CN103732403B - Electromagnetic wave shielding component - Google Patents

Abstract

Multi-layer formed body of the present invention (1) comprises the adhesive resin/filler complex (21) of the inorganic filler containing adhesive resin and 30 more than volume %, 95 below volume % and the adaptation be layered at least one interarea of described adhesive resin/filler complex (21) strengthens resin bed (11).Adaptation strengthen resin bed (11) thickness be more than 50nm, less than 9 μm, glass transition temperature is more than 120 DEG C, lower than 260 DEG C, comprises the polyimide resin of the aliphatic unit of carbon number more than 3 as principal component on main chain.

Description

Electromagnetic wave shielding component

Technical field

The present invention relates to a kind of multi-layer formed body and manufacture method thereof.In addition, the present invention relates to a kind of the electromagnetic wave shielding component and the thermal diffusivity component that possess described multi-layer formed body.

Background technology

All the time, as the thermal diffusivity component used in electronic component, electromagnetic wave shielding component, use the adhesive resin/filler complex of the sheet inorganic fillers such as the adhesive resins such as epoxy resin, organic siliconresin, acrylic rubber and conducting filler, electroconductive stuffing, magnetic fillers obtained with high density composite.For example, Patent Document 1 discloses a kind of fin, this fin is the fin metallics such as aluminium oxide being adhered to the adhesive resin such as polyester based resin, vinyl-vinyl acetate copolymer and obtains.

In patent document 2, for the height fillingization of inorganic filler, in order to improve the hardening problem become fragile of sheet-like formed body, proposing and in adhesive resin, adding rubber constituent, wet goods as the method for plasticizer, soft agent.But, in the method for patent document 2, owing to adding rubber constituent, wet goods as plasticizer, soft agent, thus there is the problem caused heat resistance and worsen.Therefore, be not suitable for having the product of the high-temperature processing technology needing solder reflow operation etc.As the method improving heat resistance, there is the method for adding thermal cross-linking agent, but can thermoplasticity be lost by the crosslinked of thermal cross-linking agent, worry the flexibility of sheet material, be difficult to the kink being applied to jog.

Fibre reinforced polyimides benzoxazole complex is proposed in patent document 3.Specifically, propose following method: be immersed in polyamic acid solution by carbon fiber cloth and silk, make its impregnation, mention containing the carbon fiber being soaked with polyamic acid solution, by dry for unnecessary polyamic acid solution strand removing, the polyimide precursor complex of gained is heated, obtains fibre reinforced polyimide composite.In the method for patent document 3, although can improve the intensity of article shaped, elastic modelling quantity is high, there is the problem being difficult to the jog, kink etc. be applied in electronic instrument.In addition, in patent document 4, propose following method: by electromagnetic wave absorb coated and molded on PET, the contour intensity base material of polyimides, strengthen, this electromagnetic wave absorb is 20 ~ 110m by the specific area being filled with 5 ~ 60mol% ²the adhesive resin of the carbon dust of/g is formed.In addition, Patent Document 5 discloses a kind of screened film be made up of the duplexer of electric conductivity adhesive linkage and protective layer, this electric conductivity adhesive linkage is dispersed in by electroconductive stuffing in the adhesive resin of the polyimides containing silicone-containing residue and forms.

In recent years, power loading device in the various uses of automobile control.Along with the multifunction high performance of this power device, compactization of electronic unit, the electromagnetic wave of caloric value, generation increases.Therefore, for preventing the technology of the misoperation caused by heat, electromagnetic wave from being very important.In this case, for thermal diffusivity component, electromagnetic wave shielding component, the technology that tight demand is a kind of to be realized than the prior aries such as patent document 4,5 more high performance high reliability.

Patent document 1: Japanese Unexamined Patent Publication 2007-048809 publication

Patent document 2: Japanese Unexamined Patent Publication 2008-163145 publication

Patent document 3: Japanese Unexamined Patent Publication 2010-168562 publication

Patent document 4: Japanese Unexamined Patent Publication 2006-19399 publication

Patent document 5: Japanese Unexamined Patent Publication 2010-161324 publication

Summary of the invention

The present invention is the invention completed in view of above-mentioned background, its objective is and provides a kind of function, simultaneously flexibility effectively embodying inorganic filler excellent and reliability much higher formable layer body and manufacture method thereof and possess thermal diffusivity component, the electromagnetic wave shielding component of described multi-layer formed body.

Multi-layer formed body of the present invention comprises the adhesive resin/filler complex of the inorganic filler containing adhesive resin and 30 more than volume %, 95 below volume % and the adaptation be layered at least one interarea of described adhesive resin/filler complex strengthens resin bed.The thickness that described adaptation strengthens resin bed be more than 50nm, less than 9 μm, glass transition temperature is more than 120 DEG C, lower than 260 DEG C, be made up of as the polyimide compositions of principal component the polyimide resin of the aliphatic unit comprising carbon number more than 3 on main chain.

According to multi-layer formed body of the present invention, by using the polyimide resin with the aliphatic unit of carbon number more than 3, and by using glass transition temperature to be more than 120 DEG C, to strengthen resin bed lower than the resins of 260 DEG C as adaptation, excellent flexibility can be provided while realizing high-fire resistance.And, because adaptation strengthen the thickness of resin bed be more than 50nm, less than 9 μm, so the function of the inorganic filler of adhesive resin/filler complex effectively can be embodied, and have enhancement adaptation concurrently simultaneously.

In preferred a kind of form of multi-layer formed body of the present invention, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, the at least one party of described tetracarboxylic dianhydride and described diamines comprises benzophenone skeletal, and comprises amino in molecular end.

Preferred a kind of form of multi-layer formed body of the present invention comprises following polyimide resin, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, and described tetracarboxylic dianhydride is the aromatic diamine with benzophenone skeletal that aromatic tetracarboxylic acid's dianhydride with benzophenone skeletal of representing of following general formula (1) and/or the diamines that forms described polyimides comprise following general formula (2) and represent;

The total content with the aromatic diamine of benzophenone skeletal that aromatic tetracarboxylic acid's dianhydride of what described general formula (1) represented have benzophenone skeletal and described general formula (2) represent is more than 5 % by mole, less than 49 % by mole relative to the formation tetracarboxylic dianhydride of described polyimide resin and the summation of diamines, and amine equivalent is more than 4000, less than 20000.

In preferred a kind of form of multi-layer formed body of the present invention, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, the aliphatic unit of described carbon number more than 3 be included in described diamines at least partially in, its ratio is more than 5 % by mole of whole diamine unit.

In preferred a kind of form of multi-layer formed body of the present invention, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, comprises the biphenyl tetracarboxylic dianhydride of more than 40mol%, below 90mol% in whole tetracarboxylic dianhydride's unit.

In preferred a kind of form of multi-layer formed body of the present invention, described polyimide resin composition is following polyimide resin composition, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, and described diamines comprises the aliphatic diamine that following general formula (3) and/or (4) represent.

(in formula (3), R ¹be the aliphatic unit of described carbon number more than 3 that main chain can comprise atom N, O atom, the summation forming the atomicity of described main chain is 3 ~ 500; The aliphatic unit of described carbon number more than 3 can also have by the side chain of the above atomic building of any one in C, N, H, O, and the summation of the atomicity of every 1 described side chain is less than 10)

H ₂N-R ²-H ₂N(4)

(in formula (4), R ²be the aliphatic unit of carbon number more than 3 that main chain can comprise atom N, O atom, the summation forming the atomicity of described main chain is 3 ~ 500; Described aliphatic unit can also have the side chain by the above atomic building of any one in C, N, H, O, and the summation of the atomicity of every 1 described side chain is less than 10)

In preferred a kind of form of multi-layer formed body of the present invention, the R of described general formula (3) ¹or the R of described general formula (4) ²be the aliphatic unit with the main chain comprising alkylidene oxygen base or polyalkylene oxide base, the carbon number of alkylidene composition of the alkylene moiety of described alkylidene oxygen base and the alkyleneoxy unit that forms described polyalkylene oxide base is 1 ~ 10.

In preferred a kind of form of multi-layer formed body of the present invention, the aliphatic diamine that described general formula (3) represents is the compound that following general formula (5) represents, the aliphatic diamine that described general formula (4) represents is the compound that following general formula (6) represents.

(in formula (5), n represents the integer of 1 ~ 50)

(in formula (6), p, q and r separately represent the integer of 0 ~ 10; Wherein, p+q+r is more than 1)

In preferred a kind of form of multi-layer formed body of the present invention, aromatic tetracarboxylic acid's dianhydride of what described general formula (1) represented have benzophenone skeletal is selected from 3,3', 4,4'-benzophenone tetracarboxylic dianhydride and 2, more than one of 3', 3,4'-benzophenone tetracarboxylic dianhydride, the aromatic diamine with benzophenone skeletal that described general formula (2) represents is selected from 3, more than one of 3'-diaminobenzophenone, 3,4'-diaminobenzophenones and 4,4'-diaminobenzophenone.

In preferred a kind of form of multi-layer formed body of the present invention, be also formed with layer of adhesive material in the outmost surface of at least one interarea.

The manufacture method of multi-layer formed body of the present invention comprises following operation: formed be made up of as the polyimide compositions of principal component the polyimide resin of the aliphatic unit comprising carbon number more than 3 on main chain, thickness is more than 50nm, the adaptation of less than 9 μm strengthens resin bed, strengthens the duplexer of the adhesive resin/filler complex of inorganic filler resin bed formed containing adhesive resin and 30 more than volume %, 95 below volume % in described adaptation.The glass transition temperature that described adaptation strengthens resin bed is more than 120 DEG C, lower than 260 DEG C.

In preferred a kind of form of the manufacture method of multi-layer formed body of the present invention, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, the at least one party of described tetracarboxylic dianhydride and described diamines comprises benzophenone skeletal, and comprises amino in molecular end.

In preferred a kind of form of the manufacture method of multi-layer formed body of the present invention, described adaptation strengthens resin bed by the polyimide compositions dissolved in organic solvent coating, drying being obtained, and makes to reach more than 80% relative to the acid imide rate of polyimide precursor.

In preferred a kind of form of the manufacture method of multi-layer formed body of the present invention; manufactured by following operation: described adaptation is strengthened resin bed and is layered on demoulding base material; stacked described adhesive resin/filler complex, then strengthens resin bed by described demoulding base material from described adaptation and peels off.

Electromagnetic wave shielding component of the present invention possesses the multi-layer formed body of above-mentioned form.

Radiating component of the present invention possesses the multi-layer formed body of above-mentioned form.

The present invention has excellent effect as described below, that is: a kind of function, simultaneously flexibility effectively embodying inorganic filler can be provided excellent and reliability much higher formable layer body and manufacture method thereof and possess thermal diffusivity component, the electromagnetic wave shielding component of described multi-layer formed body.

Accompanying drawing explanation

Fig. 1 is the schematic sectional view of an example of the multi-layer formed body representing the first embodiment.

Fig. 2 A is the schematic sectional view of an example of the multi-layer formed body representing variation.

Fig. 2 B is the schematic sectional view of an example of the multi-layer formed body representing variation.

Fig. 2 C is the schematic sectional view of an example of the multi-layer formed body representing variation.

Fig. 3 A is the schematic sectional view of an example of the manufacture method of the multi-layer formed body representing the first embodiment.

Fig. 3 B is the schematic sectional view of an example of the manufacture method of the multi-layer formed body representing the first embodiment.

Fig. 4 is the schematic sectional view of an example of the multi-layer formed body representing the second embodiment.

Fig. 5 is the schematic sectional view of an example of the multi-layer formed body representing the 4th embodiment.

Detailed description of the invention

Below, to adopting an example of embodiments of the present invention to be described.It should be noted that, as long as technological thought according to the invention, other embodiments are obviously also contained in category of the present invention.In addition, be for convenience of explanation with the size of each component in figure below, ratio, with the size of reality, ratio may not be consistent.In addition, in this description, the record of " counting A ~ several B arbitrarily arbitrarily " is Index A and the scope larger than number A, and is index B and the scope less than number B.

[the first embodiment]

Figure 1 shows that the schematic sectional view of an example of the multi-layer formed body of the first embodiment.The duplexer that the multi-layer formed body 1 of Fig. 1 strengthens resin bed 11 and adhesive resin/filler complex 21 by adaptation is formed.An interarea of adaptation enhancing resin bed 11 is laminated with adhesive resin/filler complex 21.Adaptation strengthens the effect that resin bed 11 plays the supporting mass as adhesive resin/filler complex 21.Adhesive resin/filler complex 21 has thermal diffusivity function.

Multi-layer formed body 1 can be suitable as thermal diffusivity component.Thermal diffusivity component both can be multi-layer formed body 1 itself, also can be that multi-layer formed body 1 and other components are formed.Other components are such as metal platinum, base material etc.Base material can be made up of silicon, pottery, resin or metal etc.The example of metal comprises copper, aluminium, SUS, iron, magnesium, nickel and aluminium oxide etc.The example of resin comprises polyurethane resin, epoxy resin, acrylic resin, polyimide resin, PET resin, polyamide, polyamide-imide resin etc.

By being pasted or be fixed on the device that will dispel the heat by the thermal diffusivity component with multi-layer formed body 1, the heat produced by the device that will dispel the heat is made to distribute efficiently by multi-layer formed body 1.The device dispelled the heat is such as the Electric control power device that automobile controls.In addition, in this description, the said device that will dispel the heat comprises all with the electronic unit of the large scale integrated circuit (LSI) loaded in the light supply apparatus of the flat-panel monitors such as electronic circuit board component, semiconductor devices, lithium ion battery component, solar cell component, liquid crystal display, TFT substrate, mobile phone etc., heat generating component, the heat production machine for representative such as ligthing paraphernalia that use LED, fluorescent lamp etc.

The thermal diffusivity component with multi-layer formed body 1 can directly or by base material etc. be fixedly installed by arbitrary method and the device that will dispel the heat.Both layer of adhesive material can be set in thermal diffusivity member side, also layer of adhesive material can be set in the subject side be fixedly installed with thermal diffusivity component.In addition, also can not layer of adhesive material be set, fixing by physics mode pressing.In addition, also base material and adaptation enhancing resin bed can be engaged by thermo-compressed etc.As the example of base material, above-mentioned example can be exemplified.

Multi-layer formed body can also be laminated with layer of adhesive material.That is, can be the multi-layer formed body being laminated with layer of adhesive material in the outmost surface of at least one interarea.The joint of this layer of adhesive material can exemplify other layer, base materials etc. of device, base material or the formation thermal diffusivity component that will dispel the heat.The face arranging layer of adhesive material both can be that adaptation strengthens resin bed 11 side, and also can be adhesive resin/filler complex 21 side, also can be both.Namely, can be the multi-layer formed body 1a being provided with layer of adhesive material 31 as shown in Figure 2 A in the side, outermost top layer of adaptation enhancing resin bed 11, or be provided with the multi-layer formed body 1b of layer of adhesive material 31 as shown in Figure 2 B in the side, outermost top layer of adhesive resin/filler complex 21.In addition, also can be the multi-layer formed body 1c being provided with layer of adhesive material 31,32 as shown in Figure 2 C in the adaptation enhancing side, outermost top layer of resin bed 11 and the side, outermost top layer of adhesive resin/filler complex 21.In addition, layer of adhesive material also can be taked not to be arranged at the whole contact surface of the device that will dispel the heat etc. and multi-layer formed body 11 but be arranged at the form of a part.

Adaptation strengthens the glass transition temperature of resin bed 11 and is more than 120 DEG C, lower than 260 DEG C, is made up of the polyimide resin of the aliphatic unit on main chain with carbon number more than 3 as the polyimide compositions of principal component.Strengthen candidate's resin of resin bed 11 as adaptation, also can expect the resin etc. of epoxy, phenolic aldehyde system, acrylic acid series, polyamide-based, polyamidoimide system.But the resin comprising polyamide-based, the polyamidoimide system of amide groups can cause water absorption rate to raise because hydrophily is high, worry through time performance degradation.In addition, for epoxy, phenolic aldehyde system, acrylic resin, not talkative heat resistance is enough.In addition, although the aromatic polyimide excellent heat resistance obtained by aromatic diamine and aromatic tetracarboxylic acid, in rigidity, not talkative flexibility is high.The adaptation of the first embodiment strengthens the polyimide compositions of polyimide resin as principal component that resin bed 11 uses the aliphatic unit on main chain with carbon number more than 3, and glass transition temperature is more than 120 DEG C, lower than 260 DEG C, therefore can provides the layer of heat resistance flexibility excellence.

Adaptation strengthen the thickness of resin bed 11 be thick more than 50nm, less than 9 μm.By making the thickness of adaptation enhancing resin bed 11 be less than 9 μm, the function of the inorganic filler of adhesive resin/filler complex effectively can be embodied.That is, the heat sinking function of inorganic filler can effectively be embodied.In addition, be more than 50nm by the thickness making adaptation strengthen resin bed 11, the effect of supporting mass can be played, have good enhancement adaptation concurrently.The preferred scope that adaptation strengthens the thickness of resin bed 11 is 100nm ~ 9 μm, and preferred scope is 500nm ~ 8 μm further, and particularly preferred scope is 3 μm ~ 7 μm.

Below, the polyimide resin strengthening the principal component of the polyimide compositions of resin bed 11 as formation adaptation is described.Polyimide resin be make diamines and tetracarboxylic dianhydride's composition reaction and obtain as polyimide precursor polyamic acid, then reacted the product obtained by its polyimides by cyclodehydration.Polyimide resin is relative to the polyamic acid as polyimide precursor, and acid imide rate is preferably more than 80%.Be more preferably more than 85%.By by make acid imide rate be more than 80% polyimides be dissolved in that polyimide compositions coating that organic solvent obtains is dry to be obtained, even if thus when to strengthen resin bed 11 be film to adaptation, also effectively intensity can be improved.

In polyimide resin, preferably except the aliphatic unit of carbon number more than 3, also there is benzophenone skeletal, and the end of polyimide resin is amino.The summation of aromatic tetracarboxylic acid's dianhydride with benzophenone skeletal and the aromatic diamine with benzophenone skeletal is preferably 5 ~ 49 % by mole relative to the formation tetracarboxylic dianhydride of polyimides and the summation of diamines, is more preferably 9 ~ 30 % by mole.Be more than 5 % by mole by the summation of aromatic tetracarboxylic acid's dianhydride of making there is benzophenone skeletal and the aromatic diamine with benzophenone skeletal, the terminal amino group of the carbonyl and other molecules that derive from benzophenone skeletal comprised in a molecule can be made to form hydrogen bond fully.Or the carbonyl deriving from benzophenone skeletal that comprises in same a part and terminal amino group can be made to form hydrogen bond fully.Therefore, heat resistance can be improved further, maintain the elasticity under high temperature.It should be noted that, the aliphatic unit of carbon number more than 3 and benzophenone skeletal can be incorporated in a diamines or a tetracarboxylic dianhydride.

It should be noted that, in order to make the molecular end of polyimides for amino, as long as make the diamine component of reaction (b mole) more than tetracarboxylic dianhydride's composition (a mole).Specifically, the formation tetracarboxylic dianhydride (a mole) of polyimides and the mol ratio of diamines (b mole) are preferably more than a/b=0.8, are less than 1.0, are more preferably 0.95 ~ 0.999.By making a/b be less than 1.0, molecular end can be made to be amino.Or the carbonyl deriving from benzophenone skeletal that comprises in same a part and terminal amino group can be made to form hydrogen bond fully.Therefore, more effectively heat resistance can be obtained.

The introducing of benzophenone skeletal can be introduced into any one or both in diamines, tetracarboxylic dianhydride.Preferably comprise aromatic tetracarboxylic acid's dianhydride with benzophenone skeletal.As the preference of aromatic tetracarboxylic acid's dianhydride with benzophenone skeletal, following general formula (1) can be exemplified.

In addition, as the preference of aromatic diamine with benzophenone skeletal, following general formula (2) can be exemplified.

For above-mentioned reasons, aromatic tetracarboxylic acid's dianhydride with benzophenone skeletal that general formula (1) represents and the total content with the aromatic diamine of benzophenone skeletal that general formula (2) represents are preferably more than 5 % by mole, less than 49 % by mole relative to the formation tetracarboxylic dianhydride of polyimides and the summation of diamines.Be more preferably 9 ~ 30 % by mole.In addition, the polyimides that amine equivalent is more than 4000, less than 20000 is preferably comprised.By making amine equivalent in above-mentioned scope, the viscoelastic property under high temperature can be made more good.

As the preference with aromatic tetracarboxylic acid's dianhydride of benzophenone skeletal that general formula (1) represents, 3,3' can be exemplified, 4,4'-benzophenone tetracarboxylic dianhydride and 2,3', 3,4'-benzophenone tetracarboxylic dianhydride.They can be one or more combinations.

In addition, the aromatic diamine with benzophenone skeletal that general formula (2) represents can exemplify more than one that be selected from 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenones and 4,4'-diaminobenzophenone.They can be one or more combinations.

As the preferred diamines with benzophenone skeletal beyond above-mentioned general formula (2), the compound that the following general formulas (7) such as 3,4-diaminobenzophenone represent can be exemplified.In addition, compound that following general formula (8) represents can also be exemplified as preference.

The aliphatic unit of the carbon number more than 3 on the main chain comprised in polyimide resin is introduced in polyimide resin by using any one or this aliphatic unit of comprising in both in diamines, tetracarboxylic dianhydride.Here, the main chain that " the aliphatic unit of the carbon number more than 3 on main chain " refers to the skeleton forming polyimide resin comprises the aliphatic unit of carbon number more than 3.Aliphatic unit is any one in alicyclic compound, aliphatic chain.In the aliphatic unit of carbon number more than 3, atom N, O atom can be comprised in the optional position of aliphatic unit.In addition, the main chain of the aliphatic unit of carbon number more than 3 can be bonded with side chain.

Diamines tetracarboxylic dianhydride can be separately a kind of or make two or more combination.Such as can separately use one or more aromatic diamines, aliphatic diamine as diamines.In addition, also aromatic unit and aliphatic unit can be introduced in a kind of diamines.Tetracarboxylic dianhydride is also the same with diamines.

When the aliphatic unit of carbon number more than 3 is introduced into diamines, the diamines preferably relative to whole diamine unit with the aliphatic unit of carbon number more than 3 is more than 5 % by mole.By being more than 5 % by mole, more effectively can giving adaptation and strengthening resin bed with flexibility.In order to give higher flexibility, the diamines preferably with the aliphatic unit of carbon number more than 3 is more than 10 % by mole.The ratio with the diamines of the aliphatic unit of carbon number more than 3 can be 100 % by mole, but from the viewpoint making the heat resistance of polyimides keep good, is preferably less than 45 % by mole.

As the preference of diamines of aliphatic unit with carbon number more than 3, the aliphatic diamine that following general formula (3) and/or (4) represent can be exemplified.

In general formula (3), R ¹it is the aliphatic unit of carbon number more than 3 that main chain can comprise atom N, O atom.The summation forming the atomicity of main chain is preferably 3 ~ 500, is more preferably 7 ~ 300.It should be noted that, the R of general formula (3) ¹in main chain refer to by the chain of the atomic building in the aliphatic unit of 2 phenyl connecting molecular end, beyond the atom that forms side chain.Aliphatic unit can also have the side chain by the above atomic building of any one in C, N, H, O.R ¹in side chain refer to the 1 valency group be connected with the atom forming main chain.The summation of the atomicity of every 1 described side chain is preferably less than 10.The example of side chain not only comprises the alkyl such as methyl, also comprises hydrogen atom etc.

H ₂N-R ²-H ₂N(4)

In general formula (4), R ²it is the aliphatic unit of carbon number more than 3 that main chain can comprise atom N, O atom.The summation forming the atomicity of main chain is preferably 3 ~ 500, is more preferably 7 ~ 300.It should be noted that, the R of general formula (4) ²in main chain refer to by connecting in the amino aliphatic unit of 2 of molecular end, forming the chain of the atomic building beyond the atom of side chain.Aliphatic unit can also have the side chain by the above atomic building of any one in C, N, H, O.R ¹in side chain refer to the 1 valency group be connected with the atom forming main chain.The summation of the atomicity of every 1 described side chain is preferably less than 10.The example of side chain not only comprises the alkyl such as methyl, also comprises hydrogen atom etc.

As the R of general formula (3) of aliphatic unit with carbon number more than 3 ¹or the R of general formula (4) ²preference, comprise the main chain with the structure deriving from the polyalkylene polyamines such as diethylenetriamines, trien, tetren; Comprise the main chain of alkylidene; There is the main chain of PAG structure; There is the main chain of alkyl ether structure; There is the main chain of polyalkylene carbonate structure; Comprise the main chain etc. of alkylidene oxygen base or polyalkylene oxide base, preferably exemplify the main chain comprising alkylidene oxygen base or polyalkylene oxide base.

Polyalkylene oxide base refers to and comprises the divalent linking group of alkylidene oxygen base as repetitive, can exemplify "-(the CH using ethyleneoxy units as repetitive ₂cH ₂o) _u-", "-(CH using propyleneoxy units as repetitive ₂-CH(-CH ₃) O) _v-" (u and v is repeat number) etc.The repeat number of the alkyleneoxy unit in polyalkylene oxide base is preferably 2 ~ 50, is more preferably 2 ~ 20.Polyalkylene oxide base also can comprise multiple alkyleneoxy unit.

The carbon number of alkylene moiety of the alkylene moiety of alkylidene oxygen base and the alkyleneoxy unit that forms polyalkylene oxide base is preferably 1 ~ 10, is more preferably 2 ~ 10, and more preferably 4 ~ 10.From the viewpoint of flexibility, preferred butylidene.The example forming the alkylidene of alkylidene oxygen base comprises methylene, ethylidene, propylidene and butylidene etc.

R ¹or R ²main chain in, the group that alkylidene oxygen base or polyalkylene oxide base are connected with terminal amino group is not particularly limited, can be alkylidene, arlydene, alkylenecarbonyl oxygen base, arlydene ketonic oxygen base etc., from the reactive viewpoint improving terminal amino group, preferred alkylidene.

As the preferred example of aliphatic diamine, following general formula (9) can be exemplified.

In formula (9), R ³and R ⁴separately represent and comprise the organic group of at least a kind being selected from carbonyl, oxygen base carbonyl, the aromatic group of carbon number more than 6 and the aliphatic group of carbon number more than 1.X represents-O-,-S-,-NH-,-ONH-or-OS-.L in formula (9) represent 1 ~ 50 integer, preferably 1 ~ 20 integer.M represents the integer of more than 1, preferably represents 2 ~ 10, more preferably represents the integer of 4 ~ 10.From the viewpoint of flexibility, preferred butylidene.

R ³and R ⁴in the example comprising the organic group of the aliphatic group of carbon number more than 1 comprise the alkylidene etc. of the carbon numbers 1 ~ 10 such as methylene, ethylidene, propylidene, the example comprising the organic group of the aromatic group of carbon number more than 6 comprises phenylene etc.From the viewpoint obtaining heat resistance, preferably comprise the organic group of aromatic group, from the viewpoint obtaining flexibility flexibility, preferably comprise the organic group of aliphatic group.

As the preferred example of general formula (9), general formula (10) can be exemplified.The aliphatic diamine that general formula (10) represents is because comprise long-chain alkylidene oxygen base, so the polyimides of gained has high flexibility.

R ³and R ⁴, m, l be identical with general formula (9).

As the preferred example of the aliphatic diamine that general formula (10) represents, the diamines of general formula (5) or general formula (6) can be exemplified.

In general formula (5), n represent 1 ~ 50 integer, preferably 10 ~ 20 integer.Repetitive in general formula (5) both can be introduced with block fashion, also can randomly introduce.

In general formula (6), p, q and r separately represent the integer of 0 ~ 10.Wherein, p+q+r is more than 1.Each repetitive in general formula (6) both can be introduced with block fashion, also can randomly introduce.By the aliphatic diamine using general formula (6) to represent, adaptation can be given and strengthen resin bed 11 high flexibility.

As the preference of alicyclic diamine, comprise cyclobutane diamines, 1, 2-cyclohexane diamine, 1, 3-cyclohexane diamine, 1, 4-cyclohexane diamine, two (amino methyl) cyclohexane is (except 1, two (amino methyl) cyclohexanes beyond two (amino methyl) cyclohexane of 4-), diamino bicyclic heptane, bis aminomethyl norbornane (comprising the norbornane Diamines such as norbornane diamines), diaminourea oxygen base norbornane, diaminourea methoxyl group norbornane (comprising oxa-norbornane diamines), IPD, diaminourea tristane, bis aminomethyl tristane, two (aminocyclohexyl) methane (or di-2-ethylhexylphosphine oxide (cyclohexylamine)), two (aminocyclohexyl) isopropylidene etc.Wherein can exemplify norbornane diamines, 1,2-cyclohexane diamine, 1,3-cyclohexane diamine, Isosorbide-5-Nitrae-cyclohexane diamine.

As the preference of aliphatic tetracarboxylic dianhydride of aliphatic unit main chain with carbon number more than 3, following compound can be exemplified.Namely, cyclobutane tetracarboxylic dianhydride can be exemplified, 1, 2, 3, 4-pentamethylene tetracarboxylic dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic dianhydride, dicyclo [2.2.2]-Xin-7-alkene-2, 3, 5, 6-tetracarboxylic dianhydride, dicyclo [2.2.2] octane-2, 3, 5, 6-tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, dicyclo [2.2.1] heptane-2, 3, 5-tricarboxylic acids-6-acetic acid dianhydride, 1-methyl-3-ethyl-hexamethylene-1-alkene-3-(1, 2), 5, 6-tetracarboxylic dianhydride, 4-(2, 5-dioxotetrahydro furans-3-base)-tetrahydronaphthalene-1, 2-dicarboxylic acid dianhydride, 3, 3', 4, 4'-dicyclohexyl tetracarboxylic dianhydride etc.

Diamine component for obtaining polyimides obviously can comprise other diamines beyond said structure.As the example of other diamines, m-phenylene diamine (MPD) can be exemplified, o-phenylenediamine, p-phenylenediamine (PPD), between amino-benzylamine, p-benzylamine, two (3-aminophenyl) thioether, (3-aminophenyl) (4-aminophenyl) thioether, two (4-aminophenyl) thioether, two (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, two (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, two (4-aminophenyl) sulfone, 3,3'-MDA, 3,4'-MDA, 4,4'-MDA, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, two (3-(3-amino-benzene oxygen) phenoxy group of 1,3-) benzene, two (3-(4-amino-benzene oxygen) phenoxy group of 1,3-) benzene, two (4-(3-amino-benzene oxygen) phenoxy group of 1,3-) benzene, two (3-(3-amino-benzene oxygen) phenoxy group of 1,3-)-2-methylbenzene, two (3-(4-amino-benzene oxygen) phenoxy group of 1,3-)-4-methylbenzene, two (4-(3-amino-benzene oxygen) phenoxy group of 1,3-)-2-ethylo benzene, two (3-(2-amino-benzene oxygen) phenoxy group of 1,3-)-5-sec-butylbenzene, two (4-(3-amino-benzene oxygen) phenoxy group of 1,3-)-2,5-dimethyl benzenes, two (4-(2-amino-6-methylphenoxy) phenoxy group of 1,3-) benzene, two (2-(2-amino-6-ethyl phenoxy group) phenoxy group of 1,3-) benzene, two (2-(3-the amino-benzene oxygen)-4-methylphenoxy of 1,3-) benzene, two (2-(4-the amino-benzene oxygen)-4-tert-butyl group phenoxy group of 1,3-) benzene, Isosorbide-5-Nitrae-bis-(3-(3-amino-benzene oxygen) phenoxy group)-2,5-di-tert-butyls, Isosorbide-5-Nitrae-bis-(3-(4-amino-benzene oxygen) phenoxy group)-2,3-dimethyl benzenes, Isosorbide-5-Nitrae-bis-(3-(2-amino-3-propyl group phenoxy group) phenoxy group) benzene, two (3-(3-amino-benzene oxygen) phenoxy group of 1,2-)-4-methylbenzene, two (3-(4-amino-benzene oxygen) phenoxy group of 1,2-)-3-n-butylbenzene, two (3-(2-amino-3-propyl group phenoxy group) phenoxy group of 1,2-) benzene, two (the 4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene of 4,4'-, two (the 4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene of 3,4'-, two (the 4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene of 3,3'-, two [4-(3-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] methane, 1,1-pair [4-(3-amino-benzene oxygen) phenyl] ethane, 1,1-pair [4-(4-amino-benzene oxygen) phenyl] ethane, 1,2-pair [4-(3-amino-benzene oxygen) phenyl] ethane, 1,2-pair [4-(4-amino-benzene oxygen) phenyl] ethane, 2,2-pair [4-(3-amino-benzene oxygen) phenyl] propane, 2,2-pair [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-pair [4-(3-amino-benzene oxygen) phenyl] butane, 2,2-pair [3-(3-amino-benzene oxygen) phenyl]-1,1,1,3,3,3-HFC-236fa, 2,2-pair [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3,3-HFC-236fa, two (3-amino-benzene oxygen) biphenyl of 4,4'-, two (4-amino-benzene oxygen) biphenyl of 4,4'-, two (4-amino-benzene oxygen) biphenyl of 3,3'-, two [4-(3-amino-benzene oxygen) phenyl] ketone, two [4-(4-amino-benzene oxygen) phenyl] ketone, two [4-(3-amino-benzene oxygen) phenyl] thioether, two [4-(4-amino-benzene oxygen) phenyl] thioether, two [4-(3-amino-benzene oxygen) phenyl] sulfoxide, two [4-(amino-benzene oxygen) phenyl] sulfoxide, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-[4-(3-amino-benzene oxygen) benzoyl] benzene, 1,3-pair [4-(3-amino-benzene oxygen) benzoyl] benzene, 4,4'-pair [3-(4-amino-benzene oxygen) benzoyl] diphenyl ether, 4,4'-pair [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether, 4,4'-pair [4-(4-amino-alpha, alpha-dimethylbenzyl) phenoxy group] benzophenone, 4,4'-pair [4-(4-amino-alpha, alpha-dimethylbenzyl) phenoxy group] diphenyl sulphone (DPS), two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone, Isosorbide-5-Nitrae-bis-[4-(4-amino-benzene oxygen)-alpha, alpha-dimethylbenzyl] benzene, 1,3-pair [4-(4-amino-benzene oxygen)-alpha, alpha-dimethylbenzyl] benzene etc.Wherein can exemplify 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 2, 2-pair [4-(4-amino-benzene oxygen) phenyl] propane, two (3-aminophenyl) sulfone, two (4-aminophenyl) sulfone, 4, two (the 4-aminophenyl)-1 of 4'-, 4-diisopropyl benzene, 3, two (the 4-aminophenyl)-1 of 4'-, 4-diisopropyl benzene, 3, two (the 4-aminophenyl)-1 of 3'-, 4-diisopropyl benzene, 3, two (4-amino-benzene oxygen) biphenyl of 3'-, 2, two (trifluoromethyl)-1 of 2'-, 1'-biphenyl-4, 4'-diamines, 3, 3'-dimethylbenzidine, 3, 4'-dimethylbenzidine, 4, 4'-dimethylbenzidines etc. are as preference.

Form tetracarboxylic dianhydride that the tetracarboxylic dianhydride of polyimides can also comprise the aliphatic unit with carbon number more than 3, there is benzophenone skeletal aromatic tetracarboxylic acid's dianhydride beyond other tetracarboxylic dianhydrides.Other tetracarboxylic dianhydrides are not particularly limited.As the preference of aromatic tetracarboxylic acid's dianhydride, 3,3' as biphenyl tetracarboxylic dianhydride can be exemplified, 4,4'-biphenyl tetracarboxylic dianhydride, 1,1', 2,2'-biphenyl tetracarboxylic dianhydride, 2,2', 3,3'-biphenyl tetracarboxylic dianhydride, 2,3', 3,4'-biphenyl tetracarboxylic dianhydrides etc.Pyromellitic acid anhydride can be exemplified in addition, two (3,4-dicarboxyphenyi) ether dianhydride, two (3,4-dicarboxyphenyi) thioether dianhydride, two (3,4-dicarboxyphenyi) sulfone dianhydride, two (3,4-dicarboxyphenyi) methane dianhydride, two (3, the 4-dicarboxyphenyi) propane dianhydride of 2,2-, 2,2-two (3,4-dicarboxyphenyi)-1,1,1,3,3,3-hexafluoropropane dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydride of 1,3-, Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride of 4,4'-, two [(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, two (2, the 3-dicarboxyphenyi) propane dianhydride of 2,2-, 2,2-two (2,3-dicarboxyphenyi)-1,1,1,3,3,3-hexafluoropropane dianhydride, two (2,3-dicarboxyphenyi) ether dianhydride, two (2,3-dicarboxyphenyi) thioether dianhydride, two (2,3-dicarboxyphenyi) sulfone dianhydride, two (2, the 3-di carboxyl phenyloxy) benzene dianhydride of 1,3-, Isosorbide-5-Nitrae-bis-(2,3-di carboxyl phenyloxy) benzene dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 4,4'-isophthalic diformyl diphthalic anhydrides, diazonium diphenyl-methane-3,3', 4,4'-tetracarboxylic dianhydride, diazonium diphenyl-methane-2,2', 3,3'-tetracarboxylic dianhydride, 2,3,6,7-thioxanthones tetracarboxylic dianhydride, 2,3,6,7-anthraquinone tetracarboxylic dianhydride, 2,3,6,7-xanthone tetracarboxylic dianhydride, ethylidene tetracarboxylic dianhydride etc.

When tetracarboxylic dianhydride comprises the aromatic rings such as phenyl ring, part or all of the hydrogen atom on aromatic rings can be selected from fluorine-based, methyl, methoxyl group, trifluoromethyl and trifluoromethoxy etc. group replacement.In addition, when tetracarboxylic dianhydride comprises the aromatic rings such as phenyl ring, can have according to object the group becoming crosslinking points being selected from acetenyl, benzocyclobutene-4'-base, vinyl, pi-allyl, cyano group, NCO, nitrilo-and isopropenyl etc.They can be one or more combinations.

In order to obtain high-fire resistance when damaging flexibility not significantly, preferably add aromatic tetracarboxylic acid's dianhydride as other tetracarboxylic dianhydrides.As preference, 3,3' can be exemplified, 4,4'-biphenyl tetracarboxylic dianhydride, 2,3', 3,4'-biphenyl tetracarboxylic dianhydrides, 2,3', 2,3'-biphenyl tetracarboxylic dianhydrides etc.Wherein particularly preferably 3,3', 4,4'-biphenyl tetracarboxylic dianhydrides.From the viewpoint effectively obtaining high-fire resistance when damaging flexibility not significantly, in all acid dianhydride, preferably containing more than 40mol% below 90mol%, the biphenyl tetracarboxylic dianhydride being more preferably more than 55mol% below 85mol%.

As polyimide resin, by using the aliphatic unit that main chain comprises carbon number more than 3 and comprising the benzophenone skeletal that derives from aromatic tetracarboxylic acid's dianhydride or aromatic diamine and molecular end comprises amino, also comprises the polyimide resin of biphenyl tetracarboxylic dianhydride of more than 40mol%, below 90mol% in all acid dianhydride, except the flexibility of excellence, more effectively can also improve heat resistance.

Adaptation strengthen the glass transition temperature of resin bed 11 be more than 120 DEG C, lower than 260 DEG C.Preferred scope is 130 ~ 210 DEG C.By making adaptation strengthen the glass transition temperature of resin bed 11 lower than 260 DEG C, with the adaptation of other layers when can improve multiple stratification, or realize low elastic modulus due to the good molecular structure of introducing plasticization effect, and then contribute to the raising of flexibility.In addition, by making glass transition temperature be more than 120 DEG C, the heat resistance of polyimide resin can more effectively have been given play to.In addition, even if adaptation to be strengthened resin bed 11 filming, the intensity as supporting course can also be given full play of.

It should be noted that, in this description, the glass transition temperature of said adaptation enhancing resin bed 11 refers to the value recorded by the following method.That is, the sample film that the adaptation preparing thick 50 μm strengthens resin bed, is namely made up of polyimide resin layer.The viscoelastic temperature dispersion of solid of this sample film measures and uses the RSA-II of TAinstruments Inc. to carry out under the condition measuring frequency 1Hz with stretch mode, measures storage modulus E' and loss modulus E ".Then, according to the loss tangent tan δ=E of gained, " peak value of/E' derives the value of " glass transition temperature ".

Stretching viscoplasticity under (glass transition temperature+30 DEG C) of above-mentioned sample film is preferably 1.0 × 10 ⁵more than Pa, is more preferably 1.0 × 10 ⁶more than Pa.Stretching viscoplasticity is tried to achieve as the storage modulus E' under (glass transition temperature+30 DEG C) in the viscoelastic curve of solid obtained in the mensuration of above-mentioned glass transition temperature.

Percentage elongation at 23 DEG C of above-mentioned sample film is preferably more than 50%, is more preferably more than 80%.Such polyimide resin composition is suitable for the purposes of requirement flexibility (flexibility).The percentage elongation of film with by cutting into wide 10mm, the film be made up of polyimide resin composition of long 140mm alongst represents with (length of sample film during fracture) during the speed tensile of 50mm/ minute/(raw footage of sample film) with cupping machine (Tensilon) at 23 DEG C.

The number-average molecular weight of polyimide resin is preferably 6.0 × 10 ³~ 1.0 × 10 ⁶, be more preferably 8.0 × 10 ³~ 4.0 × 10 ⁴.The number-average molecular weight of polyimide resin can be passed through gel permeation chromatography (GPC) and measure.

As mentioned above, polyimide resin derives from the benzophenone skeletal of aromatic tetracarboxylic acid's dianhydride or aromatic diamine by comprising, and molecular end is amino, the terminal amino group of the carbonyl deriving from benzophenone skeletal comprised in a polyimide molecule thus and other polyimide molecules forms hydrogen bond, can obtain high-fire resistance.In addition, if polyimides also comprises the long-chain alkylidene oxygen base deriving from aliphatic diamine, then dissolubility is in a solvent high, and the polyimide film of gained has high flexibility, therefore preferably.

The polyimide resin composition of the first embodiment can contain various additive in the scope not exceeding technological thought of the present invention.Such as suitably can add ultra-violet absorber, preserving stabilizer, bonding auxiliary agent and surface modifier etc.In addition, also other resins can be contained in the scope not impacting, do not exceed technological thought of the present invention to heat resistance flexibility.

Adhesive resin/filler complex 21 is layers of the inorganic filler containing adhesive resin and 30 more than volume %.By making the content of inorganic filler be 30 more than volume %, thermal diffusivity can be kept better.As long as the content of inorganic filler forms formed body by the combination with adhesive resin, its upper limit does not limit, if usually consider mouldability, is then 95 below volume %.Preferred scope is 30 more than volume %, 70 below volume %, is particularly preferably 30 more than volume %, 65 below volume %.Inorganic filler can be one or more combinations.

As long as the adhesive resin of adhesive resin/filler complex 21 has heat resistance and energy dispersed inorganic filler, be not particularly limited, as preference, the epoxides such as polyurethane resin, epoxy resin, acrylic resin, polyimide resin, PET resin, polyamide, polyamide-imide resin, bisphenol A type epoxy compound, bisphenol F type epoxy compound can be exemplified; The acrylate compounds such as carboxy ethyl acrylate, methacrylatoethyl, ethoxylated acrylic phenyl ester and aliphatic epoxy acrylate; The isocyanate compounds such as '-diphenylmethane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate (HDI) and XDI (XDI); The maleimide compounds such as 4,4'-diphenyl methane dimaleimide, two-(3-ethyl-5-methyl-4-maleimidophenyl) methane, meta-phenylene bismaleimide and amino-benzene oxygen benzene-BMI (APB-BMI); And thiazolinyl replaces Na Dike imide compound, the polyimide resins etc. such as Na Dike acid imide (nadimide).Under giving the photosensitive situation of polyimide resin composition, can exemplify in polyimide resin composition containing light-cured resin, light curing agents etc. such as acrylate compounds.Adaptation strengthens the polyimide resin used in resin bed also can be used as adhesive resin.

As long as inorganic filler has thermal diffusivity, be not particularly limited, as preference, boron nitride, aluminium nitride, aluminium oxide, hydrated alumina, silica, silicon nitride, carborundum, diamond, hydroxyapatite, barium titanate, copper, aluminium, silica, magnesia, titanium oxide, silicon nitride, carborundum etc. can be used to have the material of thermal conductivity.Wherein, because thermal conductivity, electrical insulating property are excellent, stable chemical nature, therefore particularly preferably aluminium oxide, boron nitride etc.The average grain diameter of inorganic filler is not particularly limited, such as, be 0.5 ~ 100 μm.

Adhesive resin/filler complex 21 at random can add additive in the scope do not impacted physical property such as thermal diffusivity heat resistances.Such as can add the dispersant for improving the compatibility of inorganic filler in adhesive resin, or in order to improve the cementability that strengthens resin bed with stacked adaptation and add bonding auxiliary agent bonding agent etc.Such as the surface modifiers etc. such as silane coupler can be added.

Next, the manufacture method of the multi-layer formed body 1 of the first embodiment is described.First make diamines and tetracarboxylic dianhydride's reaction, obtain polyamic acid, then by polyamic acid cyclodehydration, obtain polyimides.When making end be amine, be 0.95 ~ 0.999 by making the total mole number of tetracarboxylic dianhydride relative to the total mole number of diamines and easily obtain.

Polyimide resin both can be atactic polymer, also can be block polymer, because easily obtain the characteristic of diamine component, so preferred block polymer.

Polyimide resin composition of the present invention both can be varnish shape, also can be sheet (also comprising membranaceous).When polyimide resin composition is varnish shape, polyimide resin composition can also contain polar solvent as required.The example of polar solvent is except N, dinethylformamide, N, N-dimethylacetylamide, N, N-DEF, N, N-diethyl acetamide, N, N-dimethyl methoxyl acetamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, METHYLPYRROLIDONE, dimethyl sulfone, 1,3, beyond 5-trimethylbenzene etc., also comprise their two or more mixed solvent or the mixed solvent etc. of these solvents and benzene,toluene,xylene, benzonitrile, diox, cyclohexane etc.

From the viewpoint etc. improving coating, the concentration of the resin solid state component in polyimide varnish is preferably 5 ~ 50 quality %, is more preferably 10 ~ 30 quality %.Make the polyimides of 23 quality % be scattered in NMP(N-methyl pyrrolidone) and the mixed solvent of trimethylbenzene and the polyimide varnish obtained be preferably 5.0 × 10 by the viscosity that E type viscosimeter records at 25 DEG C ²~ 1.0 × 10 ⁶mPas, is more preferably 1.0 × 10 ³~ 5.0 × 10 ⁴mPas.By this, the raising such as mechanical strength of gained polyimide film.

The amine equivalent of polyimide resin is preferably 4000 ~ 20000, is more preferably 4500 ~ 18000.The amine equivalent of polyimides is defined as " quantity of the amino comprised in number-average molecular weight/1 molecule of polyimides ".The amino comprised in 1 molecule obviously comprises terminal amino group, also comprises amino etc. in addition.The polyimides of amine equivalent in above-mentioned scope because the terminal amino group of polyimides entirety to there is ratio high, so when introducing benzophenone skeletal, can and benzophenone skeletal in the carbonyl that comprises generate a large amount of hydrogen bonds, more effectively can improve the heat resistance of polyimides.

Polyimide resin composition of the present invention is because comprise the polyimides dissolving in solvent, so can use with the form of polyimide varnish.Therefore, polyimide resin composition of the present invention can be coated after on base material, dry formation polyimide layer.As mentioned above, because do not need the step of the film of polyimide resin composition of the present invention at high temperature imidizate, so also formation polyimide layer can be coated with on the base material that heat resistance is low.

The demoulding base material (such as mold release film, release sheet) 41 implementing demoulding process is coated with polyimide resin composition of the present invention as shown in Figure 3A, and then dry, the adaptation obtaining being made up of polyimide resin composition strengthens the film of resin bed 11.Now, make adaptation strengthen the thickness of resin bed be more than 50nm, less than 9 μm.When coating and dry adaptation strengthen resin bed, the baking temperature of film is preferably less than 250 DEG C.Then, as shown in Figure 3 B, previously prepared good adhesive resin/filler composite compositions is coated adaptation and strengthen on resin bed 11, then dry, obtain adhesive resin/filler complex 21.Adaptation of the present invention strengthen resin bed 11 by and adhesive resin/filler complex 21 direct formation of film at surface and show excellent cementability, but and be not precluded within adhesive resin/filler complex 21 and adaptation and strengthen and be coated with easy bonding agent etc. between resin bed 11 and engaged.Then, the multi-layer formed body 1 shown in Fig. 1 is obtained by being peeled off by demoulding base material 41.

It should be noted that, the manufacture method of multi-layer formed body 1 is not limited to said method, can carry out various distortion in the scope not exceeding technological thought of the present invention.Such as, adhesive resin/filler complex 21 and adaptation can be strengthened resin bed 11 thermo-compressed and obtain multi-layer formed body.

According to the first embodiment, not form polyimides after coating polyamic acid, but change into polyimides before film.Therefore, have and do not need to carry out this good advantage of heating process for imidizate when stacked adaptation strengthens resin bed.Therefore, do not need high-temperature heating treatment, the more much higher formable layer body of reliability can be obtained.In addition, because do not use thermosetting resin, do not need this advantage of solidification process so have yet.In addition, because heat resistance can be realized when not using thermal cross-linking agent, so can maintaining heat plasticity.Therefore, also adaptation can be strengthened resin bed 11 cycling and reutilization.It should be noted that, although the present invention can realize heat resistance when not using thermal cross-linking agent, in the scope not exceeding technological thought of the present invention, not getting rid of use thermal cross-linking agent.

In addition, the main chain strengthening the polyimide resin of resin bed 11 by being used in adaptation is introduced carbon number be more than 3 aliphatic unit and glass transition temperature be more than 120 DEG C, lower than the adaptations enhancing resin beds of 260 DEG C, can high-fire resistance be realized, give excellent flexibility simultaneously.Consequently, the adaptation with adhesive resin/filler complex 21 can be improved.Therefore, can provide reliability much higher formable layer body.And, because make adaptation strengthen the thickness of resin bed be more than 50nm, less than 9 μm, so the function of the inorganic filler of adhesive resin/filler complex effectively can be embodied, and have enhancement adaptation concurrently simultaneously.

In addition, by strengthening in adaptation the method that on resin bed 11, both engage by coating adhesive resin/filler complex 21, there is the effect of manufacturing process's this excellence easy.

In addition, multi-layer forming physical efficiency is formed as sheet (also comprising membranaceous), so can cut into desired size, is pasted onto arbitrary position, and therefore operability is excellent.In addition, because can sheet be formed, so be particularly suitable for the purposes requiring compactization.And then, strengthening resin bed by arranging the high adaptation of flexibility, can resistance to impact be improved, guarantee reliability.And then, if adhesive resin/filler complex 21 is films, then can reduce the thickness of multi-layer formed body, also can be used as the thermal diffusivity component of flexible (flexible) component.

In addition, in polyimide resin of the present invention, if also comprise the benzophenone skeletal deriving from aromatic tetracarboxylic acid's dianhydride or aromatic diamine and molecular end comprises amino except the aliphatic unit of carbon number more than 3, then by making the terminal amino group of the carbonyl and other molecules that derive from benzophenone skeletal that comprise in a molecule form hydrogen bond fully, can more excellent heat resistance be realized, maintain the elastic modelling quantity under high temperature.And then, according to polyimide resin of the present invention, by comprising the biphenyl tetracarboxylic dianhydride of more than 40mol%, below 90mol% in all acid dianhydride forming polyimide resin, more effectively heat resistance can be improved when damaging flexibility not significantly.

[the second embodiment]

Then, an example of multi-layer formed body different from the embodiment described above is described.The multi-layer formed body of the second embodiment is except following aspect, and basic formation is identical with above-mentioned first embodiment.That is, different in following: in the multi-layer formed body of the first embodiment, adaptation strengthens resin bed and only has one deck, and in the multi-layer formed body of the second embodiment, adaptation strengthens resin bed to be had two-layer.

Figure 4 shows that the schematic sectional view of an example of the multi-layer formed body of the second embodiment.Multi-layer formed body 2 is the formations clamped by adhesive resin/filler complex 21 with adaptation enhancing resin bed 11,12.

According to multi-layer formed body 2, clamp, so the addition of inorganic filler more effectively can be increased because adhesive resin/filler complex 21 is strengthened resin bed 11,12 by adaptation.Consequently, the function of inorganic filler can more effectively be embodied.

According to the multi-layer formed body of the second embodiment, because use the adaptation identical with above-mentioned first embodiment to strengthen resin bed 11,12 and adhesive resin/filler complex 21, so the effect identical with above-mentioned first embodiment can be obtained.

[the 3rd embodiment]

The multi-layer formed body of the 3rd embodiment is except following aspect, and basic formation is identical with above-mentioned first embodiment.That is, different in following: the multi-layer formed body of the first embodiment is used for thermal diffusivity component, and the multi-layer formed body of the 3rd embodiment is used for electromagnetic wave shielding component.

The inorganic filler forming the adhesive resin/filler complex of the multi-layer formed body of the 3rd embodiment is the filler with electromagnetic wave shielding performance.As such example, the filler of metal, metal oxide, amorphous carbon powder, graphite, plating can be used.As metal, copper, aluminium, nickel, iron, gold, silver, platinum, tungsten, chromium, titanium, tin, lead, palladium etc. can be exemplified.They can combinationally use for one or more.In addition, soft magnetism filler also can be used as filler.As soft magnetism filler, such as magnetic stainless steel (Fe-Cr-Al-Si alloy), Sendust (Fe-Si-Al alloy), permalloy (Fe-Ni alloy/C), copper silicon (Fe-Cu-Si alloy), Fe-Si alloy, Fe-Si-B(-Cu-Nb can be exemplified) alloy, Fe-Ni-Cr-Si alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy etc.In addition, ferrite (ferrite), pure iron particles can also be used.As ferrite, soft ferrite or the hard ferrites as permanent magnet material such as such as Mn-Zn ferrite, Ni-Zn ferrite, Mn-Mg ferrite, Mn ferrite, Cu-Zn ferrite, Cu-Mg-Zn ferrite can be exemplified.

The multi-layer formed body of the 3rd embodiment can be particularly preferred for electromagnetic wave shielding component purposes.In addition, because use the adaptation identical with above-mentioned first embodiment to strengthen resin bed and adhesive resin/filler complex, so the effect identical with above-mentioned first embodiment can be obtained.

[the 4th embodiment]

The multi-layer formed body of the 4th embodiment is except following aspect, and basic formation is identical with above-mentioned first embodiment.That is, different in following: the multi-layer formed body of the first embodiment is used for thermal diffusivity component, and the multi-layer formed body of the 4th embodiment is suitable for the thermal diffusivity electromagnetic wave shielding component having electromagnetic wave shielding function and thermal diffusivity function concurrently.

Figure 5 shows that the schematic sectional view of the multi-layer formed body of the 4th embodiment.The multi-layer formed body 3 of the 4th embodiment possesses adaptation and strengthens resin bed 11, have the adhesive resin/filler complex 21 of thermal diffusivity and have the adhesive resin/filler complex 22 of electromagnetic wave shielding performance.

According to the multi-layer formed body of the 4th embodiment, by there is the adhesive resin/filler complex 21 of thermal diffusivity to give thermal diffusivity, to give electromagnetic wave shielding performance by the adhesive resin/filler complex 22 with electromagnetic wave shielding performance.Therefore, just thermal diffusivity and electromagnetic wave shielding performance can be had concurrently by a multi-layer formed body.Intensity can be improved by stacked adaptation enhancing resin bed between adhesive resin/filler complex 21,22.In addition, also adaptation can be strengthened resin bed as the second embodiment to be configured to clamp adhesive resin/filler complex 21,22.

The multi-layer formed body of the 4th embodiment can be particularly preferred for electromagnetic wave shielding component purposes.In addition, because use the adaptation identical with above-mentioned first embodiment to strengthen resin bed and adhesive resin/filler complex, so the effect identical with above-mentioned first embodiment can be obtained.

In addition, above-mentioned embodiment can appropriately combinedly use.In addition, in above-mentioned embodiment, having set forth example adhesive resin/filler complex being formed sheet, but be not limited to sheet, can be the formed body matched with purposes.In addition, multi-layer formed body is not flat shape, also can be curve form.And then, above set forth the example being applied to thermal diffusivity component and electromagnetic wave shielding performance component, but be not limited to this, suitably can be applied to various uses.

" embodiment "

The present invention will be described in more detail by the following examples, but the present invention is not limited in any way the following examples.

[embodiment 1]

(preparation of polyimide varnish)

At 1-METHYLPYRROLIDONE (being denoted as below " NMP ") and 1,3,3 kinds of diamines (APB, 14EL, XTJ-542) and 2 kinds of acid dianhydrides (s-BPDA, BTDA), with in the solvent of the proportions of 7:3, coordinate with the mol ratio of APB:14EL:XTJ-542:s-BPDA:BTDA=0.8:0.1:0.1:0.79:0.2 by 5-trimethylbenzene.

Two (3-amino-benzene oxygen) benzene (Mitsui Chemicals, Inc.'s system) of APB:1,3-

14EL: two (PABA ester) (ELASMER1000) (her the former chemical company system) of poly-BDO

XTJ-542: the polyetheramine (ProductName: JEFFAMINE, HUNTSMAN Inc.) that following formula (11) represents

S-BPDA:3,3', 4,4'-biphenyl tetracarboxylic dianhydride (JFEChemical Inc.)

BTDA:3,3', 4,4'-benzophenone tetracarboxylic dianhydride

The mixture of gained is stirred more than 4 hours in the flask that can import drying nitrogen, obtains the polyamic acid solution that resin solid state component weight is 20 ~ 25 quality %.After the polyamic acid solution of gained is fully stirred, while stir in the flask being accompanied with Dean-Rodney Stark (dean-stark) pipe, while reaction system is heated to about 180 DEG C, the water produced by dehydration is taken out to outside system, obtains polyimide varnish A.

(manufacture of adhesive resin/filler complex)

As adhesive resin, host uses EPIFORM(registration mark) R-2100(SOMAR Inc.), curing agent uses EPIFORM(registration mark) H30(SOMAR Inc.).The alumina packing DAW07(DENKA Inc. being equivalent to 48 volume % relative to resin is coordinated respectively in host, curing agent) as filler, stir about 20 minutes with rotation-revolution formula mixer " de-bubble refining Taro AR-250 " (THINKY Inc.).After cooling, host and the mixture of filler and the mixture of curing agent and filler are coordinated according to the ratio of R2100:H-30=5:1, stir about 1 minute with de-bubble refining Taro, thus aqueous mixture before making the solidification of adhesive resin/filler complex.

(manufacture of multi-layer formed body)

Above-mentioned polyimide varnish is coated with the speed of 10mm/sec in the PET film implementing demoulding process.Coating process is not particularly limited, such as, roll coater, mould can be used to be coated with machine, bar coater, lip coater, comma coating machine etc.By the film of gained at 180 DEG C dry 10 minutes, except desolventizing, obtain polyimide layer (thickness=about 5 μm).Then, aqueous mixture before the solidification of the adhesive resin/filler complex obtained by said method is coated with dry at polyimide film surface.The film of gained was heating and curing with 80 DEG C × 1 hour, forms about 50 μm of thick adhesive resin/filler complexs.Then, PET film is peeled off from above-mentioned polyimide layer, obtain the multi-layer formed body of sheet.

(glass transition temperature)

The polyimide varnish of gained is coated after in the PET film of demoulding process with the speed of 10mm/ second, at 200 DEG C dry 10 minutes, except desolventizing.The film tweezers obtained after drying are peeled off from PET film, obtains the polyimide film of thickness 50 μm.Use the RSA-II of TAinstruments Inc. under the condition measuring frequency 1Hz, to carry out the viscoelastic temperature dispersion of solid with stretch mode to measure, thus measure storage modulus E' and the loss modulus E of the polyimide film made ".Then, according to loss tangent tan δ=E, " peak value of/E' derives glass transition temperature.

(Evaluation of Heat Tolerance)

Evaluate the heat resistance of the sheet form multilaminate formed body (sample) made.Subject sample is cut into the oblong-shaped of wide 10mm × long 100mm, as sample film.Being swum in by this sample film is heated on the scolding tin bath of set point of temperature, the heat resistance of assess sample film.The results are shown in table 1A.

After ◎: 280 DEG C, 30 seconds, also non-melting, maintains shape, and sample film can be mentioned

After zero: 260 DEG C, 60 seconds, also non-melting, maintains shape

×: melting within 260 DEG C, 60 seconds

(folding resistance evaluation)

As the index of the flexibility (flexibility) of assess sample, carry out folding resistance evaluation.Subject sample is cut into the oblong-shaped of wide 10mm × long 50mm, as sample film.The side of sample film is fixed on the fixture of Flexing Apparatus, the kink across R=3mm hangs the weight of 100g in the opposition side of sample, the folding resistance of assess sample.Acquired results is shown in table 1A, table 1B.

Zero: the sample with the folding resistance of more than 100 times

×: the sample just ruptured less than 100 times

(thermal diffusivity evaluation)

Evaluate the thermal conductivity factor of the sample made.Specifically, these measured values are substituted into following mathematical expression 1 and calculate by " the thermal diffusivity α ", " specific heat Cp " and " density p " of working sample.

(mathematical expression 1) thermal conductivity factor λ=thermal diffusivity α × specific heat Cp × density p

Thermal diffusivity passes through Measurement By Laser Flash.Determinator is laser flash method thermal constant determinator (TC-9000, ULVAC-RIKO Inc.).Specific heat is measured by DSC method.Determinator is DiamondDSC device (PerkinElmer Inc.).Use electronic balance gravimetry, area and thickness of sample calculate volume per sample, calculate density.

The thermal conductivity factor of zero: more than 1.0W/mK

×: the thermal conductivity factor being less than 1.0W/mK

(acid imide rate)

Acid imide rate is obtained by IR method.Specifically, with 1480 ~ 1500cm ^-1the neighbouring peak based on phenyl ring is benchmark, and its absorbance is set to A, by 1720cm ^-1the absorbance at the neighbouring peak based on imide ring is set to B.Subject sample was burnt till with 250 DEG C × 1 hour, using the B/A of film that makes as standard value C(acid imide rate 100%).On the other hand, subject sample was burnt till with 150 DEG C × 30 minutes, by the B/A of film that makes divided by standard value C, be multiplied by 100, using income value as acid imide rate (%).

(embodiment 2)

Except making the use level of the filler DAW07 of adhesive resin/filler complex be except 65 volume %, manufacturing multi-layer formed body by method similarly to Example 1, evaluating.

(embodiment 3)

Except make as adaptation strengthen resin bed polyimide layer drying after thickness be except 3 μm, manufacture multi-layer formed body similarly to Example 1, evaluate.

(embodiment 4)

Except make as adaptation strengthen resin bed polyimide layer drying after thickness be except 7 μm, manufacture multi-layer formed body similarly to Example 1, evaluate.

(embodiment 5)

Except using boron nitride filler UHP-1(Showa electrician Inc.) as adhesive resin/filler complex filler and use level is except 31 volume %, manufacture multi-layer formed body similarly to Example 1, evaluate.

(embodiment 6)

Except using boron nitride filler UHP-1(Showa electrician Inc.) as adhesive resin/filler complex filler and use level is except 40 volume %, manufacture multi-layer formed body similarly to Example 1, evaluate.

(embodiment 7)

Except following aspect, manufacture multi-layer formed body similarly to Example 1, evaluate.Namely, when manufacturing polyimide varnish, use pBAPP, 14EL these two kinds as diamines, use s-BPDA, BTDA these two kinds as acid dianhydride, coordinate with the mol ratio of pBAPP:14EL:s-BPDA:BTDA=0.8:0.2:0.79:0.2, thus obtain polyimide varnish B, be modulated into polyimide varnish similarly to Example 1 in addition.In addition, except using boron nitride filler UHP-1(Showa electrician Inc.) as adhesive resin/filler complex filler and use level is except 31 volume %, manufacture adhesive resin/filler complex similarly to Example 1.

Two (4-(4-amino-benzene oxygen) phenyl of pBAPP:2,2-) propane (Wakayama refine Inc.)

(embodiment 8)

When manufacturing polyimide varnish, use APB, 14EL, XTJ-542 these three kinds as diamines, use s-BPDA as acid dianhydride, coordinate with the mol ratio of APB:14EL:XTJ-542:s-BPDA=0.8:0.1:0.1:0.99, thus obtain polyimide varnish C, be modulated into polyimide varnish similarly to Example 1 in addition, evaluate.

(embodiment 9)

When manufacturing polyimide varnish, use APB, 14EL these two kinds as diamines, use s-BPDA and BTDA these two kinds as acid dianhydride, coordinate with the mol ratio of APB:14EL:s-BPDA:BTDA=0.7:0.3:0.79:0.2, thus obtain polyimide varnish F, be modulated into polyimide varnish similarly to Example 1 in addition, evaluate.

(embodiment 10)

When manufacturing polyimide varnish, use pBAPP, 14EL these two kinds as diamines, use s-BPDA and BTDA these two kinds as acid dianhydride, coordinate with the mol ratio of pBAPP:14EL:s-BPDA:BTDA=0.9:0.1:0.69:0.3, thus obtain polyimide varnish G, be modulated into polyimide varnish similarly to Example 1 in addition, evaluate.

(comparative example 1)

Except do not formed as adaptation strengthen resin bed polyimide layer but directly adhesive resin/filler complex is formed in except in the PET film of demoulding process, by the method perparation of specimen similarly to Example 1, evaluate.That is, manufacture and do not form adaptation and strengthen the independent sample of the adhesive resin/filler complex of resin bed, evaluate.

(comparative example 2)

Be that 10 volume % are used as, except the filler of adhesive resin/filler complex, by the method perparation of specimen same with comparative example 1, evaluating except making the use level of filler DAW07.

(comparative example 3)

Except make the use level of filler DAW07 be 65 volume % be used as the filler of adhesive resin/filler complex and manufacture multi-layer formed body time, as adaptation strengthen resin bed polyimide layer drying after thickness be except 15 μm, manufacture multi-layer formed body similarly to Example 1, evaluate.

(comparative example 4)

When manufacturing adhesive resin/filler complex, use boron nitride filler UHP-1(Showa electrician Inc.) as filler, and make use level be 40 volume %, make as adaptation strengthen resin bed polyimide layer drying after thickness be 15 μm, manufacture multi-layer formed body similarly to Example 1 in addition, evaluate.

(comparative example 5)

When manufacturing adhesive resin/filler complex, use 14EL as diamines, use s-BPDA as acid dianhydride, coordinate with the mol ratio of 14EL:s-BPDA=1.0:0.99, the polyimide varnish D of gained is used as adhesive resin, make mixture, and do not form the polyimide layer strengthening resin bed as adaptation, but directly said mixture is coated in the PET film of demoulding process, dry and obtain at 130 DEG C, manufacture multi-layer formed body similarly to Example 1 in addition, evaluate.

(comparative example 6)

When manufacturing polyimide varnish, use APB, pBAPP these two kinds as diamines, use s-BPDA as acid dianhydride, coordinate with the mol ratio of APB:pBAPP:s-BPDA=0.5:0.5:0.98, thus obtain polyimide varnish E, be modulated into polyimide varnish similarly to Example 1 in addition, evaluate.

The result of embodiment 1 ~ 10 is shown in table 1A, and the result of comparative example 1 ~ 6 is shown in table 1B.In addition, measure the acid imide rate of each embodiment, results verification is more than 80%.In addition, confirm that dried film is identical in fact with the acid imide rate of the polyimide varnish before coating.

From table 1A, comprise the polyimide resin of aliphatic unit main chain comprising carbon number more than 3, to strengthen the thickness of resin bed be less than 9 μm to adaptation, the inorganic filler content of adhesive resin/filler complex is that in the embodiment of 30 more than volume %, heat resistance thermal diffusivity is all good.In addition we know, in embodiment, folding resistance is all excellent.On the other hand, from table 1B, do not arrange adaptation and strengthen in the comparative example 1,2 of resin bed, folding resistance is bad.In addition, from the result of comparative example 3,4, even if comprise the polyimide resin of aliphatic unit main chain comprising carbon number more than 3, the thickness strengthening resin bed in adaptation is in the example of 15 μm, poor radiation.In addition, if although adaptation strengthens the thickness of resin bed as comparative example 6 is the polyimide resin less than 9 μm use main chains not comprising the aliphatic unit of carbon number more than 3, then obtain the result that folding resistance is bad.The known polyimides by being used in aliphatic unit main chain being introduced carbon number more than 3, can embody folding resistance effectively.

Utilizability in industry

Multi-layer forming physical efficiency of the present invention realizes the high performance brought by the height fillingization of inorganic filler, and realizes high reliability simultaneously, therefore by selecting the material of thermal diffusivity excellence as inorganic filler, can be used as thermal diffusivity component.In addition, by selecting the material of excellent electromagnetic wave shielding performance as inorganic filler, electromagnetic wave shielding component can be used as.In addition, by selecting electroconductive stuffing, also electroconductive member can be used as.As concrete object, the electronic units such as the large scale integrated circuit (LSI) loaded in flat-panel monitor, the mobile phones such as electronic circuit board component, semiconductor devices, lithium ion battery component, solar cell component, liquid crystal display can be used as, use the thermal diffusivity component, electromagnetic wave shielding component etc. of the ligthing paraphernalia of LED, fluorescent lamp etc. etc.The adaptation used in multi-layer formed body of the present invention strengthens resin bed because heat resistance flexibility is excellent, requires flexible purposes etc. so also can easily be applied to.In addition, also can be used as protection component, the inorganic filler of use insulating properties etc. and be used as insulating component etc.

This application claims the priority based on the Japanese publication Patent 2011-283611 filed an application on December 26th, 2011, here cite its whole disclosure.

Symbol description

1,2,3 multi-layer formed bodies

11,12 adaptations strengthen resin bed

21 adhesive resins/filler complex

31,32 layer of adhesive material

41 demoulding base materials

Claims (9)

1. an electromagnetic wave shielding component, it possesses multi-layer formed body, and described multi-layer formed body comprises:

Adhesive resin/filler the complex of the inorganic filler containing adhesive resin and 30 more than volume %, 95 below volume %, and

The adaptation be layered at least one interarea of described adhesive resin/filler complex strengthens resin bed;

Described adaptation strengthens resin bed and is made up of polyimide compositions, thickness be more than 50nm, less than 9 μm, glass transition temperature is more than 120 DEG C, lower than 260 DEG C, described polyimide compositions comprises the polyimide resin of the aliphatic unit of carbon number more than 3 as principal component on main chain

Described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, and at least one party of described tetracarboxylic dianhydride and described diamines comprises benzophenone skeletal, and comprises amino in molecular end,

Forming tetracarboxylic dianhydride a mole of described polyimides with the mol ratio a/b of described diamines b mole is 0.95 ~ 0.999.

2. electromagnetic wave shielding component as claimed in claim 1, is characterized in that, comprise following polyimide resin,

Described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, and described tetracarboxylic dianhydride is the aromatic diamine with benzophenone skeletal that aromatic tetracarboxylic acid's dianhydride with benzophenone skeletal of representing of following general formula (1) and/or the diamines that forms described polyimides comprise following general formula (2) and represent;

The total content with the aromatic diamine of benzophenone skeletal that aromatic tetracarboxylic acid's dianhydride of what described general formula (1) represented have benzophenone skeletal and described general formula (2) represent is more than 5 % by mole, less than 49 % by mole relative to the formation tetracarboxylic dianhydride of described polyimide resin and the summation of diamines, and amine equivalent is more than 4000, less than 20000

3. electromagnetic wave shielding component as claimed in claim 1, it is characterized in that, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, the aliphatic unit of described carbon number more than 3 be included in described diamines at least partially in, its ratio is more than 5 % by mole of whole diamine unit.

4. electromagnetic wave shielding component as claimed in claim 1, it is characterized in that, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, comprises the biphenyl tetracarboxylic dianhydride of more than 40mol%, below 90mol% in whole tetracarboxylic dianhydride's unit.

5. electromagnetic wave shielding component as claimed in claim 1, it is characterized in that, described polyimide resin composition is following polyimide resin composition, described polyimide resin is the polyimides of the polycondensation unit comprising tetracarboxylic dianhydride and diamines, and described diamines comprises the aliphatic diamine that following general formula (3) and/or (4) represent;

In formula (3), R ¹be the aliphatic unit of described carbon number more than 3 that main chain can comprise atom N, O atom, the summation forming the atomicity of described main chain is 3 ~ 500; The aliphatic unit of described carbon number more than 3 can also have by the side chain of the above atomic building of any one in C, N, H, O, and the summation of the atomicity of every 1 described side chain is less than 10;

H ₂N-R ²-H ₂N(4)

In formula (4), R ²be the aliphatic unit of carbon number more than 3 that main chain can comprise atom N, O atom, the summation forming the atomicity of described main chain is 3 ~ 500; Described aliphatic unit can also have the side chain by the above atomic building of any one in C, N, H, O, and the summation of the atomicity of every 1 described side chain is less than 10.

6. electromagnetic wave shielding component as claimed in claim 5, is characterized in that, the R of described general formula (3) ¹or the R of described general formula (4) ²be the aliphatic unit with the main chain comprising alkylidene oxygen base or polyalkylene oxide base, the carbon number of alkylidene composition of the alkylene moiety of described alkylidene oxygen base and the alkyleneoxy unit that forms described polyalkylene oxide base is 1 ~ 10.

7. electromagnetic wave shielding component as claimed in claim 5, it is characterized in that, the aliphatic diamine that described general formula (3) represents is the compound that following general formula (5) represents, the aliphatic diamine that described general formula (4) represents is the compound that following general formula (6) represents;

In formula (5), n represents the integer of 1 ~ 50;

In formula (6), p, q and r separately represent the integer of 0 ~ 10; Wherein, p+q+r is more than 1.

8. electromagnetic wave shielding component as claimed in claim 2, it is characterized in that, aromatic tetracarboxylic acid's dianhydride of what described general formula (1) represented have benzophenone skeletal is selected from 3,3', 4,4'-benzophenone tetracarboxylic dianhydride and 2,3', 3, more than one of 4'-benzophenone tetracarboxylic dianhydride, the aromatic diamine with benzophenone skeletal that described general formula (2) represents is selected from 3,3'-diaminobenzophenone, 3, more than one of 4'-diaminobenzophenone and 4,4'-diaminobenzophenone.

9. electromagnetic wave shielding component as claimed in claim 1, is characterized in that, be also formed with layer of adhesive material in the outmost surface of at least one interarea.