °, 25.2 °.Even use, also obtain printing the printed matter of describing the repeatability excellence with the printing ink of these solvents as main solvent.

Embodiment E 2

Use the version of straight line portion to carry out screen painting on the surface of the PAI perforated membrane that obtains by Production Example D1 (air side surface) with live width 20 μ m (L1).The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measured the average live width (L2) of long 500 μ m, the result is 21.2 μ m, L2/L1=1.06.Figure 22 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain printing the printing of describing the repeatability excellence.

Embodiment E 3

Use the version of straight line portion to carry out screen painting on the surface of the PEI perforated membrane that obtains by Production Example D2 (air side surface) with live width 50 μ m (L1).The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measured the average live width (L2) of long 500 μ m after, be 47.0 μ m, L2/L1=0.94.Figure 23 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain printing the printing of describing the repeatability excellence.

Need to prove that drip acetate of butyl carbitol on the surface of the PEI perforated membrane that is obtained by Production Example D2 (air side surface) and measured contact angle, the contact angle the when result drips back 300 microseconds is 20.8 °, the droplet radius of this moment is 1340 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measured contact angle on the surface of perforated membrane, the contact angle the when result drips back 300 microseconds is respectively 17 °, 12 °, 29.5 °.Even use, also obtain the printed matter of fine rule illustrative excellence with the printing ink of these solvents as main solvent.

Embodiment E 4

Use the version of straight line portion to carry out screen painting on the surface of the PEI perforated membrane that obtains by Production Example D2 (air side surface) with live width 20 μ m (L1).The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measured the average live width (L2) of long 500 μ m, the result is 23.3 μ m, L2/L1=1.17.Figure 24 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, can obtain printing the printing of describing the repeatability excellence.

Comparative Example E 1

Upward use the version of straight line portion to carry out screen painting at PETG (PET) film [Teijin DuPont film (strain) system, trade name " are washed special human relations S100 ", thickness 100 μ m] with live width 20 μ m (L1).The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measured the average live width (L2) of long 500 μ m, the result is 43.9 μ m, L2/L1=2.20.Figure 25 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, only obtain printing the printing of describing the repeatability shortage.

Need to prove that drip acetate of butyl carbitol and measured contact angle on the surface of above-mentioned PETG (PET) film, the contact angle the when result drips back 300 microseconds is 14.7 °, the droplet radius of this moment is 1690 μ m.

Comparative Example E 2

[TorayDuPont (strain) system, trade name " Kapton100H ", thickness 25 μ m] upward use the version of the straight line portion with live width 50 μ m (L1) to carry out screen painting at Kapton (PI film).The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.Use electron microscope that straight line portion is carried out macrophotography (200 times), measured the average live width (L2) of long 500 μ m, the result is 65.9 μ m, L2/L1=1.32.Figure 26 represents the enlarged photograph figure of the printing surface of the printed matter that obtains.As seen from the figure, only obtain printing the printing of describing the repeatability shortage.

Need to prove that drip acetate of butyl carbitol and measured contact angle on the surface of above-mentioned Kapton (PI film) film, the contact angle the when result drips back 300 microseconds is 12.8 °, the droplet radius of this moment is 1630 μ m.

To following embodiment, on the basis of above-mentioned evaluation, utilize following method to carry out the evaluation of close adhesion and the mensuration of hot strength.

[evaluation of close adhesion]

Scratch hardness (pencil method) test according to JIS K 5600-5-4, cut is carried out on the surface of the printed matter that dry solvent is obtained with the pencil of each hardness, observe the surface whether wound arranged, whether see the top layer the peeling off of (compacted zone or porous rete), with following standard evaluation close adhesion.Need to prove that preferred pencil hardness is at least 6B and is " zero ", further preferred pencil hardness is that 2B also is " zero ", and preferred especially pencil hardness is that 2H also is " zero ".

Zero: the surface does not have peeling off of top layer in spite of wound yet

*: the surface in spite of wound or the top layer peel off

Need to prove that condition determination is as follows.

The angle of pencil and sample thin film: 45 °

Loading: 750g

Measure temperature: 23 ℃

[mensuration of hot strength]

Measure hot strength according to JIS-K7127.In the mensuration of reality, use universal tensile testing machine [manufacturing of (strain) OLINTEC company, trade name " TENSIRON RTA-500 "].Perforated membrane monomer sample in the mensuration of F1 before the use fusion.In the mensuration of F2, perforated membrane monomer sample is placed on the strippable supporter such as teflon (registration mark) film, carry out the fusion heating after, peel off from supporter, be used for measuring.

Need to prove that condition determination is as follows.

Draw speed: 50mm/ minute

The rectangle that sample: 10mm is wide

Production Example F1

With polyamidoimide (PAI) resin solution [Japan twist flax fibers and weave (strain) system, trade name " バ イ ロ マ Star Network ス HR11N "] 100 weight portions and PVP (molecular weight 5.5 ten thousand, water-soluble polymer) 35 weight portions mix, dissolve, and make the film polymer solution.Use membrane applicator, the crack adjustment in the ranks of going forward side by side is at polyimides (PI) made membrane (base material=supporter of homogeneous; Thickness 25 μ m) carry out curtain coating to this polymer solution on, so that dried thickness is about 30 μ m.After the curtain coating, film was kept 3 minutes in 25 ℃, the atmosphere of 100%RH, impregnated in it is solidified, carry out drying then, obtain on supporter, being laminated with the duplexer of perforated membrane.

Membrane structure to the perforated membrane that obtains is observed, found that, the average pore size A1 of the micropore on the surface that contacts with air side when curtain coating is 0.2 μ m, the average pore size A2 of the micropore on the surface that contacts with substrate-side is 0.2 μ m, A1/A2=1.0, it is all films in aperture uniformly of positive and reverse side.And with the surface and the cross section of electron microscope (SEM) viewing film, the air side surface of film and base material side surface have all disperseed to have the micropore in uniform aperture as a result, and inner is homogeneous substantially, and whole thin-film memory has connective micropore.In addition, the porosity of film is 80%, and grignard value is below 10 seconds.Need to prove that A2, grignard value are measured after peeling off the PAI perforated membrane from the PI film substrate.

When the contact angle of the surface of porous rete side and water is measured, θ A ₁₀₀Be 25.4 °, θ A ₁₀₀₀Be 13.0 °, θ A ₁₀₀₀/ θ A ₁₀₀=0.51.In addition, drip acetate of butyl carbitol and measured contact angle on the surface of porous rete side, the contact angle the when result drips back 300 microseconds is 19.5 °, and the droplet radius of this moment is 1290 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measured contact angle on the surface of perforated membrane, the contact angle the when result drips back 300 microseconds is respectively 17.2 °, 13.7 °, 25.2 °.

Production Example F2

With PEI (PEI) [Japanese GE plastics (strain) manufacturing, trade name " ULTEM1000 "] and PVP (molecular weight 5.5 ten thousand; Water-soluble polymer) is dissolved in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP), makes its concentration be respectively 13.8 weight %, 25.1 weight %, make the polymer solution that film is used.Use membrane applicator and adjusting play, at PETG (PET) made membrane (base material of homogeneous; Thickness 100 μ m) carry out this polymer solution of curtain coating on, so that dried thickness is about 30 μ m.After the curtain coating, film was kept for 10 seconds in 25 ℃, the atmosphere of 100%RH, impregnated in it is solidified, carry out drying then, obtain on supporter, being laminated with the duplexer of perforated membrane.

Membrane structure to the perforated membrane that obtains is observed, found that, the average pore size A1 of the micropore on the surface that contacts with air side when curtain coating is 3.2 μ m, the average pore size A2 of the micropore on the surface that contacts with substrate-side is 3.5 μ m, A1/A2=0.91, it is all films in aperture uniformly of positive and reverse side.And with the surface and the cross section of electron microscope (SEM) viewing film, the air side surface of film and base material side surface have all disperseed to have the micropore of uniform pore size as a result, and inner is homogeneous substantially, and whole thin-film memory has connective micropore.In addition, the porosity of film is 60%, and grignard value is below 10 seconds.Need to prove that A2, grignard value are measured after peeling off the PEI perforated membrane from the PET film substrate.

The surface of porous rete side and the contact angle of water are measured, as a result θ A ₁₀₀Be 27.1 °, θ A ₁₀₀₀Be 9.5 °, θ A ₁₀₀₀/ θ A ₁₀₀=0.35.In addition, drip acetate of butyl carbitol and measure contact angle on the surface of porous rete side, the contact angle the when result drips back 300 microseconds is 20.8 °, and the droplet radius of this moment is 1340 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measure contact angle on the surface of perforated membrane, the contact angle the when result drips back 300 microseconds is respectively 17 °, 12 °, 29.5 °.

Production Example F3

With Merlon (PC) [Sumitomo DOW (strain) system, trade name " カ リ バ-200-3 "] and PVP (molecular weight 5.5 ten thousand; Water-soluble polymer) is dissolved in the solvent N-N-methyl-2-2-pyrrolidone N-(NMP), makes its concentration be respectively 15 weight %, 23 weight %, make the polymer solution that film is used.Use the membrane applicator crack adjustment in the ranks of going forward side by side, at polyamide (PI) made membrane (base material of homogeneous; Thickness 50 μ m) carry out this polymer solution of curtain coating on, so that dried thickness is about 30 μ m.After the curtain coating, film was kept 60 minutes in 25 ℃, the atmosphere of 100%RH, impregnated in it is solidified, carry out drying then, obtain on supporter, being laminated with the duplexer of perforated membrane.

Membrane structure to the perforated membrane that obtains is observed, found that, the average pore size A1 of the micropore on the surface that contacts with air side when curtain coating is 2.4 μ m, the average pore size A2 of the micropore on the surface that contacts with substrate-side is 3.3 μ m, A1/A2=0.72, it is all films in aperture uniformly of positive and reverse side.And with the surface and the cross section of electron microscope (SEM) viewing film, the air side surface of film and base material side surface have all disperseed to have the micropore of uniform pore size as a result, and inner is homogeneous substantially, and whole thin-film memory has connective micropore.The porosity of film is 70%, and grignard value is below 10 seconds.Need to prove that A2, grignard value are measured after peeling off the PC perforated membrane from the PI film substrate.

Water and contact angle to the surface of porous rete side are measured, as a result θ A ₁₀₀Be 44.3 °, θ A ₁₀₀₀Be 8.8 °, θ A ₁₀₀₀/ θ A ₁₀₀=0.20.In addition, drip acetate of butyl carbitol and measure contact angle on the surface of porous rete side, the contact angle the when result drips back 300 microseconds is 14.5 °, and the droplet radius of this moment is 1320 μ m.In addition, replace acetate of butyl carbitol, drip water, toluene, decyl alcohol and measure contact angle on the surface of perforated membrane, the contact angle the when result drips back 300 microseconds is respectively 18 °, 13 °, 33.2 °.

Embodiment F 1

Use pattern figure (straight line on the surface of the PAI of the duplexer that obtains by Production Example F1 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, drip 3 (about 0.1g) N-N-methyl-2-2-pyrrolidone N-s (NMP) (23 ℃), make it contain whole (the about 4cm that is dipped in the perforated membrane layer at the porous rete side surface of having implemented printing ²), with nonwoven press lightly wipe away superfluous NMP after, 250 ℃ dry 30 minutes down, remove NMP.

Printing surface to the printed matter that obtains is observed with electron microscope, and the result can confirm to break in the hole of porous and cause printing surface by densified.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.5 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.1%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 4.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 90.0 °, θ B ₁₀₀₀Be 81.5 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.91, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.15.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually as a result to the printed matter that obtains.

Embodiment F 2

Use pattern figure (straight line on the surface of the PAI of the duplexer that obtains by Production Example F1 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, at 3 (about 0.1g) water of porous rete side surface dropping of having implemented printing and the mixed liquor [water/NMP (weight ratio)=7/3] (23 ℃) of N-N-methyl-2-2-pyrrolidone N-(NMP), make it contain whole (the about 4cm that is dipped in the perforated membrane layer ²), with nonwoven press lightly wipe away superfluous water and NMP after, 150 ℃ dry 30 minutes down, remove and anhydrate and NMP.

Printing surface to the printed matter that obtains is observed with electron microscope, and the result can confirm to break in the hole of porous and cause printing surface by densified.In addition, use electron microscope that the straight line portion of printing is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.5 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.1%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 4.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 89.3 °, θ B ₁₀₀₀Be 80.4 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.90, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.16.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually as a result to the printed matter that obtains.

Embodiment F 3

Use pattern figure (straight line on the surface of the PAI of the duplexer that obtains by Production Example F1 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, at 3 (about 0.1g) water of porous rete side surface dropping of having implemented printing and the mixed liquor [water/GBL (weight ratio)=5/5] (23 ℃) of gamma-butyrolacton (GBL), make it contain whole (the about 4cm that is dipped in the perforated membrane layer ²), with nonwoven press lightly wipe away superfluous water and GBL after, 200 ℃ dry 60 minutes down, remove and anhydrate and GBL.

Printing surface to the printed matter that obtains is observed with electron microscope, and the result can confirm to break in the hole of porous and cause printing surface by densified.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.5 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.1%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 4.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 87.0 °, θ B ₁₀₀₀Be 81.0 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.93, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.15.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually as a result to the printed matter that obtains.

Comparative Example F 1

Use pattern figure (straight line on the surface of the PAI of the duplexer that obtains by Production Example F1 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Straight line portion to the printing of the printed matter that obtains uses electron microscope to carry out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.5 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.1%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 4.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 25.4 °, θ B ₁₀₀₀Be 13.0 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.51, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.96.In addition, by scratch hardness test research close adhesion, in spite of wound, peel off under pencil hardness 2B by the top layer under pencil hardness 6B for the result to the printed matter that obtains, and any situation all is evaluated as " * ".

Embodiment F 4

Use pattern figure (straight line on the surface of the PEI of the duplexer that obtains by Production Example F2 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, drip 3 (about 0.1g) N-N-methyl-2-2-pyrrolidone N-s (NMP) (23 ℃), make it contain whole (the about 4cm that is dipped in the perforated membrane layer at the porous rete side surface of having implemented printing ²), with nonwoven press lightly wipe away superfluous NMP after, 250 ℃ dry 30 minutes down, remove NMP.

Printing surface to the printed matter that obtains is observed with electron microscope, breaks and cause printing surface by densified in the hole that found that porous.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.3%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 5.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 21.3 °, θ B ₁₀₀₀Be 14.4 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.68, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.66.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually as a result to the printed matter that obtains.

Embodiment F 5

Use pattern figure (straight line on the surface of the PEI of the duplexer that obtains by Production Example F2 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, drip 3 (about 0.1g) two oxa-s, penta ring (23 ℃), make it contain whole (the about 4cm that is dipped in the perforated membrane layer at the porous rete side surface of having implemented printing ²), with nonwoven press lightly wipe away superfluous two oxa-s, penta ring (NMP) after, 150 ℃ dry 30 minutes down, remove two oxa-s, penta ring.

Printing surface to the printed matter that obtains is observed with electron microscope, and the result can find to break in the hole of porous and cause printing surface by densified.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.3%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 5.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 20.2 °, θ B ₁₀₀₀Be 15.6 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.77, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.61.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually as a result to the printed matter that obtains.

Comparative Example F 2

Use pattern figure (straight line on the surface of the PEI of the duplexer that obtains by Production Example F2 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Straight line portion to the printing of the printed matter that obtains uses electron microscope to carry out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.3%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 5.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 27.1 °, θ B ₁₀₀₀Be 9.5 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.35, θ A ₁₀₀₀/ θ B ₁₀₀₀=1.00.In addition, to the printed matter that obtains by scratch hardness test research close adhesion, as a result pencil hardness 6B in spite of wound, 2B peels off on the top layer, any situation all is evaluated as " * ".

Comparative Example F 3

Use pattern figure (straight line on the surface of the PEI of the duplexer that obtains by Production Example F2 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, drip 3 (about 0.1g) isopropyl alcohol (IPA) (23 ℃), make it spread all over whole (about 4cm of porous rete at the porous rete side surface of having implemented printing ²), with nonwoven press lightly wipe away superfluous IPA after, 150 ℃ dry 10 minutes down, remove IPA.

Printing surface to the printed matter that obtains is observed with electron microscope, and the hole of porous is remained untouched residually as a result, does not form compacted zone.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 47.0 μ m, 48.5 μ m, 46.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.3%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 5.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 27.1 °, θ B ₁₀₀₀Be 9.5 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.35, θ A ₁₀₀₀/ θ B ₁₀₀₀=1.00.In addition, to the printed matter that obtains by scratch hardness test research close adhesion, as a result pencil hardness 6B in spite of wound, 2B peels off on the top layer, any situation all is evaluated as " * ".

Embodiment G1

Use pattern figure (straight line on the surface of the PEI of the duplexer that obtains by Production Example F2 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, the duplexer of having implemented printing is put into heating furnace, kept 30 minutes down at 300 ℃, make the fusion of porous rete after, be cooled to room temperature and make its curing.

Printing surface to the printed matter that obtains is observed with electron microscope, and the result can find to break in the hole of porous and cause printing surface by densified.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is 48.0 μ m, 49.5 μ m, 47.7 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.1%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 4.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 21.3 °, θ B ₁₀₀₀Be 14.4 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.68, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.66.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually to the printed matter that obtains.And, measuring hot strength, the result is F16.9MPa, F2 is 66.1MPa, F2/F1=9.6.

Comparative example G1

Pattern (straight line is used on surface in the PEI of the duplexer that is obtained by Production Example F2 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, the duplexer of having implemented printing is put into heating furnace, after keeping 30 minutes under 100 ℃, be cooled to room temperature and make its curing.

Straight line portion to the printing of the printed matter that obtains uses electron microscope to carry out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is 48.3 μ m, 49.1 μ m, 47.0 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 1.1%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 4.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 26.2 °, θ B ₁₀₀₀Be 9.2 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.35, θ A ₁₀₀₀/ θ B ₁₀₀₀=1.03.In addition, to the printed matter that obtains by scratch hardness test research close adhesion, as a result pencil hardness 6B in spite of wound, 2B peels off on the top layer, any situation all is evaluated as " * ".And, measuring hot strength, F1 is 6.9MPa as a result, F2 is 6.9MPa, F2/F1=1.0.

Embodiment G2

Use pattern figure (straight line on the surface of the PC of the duplexer that obtains by Production Example F3 porous rete side; The setting value of linear width is 50 μ m) carry out screen painting.The printing ink that is used to print is for grinding electrically-conducting paint " the CA-2503 " (main solvent: acetate of butyl carbitol) of chemical industry (strain) system greatly.After the printing, under 100 ℃, made ink setting 30 minutes.

Then, the duplexer of having implemented printing is put into heating furnace, kept 30 minutes down at 250 ℃, make the fusion of porous rete after, be cooled to room temperature and make its curing.

Printing surface to the printed matter that obtains is observed with electron microscope, and the result can find to break in the hole of porous and cause printing surface by densified.In addition, use electron microscope that straight line portion is carried out macrophotography (200 times), measure average live width (LAve), maximum line width (LMax), the minimum feature (LMin) of long 500 μ m, the result is respectively 52.0 μ m, 54.2 μ m, 49.8 μ m.With the above-mentioned formula of this numerical value substitution (1), calculate change value F, the result is 2.2%.In addition, with the above-mentioned formula of this numerical value substitution (2), calculate the standard deviation ∑, the result is 8.

Contact angle to the printing surface of the printed matter that obtains is measured, as a result θ B ₁₀₀Be 23.3 °, θ B ₁₀₀₀Be 19.6 °, θ B ₁₀₀₀/ θ B ₁₀₀=0.84, θ A ₁₀₀₀/ θ B ₁₀₀₀=0.45.In addition, by scratch hardness test research close adhesion, any situation of pencil hardness 2B, 2H does not all have to be evaluated as " zero " unusually as a result to the printed matter that obtains.And, measuring hot strength, F1 is 9.2MPa as a result, F2 is 87.2MPa, F2/F1=9.5.

Description of drawings

Fig. 1 (A)～(F) is the printing ink that the expression printing contains the electric conductor particle, formed the generalized section of an example of the wiring board of distribution on porous layer (substrate) surface, as the printing ink that contains the electric conductor particle, (A) expression is adopted and to be contained many average perforates with respect to the porous layer top layer and directly be the full-bodied printing ink of the particle of the small particle diameter generalized section as an example of the formed wiring board of printing ink that contains electroconductive particle, (B) expression is adopted and to be contained many particle diameters and approach the full-bodied printing ink of particle in average perforate footpath on porous layer top layer as the generalized section of an example of the formed wiring board of printing ink that contains electroconductive particle, (C) expression is adopted and to be contained many average perforates with respect to the porous layer top layer and directly be the full-bodied printing ink of the particle of the big particle diameter generalized section as an example of the formed wiring board of printing ink that contains electroconductive particle, (D) expression is adopted and to be contained many average perforates with respect to the porous layer top layer and directly be the low viscous printing ink of the particle of the small particle diameter generalized section as an example of the formed wiring board of printing ink that contains electroconductive particle, (E) expression is adopted and to be contained the low viscous printing ink of particle in average perforate footpath that many particle diameters approach the porous layer top layer as an example that contains the formed wiring board of printing ink of electroconductive particle, and (F) expression is adopted and contained many average perforates with respect to the porous layer top layer and directly be the low viscous printing ink of the particle of the small particle diameter generalized section as an example of the formed wiring board of printing ink that contains electroconductive particle.

Fig. 2 represents the generalized section of an example of the embodiment of wiring board of the present invention.

Fig. 3 represents another routine generalized section of the embodiment of wiring board of the present invention.

Fig. 4 represents the generalized section of an example again of the embodiment of wiring board of the present invention.

Fig. 5 represents other routine generalized sections of the embodiment of wiring board of the present invention.

Fig. 6 represents another other routine generalized sections of the embodiment of wiring board of the present invention.

Fig. 7 is the figure of the printing shape among expression Embodiment C 1～C6 and the C1～C3.

Fig. 8 (a) is to use the electron micrograph of the wiring board that the pattern 2 that obtained by embodiment 7 is printed as, and (b) is the electron micrograph in A-A ' the line cross section in (a).

Fig. 9 is the key diagram of contact angle and droplet radius.

Figure 10 is the coordinate diagram of the relation of elapsed time after the dropping when being illustrated in the PAI porous film surface (air side surface) that obtained by Production Example C1 and dripping various liquid and contact angle.

Figure 11 is each film surface such as PI film of using in the PET film that uses in the PEI perforated membrane (air side surface) that is illustrated in the PAI perforated membrane (air side surface) that obtained by Production Example D1, obtained by Production Example 2, the Comparative Example D 1 and the Comparative Example D 2 when dripping acetate of butyl carbitol, the coordinate diagram of the elapsed time after the dropping and the relation of contact angle.

Figure 12 is that the PET film that uses in the PEI perforated membrane (air side surface) that is illustrated in the PAI perforated membrane (air side surface) that obtained by Production Example D1, obtained by Production Example 2, the Comparative Example D 1 and each film surface such as PI film that uses in Comparative Example D 2 drip when acetate of butyl carbitol is arranged the coordinate diagram of the elapsed time after the dropping and the relation of droplet radius.

Figure 13 is the key diagram of asking method of the standard deviation of expression live width.

The last figure of Figure 14 is the L1 of the opening portion of expression version when being straight line and the key diagram of the relation of L2, and figure below is the opening portion of the expression version L1 when circular and the key diagram of the relation of L2.

Figure 15 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment D1 has been used in expression.

Figure 16 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment D2 has been used in expression.

Figure 17 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment D3 has been used in expression.

Figure 18 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment D4 has been used in expression.

Figure 19 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by Comparative Example D 1 has been used in expression.

Figure 20 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by Comparative Example D 2 has been used in expression.

Figure 21 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment E 1 has been used in expression.

Figure 22 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment E 2 has been used in expression.

Figure 23 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment E 3 has been used in expression.

Figure 24 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by embodiment E 4 has been used in expression.

Figure 25 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by Comparative Example E 1 has been used in expression.

Figure 26 is the enlarged photograph figure of electron microscope that the printing surface of the printed matter that is obtained by Comparative Example E 2 has been used in expression.

Figure 27 is the key diagram (utilizing profile) of each operation of an example of the manufacture method of expression printed patterns of the present invention.

Figure 28 is the key diagram (utilizing profile) of each operation of other examples of the manufacture method of expression printed patterns of the present invention.

The explanation of symbol

1 porous rete

2 conductor wirings

3 compacted zones

4 liners

5 distributions (line)

6 supporters

7 printings

8 solvents

9 have infiltrated the porous rete of solvent

Porous rete after 10 fusions

11 compacted zones

Claims (95)

1. porous membrane laminated body, described porous membrane laminated body comprise base material and be layered in this base material at least the one side on porous layer, described porous layer has the micropore of many connectednesses and the average pore size of this micropore is 0.01～10 μ m, wherein, after belt stripping test based on following method, interface peel does not take place in base material and porous layer

Belt stripping test:

The ridge, temple of pasting fabric width 24mm on the porous layer surface of porous membrane laminated body makes the masking tape [film masking tape No.603 (#25)] that company of institute makes, it is sticking to be with diameter that 30mm, loading are that the roller of 200 gram forces is pressed, and uses cupping machine to carry out the T mould with peeling rate 50mm/ minute then and peels off.

2. the described porous membrane laminated body of claim 1, wherein, described base material is to have the base material of many through holes or be metallic foil substrates.

3. claim 1 or 2 described porous membrane laminated bodies, wherein, described porous layer is to be formed on by the following method on the one side at least of base material, that is, and with Polymer Solution after curtain coating on the base material becomes the film shape, it is directed in the solidification liquid, carry out drying then.

4. each described porous membrane laminated body in the claim 1～3, wherein, described Polymer Solution is the mixed solution that comprises 8～25 weight % macromolecule components, 5～50 weight % water-soluble polymers, 0～10 weight % water, 30～82 weight % water soluble polar solvent.

5. each described porous membrane laminated body in the claim 1～4, wherein, the macromolecule component that constitutes porous layer is that to be selected from polyimides be that resin, polyamidoimide are that resin, polyether sulfone are that resin, PEI are that resin, polycarbonate-based resin, polyphenylene sulfide are that resin, liquid crystalline polyester are that resin, aromatic polyamides are that resin, polyamide-based resin, polybenzoxazole are that resin, polybenzimidazoles are that resin, polybenzothiozole are that resin, polysulfones are at least a resin in resin, cellulose-based resin, the acrylic resin.

6. each described porous membrane laminated body in the claim 1～5, wherein, the material of formation base material is a resin for being selected from polyimides, polyamidoimide is a resin, polyether sulfone is a resin, PEI is a resin, polycarbonate-based resin, polyphenylene sulfide is a resin, liquid crystalline polyester is a resin, aromatic polyamides is a resin, polyamide-based resin, polybenzoxazole is a resin, polybenzimidazoles is a resin, polybenzothiozole is a resin, polysulfones is a resin, cellulose-based resin, acrylic resin, the PET series resin, PEN is a resin, polybutylene terephthalate (PBT) is a resin, polyether-ether-ketone is a resin, fluorine resin, the olefin-based resin, polyarylate is at least a resin in the resin.

7. each described porous membrane laminated body in the claim 1～6, wherein, the macromolecule component that constitutes porous layer is that to be selected from polyimides be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a resin in resin and the polyamide-based resin; The material that constitutes base material is that to be selected from polyimides be that resin, polyamidoimide are that resin, PEI are that resin, liquid crystalline polyester are that resin, aromatic polyamides are that resin, PET series resin, PEN are at least a resin in the resin.

8. each described porous membrane laminated body in the claim 2～7, wherein, the material that constitutes the base material with many through holes is at least a material that is selected from fabric, nonwoven, eyelet fabric, punching film, wire netting, punch metal, expanded metal and etching metal.

9. each described porous membrane laminated body in the claim 2～8, wherein, the macromolecule component that constitutes porous layer is that to be selected from polyimides be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a resin in resin and the polyamide-based resin; The material that constitutes the base material with many through holes is at least a material that is selected from fabric, nonwoven, eyelet fabric, punching film, wire netting, punch metal, expanded metal and the etching metal.

10. each described porous membrane laminated body in the claim 2～7, wherein, the material that constitutes metallic foil substrates is be selected from Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel, stainless steel foil at least a.

11. each described porous membrane laminated body in the claim 2～8, wherein, the macromolecule component that constitutes porous layer is that to be selected from polyimides be that resin, polyamidoimide are that resin, PEI are that resin, aromatic polyamides are at least a resin in resin and the polyamide-based resin; The material that constitutes metallic foil substrates is selected from least a in Copper Foil, aluminium foil, iron foil, nickel foil, goldleaf, silver foil, tinfoil paper, zinc paper tinsel, the stainless steel foil.

12. each described porous membrane laminated body in the claim 1～11, wherein, porous layer is covered by the resistance to chemical reagents macromolecule.

13. each described porous membrane laminated body in the claim 1～12, wherein, porous layer thickness is 0.1～100 μ m.

14. each described porous membrane laminated body in the claim 1～13, wherein, the porosity of porous layer is 30～80%.

15. each described porous membrane laminated body in the claim 2～14, wherein, the thickness of base material is 1～1000 μ m.

16. each described porous membrane laminated body in the claim 1～15, wherein, the thickness of base material is 1～300 μ m.

17. each described porous membrane laminated body in the claim 1～16, it is used for filter, battery separator, electrolyte membrane for fuel cell or catalyst carrier.

18. each described porous membrane laminated body in the claim 1～17, it is used for electromagnetic wave control material, circuit substrate or heat sink.

19. the manufacture method of a porous membrane laminated body, it comprises: with Polymer Solution after curtain coating on the base material becomes the film shape, it is directed in the solidification liquid, carries out drying then, fold porous layer to obtain each described porous membrane laminated body in the claim 1～18 at least one surface layer of base material.

20. the manufacture method of the described porous membrane laminated body of claim 19, wherein, Polymer Solution is the mixed solution that comprises 8～25 weight % macromolecule components, 5～50 weight % water-soluble polymers, 0～10 weight % water, 30～82 weight % water soluble polar solvent.

21. a composite at least one porous layer surface of its each described porous membrane laminated body in constituting claim 1～18, is laminated with metal-plated coating and/or magnetic coating layer.

22. the described composite of claim 21, it is used for circuit substrate, heat sink, electromagnetic wave control material, battery with assembly or capacitor assembly.

23. the manufacture method of a composite, its at least one stacked metal deposition layer in porous layer surface by each described porous membrane laminated body in constituting claim 1～18 obtains composite, this method comprises following operation: comprise in the porous layer surface applied of above-mentioned porous membrane laminated body and utilize illumination to penetrate and the photosensitive composite of the compound of reaction of formation group, thereby the operation of photosensitive layer is set; By mask to above-mentioned photosensitive layer expose, in the operation of exposure portion reaction of formation group; And the reactive group that exposure portion is generated combines, forms the operation of conductive pattern with metal.

24. the manufacture method of a composite, on its at least one porous layer surface by each described porous membrane laminated body in constituting claim 1～18, laminated metal coating layer and obtain composite, this method comprises following operation: comprise in the porous layer surface applied of above-mentioned porous membrane laminated body and utilize illumination to penetrate and make the photosensitive composite of the compound that reactive group disappears, thereby the operation of photosensitive layer is set; Above-mentioned photosensitive layer is exposed, makes in exposure portion the operation of reactive group disappearance by mask; And make the reactive group that remains in unexposed portion combine, form the operation of conductive pattern with metal.

25. the manufacture method of claim 23 or 24 described composites, it obtains being used for the composite of circuit substrate, heat sink or electromagnetic wave control material.

26. a composite, it utilizes printing technology at least one porous layer surface of each described porous membrane laminated body in constituting claim 1～18 to form electric conductor and obtain.

27. the described composite of claim 26, it is used to circuit substrate, heat sink or electromagnetic wave control material.

28. the described composite of claim 26, wherein, printing technology is to be selected from least a in ink jet printing, screen painting, distributor printing, letterpress, subliming type printing, hectographic printing, laser printing printing, intaglio printing, contact print, the micro-contact printing.

29. the described composite of claim 26, wherein, electric conductor is be selected from silver, gold, copper, nickel, tin indium oxide, carbon, CNT at least a.

30. each described composite in the claim 26～29, it forms electric conductor by the printing technology of having used the printing ink that contains the electric conductor particle in the porous surface utilization and obtains, wherein, and when the average perforate with the porous layer top layer directly is set at R ₁, the average grain diameter of electric conductor particle is set at R ₂The time, satisfy formula: 0.0001 ≦ R ₂/ R ₁≦ 1000.

31. each described composite in the claim 26～30 wherein, covers electric conductor with coating or insulating materials.

32. the described composite of claim 31, wherein, coating is to be selected from least a in copper coating, gold plate, the nickel coating.

33. each described composite in the claim 26～32, its residual hole of porous layer that remains untouched.

34. each described composite in the claim 26～32 wherein, is filled with resin in the hole of porous layer.

35. the described composite of claim 34, wherein, the resin that is filled in the hole of porous layer is at least a resin that is selected from epoxy resin, oxetane resin, acrylic resin, vinyl ether resin, polyimide resin, mylar, the polyamide-imide resin.

36. each described composite in the claim 26～32, it handles the pore structure that loses porous layer by solvent.

37. each described composite in the claim 26～36 wherein, is laminated with cover layer on porous layer.

38. wiring board, it exists many at least one masks with porous rete of connective micropore that conductor wirings is arranged, and it does not produce the disappearance of distribution in the disbonded test by utilizing cellophane tape [nichiban (strain) manufacturing, trade name " fabric strip (registration mark) No.405 ", fabric width 24mm] to carry out (180 ° peel off, peeling rate 50mm/ minute).

39. wiring board, it exists many at least one masks with porous rete of connective micropore that conductor wirings is arranged, and it does not produce the disappearance of distribution in the disbonded test by utilizing paper self-adhesive tape [nichiban (strain) manufacturing, trade name " paper self-adhesive tape No.208 ", fabric width 24mm] to carry out (180 ° peel off, peeling rate 50mm/ minute).

40. claim 38 or 39 described wiring boards, wherein, the average pore size of porous rete is 0.01～10 μ m.

41. a wiring board, it exists many at least one masks with porous rete of connective micropore that conductor wirings is arranged, and wherein, the average pore size of porous rete is 0.01～10 μ m, and conductor wirings utilizes print process to form.

42. each described wiring board in the claim 38～41, wherein, the porosity of porous rete is 30～80%.

43. each described wiring board in the claim 38～42, wherein, the thickness of porous rete is 0.1～100 μ m.

44. each described wiring board in the claim 38～43, wherein, the porous rete is the layer that is formed by resin.

45. the described wiring board of claim 44, wherein, the porous rete is by being that resin, PEI are that resin, polycarbonate-based resin, polyether sulfone are that resin and polyimides are that at least a resin in the resin is constituted by the material of matrix to be selected from polyamidoimide.

46. each described wiring board in the claim 38～45, wherein, the porous rete is the porous resin thin layer that utilizes phase inversion method to form.

47. the described wiring board of claim 46, wherein, the porous rete is the layer that is made of porous membrane, the following making of described porous membrane: will in polar solvent, be dissolved with solution curtain coating on substrate that the material that constitutes this porous rete forms with water-soluble polymer and become the film shape, under the atmosphere of relative humidity 70～100%, kept 0.2～15 minute, after impregnated in the solidification liquid that the non-solvent by above-mentioned material constitutes, carry out drying, desolventizing.

48. each described wiring board in the claim 38～47, wherein, the porous rete does not substantially have to form on the one or both sides of compacted zone in hole.

49. each described wiring board in claim 38～40 and 42～48, wherein, conductor wirings utilizes print process to form.

50. the manufacture method of a wiring board, it is used for making each described wiring board of claim 38～49, and wherein, the one side at least that has many micropores of connectedness and the porous rete that average pore size is 0.01～10 μ m in existence forms conductor wirings.

51. the manufacture method of the described wiring board of claim 50, wherein, the porous rete is the resin bed that utilizes phase inversion method to form.

52. the manufacture method of claim 50 or 51 described wiring boards wherein, does not substantially have to form the porous rete on the one or both sides of compacted zone in hole, in average pore size is to form conductor wirings on the surface of described porous rete of 0.01～10 μ m.

53. the manufacture method of each described wiring board in the claim 50～52 wherein, utilizes print process to form conductor wirings on the surface of porous rete.

54. the manufacture method of the described wiring board of claim 53 wherein, uses electrically conductive ink to form conductor wirings on the surface of porous rete with ink-jetting style.

55. the manufacture method of the described wiring board of claim 53 wherein, formed coating electrically conductive printing ink on the concavo-convex version with the Wiring pattern shape, is needed on the surface of porous rete with it, forms conductor wirings.

56. the manufacture method of the described wiring board of claim 53, its on the surface of porous rete by extruding conductor paste from syringe and describing to form conductor wirings.

57. the manufacture method of the described wiring board of claim 53, its surface at the porous rete forms conductor wirings by utilizing screen painting to describe conductor paste.

58. the manufacture method of each described wiring board in the claim 53～57, it further implements plating on conductor wirings.

59. the manufacture method of the described wiring board of claim 53 wherein, after the surface of porous rete utilizes ink-jetting style with Wiring pattern shape printing plating catalyst, is implemented plating, forms conductor wirings.

60. the manufacture method of the described wiring board of claim 53 wherein, is forming coating plating catalyst on the concavo-convex version with the Wiring pattern shape, it is needed on the surface of porous rete after, implement plating, form conductor wirings.

61. the manufacture method of the described wiring board of claim 53 wherein, the surface of porous rete is extruded the plating catalyst and depicted the Wiring pattern shape as from syringe after, is implemented plating, forms conductor wirings.

62. the manufacture method of the described wiring board of claim 53 wherein, after the surface of porous rete utilizes screen painting to depict the plating catalyst as the Wiring pattern shape, is implemented plating, forms conductor wirings.

63. a printed matter, its be implemented to have average live width 10～1000 μ m at least on the surface of porous rete, the printing of the straight line portion more than the long 500 μ m and the printed matter that obtains, wherein, the change value F of the live width of following formula (1) expression is below 30%,

F＝(LMax-LMin)/LAve×100 (1)

In the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m.

64. a printed matter, its be implemented to have average live width 10～1000 μ m at least on the surface of porous rete, the printing of the straight line portion more than the long 500 μ m and the printed matter that obtains, wherein, the standard deviation ∑ of the live width of following formula (2) expression is below 7,

$\mathrm{\Σ}=\sqrt{(({(\mathrm{LAve}-\mathrm{LMax})}^2+{(\mathrm{LAve}-L\min )}^2)/2)}---\left(2\right)$

In the formula, LAve represents the average live width of the straight line portion of long 500 μ m, and LMax represents the maximum line width of the straight line portion of this length 500 μ m, and LMin represents the minimum feature of the straight line portion of this length 500 μ m.

65. a printed matter, it is to have implemented printing on the surface of porous rete with version and the printed matter that obtains, wherein, and the aperture widths L of version ₁With the corresponding printing width L in printing back ₂Ratio (L ₂/ L ₁) be 0.8～1.2.

66. each described printed matter in the claim 63～65, it is to use and contains printing-ink that following liquid is main solvent or paste and implemented that printing forms, the characteristics of described liquid are as follows: dripping at the perforated membrane laminar surface behind the drop of 1 μ l in 300 microseconds, is below 60 ° at the contact angle of this perforated membrane laminar surface.

67. each described printed matter in the claim 63～66, it is to use to contain has implemented as the printing-ink of main solvent or paste with following liquid that printing forms, the characteristics of described liquid are as follows: drip at the perforated membrane laminar surface behind the drop of 1 μ l in 300 microseconds, contact angle at this perforated membrane laminar surface is below 60 °, and the droplet radius during through 300 microseconds is below the 1600 μ m.

68. each described printed matter in the claim 63～67, it is to use viscosity is that the printing-ink of 0.05～1Pa.s or paste have been implemented printing and formed.

69. each described printed matter in the claim 63～68, it is extruded to stick with paste to have implemented to print by screen cloth or metal mask and forms.

70. each described printed matter in the claim 63～69, wherein, the average pore size of porous rete is 0.01～10 μ m.

71. each described printed matter in the claim 63～70, wherein, the porosity of porous rete is 30～80%.

72. each described printed matter in the claim 63～71, wherein, the thickness of porous rete is 0.1～100 μ m.

73. each described printed matter in the claim 63～72, wherein, the porous rete is the layer that is formed by resin.

74. each described printed matter in the claim 63～73, wherein, the resin that constitutes the porous rete is a heat-resistant resin.

75. the described printed matter of claim 74, wherein, it is that resin, PEI are that resin, polycarbonate-based resin and polyether sulfone are resin that heat-resistant resin is selected from polyamidoimide.

76. each described printed matter in the claim 63～75, wherein, the porous rete is the porous resin thin layer that utilizes phase inversion method to form.

77. the described printed matter of claim 76, wherein, the porous rete is the layer that is made of perforated membrane, the following making of described perforated membrane: will in polar solvent, be dissolved with solution curtain coating on substrate that the material that constitutes this porous rete obtains with water-soluble polymer and become the film shape, under the atmosphere of relative humidity 70～100%, kept 0.2～15 minute, be impregnated in the solidification liquid that the non-solvent by above-mentioned material constitutes, carry out drying, desolventizing then.

78. each described printed matter in the claim 63～77, wherein, printed matter is a printed substrate.

79. the manufacture method of a printed patterns, it comprises the operation that forms compacted zone, and described compacted zone is made through following operation: (1) implements printing on the porous rete operation, (2A) makes operation that the porous rete of having implemented printing contacts with solvent, reaches the operation that (3A) makes solvent seasoning.

80. the manufacture method of a printed patterns, wherein, its comprise (1) on the porous rete, implement operation, (2B) of printing make the porous rete of having implemented printing carry out heat fusing operation, and (3B) carry out the operation that cooling curing forms compacted zone.

81. the manufacture method of claim 79 or 80 described printed patterns, wherein, the contact angle θ A the when surface of the porous rete that uses in operation (1) drips behind the water through 1000 microseconds ₁₀₀₀With in operation (3A), make solvent seasoning after carry out the compacted zone that cooling curing forms in the compacted zone that forms or the operation (3B) the contact angle θ B of surface when dripping behind the water through 1000 microseconds ₁₀₀₀Than θ A ₁₀₀₀/ θ B ₁₀₀₀Less than 1.

82. the manufacture method of each described printed patterns in the claim 79～81, wherein, when the porous rete that in measuring operation (1), uses and the contact angle of water, the contact angle θ A behind the surface of porous rete dropping water during through 1000 microseconds ₁₀₀₀Contact angle θ A with through 100 microseconds the time ₁₀₀Than θ A ₁₀₀₀/ θ A ₁₀₀Less than 0.6, when carrying out the contact angle of compacted zone that cooling curing forms and water in compacted zone that forms after in measuring operation (3A), making solvent seasoning or the operation (3B), the contact angle θ B behind the surface of compacted zone dropping water during through 1000 microseconds ₁₀₀₀Contact angle θ B with through 100 microseconds the time ₁₀₀Than θ B ₁₀₀₀/ θ B ₁₀₀For greater than 0.6 value.

83. the manufacture method of the described printed patterns of claim 80, wherein, in operation (3B), carry out cooling curing and the ratio F2/F1 of the hot strength F1 of the hot strength F2 of the compacted zone that obtains and the porous rete that in operation (1), uses for greater than 1 value.

84. the manufacture method of each described printed patterns in the claim 79～83, wherein, printing process is ink-jetting style, screen painting, hectographic printing, distillation mode, temperature-sensitive mode, photogravure, laser printing, paste printing or nano contact printing.

85. the manufacture method of each described printed patterns in the claim 79～84, wherein, the average pore size of porous rete is 0.01～10 μ m.

86. the manufacture method of each described printed patterns in the claim 79～85, wherein, the porosity of porous rete is 30～80%.

87. the manufacture method of the described printed patterns of claim 80, wherein, the thickness of porous rete is 0.1～1000 μ m.

88. the manufacture method of the described printed patterns of claim 79, wherein, the thickness of porous rete is 0.1～100 μ m.

89. the manufacture method of each described printed patterns in the claim 79～88, wherein, the porous rete is the layer that is formed by resin.

90. the manufacture method of the described printed patterns of claim 89, wherein, the resin that constitutes the porous rete is a heat-resistant resin.

91. the manufacture method of the described printed patterns of claim 90, wherein, it is that resin, PEI are that resin, polycarbonate-based resin and polyether sulfone are resin that heat-resistant resin is selected from polyamidoimide.

92. the manufacture method of each described printed patterns in the claim 79～92, wherein, the porous rete is the porous resin thin layer that utilizes phase inversion method to form.

93. the manufacture method of the described printed patterns of claim 92, wherein, the porous rete is the layer that is made of perforated membrane, the following making of described perforated membrane: will in polar solvent, be dissolved with the material of this porous rete of formation and solution curtain coating on substrate of water-soluble polymer and become the film shape, under the atmosphere of relative humidity 70～100%, kept 0.2～15 minute, be impregnated in the solidification liquid that the non-solvent by above-mentioned material constitutes, carry out drying, desolventizing then.

94. a printed matter, it utilizes the manufacture method of each described printed patterns in the claim 79～93 to form printed patterns.

95. the described printed matter of claim 94, wherein, printed matter is a printed substrate.

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