JP5098411B2 - Photosensitive resin composition, and photosensitive film and photosensitive permanent resist using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition, and a photosensitive film and a photosensitive permanent resist using the same.

  With the reduction in size and weight of various electronic devices, photosensitive solder resists capable of forming fine opening patterns are used for printed wiring boards, semiconductor package boards, flexible wiring boards, and the like.

  In general, the solder resist is required to have characteristics such as developability, high resolution, insulation, solder heat resistance, and gold plating resistance. In particular, for solder resists for package substrates, in addition to the above characteristics, for example, crack resistance against a temperature cycle test (TCT) of -55 ° C. to 125 ° C. and HAST characteristics between fine wirings are required. ing.

  In recent years, as a solder resist, a dry film type is attracting attention from the viewpoint of improving film thickness uniformity, surface smoothness, and thin film formability. According to such a dry film type solder resist, in addition to the above characteristics, effects such as simplification of the process for resist formation and reduction of the amount of solvent discharged during resist formation can be obtained.

  Here, as the solder resist, a two-component type photosensitive resin composition in which an epoxy resin which is a curable component and a photosensitive prepolymer containing a carboxylic acid group for imparting alkali developability are separately divided. What consists of things is common. As the photosensitive prepolymer, an alkali-developable photosensitive prepolymer obtained by adding acrylic acid to a cresol novolac type epoxy resin and then acid-modifying is widely used (for example, see Patent Document 1).

However, the conventional photosensitive resin composition is excellent in solder heat resistance among the characteristics required for a solder resist, but the cured product tends to be brittle and has insufficient crack resistance. There was a problem. In order to improve crack resistance, a method of adding an elastomer to the photosensitive resin composition is known (see, for example, Patent Document 2).
JP-A 61-243869 JP 2002-162738 A

  However, in recent years, further improvement in crack resistance has been demanded for solder resists, and it has been difficult for the conventional photosensitive resin composition to sufficiently satisfy such requirements. Moreover, all of said photosensitive resin composition was a 2 liquid type thing, and the epoxy resin and the photosensitive prepolymer would react at room temperature. Therefore, the stability (pot life) after mixing these two liquids is insufficient, and the handling is not always easy, such as difficulty in mixing timing during use. Furthermore, the solder resist obtained from the above-mentioned conventional photosensitive resin composition is susceptible to contamination by the metal constituting the circuit at high temperature and high humidity, and it is difficult to maintain the properties such as insulation for a long time. There was a tendency.

  Accordingly, the present invention has been made in view of such circumstances, and is capable of forming a dry film type solder resist having excellent crack resistance and sufficient HAST resistance, and is capable of forming an alkali developing one-pack type. An object of the present invention is to provide a photosensitive resin composition. Another object of the present invention is to provide a photosensitive film and a photosensitive permanent resist using such a photosensitive resin composition.

In order to achieve the above object, the photosensitive resin composition of the present invention comprises (a) a binder polymer having a carboxyl group, (b) a photopolymerizable monomer having at least one ethylenically unsaturated group, and (c) a polyurethane compound. ( D) a photopolymerization initiator and (e) a block type isocyanate , and (a) a binder polymer obtained by using (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component containing system copolymer compound, (c) an polyurethane compound, an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound obtained by reacting a diol compound having a carboxyl group It is characterized by that.

  The photosensitive resin composition of the present invention is a one-component composition containing the above components (a) to (d) and including both a curable component and a component for imparting alkali developability. These components hardly react with each other even when stored at room temperature. Therefore, the photosensitive resin composition of the present invention has a characteristic that it is excellent in stability despite being a one-pack type. Moreover, since this photosensitive resin composition contains (c) component especially, it can form the cured film which was tough and excellent in elongation after hardening. Therefore, a solder resist having excellent crack resistance can be formed. Furthermore, since the solder resist obtained from the photosensitive resin composition of the present invention is hardly contaminated even under high temperature and high humidity conditions, it has excellent HAST resistance.

  The photosensitive resin composition of the present invention preferably further contains (e) a block type isocyanate. The photosensitive resin composition containing the component (e) has excellent storage stability, and particularly excellent storage stability is obtained even when a dry film type solder resist is formed.

  The binder polymer (a) is preferably a vinyl copolymer compound obtained by using (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component. By including such a binder polymer, the developability of the photosensitive resin composition is further improved.

  The present invention also provides a photosensitive film comprising a support and a layer made of the above-described photosensitive resin composition of the present invention formed on the support. According to such a photosensitive film, a dry film type solder resist made of the photosensitive resin composition of the present invention can be easily formed.

  Furthermore, this invention provides the photosensitive permanent resist which consists of a photocured material of the said photosensitive resin composition of this invention apply | coated on the board | substrate for printed wiring boards. Since this permanent resist is formed from the photosensitive resin composition of the present invention, the permanent resist has excellent crack resistance and sufficient HAST resistance.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the one-pack type photosensitive resin composition which can form the dry film type solder resist which is excellent in crack resistance and has sufficient HAST resistance, and which can be developed with alkali. It becomes. Moreover, according to this invention, the photosensitive film and photosensitive permanent resist which were obtained using this photosensitive resin composition can be provided.

Hereinafter, preferred embodiments of the present invention will be described.
[Photosensitive resin composition]

  First, the photosensitive resin composition which concerns on suitable embodiment is demonstrated. The photosensitive resin composition of this embodiment contains (a) a binder polymer, (b) a photopolymerizable monomer, (c) a polyurethane compound, and (d) a photopolymerization initiator. Hereinafter, each of these components will be described.

(C) Polyurethane Compound First, the polyurethane compound which is a particularly characteristic component (c) in the photosensitive resin composition of the present embodiment will be described. The polyurethane compound is a polyurethane compound obtained by reacting an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group, a diisocyanate compound, and a diol compound having a carboxyl group.

  As a polyurethane compound, what has a bisphenol A type structure as a hard segment part formed from the epoxy acrylate compound which has a 2 or more hydroxyl group and ethylenically unsaturated group is preferable. Examples of preferred polyurethane compounds include UXE-3011 and UXE-3012 (sample name, above, manufactured by Nippon Kayaku Co., Ltd.).

  As described above, the polyurethane compound is an epoxy acrylate compound having two or more hydroxyl groups and an ethylenically unsaturated group (hereinafter referred to as “raw material epoxy acrylate”), a diisocyanate compound (hereinafter referred to as “raw material diisocyanate”), and It is a compound obtained using a diol compound having a carboxyl group (hereinafter referred to as “raw diol”) as a raw material component. First, these raw material components will be described.

  Examples of the raw material epoxy acrylate include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, novolac type epoxy compounds, compounds obtained by reacting (meth) acrylic acid with epoxy compounds having a fluorene skeleton, and the like.

  As the raw material diisocyanate, any compound having two isocyanato groups can be used without particular limitation. For example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolden diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, norbornane-diisocyanate methyl and the like can be mentioned. As a diisocyanate compound, it can apply individually by 1 type or in combination of 2 or more types.

  The raw material diol is a compound having two hydroxyl groups such as alcoholic hydroxyl group and phenolic hydroxyl group in the molecule, and also having a carboxyl group. The hydroxyl group preferably has an alcoholic hydroxyl group from the viewpoint of improving the developability of the photosensitive resin composition with an alkaline aqueous solution. Examples of such diol compounds include dimethylolpropionic acid and dimethylolbutanoic acid.

  Here, the (meth) acryl group refers to an acryl group and / or a methacryl group corresponding thereto. Similarly, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant, and the (meth) acryloxy group means an acryloxy group and a methacryloxy group corresponding thereto.

  Next, an example of a process for producing a polyurethane compound using the raw material components described above will be described.

  That is, in the production process of the polyurethane compound, first, the raw material epoxy acrylate and the raw material diol are reacted with the raw material diisocyanate. In this reaction, a so-called urethanization reaction occurs mainly between the hydroxyl group in the raw material acrylate and the isocyanate group in the raw material diisocyanate and between the hydroxyl group in the raw material diol and the isocyanate group in the raw material diisocyanate. By this reaction, for example, an intermediate in which a structural unit derived from a raw material epoxy acrylate and a structural unit derived from a raw material diol are alternately or block-polymerized via a structural unit derived from a raw material diisocyanate. Arise.

  Next, such an intermediate and raw material epoxy are reacted to obtain a polyurethane compound. In this reaction, a so-called epoxycarboxylation reaction occurs mainly between the carboxyl group derived from the diol compound in the intermediate and the epoxy group of the raw material epoxy. The polyurethane compound thus obtained has, for example, a main chain formed from the above-described intermediate and a side chain containing an ethylenically unsaturated group derived from the raw material epoxy acrylate or the raw material epoxy.

  In the process for producing the polyurethane compound described above, in the step of obtaining the intermediate, in addition to the raw material epoxy acrylate, the raw material diol and the raw material diisocyanate, a diol compound different from these may be further added. Thereby, it becomes possible to change the main chain structure of the obtained polyurethane compound, and the characteristics such as the acid value described later can be adjusted to a desired range. Moreover, in each process mentioned above, you may use a catalyst etc. suitably.

ここで、式（１）中、Ｒ^１１はエポキシアクリレートの残基、Ｒ^１２はジイソシアネートの残基、Ｒ^１３は炭素数１〜５のアルキル基、Ｒ^１４は水素原子又はメチル基を示す。なお、残基とは、原料成分から結合に供された官能基を除いた部分の構造をいう。また、式中に複数ある基は、それぞれ同一でも異なっていてもよい。 As such a polyurethane compound, the compound represented by following General formula (1) can be illustrated, for example.

Here, in formula (1), R ¹¹ is a residue of epoxy acrylate, R ¹² is a residue of diisocyanate, R ¹³ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁴ is a hydrogen atom or a methyl group. In addition, a residue means the structure of the part remove | excluding the functional group used for the coupling | bonding from the raw material component. In addition, a plurality of groups in the formula may be the same or different.

  The polyurethane compound preferably has an acid value of 20 to 130 mgKOH / g, and more preferably has an acid value of 40 to 110 mgKOH / g. Thereby, the developability with the alkaline aqueous solution of the photosensitive resin composition becomes good, and an excellent resolution can be obtained. Further, the weight average molecular weight of the polyurethane compound is preferably 3000 to 30000 from the viewpoint of obtaining good coating properties with the photosensitive resin composition, crack resistance and HAST resistance of the cured film, and 5000 to 20000. Is more preferable.

Here, the acid value can be measured as follows. That is, first, about 1 g of a resin solution whose acid value is to be measured is precisely weighed, and then 30 g of acetone is added to this resin solution to dissolve it uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
A = 10 × Vf × 56.1 / (Wp × I)

  In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of phenolphthalein, Wp represents the weight (g) of the measured resin solution, and I represents the measured resin solution The ratio (% by mass) of the nonvolatile content of Such an acid value measuring method can be similarly applied to the following (a) binder polymer and the like.

  Since such a polyurethane compound is easily compatible with (a) a binder polymer described later, a uniform photosensitive resin composition is easily obtained by including such a polyurethane compound. Moreover, since this polyurethane compound can form a tough and excellent cured film, the crack resistance of the cured film of the photosensitive resin composition can be improved. When it is contained together with (e) block type isocyanate which will be described later, such characteristics can be exhibited particularly well.

(A) Binder polymer The binder polymer as the component (a) is a polymer having a carboxyl group in the molecule. The weight average molecular weight (Mw) of this binder polymer is preferably 20000 to 150,000, and more preferably 30000 to 120,000. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene).

  The binder polymer may further have an ethylenically unsaturated group, and may be a polymer that functions as a so-called photosensitive prepolymer.

  As the binder polymer, known resins such as acrylic, polyurethane, epoxy, phenoxy, polyester, polyamide, polyimide, polyamideimide, polyesterimide, polycarbonate, melamine resin, polyphenylene sulfide, polyoxybenzoyl, and acid-modified resins thereof, The thing which has a carboxyl group in a molecule | numerator is mentioned. For example, in the case of an acrylic or acid-modified polyester binder polymer, the acid value of the binder polymer is preferably 50 to 170 mgKOH / g, and more preferably 60 to 150 mgKOH / g.

  Among them, an acrylic binder polymer is preferable as the binder polymer. As the acrylic binder polymer, for example, a vinyl copolymer compound obtained by using (meth) acrylic acid, (meth) acrylic acid alkyl ester or the like as a copolymerization component is suitable. In particular, a vinyl copolymer compound obtained by using methacrylic acid, alkyl acrylate ester and alkyl methacrylate ester as a copolymerization component is preferable.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like.

  As this vinyl copolymer compound, those obtained by copolymerizing (meth) acrylic acid alkyl ester or (meth) acrylic acid and a vinyl monomer copolymerizable therewith are also preferred. Examples of such vinyl monomers include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2- Examples include trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like.

  Moreover, what contains the acrylic acrylate which has an ethylenically unsaturated group as a copolymerization component as a vinyl-type copolymer compound which is an acrylic binder polymer is also applicable.

  As the binder polymer, an acid-modified polyester resin is also preferable. Examples of the acid-modified polyester resin include a chain structure including an ester bond formed by a polymerization reaction between a diglycidyl ether type epoxy compound and a dibasic acid using a tertiary amine having a pKa of 9.0 or less as a catalyst. And a resin having a carboxyl group formed by adding an acid anhydride to this chain structure.

  Diglycidyl ether type epoxy compounds for forming this acid-modified polyester resin include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S diester. Bisphenol S type epoxy resins such as glycidyl ether, biphenol type epoxy resins such as biphenol diglycidyl ether, bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resins such as hydrogenated bisphenol A glycidyl ether, These dibasic acid-modified diglycidyl ether type epoxy resins and the like can be mentioned. Among these, bisphenol A type epoxy resins are preferred because they are excellent in heat resistance and chemical resistance and do not relatively shrink due to curing. These can be used alone or in combination of two or more.

(B) Photopolymerizable monomer The photopolymerizable monomer as the component (b) is a compound having at least one ethylenically unsaturated group in the molecule. Examples of such a photopolymerizable monomer include a bisphenol A-based (meth) acrylate compound; a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid; a glycidyl group-containing compound with α, β- Compounds obtained by reacting an unsaturated carboxylic acid; urethane monomers or urethane oligomers such as (meth) acrylate compounds having a urethane bond in the molecule. Besides these, nonylphenoxy polyoxyethylene acrylate; γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxy Examples thereof include phthalic acid compounds such as alkyl-o-phthalate; (meth) acrylic acid alkyl ester, EO-modified nonylphenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Can be mentioned.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl), 2,2- Bis (4-((meth) acryloxydodecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl), 2,2-bis (4-((meth) acrylic) Loxytetradecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl), etc. Is mentioned.

  Of these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). , 2-bis (4- (methacryloxypentadecaethoxy) phenyl) is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). You may use these individually or in combination of 2 or more types.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4- ( (Meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecapropoxy) ) Phenyl) and the like. These may be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) A Examples thereof include acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH ₂ —CH _2). -O-) having a block structure.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl and the like. Examples of the α, β-unsaturated carboxylic acid for obtaining the above compound include (meth) acrylic acid.

  Examples of urethane monomers include (meth) acrylic monomers having an OH group at the β-position and diisocyanates such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples include addition reaction products with compounds, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO or PO-modified urethane di (meth) acrylate, and the like.

  Furthermore, examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like. It is done. These (b) components can be used individually by 1 type or in combination of 2 or more types.

(D) Photopolymerization initiator As the photopolymerization initiator (d) component, for example, benzophenone, N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1 Aromatic ketones such as-(4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 4,4'-bis (dimethylamino) Benzophenone (Mihera ketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-morpholinophenone) -butanone-1,2-ethylanthraquinone , Aromatic ketones such as phenanthrenequinone, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoin phenyl ether, benzoins such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl 2,4 such as imidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer , 5-triarylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-a Lysinyl) acridine derivatives such as heptane, N- phenylglycine, N- phenylglycine derivatives, coumarin-based compounds. These can be used singly or in combination of two or more.

(E) Block-type isocyanate It is preferable that the photosensitive resin composition of suitable embodiment further contains (e) block-type isocyanate. The block type isocyanate is inactive at room temperature, but is a compound that regenerates the isocyanate group by reversibly dissociating the blocking agent when heated. The dissociation temperature of the blocking agent is preferably 120 to 200 ° C.

  Examples of such isocyanate compounds include isocyanurate type, biuret type, and adduct type. Among these, the isocyanurate type is preferable from the viewpoint of improving the adhesion by the photosensitive resin composition. These can be used alone or in combination of two or more.

  In the block type isocyanate compound, examples of the blocking agent bonded to the isocyanate include at least one selected from diketones, oximes, phenols, alkanols and caprolactams. Specific examples include methyl ethyl ketone oxime and ε-caprolactam.

  Examples of such a block type isocyanate include Sumidur BL-3175, Death Module TPLS-2957, TPLS-2062, TPLS-2957, TPLS-2078, BL4165, TPLS2117, BL1100, BL1265, Desmotherm 2170, Desmotherm 2265 (Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B-846, B-870, B- 874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.) and the like.

  When the insulating property excellent in the photosensitive resin composition is calculated | required, as above-mentioned, as a block type isocyanate, what contains aromatic rings, such as an isocyanuric skeleton and a benzene ring, is preferable in the structure. Examples of such a block type isocyanate include Sumijoule BL-3175, Sumijoule BL-4265, B-870 and the like.

  In addition to the components (a) to (e) described above, the photosensitive resin composition may further include other components according to desired characteristics.

  As other components, first, a diluent may be mentioned. By including a diluent, the viscosity of the photosensitive resin composition is adjusted, and application on a predetermined substrate becomes easy. Examples of the diluent include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol, hydrocarbons such as benzyl alcohol and cyclohexane, diacetone alcohol, Aliphatic ketones such as 3-methoxy-1-butanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, pro Ethylene glycol alkyl ethers such as lenglycol diacetate, propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate And its acetate, diethylene glycol monoalkyl ether and its acetate, diethylene glycol dialkyl ether, triethylene glycol alkyl ether, propylene glycol alkyl ether and its acetate, dipropylene glycol alkyl ether and the like.

  Also, petroleum solvents such as toluene, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha or solvent naphtha, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate Carboxylic acid esters such as ethyl propionate, methyl butyrate and ethyl butyrate, amines and amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl Examples of the solvent include sulfoxide, dioxane, tetrahydrofuran, cyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-pentanone, and 6-hydroxy-2-hexanone. These can be used alone or in combination of two or more.

  In addition, the photosensitive resin composition may further contain an adhesion improver for the purpose of improving the adhesion to a metal such as copper used in a circuit such as a printed wiring board. Examples of the adhesion improver include additives such as melamine, dicyandiamide, triazine compound and derivatives thereof, imidazole, thiazole, triazole, and silane coupling agents.

  More specifically, examples of the adhesion improver include melamine, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, dicyandiamide, manufactured by Shikoku Kasei Kogyo Co., Ltd .; 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE. 2MA-OK and the like. Also, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine can be exemplified. These adhesion improvers can improve the adhesion to a circuit made of copper or the like, and can also improve the PCT resistance and the electric corrosion resistance of the layer made of the photosensitive resin composition.

  Furthermore, the photosensitive resin composition may further contain a filler (inorganic and / or organic filler) for the purpose of improving adhesion and improving the hardness of the cured product. Examples of the inorganic filler include barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Examples of the organic filler include diallyl phthalate, diallyl phthalate prepolymer, acrylic rubber, nitrile rubber (NBR), silicone powder, nylon powder, aerosil, benton, and montmorillonite.

  Furthermore, the photosensitive resin composition can be used as required, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, malachite green, crystal violet, titanium oxide, carbon black, naphthalene black, azo organic pigments, etc. It may contain colorants, dyes and the like. In addition, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, thixotropic agents such as benton, montmorillonite, aerosil, amide wax, antifoaming such as silicone, fluorine, and polymer An agent and a leveling agent may be included as long as the desired properties of the photosensitive resin composition are not affected.

  Next, the suitable content rate of each component in the photosensitive resin composition is demonstrated.

  First, the preferable content of the components (a), (b) and (c) is 30 to 50 parts by weight, 20 parts per 100 parts by weight of the total of the components (a), (b) and (c), respectively. -40 parts by weight and 20-40 parts by weight.

  In addition, the content of the component (d) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the components (a), (b) and (c), Part is more preferable. When the content of the component (d) is in such a range, the photosensitivity and solder heat resistance of the photosensitive resin composition are improved.

  Furthermore, when the photosensitive resin composition contains the component (e), the content thereof is 5 to 40 parts by weight with respect to 100 parts by weight of the total of the components (a), (b) and (c). The amount is preferably 10 to 30 parts by weight.

  When the photosensitive resin composition is applied as a liquid composition, the content of the diluent is preferably 5 to 40% by weight based on the total weight. On the other hand, when a photosensitive resin composition layer is formed on a support like a photosensitive film described later, the content of the diluent is 30 to 70 weight in a varnish state before being applied to the support. It is preferable that the content be 3% by weight or less after coating.

Moreover, when the photosensitive resin composition contains an adhesion improver, the content is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the components (a), (b) and (c). It is preferable. Furthermore, the suitable usage-amount of a filler is 0 to 70 weight% with respect to the total amount of the photosensitive resin composition.
[Photosensitive film]

  Next, the photosensitive film of suitable embodiment is demonstrated. FIG. 1 is a diagram schematically showing a cross-sectional configuration of a photosensitive film according to a preferred embodiment. As shown in FIG. 1, the photosensitive film 1 includes a support 10 and a photosensitive resin composition layer 20 made of a photosensitive resin composition formed on the support 10. Moreover, as shown in the figure, a protective film 30 that covers the layer may be further provided on the photosensitive resin composition layer 20.

  The photosensitive resin composition layer 20 is a layer made of the photosensitive resin composition of the preferred embodiment described above. The photosensitive resin composition layer 20 is prepared by dissolving the photosensitive resin composition in a solvent such as a diluent as described above to obtain a solution having a solid content of about 30 to 80% by weight. It is preferable to form by coating.

  Although the thickness of the photosensitive resin composition layer 20 varies depending on the use, it is preferably 10 to 100 μm and more preferably 20 to 60 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. preferable. The thickness of less than 10 μm tends to be difficult because it is difficult to apply industrially. On the other hand, when exceeding 100 micrometers, the effect show | played by using the photosensitive resin composition of embodiment mentioned above tends to become small, and there exists a tendency for a flexibility and a resolution to fall especially.

  Moreover, as the support body 10 with which the photosensitive film 1 is provided, the polymer film etc. which have heat resistance and solvent resistance, such as a polyethylene terephthalate, a polypropylene, polyethylene, polyester, etc. are mentioned, for example.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. When the thickness is less than 5 μm, the support 10 tends to be easily broken when the support 10 is peeled off before development. On the other hand, when it exceeds 100 μm, the resolution and flexibility tend to decrease.

  The photosensitive film 1 composed of two layers of the support 10 and the photosensitive resin composition layer 20 as described above, or the photosensitive property composed of three layers of the support 10, the photosensitive resin composition layer 20 and the protective film 30. The film 1 may be stored as it is, for example, or may be stored in a roll shape around a winding core with a protective film interposed.

Since the photosensitive film 1 having such a configuration includes the photosensitive resin composition layer 20 made of the photosensitive resin composition of the above-described embodiment, it is a case where the support 10 is made thicker than before. However, sufficient flexibility can be maintained, and excellent resolution can be exhibited.
[Method of forming resist pattern]

  Next, a preferred embodiment of a method for forming a resist pattern using the above-described photosensitive resin composition will be described.

  First, the photosensitive resin composition layer which consists of the photosensitive resin composition of embodiment mentioned above is formed on the board | substrate which should form a resist. The photosensitive resin composition layer is formed by a method of applying the varnish of the photosensitive resin composition by a known method such as a screen printing method or a method of applying by a roll coater, or by using the above-described photosensitive film 1 and laminating. It can be formed by a method of attaching the photosensitive resin composition layer 20 or the like. When using the photosensitive film 1, you may perform the removal process which removes the protective film 30 before affixing. Examples of the substrate on which the resist is to be formed include a printed wiring board, a semiconductor package substrate, and a flexible wiring board.

  Next, an exposure process is performed in which the photosensitive resin composition layer is irradiated with actinic rays through a mask pattern having a predetermined pattern shape, and a predetermined region of the photosensitive resin composition layer is photocured. As the light source of the actinic ray, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp can be used. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can be used.

  Then, a removal step is performed in which a region (uncured portion) that has not been cured without being irradiated with actinic rays in the photosensitive resin composition layer is removed by, for example, dissolving in a developer. Thereby, a resist pattern having a predetermined pattern shape is formed. As the developer, an alkali developer is used, and for example, a dilute solution (1 to 5 wt% aqueous solution) of sodium carbonate at 20 to 50 ° C. is suitable. Development can be performed by a known method such as spraying, rocking dipping, brushing, scraping or the like.

After the development process is completed, it is preferable to further irradiate the resist pattern with ultraviolet rays or heat with a high-pressure mercury lamp for the purpose of improving the solder heat resistance, chemical resistance, etc. of the resist pattern. When irradiating with ultraviolet rays, it is preferable to adjust the irradiation amount as necessary. For example, irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out on the conditions for about 15 to 90 minutes in the range of about 100-170 degreeC.

  Both ultraviolet irradiation and heating may be performed. In this case, both may be performed at the same time, and after either one is performed, the other may be performed. When performing ultraviolet irradiation and a heating simultaneously, it is more preferable to heat to 60-150 degreeC from a viewpoint of providing solder heat resistance, chemical resistance, etc. more favorably.

  The solder resist thus formed is used, for example, as a plating resist or etching resist when plating or etching is performed on the substrate, and is left on the substrate as it is to protect wiring and the like. Used as a protective film (photosensitive permanent resist).

  And since said resist pattern is formed from the photosensitive resin composition of embodiment mentioned above, since it has the outstanding gold-plating property besides the outstanding crack resistance and HAST resistance, a printed wiring board It is effective as a solder resist for semiconductor package substrates and flexible wiring boards. Then, the substrate on which the resist pattern is formed is mounted with components such as LSI (for example, wire bonding, solder connection), and further mounted on an electronic device such as a personal computer.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Production of acid-modified polyester resin]

(Production Example 1)
First, in a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, a bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 479 g / eq, trade name Epototo YD-011) 182.7 Reflux dehydration of moisture contained in epoxy resin by charging mass part, 64.0 parts by mass of propylene glycol monomethyl ether acetate and 30.0 parts by mass of toluene and stirring while heating to 130 ° C. while blowing nitrogen gas Went.

  Next, 34.9 parts by mass of tetrahydrophthalic acid (manufactured by Shin Nippon Rika Co., Ltd.) and 3.6 parts by mass of dimethyl paratoluidine (manufactured by Samsung Chemical Co., Ltd.) were added thereto, and the mixture was kept at 140 ° C. for 4 hours. Then, 108.0 parts of tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd.) was added, and kept at 120 ° C. for 3 hours to obtain an acid-modified polyester resin (resin (1)).

Thereafter, this acid-modified polyester resin was diluted with 127.0 parts by mass of methyl ethyl ketone. The obtained modified epoxy resin had a weight average molecular weight of 38000, a solid content of 58.0%, and an acid value of 130 mgKOH / g.
[Preparation of photosensitive film]

(Examples 1-5, Comparative Examples 1-2)
First, the solution of the photosensitive resin composition was obtained by mixing the component (1) -component (5) shown in Table 1 and other components by the compounding ratio (mass basis) of solid content shown in a table | surface. In the table, the resin (1) in the component (1) is the acid-modified epoxy resin obtained in Production Example 1 described above, and the resin (2) is a carboxyl group-containing acrylic polymer, which includes methacrylic acid, It is a copolymer of methyl methacrylate and butyl acrylate (methacrylic acid: methyl methacrylate: butyl acrylate = 17% by weight: 62% by weight: 21% by weight) with a weight average molecular weight of 100,000 and an acid value of 110 mgKOH / g. . These components (1) correspond to the component (a) in the above-described embodiment.

  In addition, DPHA in component (2) is dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA), and FA-321M is bisphenol A polyoxyethylene dimethacrylate (Hitachi Chemical Industry Co., Ltd.). Product name FA-321M). These correspond to the component (b) in the above-described embodiment.

  Furthermore, UXE-3011 in component (3) is a polyurethane compound (manufactured by Nippon Kayaku Co., Ltd., sample name UXE-3011, weight average molecular weight: 10,000), and corresponds to component (c) in the above-described embodiment. To do. On the other hand, ZFR-1158 is bisphenol F-type acid-modified epoxy acrylate (Nippon Kayaku Co., Ltd., trade name, weight average molecular weight: 10,000), and ZAR-2003H is bisphenol A-type acid-modified epoxy acrylate (Nippon Kay). This is a product name, weight average molecular weight: 10,000, manufactured by Yakuhin Co., Ltd.

  Furthermore, I-369 in the component (4) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name I-369). And corresponds to the component (d) in the above-described embodiment.

  Furthermore, BL-3175 in the component (5) is a block type isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name BL-3175) and corresponds to the component (e) in the above-described embodiment. On the other hand, Epicoat 9001 is a bisphenol A type epoxy resin (product name Epicoat 1009, manufactured by Japan Epoxy Resin Co., Ltd.).

In addition, to these photosensitive resin compositions, methyl ethyl ketone, which is also used in acid-modified polyester resins, was added as a diluent.

  Next, these photosensitive resin composition solutions are uniformly applied onto a 16 μm polyethylene terephthalate film (trade name G2-16, manufactured by Teijin Limited), which is a support layer, on the support layer. A photosensitive resin composition layer was formed. This photosensitive resin composition layer was dried at 100 ° C. for 10 minutes using a hot air convection dryer. The film thickness after drying of the photosensitive resin composition layer was 25 μm.

Subsequently, on the surface of the photosensitive resin composition layer opposite to the side in contact with the support layer, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name NF-15) is bonded as a protective film, and the photosensitive film Got.
[Characteristic evaluation]

  Each of the following tests was carried out using the photosensitive elements of Examples 1 to 5 and Comparative Examples 1 and 2, respectively, and the coating properties, solder heat resistance, crack resistance, HAST resistance when each photosensitive element was used. And storage stability was evaluated. The results are summarized in Table 2.

(Coating properties)
The polyethylene terephthalate on the photosensitive resin composition layer was peeled off without performing exposure to the photosensitive film. A finger was lightly pressed against the surface of the coating film, and the degree of sticking to the finger was evaluated according to the following criteria. That is, “O” indicates that sticking to the finger is not or hardly recognized, and “X” indicates that sticking to the finger is recognized.

(Solder heat resistance)
First, an evaluation substrate was prepared as follows using each photosensitive film. That is, first, the copper surface of a printed wiring board substrate (E-679, manufactured by Hitachi Chemical Co., Ltd., trade name) in which a 12 μm thick copper foil is laminated on a glass epoxy substrate is polished with an abrasive brush and washed with water. And then dried. Using a continuous press type vacuum laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho) on this printed wiring board substrate, the press hot plate temperature is 70 ° C., the evacuation time is 20 seconds, the lamination press time is 30 seconds, and the atmospheric pressure is 4 kPa. Hereinafter, the polyethylene film of the photosensitive film was peeled and laminated under the condition of a pressure bonding pressure of 0.4 MPa to obtain a laminate for evaluation.

  Next, a photo tool having a 2 mm square pattern as a negative is brought into intimate contact with the laminate for evaluation, and the remaining after development of the stopher 21-step tablet using an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. The exposure was performed with an energy amount at which the step number was 8.0.

  The evaluation laminate after exposure was allowed to stand at room temperature for 1 hour, and then the polyethylene terephthalate on this laminate was peeled off, and the minimum development time (the unexposed area was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. Spray development was performed in 1.5 times the minimum time. Thereby, the pattern formed by hardening the photosensitive resin composition layer was formed.

Subsequently, ultraviolet irradiation is performed with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., and further heat treatment is performed at 160 ° C. for 60 minutes, so that 2 mm is formed on the printed wiring board substrate. An evaluation substrate on which a solder resist having a corner opening was formed was obtained.

  And evaluation of solder heat resistance was performed as follows using each board | substrate for evaluation obtained in this way. That is, after applying a rosin flux (product name: MH-820V, manufactured by Tamura Kaken Co., Ltd.) to the substrate for evaluation, a soldering treatment was performed in which the substrate was immersed in a 260 ° C. solder bath for 30 seconds.

  In this way, the crack generation state of the solder resist on the evaluation substrate subjected to the solder plating, and the degree of floating and peeling of the solder resist from the substrate were visually observed. The results were evaluated according to the following criteria. In other words, “O” indicates that no cracking of the solder resist was observed and no solder resist was lifted or peeled off, and “X” indicates that any of them was recognized.

(Crack resistance)
The substrate for evaluation having a solder resist produced in the same manner as described above was exposed to the atmosphere at −55 ° C. for 15 minutes, then heated at a rate of temperature increase of 180 ° C./min, and then in the atmosphere at 125 ° C. Then, the test was repeated 1000 times for the thermal cycle in which the temperature was decreased at a rate of temperature decrease of 180 ° C./min.

  And after such a test, the crack and peeling degree of the soldering resist (permanent resist film) of the board | substrate for evaluation were observed with the metal microscope of 100 times, and the following reference | standard evaluated. That is, those that could not observe cracks and peeling of the solder resist were marked with “◯”, and those that could confirm any of them were marked with “x”.

(HAST resistance)
First, a copper surface of a printed wiring board substrate (trade name E-679, manufactured by Hitachi Chemical Co., Ltd.) in which a 12 μm thick copper foil is laminated on a glass epoxy base material is etched to have a line / space of 50 μm / 50 μm. It was processed into a comb-type electrode. This was used as an evaluation wiring board.

  A solder resist made of a cured product of a resist was formed on the comb-shaped electrode of the wiring board for evaluation in the same manner as in the “solder heat resistance” test, and this was used as an evaluation substrate. This evaluation substrate was post-exposed for 100 hours under conditions of 130 ° C./85%/5V. And the extent of the generation | occurrence | production of the migration in each board | substrate for evaluation was observed with the metal microscope of 100 times, and the following reference | standard evaluated. That is, “◯” indicates that no significant migration occurred in the solder resist (permanent resist film), and “X” indicates that significant migration occurred.

(Gold plating property)
In the same manner as in the “solder heat resistance” test, an evaluation substrate on which a solder resist was formed was prepared. A commercially available electroless nickel / gold plating solution was used, and a nickel plating thickness of 5 μm and a gold plating thickness of 0. Plating was performed to 1 μm. Then, the appearance of the solder resist was observed and evaluated according to the following criteria. That is, the solder resist that was not whitened was rated as “◯” and the solder resist that was recognized as “×”.

(Storage stability)
After the photosensitive film of each Example or Comparative Example was allowed to stand at room temperature (23 ° C.) for 20 days, it was subjected to exposure, development, UV irradiation, and heating similar to the above “solder heat resistance” test. went. And the pattern formed in this way was observed with the stereomicroscope, and the following references | standards determined. In Table 2, ◯ indicates that there is no resin residue in the unexposed portion, and x indicates that there is resin residue in the unexposed portion.

  From Table 2, when the photosensitive resin composition containing all of the components (a) to (d) was used (Examples 1 to 5), in addition to excellent storage stability, excellent crack resistance and sufficient HAST It was confirmed that tolerance was obtained. On the other hand, in Comparative Examples 1 and 2 not including all of the components (a) to (d), at least one of crack resistance and HAST resistance was insufficient. Moreover, in Examples 1-5, it turned out that the coating-film property, solder heat resistance, and gold-plating tolerance which were excellent compared with Comparative Examples 1-2 were obtained reliably.

It is a figure which shows typically the cross-sectional structure of the photosensitive film of suitable embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive film, 10 ... Support body, 20 ... Photosensitive resin composition layer, 30 ... Protective film.

Claims (4)

(A) a binder polymer having a carboxyl group, (b) a photopolymerizable monomer having at least one ethylenically unsaturated group, (c) a polyurethane compound , ( d) a photopolymerization initiator , and (e) Contains block type isocyanate ,
The (a) binder polymer contains a vinyl copolymer compound obtained by using (meth) acrylic acid and (meth) acrylic acid alkyl ester as a copolymerization component,
The photosensitivity wherein the polyurethane compound (c) is obtained by reacting an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group. Resin composition. A photosensitive film provided with a support body and the layer which consists of a photosensitive resin composition of Claim 1 formed on this support body. Forming a photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 on a substrate;
Irradiating the photosensitive resin composition layer with actinic rays and photocuring a predetermined region;
Removing a non-cured portion in the photosensitive resin composition layer to form a resist pattern;
A resist pattern forming method including: The photosensitive permanent resist which consists of a photocured material of the photosensitive resin composition of Claim 1 apply | coated on the board | substrate for printed wiring boards.

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