CN106997148A - Layered product - Google Patents

Abstract

The present invention provides a kind of layered product.[problem], which is provided, can take into account the layered product that erosion resistant possesses photosensitive polymer combination for the photosensitive polymer combination of the poor short circuit inhibition after the tracing ability and etch process of substrate and on basilar memebrane.[solution] layered product possesses the photosensitive layer of basilar memebrane and the photosensitive resin composition being arranged on basilar memebrane, photosensitive polymer combination includes (A) alkali solubility macromolecule, the compound containing ethylenic unsaturated bond and (C) Photoepolymerizationinitiater initiater, aforementioned substrates film can be peeled off from photosensitive layer, and photosensitive polymer combination meets the relation shown in following mathematical expressions (1)：W_X‑D_X≤5μm(1).In formula, W_XAnd D_XShown in being defined in the description }.

Description

Layered product

Technical field

The present invention relates to layered product etc..

Background technology

In the past, printed circuit board (PCB) was generally manufactured with photoetching process.In photoetching process, first, for being laminated to copper clad laminate, soft Property the substrate such as substrate on photo-sensitive resin carry out pattern exposure.It is (negative that the exposure portion of photo-sensitive resin carries out polymerizing curable During type) or relative to developer solution be solubilized (during eurymeric).Then, remove unexposed portion's (during minus) with developer solution or expose Light portion (during eurymeric), forms corrosion-resisting pattern on substrate.And then, implement etching or plating processing and formed after conductive pattern, will Solidify corrosion-resisting pattern (hereinafter also referred to " corrosion-resisting pattern ") and removal is peeled off from substrate.By via these processes, on substrate Form conductive pattern.

In photoetching process, usually using any one of following methods：By the solution coating of photosensitive polymer combination in base Plate and the method for drying it；Or, by dry film against corrosion, (photo-sensitive resin formed by photosensitive polymer combination is laminated to Photosensitive-resin layered product obtained from supporting mass) photo-sensitive resin be layered in method on substrate.Especially, in print In the manufacture of printed circuit board, the latter is commonly used.

In recent years, with the miniaturization and lightweight of e-machine, the miniaturization and densification of printed circuit board (PCB) are promoted, For the manufacture method of printed circuit board (PCB), seek to assign functional high-performance such as high-resolution dry film against corrosion.For Realize the high-resolution of the printed circuit board (PCB) formed using dry film against corrosion, it is proposed that such as sense comprising benzotriazole derivatives Photosensitive resin composition (patent document 1).

In photoetching process using dry film against corrosion, also using having various shapes (such as plane, bumps, on-plane surface, groove, pre- Line width/spacing being initially formed etc.) substrate.The lamination that substrate and dry film against corrosion on the profile beyond with plane are formed Body, in order to suppress that undesirable air or chemical substance are remained between substrate and dry film against corrosion, it is also proposed that following methods： When being laminated dry film against corrosion on substrate, liquid is applied between substrate and dry film against corrosion, substrate and dry film against corrosion are filled with liquid The method (so-called " wet type laminating technology ") (patent document 2) in gap.

Prior art literature

Patent document

Patent document 1：International Publication No. 2006/016658

Patent document 2：Japanese Unexamined Patent Publication 2009-147295 publications

The content of the invention

Problems to be solved by the invention

In patent document 1, from ensure photo-sensitive resin for the adaptation of substrate copper face and suppress copper face discoloration sight Point sets out, and makes to include the benzotriazole derivatives with specific structure in photosensitive polymer combination.However, the institute of patent document 1 It is not yet abundant for the application in wet type laminating technology in the photo-sensitive resin formed by photosensitive polymer combination stated Research, be deteriorated the leeway for still having improvement with the poor short circuit after etch process for the resolution ratio after wet type laminating technology.

Patent document 2 proposes the lamination liquid comprising water and modification to the surface energy agent, also, lamination liquid attempts landfill together layer The gap of the substrate of pressure and dry film against corrosion.Wet type laminating technology as described in patent document 2, by suppress substrate with it is against corrosion Undesirable air is remained between dry film to improve the tracing ability of dry film against corrosion, but presence is helpless to final circuit board resolution ratio The problem of this essence.And then, the wet type laminating technology described in patent document 2 is directed to the resolution ratio after wet type laminating technology and become Difference with and subsequent etch process after poor short circuit still have the leeway of improvement.

Therefore, the problem to be solved in the present invention be there is provided can take into account erosion resistant for the tracing ability of substrate and The photosensitive polymer combination of poor short circuit inhibition after etch process and possesses photosensitive resin composition on basilar memebrane The layered product of thing.

The solution used to solve the problem

The inventors discovered that：Above-mentioned problem is can solve the problem that by following technological means.

[1] a kind of layered product, it is characterised in that it, which possesses basilar memebrane and is arranged on aforementioned substrates film, includes sense The photo-sensitive resin of photosensitive resin composition,

Photosensitive resin combination comprising (A) alkali solubility macromolecule, the compound of (B) containing ethylenic unsaturated bond, with And (C) Photoepolymerizationinitiater initiater,

Aforementioned substrates film can be peeled off from foregoing photo-sensitive resin, and

Photosensitive resin combination meets the relation shown in following mathematical expressions (1)：

W_X-D_X≤5μm (1)

In formula, W_XRefer to：Photosensitive resin bed is laminated in the presence of liquid with 100 μm wide and 5 μm of depths Groove substrate on, then by corrosion-resisting pattern obtained from exposed and developed, with relative to line width against corrosion 200 μm wide Resolution ratio (μm) as defined in the form of minimum spacing width, and

D_XRefer to：Photosensitive resin bed is laminated on aforesaid base plate under in the absence of liquid, then passes through exposure In corrosion-resisting pattern obtained from development, as defined in the form of the minimum spacing width of the line width against corrosion wide relative to 200 μm Resolution ratio (μm) }.

[2] layered product according to [1], wherein, photosensitive resin combination hinders comprising (D) additive and (E) Poly- agent,

Foregoing (D) additive includes the benzotriazole cpd containing amino without carboxyl,

Foregoing (E) polymerization inhibitor includes epoxide.

[3] layered product according to [1] or [2], wherein, it is used as the foregoing compound of (B) containing ethylenic unsaturated bond, bag Polyaddition monomer containing the oxyalkylene unit in the molecule with more than 20 moles.

[4] layered product according to any one of [1]~[3], wherein, as foregoing (B) containing ethylenic unsaturated bond Compound, comprising oxyalkylene modified bisphenol A type two (methyl) acrylate compounds shown in following logical formula (II)s,

In formula, R₃And R₄Hydrogen atom or methyl are represented independently of one another, and A is C₂H₄, B is C₃H₆, n₁、n₂、n₃And n₄It is full Sufficient n₁+n₂+n₃+n₄The integer of=2~50 relation, the arrangement of-(A-O)-and-(B-O)-repeat unit be optionally it is random or Block, in the case of block ,-(A-O)-is with-(B-O)-optionally in xenyl side }.

[5] layered product according to any one of [1]~[4], wherein, the foregoing chemical combination of (B) containing ethylenic unsaturated bond Thing, which is included, to be selected from as three (methyl) acrylate compounds shown in following logical formula (III)s, the amino shown in following logical formula (IV)s The group of phthalate compound composition shown in (methyl) acrylate compounds of formic acid esters two and following logical formula (VI)s In it is at least one kind of,

In formula, R₅、R₆And R₇Hydrogen atom or methyl are represented independently of one another；X represents the alkylidene of carbon number 2~6；m₂、m₃With m₄It is each independently 0~40 integer, m₂+m₃+m₄For 1~40, also, m₂+m₃+m₄For more than 2 when, multiple X are mutually the same Or different

In formula, R₈And R₉Hydrogen atom or methyl are represented independently of one another；Y represents the alkylidene of carbon number 2~6；Z represents divalent Organic group；S and t are each independently 0~40 integer, and s+t >=1 }

{ in formula, A represents C₂H₄；R₆₁Represent hydrogen atom or methyl；R₆₂Represent hydrogen atom, methyl or halogenated methyl；R₆₃Represent Alkyl, halogen atom or the hydroxyl of carbon number 1~6；A is 1~4 integer；K is 0~4 integer, also, k is more than 2 integer When, multiple R₆₃It is identical or different }.

[6] layered product according to any one of [1]~[5], wherein, foregoing (C) Photoepolymerizationinitiater initiater includes N- virtues Base amino acid or its ester compounds.

[7] layered product according to [6], wherein, foregoing (C) Photoepolymerizationinitiater initiater includes N-phenylglycine or its ester Compound.

[8] layered product according to any one of [1]~[7], wherein, foregoing (A) alkali solubility macromolecule is included with structure Styrol structural units more than 40 mass % is calculated as on the basis of into the gross mass of the high molecular monomer of foregoing (A) alkali solubility.

[9] layered product according to any one of [1]~[8], it is used for direct imaging exposure.

[10] a kind of forming method of corrosion-resisting pattern, it includes：

The photosensitive resin combination of layered product any one of [1]~[9] is laminated to the layer of supporting mass Press process；The exposure process being exposed to the photosensitive polymer combination；And

The developing procedure that the exposed photosensitive polymer combination is developed.

[11] a kind of manufacture method of circuit board, it includes：

The photosensitive resin combination of layered product any one of [1]~[9] is laminated to the lamination of substrate Process；

The exposure process being exposed to the photosensitive polymer combination；

The exposed photosensitive polymer combination is developed, so as to obtain being formed with the aobvious of the substrate of corrosion-resisting pattern Shadow process；

The substrate for being formed with corrosion-resisting pattern is etched or plating conductive pattern formation process；And

Peel off the stripping process of the corrosion-resisting pattern.

The effect of invention

According to the present invention, there is provided can take into account erosion resistant for the poor short circuit after the tracing ability and etch process of substrate The photosensitive polymer combination of inhibition and the layered product for possessing photosensitive polymer combination on basilar memebrane, thereby, it is possible to Improve the resolution ratio of the printed circuit board (PCB) formed using dry film against corrosion.

Embodiment

Hereinafter, it is specifically described for embodiment of the present invention (hereinafter abbreviated as " present embodiment ").It should illustrate, In this specification, term " (methyl) acrylic acid " refers to acrylic or methacrylic acid.Term " (methyl) acryloyl group " refers to Acryloyl group or methylacryloyl.Term " (methyl) acrylate " refers to " acrylate " or " methacrylate ".

<Photosensitive polymer combination>

In present embodiment, photosensitive polymer combination is comprising (A) alkali solubility macromolecule, (B) containing ethylenic unsaturated bond Compound and (C) Photoepolymerizationinitiater initiater.According to expectation, photosensitive resin composition can also be inhibited comprising (D) additive, (E) The others composition such as agent.

In present embodiment, photosensitive polymer combination meets the relation shown in following mathematical expressions (1)：

W_X-D_X≤5μm (1)

In formula, W_XRefer to：The photo-sensitive resin formed by photosensitive polymer combination is laminated in the presence of liquid With 100 μm on the substrate of wide and 5 μm of depths groove, then by corrosion-resisting pattern obtained from exposed and developed, with relative Resolution ratio (μm) as defined in form in the minimum spacing width of line width against corrosion 200 μm wide, and

D_XRefer to：Photo-sensitive resin is laminated on substrate under in the absence of liquid, then by exposed and developed In obtained corrosion-resisting pattern, resolution ratio (μ as defined in the form of the minimum spacing width of the line width against corrosion wide relative to 200 μm m)}。

In mathematical expression (1), W_X-D_XRefer to：The photonasty that will be formed as the photosensitive polymer combination described in present embodiment Resin bed is (so-called wet when being laminated in the presence of liquid on the substrate with specific groove width (100 μm) and groove depth (5 μm) Formula is laminated) by the resolution ratio of corrosion-resisting pattern obtained from exposed and developed, subtract (the institute when being laminated under in the absence of liquid The dry lamination of meaning) by the difference of the resolution ratio of corrosion-resisting pattern obtained from exposed and developed (hereinafter also referred to as " wet type-dry type It is laminated the difference of resolution ratio ").

When the difference of wet type-dry lamination resolution ratio is less than 5 μm, it can reduce in the production technology being laminated using wet type Poor short circuit.General printed circuit board (PCB) can produce the scar produced by operation or bumps and the bumps from internal layer.It is wet The liquid applied in formula lamination is stranded in the bumps etc. sometimes.When the difference of wet type-dry lamination resolution ratio is more than 5 μm, this is recessed The resolution ratio of convex portion is deteriorated, so as to cause the generation of poor short circuit.According to the present invention, regardless of whether exist base material bumps or Scar, the Wiring pattern that can be stablized in substrate.

In addition, wet type lamination can improve the tracing ability of dry film against corrosion, therefore, even in the situation of the thickness of thin of resist layer Under can also ensure that sufficient tracing ability.If the filming of resist layer can be realized, the resolution ratio after etching can be improved.Cause This, in accordance with the invention it is possible to take into account becoming more meticulous for tracing ability in wet type laminating technology and Wiring pattern.

The reason for difference being produced as wet type-dry lamination resolution ratio, it is believed that be the presence of the metal ion of base material. It is considered that：The presence of liquid applied in being laminated due to wet type, the especially retentate portion in liquid, the metal of substrate from Son, such as copper ion migration are into resist layer.It is considered that：Raolical polymerizable is promoted by the metal ion, wet type Resolution ratio during lamination is deteriorated.The composition of photosensitive polymer combination for suppressing copper ion migration passes through wet type-dry type layer The difference of pressure resolution ratio confirms for less than 5 μm.Found by the present invention：Extent of migration of the copper into photosensitive polymer combination With the difference correlation of above-mentioned wet type-dry type resolution ratio.

In mathematical expression (1), from the viewpoint of tracing ability and poor short circuit inhibition is taken into account, W_X-D_XLess than 5 μm, further preferably For less than 4 μm, less than 3 μm, less than 2 μm, less than 1 μm or 0 μm.

Adjust to the means in less than 5 μm of scope, not especially limit as by the difference of wet type-dry lamination resolution ratio It is fixed, it can include and for example adjust each composition in the composition of photosensitive polymer combination respectively like that as described later.

Method that the difference of wet type-dry lamination resolution ratio is recorded by embodiment is determined.

For each composition included in the photosensitive polymer combination described in present embodiment, it is described below.

(A) alkali solubility macromolecule

(A) alkali solubility macromolecule is can be dissolved in the macromolecule of alkaloid substance.(A) alkali solubility macromolecule can be single kind The mixture of the copolymer of class, the mixture of a variety of copolymers and/or a variety of homopolymers.

It is related to alkali solubility, from the resistance to developability of photo-sensitive resin and the resistance to developability of corrosion-resisting pattern, resolution ratio and From the viewpoint of adaptation, the high molecular acid equivalent of (A) alkali solubility (is that its mixture is whole when (A) composition includes a variety of copolymers The acid equivalent of body) be preferably more than 100, from the viewpoint of the developability and fissility of photo-sensitive resin, preferably 900 with Under.(A) the high molecular acid equivalent of alkali solubility is more preferably 200~600, more preferably 250~500.Acid equivalent refers to it In have 1 equivalent carboxyl linear polymer quality.

In present embodiment, from the viewpoint of the resolution ratio for improving corrosion-resisting pattern, (A) alkali solubility macromolecule is to constitute (A) counted on the basis of the gross mass of the high molecular monomer of alkali solubility, preferably comprise styrol structural units more than 40 mass %. (A) when alkali solubility macromolecule includes a variety of copolymers, the compounding ratio of each EVA in (A) alkali solubility macromolecule entirety with it is each The weighted average of the containing ratio of styrol structural unit in copolymer is preferably more than 40 mass %.(A) alkali solubility macromolecule In styrol structural unit content by the basis of constituting the gross mass of the high molecular monomer of (A) alkali solubility count, from developability From the viewpoint of fissility, preferably below 90 mass %, more preferably below 85 mass %, below 80 mass %, 70 matter Measure below % or below 60 mass %.

(A) alkali solubility macromolecule can comprising the homopolymer of aftermentioned first monomer, the homopolymer of aftermentioned second comonomer, make bag Copolymer etc. obtained from copolymer composition copolymerization containing more than a kind the first monomer and/or more than a kind second comonomer.

First monomer is the monomer containing carboxyl in the molecule.As the first monomer, such as (methyl) propylene can be included Acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and acid half ester etc..Among these, from alkali-soluble viewpoint Set out, be preferably (methyl) acrylic acid.

Second comonomer be nonacid and molecule in have at least one polymerism unsaturated group monomer.It is single as second Body, can include such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) third Isopropyl gadoleate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- ethyl hexyls The esters of the vinyl alcohols such as ester, (methyl) benzyl acrylate, vinylacetate；(methyl) acrylonitrile；Styrene, the benzene that can polymerize Ethene derivatives etc..

It is preferably (methyl) acrylic acid from the viewpoint of the covering (テ Application ト) for improving corrosion-resisting pattern among these Methyl esters, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate or (methyl) tert-butyl acrylate, from the viewpoint of covering Set out, more preferably (methyl) n-butyl acrylate, also, from the viewpoint of resolution ratio, styrene or can preferably gather The styrene derivative of conjunction.

As the styrene derivative that can polymerize, such as methyl styrene, vinyltoluene, tert-butoxy can be included Styrene, acetoxy-styrene, 4- vinyl benzoic acids, styrene dimer thing, styrene terpolymer etc..

(A) alkali solubility macromolecule is preferably as follows synthesis：Above-mentioned monomer is mixed and with solvent such as acetone, MEK, first Alcohol, ethanol, normal propyl alcohol or isopropanol, the appropriate addition radical polymerization initiator such as benzoyl peroxide first into resulting solution Acyl, azo isobutyronitrile etc., carry out heating stirring, so as to synthesize.Also sometimes while a part of mixture, one are added dropwise into reaction solution Side carries out the high molecular synthesis of (A) alkali solubility.After reaction terminates, also further solvent is added in product sometimes, and adjusts To desired concentration.As synthesizing mean, in addition to using polymerisation in solution, can also use polymerisation in bulk, suspension polymerisation or Emulsion polymerization.

(A) the high molecular weight average molecular weight of alkali solubility (is whole for its mixture when (A) composition includes a variety of copolymers The weight average molecular weight of body) it is preferably 5,000~500,000.From equably maintaining the thickness of dry film against corrosion, obtain relative to development From the viewpoint of the patience of liquid, the high molecular weight average molecular weight of (A) alkali solubility is preferably 5, more than 000, from maintenance dry film against corrosion Developability from the viewpoint of, preferably 500, less than 000.(A) the high molecular weight average molecular weight of alkali solubility is more preferably 10, 000~200,000, it is more preferably 20,000~100,000.(A) the high molecular decentralization of alkali solubility be preferably 1.0~ 6.0。

In present embodiment, the high molecular content of (A) alkali solubility in photosensitive polymer combination is with photoresist group Meter (is same for respectively containing composition below, in the case of no especially record on the basis of the solid constituent total amount of compound ), the mass %, more preferably 40 mass % of the mass % of preferably 10 mass %~90, more preferably 20 mass %~80 In the range of~60 mass %.From the viewpoint of the alkali-developable for maintaining photo-sensitive resin, (A) alkali solubility is high molecular to be contained Amount is preferably more than 10 mass %, from the performance given full play of by corrosion-resisting pattern formed by exposure as erosion resistant Viewpoint is set out, preferably below 90 mass %.

(B) compound containing ethylenic unsaturated bond

(B) compound containing ethylenic unsaturated bond is with polymerism by having ethylenically unsaturated group in its structure Compound.From the viewpoint of polyaddition, ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group.

From the viewpoint of the poor short circuit inhibition after etch process, the compound of (B) containing ethylenic unsaturated bond is preferred Include the oxyalkylene unit in the molecule with more than 20 moles, more than 21 moles, more than 25 moles or more than 30 moles Polyaddition monomer.For the upper limit of the addition amount of the oxyalkylene unit in molecule, it is not particularly limited, from against corrosion after development From the viewpoint of layer resolution ratio, preferably less than 60 moles, more preferably less than 50 moles or less than 40 moles.

As oxyalkylene, it can include such as ethylene oxide, propylene oxide.

(B) compound containing ethylenic unsaturated bond can be included and is selected from by following (b₁)~(b₇) composition group at least It is a kind of：

(b₁) ethylene glycol two (methyl) acrylate compounds shown in following logical formula (I)s；

In formula, R₁And R₂Hydrogen atom or methyl, and m are represented independently of one another₁It is the numerical value of satisfaction 2~40.}

(b₂) oxyalkylene modified bisphenol A type two (methyl) acrylate compounds shown in following logical formula (II)s；

In formula, R₃And R₄Hydrogen atom or methyl are represented independently of one another；A is C₂H₄；B is C₃H₆；n₁、n₂、n₃And n₄It is full Sufficient n₁+n₂+n₃+n₄The integer of=2~50 relation；The arrangement of-(A-O)-and-(B-O)-repeat unit be optionally it is random or Block, in the case of block ,-(A-O)-is with-(B-O)-optionally in xenyl side.}

(b₃) three (methyl) acrylate compounds shown in following logical formula (III)s；

In formula, R₅~R₇Hydrogen atom or methyl are represented independently of one another；X represents the alkylidene of carbon number 2~6；m₂、m₃And m₄ It is each independently 0~40 integer, m₂+m₃+m₄For 1~40, also, m₂+m₃+m₄For more than 2 when, multiple X it is mutually the same or It is different }

(b₄) carbamate two (methyl) acrylate compounds shown in following logical formula (IV)s；

In formula, R₈And R₉Hydrogen atom or methyl are represented independently of one another；Y represents the alkylidene of carbon number 2~6；Z represents divalent Organic group；And s and t are each independently 0~40 integer, and s+t >=1 }

(b₅) six (methyl) acrylate compounds shown in following logical formula (V)s；

{ in formula, R represents hydrogen atom or methyl independently of one another, and n is 0~30 integer, and all n aggregate value is 1 More than

(b₆) phthalate compound shown in following logical formula (VI)s；

{ in formula, A represents C₂H₄；R₆₁Represent hydrogen atom or methyl；R₆₂Represent hydrogen atom, methyl or halogenated methyl；R₆₃Represent Alkyl, halogen atom or the hydroxyl of carbon number 1~6；A is 1~4 integer；K is 0~4 integer；Also, k is more than 2 integer When, multiple R₆₃It is identical or different }；

And, (b₇) except above-mentioned (b₁)~(b₆) outside polyaddition monomer.

From the viewpoint of the splitting time and the size of stripping film for adjusting corrosion-resisting pattern, (B) is containing ethylenic unsaturated bond Compound preferably comprises (b₁) ethylene glycol two (methyl) acrylate compounds shown in logical formula (I).

In logical formula (I), from the viewpoint of splitting time and stripping chip size, m₁Preferably more than 2, after etch process Poor short circuit inhibition from the viewpoint of, preferably more than 20, go out from the viewpoint of resolution ratio, resistance to plating and elching resistant Hair, m₁Preferably less than 40.m₁More preferably 4~20, more preferably 6~12.From take into account resolution ratio and etching poor short circuit From the viewpoint of inhibition, the compound of (B) containing ethylenic unsaturated bond preferably contains in logical formula (I) simultaneously meets m₁=4~20 Compound and logical formula (I) in meet m₁=20~40 compound.

It is used as the concrete example of ethylene glycol two (methyl) acrylate compounds shown in logical formula (I), preferably m₁The four of=4 Ethylene glycol two (methyl) acrylate, m₁=9 nine ethylene glycol two (methyl) acrylate, m₁=14 (first of polyethylene glycol two Base) acrylate or m₁=23 polyethylene glycol two (methyl) acrylate.

In order to suppress the poor short circuit after etch process, the compound of (B) containing ethylenic unsaturated bond preferably comprises (b₂) logical Oxyalkylene modified bisphenol A type two (methyl) acrylate compounds shown in formula (II).B in logical formula (II) can for- CH₂CH₂CH₂- or-CH (CH₃)CH₂-。

The hydrogen atom on aromatic rings in logical formula (II) is optionally replaced by hetero atom and/or substituent., can as hetero atom Include such as halogen atom, also, as substituent, alkyl, the cycloalkanes of carbon number 3~10 of carbon number 1~20 can be included Base, the aryl of carbon number 6~18, phenacyl, amino, the alkyl amino of carbon number 1~10, the dialkyl amido of carbon number 2~20, Nitro, cyano group, carbonyl, sulfydryl, the alkyl thiol of carbon number 1~10, aryl, hydroxyl, the hydroxy alkyl of carbon number 1~20, carboxyl, alkane Acyl group that carboxyalkyl that the carbon number of base is 1~10, the carbon number of alkyl are 1~10, the alkoxy of carbon number 1~20, carbon number 1~20 Alkoxy carbonyl, the alkyl-carbonyl of carbon number 2~10, the alkenyl of carbon number 2~10, the N- alkyl-carbamoyls of carbon number 2~10 Or group comprising heterocycle or the aryl that is replaced by these substituents etc..These substituents optionally formed condensed ring or this Hydrogen atom in a little substituents is optionally replaced by hetero atoms such as halogen atoms.Aromatic rings in logical formula (II) has multiple substituents When, multiple substituents can be with identical or different.

R in logical formula (II)₃And R₄Hydrogen atom or methyl can be each independently, from by photosensitive polymer combination From the viewpoint of ensuring contrast after the just exposure of the photo-sensitive resin of formation, R₃With R₄One or both of be preferably that hydrogen is former Son, more preferably R₃And R₄Both are hydrogen atom.

From the viewpoint of etching poor short circuit is suppressed, (b₂) oxyalkylene modified bisphenol A type two shown in logical formula (II) More than 20 moles of oxyalkylene of (methyl) acrylate compounds preferred additions.More specifically, lead in formula (II), n₁、 n₂、n₃And n₄It is preferred that meeting n₁+n₂+n₃+n₄=4~50 relation, more preferably meets n₁+n₂+n₃+n₄=10~50 relation, enters One step preferably meets n₁+n₂+n₃+n₄=20~50 relation, particularly preferably meets n₁+n₂+n₃+n₄=30~50 relation.

From the viewpoint of resolution ratio, more than the 40 mass % among the compound of (B) containing ethylenic unsaturated bond are preferably (b₂) oxyalkylene modified bisphenol A type two (methyl) acrylate compounds shown in logical formula (II), more preferably lead to formula (II) In n₁、n₂、n₃And n₄Meet n₁+n₂+n₃+n₄Oxyalkylene modified bisphenol A type two (methyl) acrylic acid of=30~50 relation Ester compounds.50 mass %, more preferably more than 55 mass % preferably, among the compound of (B) containing ethylenic unsaturated bond, Further preferred 60 mass %, most preferably 80 mass % are (b₂) (the first of oxyalkylene modified bisphenol A type two shown in logical formula (II) Base) acrylate compounds.

It is used as (b₂) oxyalkylene modified bisphenol A type two (methyl) acrylate compounds shown in logical formula (II) it is preferred Concrete example, can include the two ends of bisphenol-A respectively addition have average 1 unit ethylene oxide polyethylene glycol two (methyl) third Olefin(e) acid ester, the two ends of bisphenol-A respectively addition have average 2 unit ethylene oxides polyethylene glycol two (methyl) acrylate, The two ends of bisphenol-A respectively addition have average 5 unit ethylene oxides polyethylene glycol two (methyl) acrylate, in bisphenol-A Two ends respectively addition have average 7 unit ethylene oxides polyethylene glycol two (methyl) acrylate, at the two ends of bisphenol-A point Other addition have the PAG of average 6 unit ethylene oxides and average 2 unit propylene oxides two (methyl) acrylate, The two ends of bisphenol-A respectively addition have average 15 unit ethylene oxides PAG two (methyl) acrylate, Addition has average 15 unit ethylene oxides and averagely the two of the PAG of 2 unit propylene oxides respectively at the two ends of bisphenol-A (methyl) acrylate etc..

In logical formula (II), from the viewpoint of resolution ratio, n₁、n₂、n₃And n₄Further preferably meet n₁+n₂+n₃+n₄=2~10 Relation, it is also particularly that and meet n₁+n₂+n₃+n₄=2~4 relation.

From the viewpoint of resolution ratio and etching poor short circuit inhibition is taken into account, the compound of (B) containing ethylenic unsaturated bond Particularly preferably contain simultaneously in logical formula (II) and meet n₁+n₂+n₃+n₄N is met in=30~50 compound and logical formula (II)₁+ n₂+n₃+n₄=2~10 compound.

From the viewpoint of resolution ratio, the compound of (B) containing ethylenic unsaturated bond preferably comprises (b₃) lead to shown in formula (III) Three (methyl) acrylate compounds.X in logical formula (III) is the alkylidene of carbon number 2~6, for example, can be-CH₂CH₂-、- CH₂CH₂CH₂-、-CH(CH₃)CH₂- etc..

From the viewpoint of the poor short circuit inhibition after covering, cured film flexibility and etch process, (b₃) formula (III) three (methyl) acrylate compounds shown in preferably have the longer oxyalkylene part of chain.More specifically, formula (III) in, m₂+m₃+m₄Preferably 20~40.

It is used as (b₃) three (methyl) acrylate compounds shown in logical formula (III) preferred concrete example, oxygen can be included Change ethene (EO) and be modified trimethylolpropane tris (methyl) acrylate (average addition molal quantitys of EO：10~40), propylene oxide (PO) modified trimethylolpropane tris (methyl) acrylate (average addition molal quantitys of PO：10~40) etc..Particularly preferably oxygen Change ethene (EO) and be modified trimethylolpropane tris (methyl) acrylate (average addition molal quantitys of EO：21).

From the viewpoint of resolution ratio, the compound of (B) containing ethylenic unsaturated bond preferably comprises (b₄) lead to shown in formula (IV) Carbamate two (methyl) acrylate compounds.

In logical formula (IV), Z represents divalent organic group, for example, can be alkylidene, the oxygen of carbon number 2~10 of carbon number 1~10 Alkylidene, optionally divalent ester ring type group of carbon number 3~10 with substituent etc..

In logical formula (IV), Y represents the alkylidene of carbon number 2~6, for example, can be-CH₂CH₂-、-CH₂CH₂CH₂-、-CH (CH₃)CH₂- etc..

From the viewpoint of further raising covering, in logical formula (IV)-(Y-O)_s- partly and-(Y-O)_t- part is also It is preferred that independently of one another by-(C₂H₄O)-(C₃H₆O)₉- substitution.From the viewpoint of the poor short circuit inhibition after etch process, Preferably s+t=20~40.

It is used as (b₄) carbamate two (methyl) acrylate compounds shown in logical formula (IV) preferred concrete example, can Include in β (methyl) acrylic monomers with hydroxyl and IPDI, 2,6- toluene diisocynates The addition reaction of the diisocyanate cpds such as ester, 2,4 toluene diisocyanate and 1,6- hexamethylene diisocyanates formation Thing；Three ((methyl) acryloxy tetraethylene glycol isocyanates) hexa-methylene isocyanuric acid esters, EO modified urethanes two (methyl) acrylate and EO, PO modified urethane two (methyl) acrylate.It should illustrate, EO represents to aoxidize second Alkene, the block structure through the EO compounds being modified with oxygen ethylidene.In addition, PO represents propylene oxide, the chemical combination being modified through PO Thing has the block structure of oxygen propylidene.As EO modified urethanes two (methyl) acrylate, it can include for example new Trade name " UA-11 " of middle village's chemical industry Co., Ltd. manufacture etc..In addition, being used as the EO, (first of PO modified urethanes two Base) acrylate, it can include such as the trade name " UA-13 " that chemical industry Co., Ltd. of Xin Zhong villages manufactures.They can be with It is used alone a kind or is applied in combination two or more.

From the viewpoint of resolution ratio, the compound of (B) containing ethylenic unsaturated bond preferably comprises (b₅) lead to shown in formula (V) Six (methyl) acrylate compounds.

In order to further improve resolution ratio, it is preferred that all n average value is more than 6 or n points in logical formula (V) Wei more than 1.On n aggregate value, it is not particularly limited, from the viewpoint of the poor short circuit inhibition after etch process, n Aggregate value be preferably 20~30.

It is used as (b₅) six (methyl) acrylate compounds shown in logical formula (V) preferred concrete example, can include for two seasons Penta tetrol six (methyl) acrylate, 6 terminal additions of dipentaerythritol have the six of total 1~36 mole of ethylene oxide 6 terminal additions of (methyl) acrylate and dipentaerythritol have six (methyl) of total 1~10 mole of 6-caprolactone Acrylate.6 terminal additions of particularly preferably dipentaerythritol have six (first of total more than 24 moles of ethylene oxide Base) acrylate.

From the viewpoint of resolution ratio, the compound of (B) containing ethylenic unsaturated bond preferably comprises (b₆) lead to shown in formula (VI) Phthalate compound.

As the phthalate compound shown in logical formula (VI), can include such as phthalic acid-γ-chloro- β- Hydroxypropyl-β '-(methyl) acryloyl group epoxide ethyl ester, phthalic acid-beta-hydroxy ethyl-β '-(methyl) acryloyl group oxygen Base ethyl ester and phthalic acid-beta-hydroxy propyl group-β '-(methyl) acryloyl group epoxide ethyl ester etc..Among these, it is preferably Phthalic acid-γ-chloro- beta-hydroxy propyl group-β '-(methyl) acryloyloxyethyl ester.They can be used alone, or It is applied in combination two or more.

(B) in the compound containing ethylenic unsaturated bond, it is used as (b₇) composition, it can include except (b₁)~(b₄) into point it Outer polyaddition monomer.

It is used as (b₇) composition, it can include except (b₁) and (b₂) two (methyl) acrylate outside composition, such as poly- third PAG two (methyl) acrylate such as glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate. As PAG two (methyl) acrylate, can include for example has poly- the third of average 12 mole propylene oxides in addition Further addition has the dimethacrylate of averagely PAG obtained from 3 mole ethylene oxides respectively at the two ends of glycol Ester, having in addition the two ends of polypropylene glycol of average 18 mole propylene oxides, further addition has average 15 moles second respectively Dimethylacrylate of PAG obtained from alkene etc..

And then, it is used as (b₇) composition, following material can be included：

Except (b₃) three (methyl) acrylate outside composition, such as trimethylolpropane tris (methyl) acrylate, Ethoxylated glycerol three (methyl) acrylate, ethoxylation isocyanuric acid three (methyl) acrylate, (first of pentaerythrite three Base) acrylate etc.；

Four (methyl) acrylate, such as double trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) Acrylate, dipentaerythritol four (methyl) acrylate, (methyl) acrylate of pentaerythrite (poly-) alkoxy four etc.；

Five (methyl) acrylate, such as dipentaerythritol five (methyl) acrylate；

Make polyalcohol and compound obtained from alpha, beta-unsaturated carboxylic acid reaction；And,

Make the compound containing glycidyl and compound obtained from alpha, beta-unsaturated carboxylic acid reaction.

In present embodiment, from the viewpoint of the poor short circuit inhibition after resolution ratio and etching, photoresist group The total content of all compounds of (B) containing ethylenic unsaturated bond in compound is preferably the mass % of 1 mass %~70, more preferably The mass % of the mass %, particularly preferably 20 mass % of the mass % of 2 mass %~60, more preferably 4 mass %~50~50 In the range of.

From the viewpoint of the poor short circuit inhibition after etch process, the compound of (B) containing ethylenic unsaturated bond is preferred There is more than 20 moles of oxyalkylene unit in the molecule.From the viewpoint of the poor short circuit inhibition after etch process, The content in molecule with the compound containing ethylenic unsaturated bond of more than 20 moles of oxyalkylene unit is preferably photonasty Overall more than the 5 mass % of resin combination, more preferably more than 10 mass %, it is excellent after development from the viewpoint of resolution ratio Elect as below 40 mass %, be more preferably below 30 mass % or below 20 mass %.

(C) Photoepolymerizationinitiater initiater

(C) Photoepolymerizationinitiater initiater is the compound for polymerizeing monomer by light.Photosensitive polymer combination includes conduct Photoepolymerizationinitiater initiater and commonly known compound in the art.

The content of (C) Photoepolymerizationinitiater initiater in photosensitive polymer combination be preferably the mass % of 0.01 mass %~20, In the range of the mass % of the mass % of more preferably 0.05 mass %~10, more preferably 0.1 mass %~7.From being filled From the viewpoint of the sensitivity divided, the content of (C) Photoepolymerizationinitiater initiater is preferably more than 0.01 mass %, fully to be transmitted from light is made To resist layer bottom surface, obtain good high-resolution from the viewpoint of, preferably below 20 mass %.

As (C) Photoepolymerizationinitiater initiater, quinones, aromatic series ketone, acetophenones, acylphosphine oxide class, benzene can be included Acyloin or benzoin ethers, dialkyl group ketal class, thioxanthene ketone class, dialkylamino benzoates, oxime esters, acridine etc., enter And six aryl bisglyoxalines, pyrazoline compounds, N- aryl amino acids or its ester compounds can be included (for example, the sweet ammonia of N- phenyl Acid), organohalogen compounds etc..They can be used alone, or two or more is applied in combination.

Among these, acridine is particularly suitable for direct imaging exposure, also, from the sensitivity of photo-sensitive resin and anti- From the viewpoint of the resolution ratio of corrosion figure case, preferably N- aryl amino acids or its ester compounds.

As acridine, double (9- acridinyls) hexanes of such as acridine, 9- phenylacridines, 1,6-, the double (9- of 1,7- can be included Acridinyl) heptane, double (9- acridinyls) octanes of 1,8-, double (9- acridinyls) nonanes of 1,9-, double (9- acridinyls) decane of 1,10-, The acridine derivatives such as double (9- acridinyls) hendecanes of 1,11-, double (9- acridinyls) dodecanes of 1,12-.Exposed from for direct imaging From the viewpoint of the adaptability of light, the content of the acridine in photosensitive polymer combination is preferably the matter of 0.1 mass %~5 In the range of measuring the mass % of %, the more preferably mass % of 0.3 mass %~3, more preferably 0.5 mass %~2.

As aromatic series ketone, such as benzophenone, Michler's keton, [4,4 '-bis- (dimethylamino) hexichol first can be included Ketone], 4,4 '-bis- (diethylamino) benzophenone, 4- -4 '-dimethylamino benzophenones of methoxyl group.They can individually make With a kind, or two or more is applied in combination.Among these, from the viewpoint of adaptation, preferably 4,4 '-bis- (diethyl aminos Base) benzophenone.And then, from the viewpoint of transmissivity, the content of the aromatic series ketone in photosensitive polymer combination is preferred In the range of the mass % of the mass % of 0.01 mass %~0.5, more preferably 0.02 mass %~0.3.

As the example of six aryl bisglyoxalines, 2- (Chloro-O-Phenyl) -4,5- diphenyl bisglyoxaline, 2,2 ', 5- can be included Three (Chloro-O-Phenyl) -4- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl bisglyoxaline, 2,4- pairs-(Chloro-O-Phenyl) -5- (3, 4- Dimethoxyphenyls) diphenyl bisglyoxaline, (Chloro-O-Phenyl) diphenyl of 2,4,5- tri- bisglyoxaline, 2- (Chloro-O-Phenyl)-bis- -4, 5- (3,4- Dimethoxyphenyls) bisglyoxaline, 2,2 '-bis--(2- fluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) connection miaow Azoles, 2,2 '-bis--(2,3- difluoromethyls phenyl) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxaline, 2,2 '-bis--(2,4- Difluorophenyl) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxalines, 2,2 '-bis- (2,5- difluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxaline, 2,2 '-bis--(2,6- difluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxaline, 2,2 '-bis--(2,3,4- trifluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxaline, 2,2 '-bis--(2,3,5- trifluoros Phenyl) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxalines, 2,2 '-bis--(2,3,6- trifluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxaline, 2,2 '-bis--(2,4,5- trifluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) connection miaow Azoles, 2,2 '-bis--(2,4,6- trifluorophenyls) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxaline, 2,2 '-it is bis--(2,3,4, 5- tetrafluoros phenyl) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxalines, 2,2 '-bis--(2,3,4,6- tetrafluoros phenyl) -4,4 ', 5,5 '-four (3- methoxyphenyls) bisglyoxalines and 2,2 '-bis--(2,3,4,5,6- pentafluorophenyl groups) -4,4 ', 5,5 '-four (3- Methoxyphenyl) bisglyoxaline etc., they can be used alone, or two or more is applied in combination.From high sensitivity, resolution ratio From the viewpoint of adaptation, preferably 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimers.

In present embodiment, from the viewpoint of the peel property and/or sensitivity for improving photo-sensitive resin, photonasty The content of six aryl united imidazoles in resin combination is preferably the mass % of 0.05 mass %~7, more preferably 0.1 matter In the range of measuring the mass % of the mass % of %~6, more preferably 1 mass %~4.

As N- aryl amino acids, can include such as N-phenylglycine, N- Methyl-N-phenyls glycine, N- ethyls- N-phenylglycine etc..Wherein, it is especially excellent from the viewpoint of the resolution ratio of the sensitivity of photo-sensitive resin or corrosion-resisting pattern Elect N-phenylglycine as.

As the ester compounds of N- aryl amino acids, such as N-phenylglycine ethyl ester can be included.From photoresist From the viewpoint of the sensitivity of layer or the resolution ratio of corrosion-resisting pattern, particularly preferably N-phenylglycine ethyl ester.

From the viewpoint of peel property and/or sensitivity is improved, the N- aryl amino acids in photosensitive polymer combination Or the content of its ester compounds is preferably the matter of 0.05 mass %~5 relative to the solid constituent total amount of photosensitive polymer combination Measure %, more preferably 0.1~2 mass %.

As organohalogen compounds, such as amyl bromide, isoamyl bromide, brominated isobutylene, bromine ethene, diphenylmethyl can be included Bromide, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2,3- dibromopropyls) phosphates, tribromo-acetyl Amine, amyl iodide, isobutyl iodide, 1, double (rubigan) ethane of 1,1- tri- chloro- 2,2- and chlorination triaizine compounds, wherein, especially Preferably use trisbromomethyl phenyl sulfone.From the viewpoint of peel property and/or sensitivity is improved, in photosensitive resin composition The contents of organohalogen compounds relative to the solid constituent total amount of photosensitive polymer combination be preferably the matter of 0.05 mass %~5 Measure %, more preferably the mass % of 0.1 mass %~3.

As other sensitising agents, such as 2- EAQs, octaethyl anthraquinone, 1,2- benzos anthraquinone, 2,3- benzene can be included And anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl-1,4-naphthaquinones, The quinones such as 2,3- dimethyl anthraquinone and 3- chloro-2-methyl anthraquinones；Benzoin, benzoin ethyl ether, benzoin phenylate, methylbenzoin With the benzoin ethers such as ethyl benzoin；Benzil dimethyl ketal, benzil diethyl ketal and 1- phenyl -1,2- the third two The oxime esters such as ketone -2-O- cuprons and 1- phenyl -1,2- propanedione -2- (O- ethoxy carbonyls) oxime.Spy is peeled off from improving From the viewpoint of property and/or sensitivity, the content of the sensitising agent in photosensitive polymer combination is relative to photosensitive resin composition The solid constituent total amount of thing is preferably the mass % of the mass % of 0.05 mass %~5, more preferably 0.1 mass %~3.

In addition, in present embodiment, photosensitive polymer combination further preferably contains pyrazoline compounds as sensitising agent.Make For pyrazoline compounds, preferably 1- phenyl -3- (4- t-butyl styrenes base) -5- (4- tert-butyl-phenyls)-pyrazoline, 1- (4- (benzoxazole -2- bases) phenyl) -3- (4- t-butyl styrenes base) -5- (4- tert-butyl-phenyls)-pyrazoline, 1- phenyl - 3- (4- xenyls) -5- (4- tert-butyl-phenyls)-pyrazolines and 1- phenyl -3- (4- xenyls) -5- (4- t-octyls phenyl)-pyrrole Oxazoline.

(D) additive

In present embodiment, from the viewpoint of the poor short circuit inhibition after etching, photosensitive polymer combination is preferred Benzotriazole cpd (hereinafter abbreviated as " (i) chemical combination comprising (i) as (D) additive without carboxyl containing amino Thing ") and (ii) as polymerization inhibitor (E) epoxide.

The reason for as the difference for producing wet type-dry lamination resolution ratio, it is believed that be the presence of the metal ion of base material. It is considered that：The presence for the liquid applied in being laminated due to wet type, the especially retentate portion in liquid, the metal ion of substrate For example copper ion migration is into resist layer.It is considered that：Raolical polymerizable is promoted by the metal ion, wet type lamination When resolution ratio be deteriorated.

It is considered that：(i) compound and/or (ii) epoxide suppress unnecessary by capturing the metal ion Reaction, so that the effect with the difference for reducing wet type-dry lamination resolution ratio.

From the viewpoint of the poor short circuit inhibition after etching is improved, (i) compound preferably has amino in the molecule. Amino and BTA skeleton can improve for capture the metal migrated by the delay of liquid applied in wet type lamination from The ability of son, can improve the poor short circuit after etching.From the viewpoint of the poor short circuit inhibition after etching is improved, (i) Compound is preferably free of carboxyl in the molecule.It is considered that：The delay of liquid applied in the lamination of carboxylase gene wet type and produce hydrogen Ion, the hydrogen ion intervenes Raolical polymerizable, so as to cause the poor short circuit after etching to be deteriorated.

As (i) compound, such as 1- (double (2- ethylhexyls) amino methyls of N, N-) BTA, 1- can be included (double (2- ethylhexyls) amino methyls of N, N-) methylbenzotrazole, 2,2 '-(((methyl isophthalic acid-H- BTA -1- bases) methyl) Imino group) di-methylcarbinol, 2,2 '-(((1-H- BTA -1- bases) methyl) imino group) di-methylcarbinols, 1- (2- ethylhexyl ammonia Base)-BTA, 1- (2- di-n-octyls amino methyl)-BTA, 1- hydroxy-benzotriazoles, 1- [double (2- hydroxyl second Base) amino methyl] -5- methyl isophthalic acid H- BTAs etc..

In present embodiment, the content of (i) compound in photosensitive polymer combination is preferably 0.001 mass %~3 In the range of the mass % of quality %, more preferably the mass % of 0.01 mass %~2, more preferably 0.05 mass %~1.From Suppress from the viewpoint of the poor short circuit after etching, the content of (i) compound is preferably more than 0.001 mass %, from maintenance sense From the viewpoint of the sensitivity of photosensitive resin layer and maintenance resolution ratio, preferably below 3 mass %.

(ii) epoxide is the compound with epoxy radicals.As (ii) epoxide, such as oxygen can be included Change olefin(e) compound etc..Olefinic compounds preferably include at least two glycidyl in intramolecular.Epoxide can hinder Polymerisation caused by the metal ion for hindering the delay of the liquid because being applied in wet type lamination and migrating, improves short after etching Road is bad.

As olefinic compounds, the compound shown in for example following logical formula (VII)s can be included.

In formula, X₇For oxygen atom or formula-O-X₈- O- (in formula, X₈For containing selected from the straight chain or branch by carbon number 1~100 At least one kind of hydrocarbon in the group of the arlydene composition of the alkylidene of chain, the ester ring type alkylidene of carbon number 3~10 and carbon number 5~20 The divalent group of base, also, the alkyl be optionally selected from it is at least one kind of in the group being made up of halogen atom, oxygen atom and nitrogen-atoms Atom replace) shown in group；R₇₈And R₇₉It is each independently containing the alkylene selected from the straight or branched by carbon number 1~100 The divalent of at least one kind of alkyl in the group of the arlydene composition of base, the ester ring type alkylidene of carbon number 3~10 and carbon number 5~20 Group, also, at least one kind of atom that the alkyl is optionally selected from the group being made up of halogen atom, oxygen atom and nitrogen-atoms takes Generation, also, R₇₈And R₇₉In the presence of, R₇₈And R₇₉Optional identical or different, R₇₈And R₇₉When different ,-(R₇₈- O)-and-(R₇₉- O)-the arrangement of repeat unit be optionally block or random；Also, l and m are each independently 0~50 integer, and l+m is 0 ~50 integer }.

It is used as the X in logical formula (VII)₇, from the viewpoint of resolution ratio, preferably oxygen atom, from the hydroxyl of bisphenol-A Divalent group obtained from dehydrogenation (hereinafter also referred to bisphenol A-type group) and go dehydrogenation from the hydroxyl of hydrogenated bisphenol A and obtain The divalent group (hereinafter also referred to hydrogenated bisphenol A type group) arrived, more preferably bisphenol A-type group and hydrogenated bisphenol A type group.

As the preference of olefinic compounds, the X in logical formula (VII)₇In the case of for oxygen atom, it can include Ethylene glycol diglycidylether (for example, エ Port ラ イ ト 40E of Kyoeisha Chemical Co., Ltd.'s manufacture), diethylene glycol diglycidyl Glycerin ether (for example, エ Port ラ イ ト 100E of Kyoeisha Chemical Co., Ltd.'s manufacture), Triethylene Glycol Diglycidyl Ether, tetrem Hexanediol diglycidyl ether (for example, エ Port ラ イ ト 200E of Kyoeisha Chemical Co., Ltd.'s manufacture), five ethylene glycol two shrink sweet Oily ether, six ethylene glycol diglycidylethers, seven ethylene glycol diglycidylethers, eight ethylene glycol diglycidylethers, nine ethylene glycol Diglycidyl ether (for example, エ Port ラ イ ト 400E of Kyoeisha Chemical Co., Ltd.'s manufacture), ten ethylene glycol diglycidyls Ether, propylene glycol diglycidylether (for example, エ Port ラ イ ト 70P of Kyoeisha Chemical Co., Ltd.'s manufacture), DPG two contract Water glycerin ether, tripropyleneglycol diglycidyl ether (for example, エ Port ラ イ ト 200P of Kyoeisha Chemical Co., Ltd.'s manufacture), four Propylene glycol diglycidylether, five propylene glycol diglycidylethers, six propylene glycol diglycidylethers, seven propane diols two shrink sweet Oily ether (for example, エ Port ラ イ ト 400P of Kyoeisha Chemical Co., Ltd.'s manufacture), neopentylglycol diglycidyl ether are (for example, altogether The エ Port ラ イ ト 1500NP of Rong She KCCs manufacture), 1,6- hexanediol diglycidyl ethers are (for example, common prosperity society is chemical The エ Port ラ イ ト 1600 of Co., Ltd.'s manufacture), hydrogenated bisphenol A diglycidyl ether is (for example, Kyoeisha Chemical Co., Ltd.'s system The エ Port ラ イ ト 4000 made) etc..Wherein, preferably hydrogenated bisphenol A diglycidyl ether.

In addition, the X in logical formula (VII)₇In the case of for bisphenol A-type group, the preferred of olefinic compounds is used as Example, can include 2 moles of addition product diglycidyl ethers of bisphenol-A-propylene oxide (for example, Kyoeisha Chemical Co., Ltd. manufactures エ Port ラ イ ト 3002), 4 moles of addition product diglycidyl ethers of bisphenol-A-propylene oxide, 6 moles of bisphenol-A-propylene oxide plus Add into thing diglycidyl ether, 8 moles of addition product diglycidyl ethers of bisphenol-A-propylene oxide, 10 moles of bisphenol-A-propylene oxide Add into thing diglycidyl ether, 2 moles of addition product diglycidyl ethers of bisphenol-A-ethylene oxide, 4 moles of bisphenol-A-ethylene oxide Add into thing diglycidyl ether, 6 moles of addition product diglycidyl ethers of bisphenol-A-ethylene oxide, 8 moles of bisphenol-A-ethylene oxide Into thing diglycidyl ether, 10 moles of addition product diglycidyl ethers of bisphenol-A-ethylene oxide etc..Wherein, preferably bisphenol-A-oxygen Change 2 moles of addition product diglycidyl ethers of propylene.

In addition, the X in logical formula (VII)₇In the case of for hydrogenated bisphenol A type group, olefinic compounds are used as Preference, can include 2 moles of addition product diglycidyl ethers of hydrogenated bisphenol A-ethylene oxide, hydrogenated bisphenol A-ethylene oxide 4 Mole addition product diglycidyl ether, 6 moles of addition product diglycidyl ethers of hydrogenated bisphenol A-ethylene oxide, hydrogenated bisphenol A-oxygen Change 8 moles of addition product diglycidyl ethers of ethene, 10 moles of addition product diglycidyl ethers of hydrogenated bisphenol A-ethylene oxide, hydrogenation 2 moles of addition product diglycidyl ethers of bisphenol-A-propylene oxide, 4 moles of addition product 2-glycidyls of hydrogenated bisphenol A-propylene oxide Ether, 6 moles of addition product diglycidyl ethers of hydrogenated bisphenol A-propylene oxide, 8 moles of addition products two of hydrogenated bisphenol A-propylene oxide Glycidol ether, 10 moles of addition product diglycidyl ethers of hydrogenated bisphenol A-propylene oxide etc..

The content of epoxide in photosensitive polymer combination is preferably the mass % of 0.001 mass %~3, more preferably In the range of the mass % of the mass % of 0.01 mass %~2, more preferably 0.05 mass %~1.5.After suppression etching Poor short circuit from the viewpoint of, the content of epoxide is preferably more than 0.001 mass %, from maintaining photo-sensitive resin Sensitivity from the viewpoint of, preferably below 3 mass %.

Photosensitive polymer combination is according to expect can also be comprising stabilization agent, colour-changing agent, dyestuff, plasticizer, anti-oxidant The additives such as agent.

Go out from the etching poor short circuit and heat endurance or the viewpoint of storage stability for suppressing photosensitive polymer combination Hair, the additive that photosensitive polymer combination can contain outside (i) compound is used as stabilization agent.

It is used as the additive outside (i) compound, it is however preferred to have tetrazolium skeleton, imidazole skeleton, triazole skeleton and thiazole Compound of skeleton etc..These compounds further preferably sulfydryl.

As the example of aforesaid compound, example material described as follows can be included：

Imidazoles, such as 2- sulfydryls -1- methylimidazoles, 2-mercaptobenzimidazole, 2- sulfydryl -5- methyl-benzoimidazoles, 5- Chloro- 2-mercaptobenzimidazole, 5- methoxyl groups -2-mercaptobenzimidazole；

Thiazoles, such as 2-mercaptobenzothiazole, 6- amino-2-mercapto phenyl formics benzothiazole, 2- sulfydryl -5- methoxyl group benzo thiophenes The chloro- 2-mercaptobenzothiazole of azoles, 5-；

Four azoles, such as 1- methyl -5- sulfydryls -1H-TETRAZOLE, 1- phenyl -5- sulfydryls -1H-TETRAZOLE, 1- methyl -5- amino - Tetrazolium, 5- amino -1H-TETRAZOLE, 5- benzyls -1H-TETRAZOLE, 5- methyl tetrazolium, 1- methyl isophthalic acid H- tetrazoliums, 5- methyl mercaptos -1H- four Azoles, 5- phenyltetrazoles, 5- ethylmercapto groups -1H-TETRAZOLE, 5- benzylthios -1H-TETRAZOLE；

It is not condensed the triazole type of aromatic ring, such as 1,2,4- triazoles, 1,2,3-triazoles, 3- sulfydryls -1,2,4- triazoles, 1,3,4- triazole -3- alcohol, 3- sulfydryl -4- methyl isophthalic acids, 2,4- triazoles, 3- amino -5- sulfydryl -1,2,4- triazoles, 3- amino -1,2, 4- triazoles；

Benzotriazole, such as 1,2,3- BTAs, 5- chloro- 1,2,3- BTAs, carboxyl benzotriazole；

Benzooxazole kind, such as 2- mercaptobenzoxazoles.

Go out from the etching poor short circuit and heat endurance or the viewpoint of storage stability for suppressing photosensitive polymer combination Hair, the polymerization inhibitor (E) that photosensitive polymer combination preferably comprises outside (ii) epoxide is used as stabilization agent.

As the polymerization inhibitor outside (ii) epoxide, such as compound with phenolic hydroxyl group, amine system can be included Polymerization inhibitor.Among these, from the viewpoint of the poor short circuit inhibition after etching, it is however preferred to have the chemical combination of phenolic hydroxyl group Thing.

As the compound with phenolic hydroxyl group, can include for example p methoxy phenol, hydroquinones, biphenyl 3 phenol, Tert-butyl catechol, DBPC 2,6 ditertiary butyl p cresol, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2,2 '-Asia Methyl double (4- ethyl -6- tert-butyl phenols), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), triethylene glycols-bis- (3- The 3- tert-butyl group -5- methyl -4- hydroxy-phenylpropionic acids ester) etc..

As amine system polymerization inhibitor, such as naphthylamines, diphenyl nitroso-amines and nitrosophenylhydroxylamine aluminium salt can be included Deng.

In present embodiment, the total content of all stabilization agents in photosensitive polymer combination is preferably 0.001 matter Measure the mass %'s of the mass %, more preferably 0.05 mass % of the mass % of %~3, more preferably 0.01 mass %~2~1.5 In the range of.From assigning good this viewpoint of storage stability, the total content of stabilization agent to photosensitive resin composition Preferably more than 0.001 mass %, from the viewpoint of the sensitivity for maintaining photo-sensitive resin, preferably below 3 mass %.

As colour-changing agent, leuco dye, fluoran dyes etc. can be exemplified.In terms of the identification developed the color based on exposed portion For, preferably use colour-changing agent.In addition, detector etc. read for exposure position alignment mark when, exposure portion with it is unexposed When contrast between portion is big, position is easily recognized, therefore be favourable.

As leuco dye, three (4- dimethylamino phenyls) methane [leuco crystal violet], double (4- dimethylaminos can be included Phenyl) phenylmethane [leucogentian violet] etc..Especially, from the viewpoint of contrast becomes good, as leuco dye, Preferably use leuco crystal violet.The content of leuco dye in photosensitive resin composition is preferably the matter of 0.1 mass %~10 Measure %.From the viewpoint of contrast between exposed portion and unexposed portion, the content is preferably more than 0.1 mass %, From the viewpoint of storage stability is maintained, preferably below 10 mass %.

As base dye, can including such as Viride Nitens 1, [CAS numbers (same as below)：633-03-4] (for example, Aizen Diamond Green GH, trade name, Baotugu Chemical Industrial Co., Ltd's system), malachite green oxalates [2437- 29-8] (for example, Aizen Malachite Green, trade name, Baotugu Chemical Industrial Co., Ltd's system), BG [633- 03-4], pinkish red [632-99-5], crystal violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], first Base green [82-94-0], victoria blue B [2580-56-5], Blue 7 [2390-60-5] are (for example, Aizen Victoria Pure Blue BOH, trade name, Baotugu Chemical Industrial Co., Ltd's system), rhodamine B [81-88-9], rhodamine 6G [989- 38-8], basic yellow 2 [2465-27-2] etc..Wherein, preferably Viride Nitens 1, malachite green oxalates and Blue 7, from raising From the viewpoint of form and aspect stability and exposure contrast, particularly preferably Viride Nitens 1.

In present embodiment, the content of the base dye in photosensitive polymer combination is preferably the matter of 0.001 mass %~3 In the range of measuring the mass % of %, the more preferably mass % of 0.01 mass %~2, more preferably 0.01 mass %~1.From To from the viewpoint of good coloring, the content of dyestuff is preferably more than 0.001 mass %, from the spirit for maintaining photo-sensitive resin From the viewpoint of sensitivity, preferably below 3 mass %.

As plasticizer, the toluenesulfonic acid acid amides such as o-toluene sulfonic acid acid amides, p-methyl benzenesulfonic acid acid amides can be included；It is poly- Ethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxy The diol-lipids such as propylene monomethyl ether, polyoxyethylene list ether, polyoxypropylene list ether, polyoxyethylene polyoxypropylene list ether； The phthalates such as diethyl phthalate；ATBC, triethyl citrate, the second of acetyl citrate three Ester, the n-propyl of acetyl citrate three and acetyl tributyl citrate；In the both sides of bisphenol-A, addition has propylene oxide respectively Propane diols, in the both sides of bisphenol-A, addition has the ethylene glycol etc. of ethylene oxide respectively.

In present embodiment, the content of the plasticizer in photosensitive polymer combination is preferably the matter of 0.1 mass %~5 In the range of measuring %, more preferably the mass % of 1 mass %~4.

The additive of described above can be used alone, or two or more is applied in combination.

<Photosensitive polymer combination distiller liquor>

In present embodiment, by adding solvent into photosensitive polymer combination, photosensitive resin composition can be formed Thing distiller liquor.As suitable solvent, ketone can be included, such as acetone, MEK (MEK)；And alcohols, such as first Alcohol, ethanol, isopropanol etc..It is preferred that with the viscosity of photosensitive polymer combination distiller liquor be issued at 25 DEG C 500mPa seconds~ The mode of 4000mPa seconds, solvent is added in photosensitive polymer combination.

<Photosensitive-resin layered product>

Layered product (hereinafter also referred to " photosensitive-resin layered product ") described in present embodiment possesses basilar memebrane, Yi Jishe Put the photo-sensitive resin for including above-mentioned photosensitive polymer combination on basilar memebrane.Photosensitive-resin layered product is according to expectation With basilar memebrane side opposite side there can be protective layer in photo-sensitive resin.

Basilar memebrane can be peeled off from photo-sensitive resin.Basilar memebrane is not particularly limited, and preferred transmission is from exposure light source The light radiated.As this basilar memebrane, such as polyethylene terephthalate film, polyvinyl alcohol film, polychlorostyrene can be included Vinyl film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer membrane, polymethyl methacrylate copolymer Film, polystyrene film, polyacrylonitrile film, styrol copolymer film, PA membrane and cellulose derivative film.These films are according to need It can be stretched.The mist degree of film is preferably 0.01%~5.0%, is more preferably 0.01%~2.5%, more preferably 0.01%~1.0%.On the thickness of film, film is more thin, in terms of image formative and the economy for be favourable, but Due to needing to maintain intensity, therefore preferably 10 μm~30 μm.

In addition, the key property of the protective layer used in photosensitive-resin layered product is, it is desirable to protective layer and photonasty tree The closing force of lipid layer is less than the closing force of basilar memebrane and photo-sensitive resin, can be easily peeled off.As protective layer, preferably exemplified by Such as polyethylene film, polypropylene screen.It is, for example, possible to use the fissility that Japanese Unexamined Patent Application 59-202457 publications are recorded is excellent Film.The thickness of protective layer is preferably 10 μm~100 μm, more preferably 10 μm~50 μm.

In present embodiment, the thickness of the photo-sensitive resin in photosensitive-resin layered product is preferably 5 μm~100 μm, More preferably 7 μm~60 μm.The thickness of photo-sensitive resin is smaller, then the resolution ratio of corrosion-resisting pattern is more improved, on the other hand, sense The thickness of photosensitive resin layer is bigger, then solidifies film strength and more improve, therefore can be selected according to purposes.

As being sequentially laminated basilar memebrane, photo-sensitive resin and make photoresist according to desired protective layer The method of layered product, can use known method.As described above, by by the photonasty described in present embodiment The difference of the wet type of resin combination-dry lamination resolution ratio is adjusted to less than 5 μm, can take into account tracing ability and poor short circuit suppresses Property, therefore, photosensitive polymer combination can arbitrarily be used for wet type lamination and dry lamination.

For example, preparing above-mentioned photosensitive polymer combination distiller liquor, then, substrate is coated on using bar coater or roll coater On film and it is dried, the photo-sensitive resin formed by photosensitive polymer combination distiller liquor is laminated on basilar memebrane.And then, According to expectation, by being laminated protective layer on photo-sensitive resin, photosensitive-resin layered product can be made.

<Corrosion-resisting pattern forming method>

The forming method of corrosion-resisting pattern preferably includes successively：The photoresist of above-mentioned photosensitive polymer combination will be included The lamination process of supporting mass is pressed on layer by layer；The exposure process being exposed to photo-sensitive resin；And, will be exposed photosensitive The developing procedure that property resin bed is developed.In present embodiment, one of the specific method described below for forming corrosion-resisting pattern.

First, in lamination process, photo-sensitive resin is formed on substrate using laminating machine.Specifically, photosensitive Property resin laminate there is protective layer in the case of, peel off after protective layer, with laminating machine by photo-sensitive resin heating be crimped to Substrate surface is laminated.As the material of substrate, such as copper, stainless steel (SUS), glass, tin indium oxide can be included (ITO) etc..

In present embodiment, photo-sensitive resin can only be laminated to the one side of substrate surface, or lamination as needed In two sides.Heating-up temperature during lamination is usually 40 DEG C~160 DEG C.In addition, by carrying out the heating pressure of more than 2 times in lamination Connect, it is possible to increase adaptation of the gained corrosion-resisting pattern for substrate.During heating crimping, the two-part for possessing two company's rollers can be used Laminating machine is crimped, or, make the substrate repeatedly pass repeatedly through roller to crimp with the laminate of photo-sensitive resin.In wet type lamination In the case of, before lamination, substrate is contacted or to Direct spraying liquid on substrate by making to be impregnated with the sponge roller of liquid Method, substrate impregnated into method in a liquid etc., liquid is coated with to substrate surface.

Then, in exposure process, using exposure machine by photoresist group layer exposed to active light.Exposure can be according to the phase Hope after supporting mass is peeled off and carry out.When photomask is exposed, light exposure is determined according to light illumination and time for exposure It is fixed, quantometer can be used to determine.In exposure process, direct imaging exposure can also be carried out.In direct imaging exposure, do not make It is exposed with photomask on substrate using direct describing device.As light source, can use wavelength for 350nm~ 410nm semiconductor laser or ultrahigh pressure mercury lamp.When drawing pattern and being controlled with computer, light exposure is according to exposure light source Illumination and the translational speed of substrate are determined.

Then, in developing procedure, not exposing for the photo-sensitive resin after exposure is removed using developer solution using developing apparatus Light portion or exposure portion.After exposure, removed it in the case of there is basilar memebrane or supporting mass on photo-sensitive resin.Then, Using the developer solution comprising aqueous alkali, development removes unexposed portion or exposure portion, obtains resist pattern picture.

It is used as aqueous alkali, preferably Na₂CO₃、K₂CO₃Deng the aqueous solution.Aqueous alkali is combined with photo-sensitive resin Characteristic is selected, usually using the Na that concentration is the mass % of 0.2 mass %~2₂CO₃The aqueous solution.Can be with mixture table in aqueous alkali Face activating agent, defoamer, a small amount of organic solvent developed for promotion etc..The temperature of developer solution in developing procedure is preferably 20 DEG C~40 DEG C in the range of remain it is constant.

Corrosion-resisting pattern is obtained by above-mentioned operation, according to expectation, further can also be added with 100 DEG C~300 DEG C Thermal technology's sequence.By implementing the heating process, it is possible to increase the chemical reagent resistance of corrosion-resisting pattern.Heating process can be used and used The heating furnace of hot blast, infrared ray or far infrared mode.

The photosensitive polymer combination of present embodiment can be suitably employed in the circuit to form printed base plate.In general, As the circuit forming method of printed base plate, it can use and subtract technique and half additive process (SAP).

It is only to remove inverter circuit part from being configured on the conductor in the whole face of substrate by etching to subtract technique, so as to form electricity The method on road.

SAP is after forming resist layer in the inverter circuit part being configured in the conductor Seed Layer in the whole face of substrate, to pass through plating The method for only forming circuit part.

<The manufacture method of conductive pattern>

The manufacture method of conductive pattern preferably includes successively：Be laminated on the substrates such as metallic plate, metal film coated insulation board by The lamination process of the photo-sensitive resin of above-mentioned photosensitive resin composition formation；The exposure being exposed to photo-sensitive resin Process；Unexposed portion or the exposure portion of exposed photo-sensitive resin are removed using developer solution, so as to obtain being formed with against corrosion The developing procedure of the substrate of pattern；And, the substrate for being formed with corrosion-resisting pattern is etched or the conductive pattern of plating is formed Process.

In present embodiment, the manufacture method of conductive pattern is carried out as follows：Covered as substrate using metallic plate or metal Film insulation board, forms corrosion-resisting pattern by above-mentioned corrosion-resisting pattern forming method, then enters via conductive pattern formation process OK.In conductive pattern formation process, on the substrate surface (such as copper face) exposed by development, known etching is used Method or plating form conductive pattern.

And then, the present invention is suitable for for example following purposes.

<The manufacture method of circuit board>

Manufactured by the manufacture method of conductive pattern after conductive pattern, further enter to be about to corrosion-resisting pattern and use with than aobvious The stripping process that the stronger alkaline aqueous solution of shadow liquid is peeled off from substrate, so as to obtain with desired Wiring pattern Circuit board (such as printed circuit board (PCB)).

For the aqueous alkali (hereinafter also referred to " stripper ") of stripping, it is not particularly limited, is 2 usually using concentration The mass % of quality %~5 NaOH or the KOH aqueous solution or organic amine system stripper.It can be added in stripper a small amount of Water-soluble solvent.As water-soluble solvent, it can include such as alcohol.The temperature of stripper in stripping process is preferably 40 DEG C In the range of~70 DEG C.

<The manufacture of lead frame>

The metallic plate of copper, copper alloy or iron-based alloy etc. is used as substrate, by corrosion-resisting pattern forming method come shape Into after corrosion-resisting pattern, via following processes, so as to manufacture lead frame.First, the substrate exposed by development is carried out Etch to carry out the formation process of conductive pattern.Thereafter, using the manufacture method identical method with circuit board, stripping is carried out anti- The stripping process of corrosion figure case, can obtain desired lead frame.

<The manufacture of base material with relief pattern>

When the corrosion-resisting pattern formed by corrosion-resisting pattern forming method can be used as that substrate is implemented to process by sandblasting engineering method Protection mask parts.Now, as substrate, such as glass, silicon wafer, non-crystalline silicon, polysilicon, ceramics, Lan Bao can be included Stone, metal material etc..On these substrates, by forming corrosion-resisting pattern with corrosion-resisting pattern forming method identical method.Its Afterwards, following processes are carried out, the base material on substrate with micro concavo-convex pattern can be manufactured：Blow attached from the corrosion-resisting pattern of formation Blasting materials, cut into the blasting treatment process of target depth；And, it will be remained in using alkali stripper etc. against corrosion on substrate The stripping process that pattern part is removed from substrate.

In blasting treatment process, known blasting materials can be used, such as it is usually used to include SiC, SiO₂、Al₂O₃、 CaCO₃, ZrO, glass, the particulate that the particle diameter of stainless steel etc. is 2 μm~100 μm.

<The manufacture of semiconductor packages>

As substrate, using the chip for foring large scale integration circuit (LSI), by corrosion-resisting pattern forming method Formed on chip after corrosion-resisting pattern, by the way that via following processes, semiconductor packages can be manufactured.First, to by development The column plating of copper, solder etc. is implemented in the opening portion exposed, and carries out the formation process of conductive pattern.Thereafter, using with circuit board Manufacture method identical method, carry out peel off corrosion-resisting pattern stripping process, and then, carry out using etching remove except column The process of the thin metal layer of part outside plating, so as to obtain desired semiconductor packages.

In present embodiment, photosensitive polymer combination can be used for the manufacture of printed circuit board (PCB)；IC chip carrying lead The manufacture of frame；The metal foil Precision Machining of metal mask manufacture etc.；Welded ball array encapsulation (BGA), chip size packages (CSP) etc. The manufacture of packaging body；The manufacture of the belt substrates such as chip on film (COF), tape-automated bonding (TAB)；The system of semiconductor projection Make；And, the manufacture of the partition wall of the flat-panel screens such as ITO electrode, address electrode, electromagnetic wave shield.

It should illustrate, for above-mentioned each parameter value, in the case of no especially record, according in aftermentioned embodiment Assay method is measured.

Embodiment

Illustrate the making side of the measure and embodiment of the physics value of macromolecule and monomer and the sample for evaluation of comparative example Method.Then, the relevant evaluation method and its evaluation result of gained sample are shown.

(1) measure of physics value or calculating

<The measure of high molecular weight average molecular weight or number-average molecular weight>

On high molecular weight average molecular weight or number-average molecular weight, the gel infiltration manufactured by Japan Spectroscopy Corporation Chromatograph (GPC) (pump：Gulliver, PU-1580 type；Post：The Shodex (registration mark) of Showa Denko K. K's manufacture (KF-807, KF-806M, KF-806M, KF-802.5) 4 series connection；Fluidized bed solvent：Tetrahydrofuran, using based on polystyrene The standard curve of standard sample (the Shodex STANDARD SM-105 of Showa Denko K. K's manufacture)), with polystyrene The mode of conversion is obtained.

And then, high molecular decentralization with weight average molecular weight, relative to the ratio between number-average molecular weight, (divide equally by weight average molecular weight/number Son amount) form calculate.

<Acid equivalent>

In this specification, acid equivalent refers to the quality (gram) of the polymer with 1 equivalent carboxyl in molecule.Produced using flat natural pond The flat natural pond automatic titration device (COM-555) of industry Co., Ltd. manufacture, using 0.1mol/L sodium hydrate aqueous solution, passes through electricity Potential difference titration measuring acid equivalent.

(2) preparation method of sample for evaluation

Operate to make the sample for evaluation in embodiment 1~17 and comparative example 1~7 as follows.

<The making of photosensitive-resin layered product>

Be sufficiently stirred for, mix shown in table 1 below or 2 composition (wherein, each composition numeral represent in terms of solid constituent Compounding amount (mass parts)) and solvent, obtain photosensitive polymer combination distiller liquor.The composition that will be represented in Tables 1 and 2 with abbreviation Title be shown in Table 3 below.As support membrane, polyethylene terephthalate film (Mitsubishi's resin strain formula of 16 μ m-thicks is used Commercial firm's system, R310-16B), the distiller liquor is uniformly coated with it using bar coater, 2 points are dried in 95 DEG C of drying machine Clock, so as to form photosensitive polymer combination layer.The dry thickness of photosensitive polymer combination layer is 20 μm.

Then, not being laminated on a side surface of polyethylene terephthalate film in photosensitive polymer combination layer, The polyethylene film (タ マ Port リ Co. Ltd. systems, GF-818) of 19 μ m-thicks as protective layer is pasted, so as to obtain photoresist Layered product.

<The whole face of substrate>

Using grinding material (Japanese カ ー リ ッ ト Co. Ltd. systems, サ Network ラ Application ダ system R (registration mark #220)), utilize 0.2MPa atomisation pressure is ground to being laminated with the copper clad laminate progress jet frosted that 35 μm of rolled copper foils and thickness are 0.4mm Mill, so as to make evaluation substrate.And then, using the dry film against corrosion of 25 μ m thicks, using etching engineering method in evaluation real estate On by it is parallel, perpendicular to evaluate substrate processing direction in the way of formed respectively 100 μm of width, 5 μm of depth groove.

<Dry lamination>

While the polyethylene film of photosensitive-resin layered product is peeled off, while utilizing hot roll laminator (Asahi Kasei Corporation System, AL-700) photosensitive-resin layered product is laminated on the evaluation substrate for being pre-heated to 50 DEG C at 105 DEG C of roll temperature, So as to obtain test film.Air pressure is set to 0.35MPa, and laminate speed is set to 2.0m/ minutes.

<Wet type is laminated>

As lamination liquid, prepare ion exchange water.Slotted evaluation will be formed and be impregnated in ion exchange water with substrate, in base Plate surface is coated with ion exchange water.Peel the polyethylene film of photosensitive-resin layered product off, utilize hot roll laminator (Asahi Chemical Industry's strain formula Commercial firm's system, AL-700) photosensitive-resin layered product is laminated to the evaluation use impregnated of ion exchange water at 105 DEG C of roll temperature On substrate, so as to obtain test film.Air pressure is set to 0.35MPa, and laminate speed is set to 2.0m/ minutes.

<Exposure>

By directly drawing formula exposure device (Japanese オ Le ボ テ ッ Network Co. Ltd. system, Paragon Ultra-100, master Wavelength is 355nm), this figure is taken to 21 grades of exposure guide rules as mask, is exposed with various light exposures.Now, with exposing patterns Mode perpendicular to the groove for evaluating substrate is exposed.It should illustrate, using can be as every 1 μm of ground obtains the value of resolution ratio Pattern is drawn to be exposed.

<Development>

Peeled off from photosensitive-resin layered product after polyethylene terephthalate film, use Fuji Kiko KK's system The developing apparatus made, using solid cone spray nozzle, with 0.15MPa development atomisation pressure, by 30 DEG C of 1 mass %Na₂CO₃It is water-soluble Liquid sprays special time to be developed, and dissolving removes the unexposed portion of photo-sensitive resin.Now, by unexposed portion Shortest time needed for photo-sensitive resin is completely dissolved is measured as minimum developing time, with minimum developing time 2 times of times are developed to make corrosion-resisting pattern.Now, washing step utilizes 0.15MPa water washing spray by flat shaped nozzle Mist pressure, with the same time-triggered protocol of developing procedure.

(3) evaluation method of sample

<Dry lamination resolution ratio (after development)>

For after above-mentioned dry lamination by it is above-mentioned it is exposed and developed obtained from solidify corrosion-resisting pattern, will with relative to The value of resolution ratio is obtained as dry lamination resolution ratio as defined in the form of the minimum spacing width of line width against corrosion 200 μm wide .Above-mentioned exposure process is carried out using the residual film limit series after developing as 6 grades of light exposure.It should illustrate, it is anti-for solidification Corrosion figure case, evaluates the minimum spacing width being normally formed as follows：Resist layer is not remained in the substrate surface of unexposed portion, Substrate surface exposes, also not from the projection of composition against corrosion as solidification resist layer wire drawing, and the linearity of line width is also good, Resist layer is not solidified mutual closely sealed.

<Wet type lamination resolution ratio (after development)>

In addition to substituting above-mentioned dry lamination, (develop with above-mentioned dry lamination resolution ratio except carrying out above-mentioned wet type lamination Determination method afterwards) similarly obtains wet type lamination resolution ratio (after development).

<The difference of wet type-dry lamination resolution ratio>

Dry lamination resolution ratio (after development) is subtracted by being laminated resolution ratio (after development) by wet type, wet type-dry type is calculated The difference of resolution ratio is laminated, is evaluated using following benchmark.

Zero (good)：The difference of wet type-dry lamination resolution ratio is less than 5 μm.

× (bad)：The difference of wet type-dry lamination resolution ratio is more than 5 μm.

<Sensitivity (necessary light exposure)>

After above-mentioned dry lamination, in above-mentioned exposed and developed process, it is 6 grades to obtain the residual film limit series after development Light exposure, evaluated using following benchmark.

Zero (good)：Light exposure is less than 20mJ/cm²。

△ (permission)：Light exposure is 20mJ/cm²More than.

<Resolution ratio after etching>

Using wet type lamination resolution ratio (after development) as resolution ratio after etching, evaluated using following benchmark.

◎ (substantially good)：Resolution ratio is less than 17 μm after etching.

Zero (good)：Resolution ratio is more than 17 μm and less than 20 μm after etching.

△ (permission)：Resolution ratio is more than 20 μm and less than 25 μm after etching.

× (bad)：Resolution ratio is more than 25 μm after etching.

<Resolution ratio (routine)>

Resolution ratio (routine) is used as using dry lamination resolution ratio (after development).

(4) evaluation result

The evaluation result of embodiment 1~17 and comparative example 1~7 is shown in table 1 below, 2 or 3.It should illustrate, table 1 and 2 In, referred to as " long-chain RO monomers " represents the monomer in the molecule with more than 20 moles of oxyalkylene unit.

[table 1]

[table 2]

[table 3]

Claims (11)

1. a kind of layered product, it is characterised in that it, which possesses basilar memebrane and is arranged on the basilar memebrane, includes photonasty tree The photo-sensitive resin of oil/fat composition,

The photosensitive polymer combination is comprising (A) alkali solubility macromolecule, (B) compound and (C) containing ethylenic unsaturated bond Photoepolymerizationinitiater initiater,

The basilar memebrane can be peeled off from the photo-sensitive resin, and

The photosensitive polymer combination meets the relation shown in following mathematical expressions (1)：

W_X-D_X≤5μm (1)

In formula (1), W_XRefer to：The photo-sensitive resin is laminated in the presence of liquid with 100 μm wide and 5 μm of depths On the substrate of groove, then by corrosion-resisting pattern obtained from exposed and developed, with relative to line width against corrosion 200 μm wide most Resolution ratio (μm) as defined in the form of small spacing width, and

D_XRefer to：Under in the absence of liquid by photo-sensitive resin lamination on the substrate, then by exposed and developed Obtained from corrosion-resisting pattern, resolution ratio as defined in the form of the minimum spacing width of the line width against corrosion wide relative to 200 μm (μm)。

2. layered product according to claim 1, wherein, the photosensitive polymer combination hinders comprising (D) additive and (E) Poly- agent,

(D) additive includes the benzotriazole cpd containing amino without carboxyl,

(E) polymerization inhibitor includes epoxide.

3. layered product according to claim 1 or 2, wherein, it is used as the compound of (B) containing ethylenic unsaturated bond, bag Polyaddition monomer containing the oxyalkylene unit in the molecule with more than 20 moles.

4. according to layered product according to any one of claims 1 to 3, wherein, it is used as the change of (B) containing ethylenic unsaturated bond Compound, comprising oxyalkylene modified bisphenol A type two (methyl) acrylate compounds shown in following logical formula (II)s,

In formula (II), R₃And R₄Hydrogen atom or methyl are represented independently of one another；A is C₂H₄；B is C₃H₆；n₁、n₂、n₃And n₄It is to meet n₁+n₂+n₃+n₄The integer of=2~50 relation；The arrangement of the repeat unit of-(A-O)-and-(B-O)-is optionally random or embedding Section, in the case of block ,-(A-O)-is with-(B-O)-optionally in xenyl side.

5. according to layered product according to any one of claims 1 to 4, wherein, the compound of (B) containing ethylenic unsaturated bond Comprising selected from as three (methyl) acrylate compounds shown in following logical formula (III)s, the amino first shown in following logical formula (IV)s In the group of phthalate compound composition shown in (methyl) acrylate compounds of acid esters two and following logical formula (VI)s It is at least one kind of,

In formula (III), R₅、R₆And R₇Hydrogen atom or methyl are represented independently of one another；X represents the alkylidene of carbon number 2~6；m₂、m₃With m₄It is each independently 0~40 integer, m₂+m₃+m₄For 1~40, also, m₂+m₃+m₄For more than 2 when, multiple X are mutually the same Or it is different；

In formula (IV), R₈And R₉Hydrogen atom or methyl are represented independently of one another；Y represents the alkylidene of carbon number 2~6；Z represents that divalent has Machine group；S and t are each independently 0~40 integer, and s+t >=1；

In formula (VI), A represents C₂H₄；R₆₁Represent hydrogen atom or methyl；R₆₂Represent hydrogen atom, methyl or halogenated methyl；R₆₃Represent Alkyl, halogen atom or the hydroxyl of carbon number 1~6；A is 1~4 integer；K is 0~4 integer, also, k is more than 2 integer When, multiple R₆₃It is identical or different.

6. according to layered product according to any one of claims 1 to 5, wherein, (C) Photoepolymerizationinitiater initiater includes N- aryl Amino acid or its ester compounds.

7. layered product according to claim 6, wherein, (C) Photoepolymerizationinitiater initiater comprising N-phenylglycine or its Ester compounds.

8. according to layered product according to any one of claims 1 to 7, wherein, (A) the alkali solubility macromolecule includes to constitute Styrol structural units more than 40 mass % is calculated as on the basis of the gross mass of the high molecular monomer of (A) alkali solubility.

9. according to layered product according to any one of claims 1 to 8, it is used for direct imaging exposure.

10. a kind of forming method of corrosion-resisting pattern, it includes：

The photosensitive polymer combination of layered product according to any one of claims 1 to 9 is laminated to the layer of supporting mass Press process；

The exposure process being exposed to the photosensitive polymer combination；And

The developing procedure that the exposed photosensitive polymer combination is developed.

11. a kind of manufacture method of circuit board, it includes：

The photosensitive polymer combination of layered product according to any one of claims 1 to 9 is laminated to the lamination of substrate Process；

The exposure process being exposed to the photosensitive polymer combination；

The exposed photosensitive polymer combination is developed, so as to obtain being formed with the development work of the substrate of corrosion-resisting pattern Sequence；

The substrate for being formed with corrosion-resisting pattern is etched or plating conductive pattern formation process；And

Peel off the stripping process of the corrosion-resisting pattern.