JP5061938B2 - Photosensitive resin composition, and photosensitive element and permanent mask resist using the same - Google Patents

Description

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

  In recent years, a film-like flexible printed wiring board (hereinafter referred to as “FPC”) that can be folded and incorporated in a small device such as a camera or a mobile phone is frequently used as a printed wiring board. This FPC also requires a permanent mask resist for limiting the soldering position and protecting the wiring, like a general printed wiring board, and the permanent mask resist is called a cover lay or a cover coat. .

  Permanent mask resists (hereinafter sometimes referred to as “coverlays”) usually require properties such as flexibility, chemical resistance, plating resistance, resolution, adhesion, flame resistance, and heat resistance. Is done. When a thick dry film type is used as the coverlay, followability to unevenness due to wiring on the substrate surface is required.

  On the other hand, as a method for forming a permanent mask resist, since a high-resolution resist pattern can be formed and workability is good, a photographic development method using a photosensitive resin composition (after image exposure, an image is developed by development). Is attracting attention.

Examples of the photosensitive resin composition for forming a permanent mask resist include, for example, a flame-retardant photosensitive resin composition mainly composed of an acrylic polymer and a photopolymerizable monomer (for example, Patent Documents 1 and 2), and an epoxy resin. And a heat-resistant photosensitive resin composition mainly composed of an epoxy resin curing agent (for example, Patent Document 3), a photosensitive epoxy resin having a chalcone group in the main chain, and a high stability mainly composed of an epoxy resin curing agent Photosensitive resin composition (for example, Patent Document 4), a novolak type epoxy acrylate having an epoxy group and a photopolymerization initiator as main components, and a photosensitive resin composition having excellent curability, solvent resistance, plating resistance, and the like. Product (for example, Patent Document 5), a carboxyl group-containing polymer, a monomer, a photopolymerizable initiator, and a photosensitive resin composition containing a thermosetting resin as main components (for example, Patent Document 6) 9), and the like have been proposed.
JP-A-53-56018 Japanese Patent Laid-Open No. 54-1018 JP 54-82073 A JP 58-62636 A JP-A-61-272 JP 48-73148 A JP 57-178237 A Japanese Patent Laid-Open No. 58-42040 JP 59-151152 A

  Recently, for the purpose of protecting the design information of the wiring pattern and for the purpose of preventing image noise due to the irregular reflection of light on the resist surface when an FPC is built in a camera module or the like, a black permanent that absorbs visible light. A mask resist (hereinafter, sometimes referred to as “black coverlay”) is required.

  However, the present inventors have examined the blackening of the permanent mask resist. When black pigment is blended with the conventional photosensitive resin composition, the adhesion of the resist is lowered or the bottom of the resist is shown in FIG. It has been found that chipping as shown may occur. When the present inventors form a thick resist pattern, the black pigment tends to agglomerate and settle, and the black pigment hinders or absorbs ultraviolet light, resulting in insufficient exposure, and the photosensitive resin composition. This is thought to be due to the fact that photocuring at the bottom of the photosensitive layer, which is a product layer, is difficult to proceed.

  In order to advance photocuring of the bottom of the photosensitive layer, a method of increasing the ultraviolet irradiation amount is conceivable. However, in such a method, halation increases as the irradiation amount increases, and the resolution deteriorates. ,There is a limit.

  The present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a black permanent mask resist having a good resist shape and sufficient adhesion on a printed wiring board, and It is an object of the present invention to provide a used photosensitive element and a permanent mask resist.

  In order to achieve the above object, the present invention is a photosensitive resin composition used for forming a permanent mask resist on a printed wiring board, comprising (A) (A1) an acid-modified vinyl group-containing epoxy resin, A binder polymer containing (A2) an acrylic resin, (B) (B1) a compound represented by the following general formula (1), and (B2) a compound represented by the following general formula (2) A photosensitive resin composition comprising: (C) a photopolymerizable compound having an ethylenically unsaturated group; and (D) a black pigment.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a carboxyl group. , R ^{3 to} R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, k represents an integer of 0 to 4, and l represents an integer of 0 to 5. A plurality of R ¹ and R ² may be the same or different.

In general formula (2), R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a carboxyl group. , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n each independently represents an integer of 0 to 5. A plurality of R ⁶ and R ⁷ may be the same or different.

  According to the photosensitive resin composition of the present invention, by having the above-described configuration, sufficient photocurability can be obtained up to the bottom even when the film is thickened. Therefore, a black permanent mask resist having desired light absorption can be formed on the printed wiring board in a state satisfying a good resist shape and sufficient adhesion. Moreover, according to the photosensitive resin composition of the present invention, in addition to being able to form a black permanent mask resist having a good resist shape and sufficient adhesion on a printed wiring board, it is required for a conventional permanent mask resist. A black permanent mask resist having excellent performance, flexibility, chemical resistance, plating resistance, resolution and followability to the substrate can be formed.

  Furthermore, since the photosensitive resin composition of the present invention is excellent in curability, it can prevent an increase in halation due to an increase in the amount of ultraviolet irradiation and a deterioration in resolution due to an increase in halation, and a high resolution resist. The pattern can be formed in a good shape.

  In the photosensitive resin composition of the present invention, (C) the photopolymerizable compound having an ethylenically unsaturated group is (C1) a compound having a weight average molecular weight of 1000 to 20000 having a urethane bond and an ethylenically unsaturated group in the molecule. It is preferable to contain.

  (C) When the photopolymerizable compound having an ethylenically unsaturated group contains such a compound, flexibility, resolution, and plating resistance can be further improved.

  The present invention also provides a photosensitive element comprising a support and a photosensitive layer made of the photosensitive resin composition formed on the support. Such a photosensitive element has a photosensitive layer made of the above-described photosensitive resin composition, so that even when the photosensitive layer is thickened, sufficient photocuring can be obtained up to the bottom, and on the printed wiring board. A black permanent mask resist having a good resist shape and sufficient adhesion can be formed. Furthermore, according to such a photosensitive element, a black permanent mask that is excellent in flexibility, chemical resistance, plating resistance, resolution, and followability to the substrate, which is a performance required for a conventional permanent mask resist. A resist can be formed.

  The present invention further provides a permanent mask resist obtained by curing the photosensitive resin composition by light irradiation. Since this permanent mask resist is obtained by curing the photosensitive resin composition of the present invention that exhibits the above effects, it has a good resist shape and sufficient adhesion on a printed wiring board. Further, such a permanent mask resist is excellent in flexibility, chemical resistance, plating resistance, resolution, and followability to the substrate.

  According to the present invention, a photosensitive resin composition capable of forming a black permanent mask resist having a good resist shape and sufficient adhesion on a printed wiring board, and a photosensitive element and a permanent mask resist using the same. Can be provided.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings as the case may be. In the description of the drawings, the same reference numerals are used for the same or equivalent elements, and duplicate descriptions are omitted. In this specification, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl means acryloyl and it. Means the corresponding methacryloyl.

  First, the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of this invention is a photosensitive resin composition used for the permanent mask resist for printed wiring boards, Comprising: (A) Binder polymer (it is hereafter called (A) component depending on the case), ( B) a photopolymerization initiator (hereinafter sometimes referred to as component (B)), (C) a photopolymerizable compound having an ethylenically unsaturated group (hereinafter sometimes referred to as component (C)), and (D ) A black pigment (hereinafter sometimes referred to as component (D)), (A) the binder polymer contains (A1) an acid-modified vinyl group-containing epoxy resin, and (A2) an acrylic resin, (B) The photopolymerization initiator contains (B1) a compound represented by the above general formula (1) and (B2) a compound represented by the above general formula (2). Hereinafter, the components (A) to (D) will be described in detail.

  (A) The binder polymer is an essential component for use in combination with the components (B) to (D) to form a liquid or solid photosensitive resin composition, and when the photosensitive resin composition is used in the form of a film. Demonstrate film forming ability. The component (A) is a resin containing (A1) an acid-modified vinyl group-containing epoxy resin and (A2) an acrylic resin, and any resin can be adopted as long as it has such a structure.

  The (A1) acid-modified vinyl group-containing epoxy resin, that is, the (A1) component can be obtained, for example, by the following two-stage reaction. In the first reaction (hereinafter referred to as “first reaction” for the sake of convenience), (a1) an epoxy resin represented by the following general formulas (3) to (5) and the like, that is, the component (a1) and (a2) ) A vinyl group-containing monocarboxylic acid is reacted. In this first reaction, a hydroxyl group is generated by an addition reaction between the epoxy group of the component (a1) and the carboxyl group of the (a2) vinyl group-containing monocarboxylic acid.

  In general formulas (3) to (5), X represents a hydrogen atom or a glycidyl group, r represents an integer of 0 to 3, s represents an integer of 1 or more, and R represents a hydrogen atom or a methyl group. A plurality of Xs may be the same or different, and the molar ratio of hydrogen atoms / glycidyl groups in the whole X in one molecule is 0/100 to 70/30.

  Among the components (a1), the novolac type epoxy resin represented by the general formula (3) includes a phenol novolac type epoxy resin and a cresol novolac type epoxy resin, and these resins include a phenol novolac resin or a cresol novolac resin. It can be obtained by a known method of reacting with epichlorohydrin.

  The trisphenol methane type epoxy resin represented by the general formula (4) can be obtained by purchasing a commercially available product. Specifically, FAE-2500, EPPN-501H, EPPN-502H (Nippon Kayaku Co., Ltd. make, brand name) etc. are mentioned.

  The bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (5) can be obtained by purchasing a commercially available product. Specific examples include Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name) or YDF2001 (manufactured by Toto Kasei Co., Ltd., trade name).

  When the photosensitive resin composition according to the present embodiment is prepared, the component (a1) includes a novolac type epoxy resin represented by the general formula (3) and a trisphenolmethane type epoxy resin represented by the general formula (4). It is preferable that the novolac type epoxy resin represented by the general formula (3) is a cresol novolac type epoxy resin.

  (A2) Examples of the vinyl group-containing monocarboxylic acid include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyano. Cinnamic acid or the like can be used. Further, (a2) as a vinyl group-containing monocarboxylic acid, a half ester compound that is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated group-containing dibasic acid anhydride, and a vinyl group-containing monoglycidyl ether or a vinyl group A half ester compound which is a reaction product of a monoglycidyl ester and a saturated or unsaturated group-containing dibasic acid anhydride can also be used. Here, the half-ester compound refers to a compound in which only one of two carboxyl groups is esterified, for example. These can be used alone or in combination of two or more.

  The half ester compound can be obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated group-containing dibasic acid anhydride in an equimolar ratio.

  Examples of the hydroxyl group-containing acrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, and trimethylol. Propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycidyl acrylate, glycidyl methacrylate, and the like can be used.

  As the vinyl group-containing monoglycidyl ether or vinyl group-containing monoglycidyl ester, glycidyl (meth) acrylate or the like can be used.

  Examples of the saturated or unsaturated group-containing dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like can be used.

  The first reaction is preferably carried out at a ratio such that (a2) vinyl group-containing monocarboxylic acid is 0.3 to 1.05 equivalent to 1 equivalent of the epoxy group of component (a1), and 0.7 to More preferably, the ratio is 1.0 equivalent.

  The first reaction can be performed by dissolving both the component (a1) and the component (a2) vinyl group-containing monocarboxylic acid in an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate, octane and decane, etc. Petroleum solvents such as aliphatic hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be used.

  In the first reaction, it is preferable to use a catalyst for promoting the reaction. Examples of the catalyst that can be used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. It is preferable that the usage-amount of a catalyst is 0.1-10 mass parts with respect to a total of 100 mass parts of (a1) component and (a2) vinyl group containing monocarboxylic acid.

  In the first reaction, in order to prevent polymerization between (a1) components, (a2) vinyl group-containing monocarboxylic acids, or (a1) component and (a2) vinyl group-containing monocarboxylic acids, a polymerization inhibitor is added. It is preferable to use it.

  As the polymerization inhibitor, for example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like can be used.

  It is preferable that the usage-amount of a polymerization inhibitor shall be 0.01-1 mass part with respect to a total of 100 mass parts of (a1) component and (a2) vinyl group containing monocarboxylic acid. 60-150 degreeC is preferable and, as for the reaction temperature of a 1st reaction, 80-120 degreeC is more preferable.

  In the first reaction, in addition to the component (a1) and the (a2) vinyl group-containing monocarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, if necessary Polybasic acid anhydrides such as products and phenol derivatives can be used.

  In addition, (a1) component is a range other than the trisphenol methane type | mold epoxy resin represented by the novolak-type epoxy resin represented by General formula (1), and General formula (2) in the range which does not impair the effect of this invention. Other epoxy resins may be included.

  In the reaction performed after the first reaction (hereinafter referred to as “second reaction” for convenience), the resin obtained in the first reaction and (a3) the polybasic acid anhydride react with each other. . (A3) As the polybasic acid anhydride, a polybasic acid anhydride containing one or both of a saturated group and an unsaturated group can be used. In the second reaction, the hydroxyl group produced by the first reaction, the hydroxyl group originally present in the component (a1), and the acid anhydride group of the (a3) polybasic acid anhydride undergo a half-ester reaction. Inferred.

  (A3) Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydro Phthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like can be used.

  In the second reaction, 0.1 to 1.0 equivalent of (a3) polybasic acid anhydride is reacted with 1 equivalent of hydroxyl group in the resin obtained by the first reaction. By changing the amount of the (a3) polybasic acid anhydride to be reacted, the acid value of the component (A1) to be produced can be adjusted.

  The acid value of the component (A1) is preferably 50 to 200 mgKOH / g, more preferably 70 to 150 mgKOH / g, and further preferably 80 to 120 mgKOH / g. When the acid value is less than 50 mgKOH / g, the developability tends to decrease, and when the acid value exceeds 200 mgKOH / g, the adhesion to a substrate or the like after curing tends to decrease. The reaction temperature of the second reaction is preferably 60 to 120 ° C.

  The weight average molecular weight of the component (A1) is not particularly limited, but from the viewpoint of improving the adhesion between the photosensitive layer and the support, that is, tackiness, and the compatibility with the component (A2), It is preferably 3000 to 50000, more preferably 5000 to 30000, and still more preferably 7000 to 20000. When the weight average molecular weight of the component (A1) is less than 3000, tackiness tends to increase, and when it exceeds 50000, the compatibility with the component (A2) tends to decrease.

  The content ratio of the component (A1) in the photosensitive resin composition of the present invention is preferably 1 to 50% by mass in terms of solid content (nonvolatile content) based on the entire photosensitive resin composition, More preferably, it is 30 mass%, and it is further more preferable that it is 8-20 mass%. When the content ratio of the component (A1) is less than 1% by mass, a desired resist shape tends to be hardly obtained when forming a black coverlay, and the content ratio of the component (A1) exceeds 50% by mass. Then, the tackiness of the surface of the photosensitive layer tends to be strong.

  (A1) Acid-modified vinyl group-containing epoxy resins include CCR-1171H, CCR-1218H, CCR-1159H, CCR-1222H, PCR-1191H, TCR-1335H, etc. (above, Nippon Kayaku Co., Ltd., product Name) etc. can be obtained.

  In addition, (A1) component may contain acid-modified vinyl group containing epoxy resins other than resin obtained by said 1st reaction and 2nd reaction, as long as the effect of this invention is not impaired.

  The (A2) acrylic resin, that is, the (A2) component can be produced, for example, by radical polymerization of (meth) acrylic acid and (meth) acrylic acid alkyl ester.

  Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (6) and those in which the alkyl group of this compound is substituted with a hydroxyl group, an epoxy group, a halogen, or the like.

In the general formula (6), R ¹⁰ represents a hydrogen atom or a methyl group, and R ¹¹ represents an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group represented by R ¹¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and These structural isomers are mentioned.

  Examples of the compound represented by the general formula (6) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) Acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid-2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth ) Acrylic acid decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester can be used. These can be used alone or in combination of two or more.

From the viewpoint of plating resistance, it is preferable that R ¹¹ contains an alkyl group having 4 to 12 carbon atoms as the compound represented by the general formula (6).

  The component (A2) may contain a constituent monomer that is neither (meth) acrylic acid nor (meth) acrylic acid alkyl ester. Examples of the constituent monomer that is neither (meth) acrylic acid nor (meth) acrylic acid alkyl ester include polymerizable styrene substituted at the α-position or aromatic ring such as styrene, vinyltoluene, and α-methylstyrene. Derivatives, acrylamides such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile, vinyl-n-butyl ether, benzyl (meth) acrylate, tetrahydrofurfuryl ester (meth) acrylate, dimethylaminoethyl ester (meth) acrylate , (Meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α- Bromo (Meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, maleic acid Maleic acid monoesters such as monoisopropyl, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid can be used. These can be used alone or in combination of two or more.

  The proportion of the constituent monomer containing the carboxyl group of the component (A2) is preferably 5 to 50 mol%, more preferably 10 to 45 mol%, based on all the constituent monomers of the component (A2). More preferably, it is 40 mol%. If this ratio is less than 5 mol%, the alkali developability of the photosensitive resin composition tends to be lowered, and if it exceeds 50 mol%, pattern formation of the permanent mask resist tends to be difficult.

  The component (A2) is preferably soluble or swellable in an aqueous alkali solution from the viewpoint of improving the alkali developability of the photosensitive resin composition. The acid value of the component (A2) is preferably 30 to 200 mgKOH / g, more preferably 80 to 190 mgKOH / g, and still more preferably 100 to 180 mgKOH / g. When the acid value is less than 30 mg KOH / g, the development time tends to be long, and when it exceeds 200 mg KOH / g, the developer resistance of the photocured photosensitive layer tends to be lowered.

  The weight average molecular weight of the component (A2) is not particularly limited, but from the viewpoint of achieving both good alkali developability of the photosensitive resin composition and good mechanical strength of the permanent mask resist after curing, It is preferably 20000 to 300000, more preferably 30000 to 200000, and further preferably 40000 to 120,000. If the weight average molecular weight is less than 20,000, the film-forming property of the photosensitive resin composition tends to decrease, and if it exceeds 300,000, the development time tends to be long.

  In addition, the weight average molecular weight in this invention can be obtained by measuring by the gel permeation chromatography method and converting with the analytical curve created using standard polystyrene.

  The content ratio of the component (A2) in the photosensitive resin composition of the present invention is preferably 10 to 60% by mass, preferably 15 to 50% by mass, based on the entire photosensitive resin composition. More preferably, it is more preferably 20 to 40% by mass. When the content of the component (A2) is less than 10% by mass, the alkali developability tends to decrease, and when it exceeds 60% by mass, the tackiness of the surface of the photosensitive layer tends to increase, and a black coverlay is formed. In this case, a desired resist shape tends to be difficult to obtain.

  (B) The photopolymerization initiator, that is, the component (B) is a component that generates active species such as radicals upon irradiation with actinic rays and initiates the polymerization reaction, and is represented by (B1) the above general formula (1). A compound and (B2) the compound represented by the general formula (2) are contained.

Here, in General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a carboxyl group. R < ³ > -R < ⁵ > shows a hydrogen atom or a C1-C6 alkyl group each independently, k shows the integer of 0-4, l shows the integer of 0-5. A plurality of R ¹ and R ² may be the same or different.

In general formula (2), R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a carboxyl group. , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n each independently represents an integer of 0 to 5. A plurality of R ⁶ and R ⁷ may be the same or different.

  Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, Examples include n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group and the like.

Here, it is preferable that R < ³ > -R < ⁵ > is a hydrogen atom or a C1-C3 alkyl group each independently. k and l are preferably integers of 0 to 2, and more preferably 0. R ⁸ and R ⁹ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m and n are preferably integers of 0 to 2, and more preferably 0.

As the component (B1), that is, the photopolymerization initiator represented by the general formula (1), R ³ and R ⁴ are methyl groups, k and l are 0, and R ⁵ is an ethyl group. Preferably it includes 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. As 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, commercially available products such as IRGACURE-369 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) can be obtained.

  The content ratio of the component (B1) in the photosensitive resin composition of the present invention is preferably 10 to 80% by mass in terms of the solid content (nonvolatile content), based on the entire component (B), and is preferably 20 to 70%. It is more preferable that it is mass%, and it is further more preferable that it is 30-60 mass%. If this proportion is less than 10% by mass, the photosensitivity tends to be insufficient, and if it exceeds 80% by mass, the curability on the composition surface tends to be high and the internal photocuring tends to be insufficient.

In addition, as the component (B2), that is, the photopolymerization initiator represented by the general formula (2), 2,2-dimethoxy-, wherein m and n are 0, and R ⁸ and R ⁹ are methyl groups Preferably it contains 1,2-diphenylethane-1-one. As 2,2-dimethoxy-1,2-diphenylethane-1-one, commercially available products such as IRGACURE-651 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) can be obtained.

  The content ratio of the component (B2) in the photosensitive resin composition of the present invention is preferably 10 to 90% by mass in terms of the solid content based on the entire component (B), and is 20 to 80% by mass. It is more preferable, and it is further more preferable that it is 30-70 mass%. If this ratio is less than 10% by mass, the photosensitivity tends to be insufficient, and if it exceeds 90% by mass, the substrate tends to warp during heating due to sublimation of the component (B2) from the resist.

  Here, the ratio of the content of the component (B1) and the component (B2) is preferably 1: 2 to 2: 1 in terms of mass ratio of the solid content (nonvolatile content). 1 is more preferable. In particular, by setting the content ratio of the component (B1) and the component (B2) within the range of 1: 2 to 1: 1, the resist bottom portion can be formed on both the copper foil and the substrate. Chipping can be prevented more reliably.

  Moreover, the photosensitive resin composition of this invention may contain photoinitiators other than the said (B1) component and (B2) component to such an extent that the effect of this invention is not impaired. Examples of the photopolymerization initiator other than the components (B1) and (B2) include benzophenone, N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- Aromatic ketones such as (4-morpholinophenyl) -butanone-1 and 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 , And aromatic ketones such as phenanthrenequinone, benzoin methyl ether, benzoin ethyl Benzoin ethers such as benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl 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-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-triarylimidazole dimer, 9-phenylacridine and 1 7- bis (9,9'-acridinyl) acridine derivatives such as heptane, N- phenylglycine, N- phenylglycine derivatives, coumarin-based compounds. These are used individually by 1 type or in combination of 2 or more types.

  In addition, it is preferable that the content rate of (B) component in the photosensitive resin composition of this invention is 0.02-20 mass% in the ratio of solid content on the basis of the whole photosensitive resin composition, and is 0.00. The content is more preferably 1 to 15% by mass, and further preferably 1 to 10% by mass. When the content ratio of the component (B) is less than 0.1% by mass, the photosensitivity tends to be insufficient, and when it exceeds 20% by mass, absorption on the surface of the composition increases during exposure, and the internal Photocuring tends to be inadequate.

  (C) The photopolymerizable compound having an ethylenically unsaturated group is a compound having a polymerizable ethylenically unsaturated group in the molecule. (C) The photopolymerizable compound having an ethylenically unsaturated group, that is, the component (C) includes, for example, tricyclodecane dimethanol, neopentyl glycol-modified trimethylolpropane diacrylate, α, β-unsaturated polyhydric alcohol. Compound obtained by reacting saturated carboxylic acid, compound obtained by reacting glycidyl group-containing compound with α, β-unsaturated carboxylic acid, compound having urethane bond and ethylenically unsaturated group, nonylphenyldixylene (meta ) Acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl- β ′-(meth) acryloyloxyethyl-o-phthalate, T) Acrylic acid alkyl ester, EO-modified nonylphenyl (meth) acrylate, and the like. 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, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane Methylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) a Chlorate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and bisphenol A type | system | group (meth) acrylate etc. can be used.

  The component (C) preferably includes (C1) a compound having a urethane bond and an ethylenically unsaturated group in the molecule and having a weight average molecular weight of 1,000 to 20,000 (hereinafter sometimes referred to as “(C1) compound”). By including such a compound, the flexibility, resolution, and plating resistance of the formed permanent mask resist can be improved.

  The compound (C1) has, for example, a urethane compound having a urethane bond derived from a reaction between a hydroxyl group at a terminal of a polycarbonate compound and / or a polyester compound and an isocyanate group of a diisocyanate compound and having an isocyanate group at a plurality of terminals; It can be obtained by subjecting a compound having a hydroxyl group and an ethylenically unsaturated group to a condensation reaction.

  The urethane compound used for the synthesis of the compound (C1) is a polycarbonate compound and / or a polyester compound having hydroxyl groups at both ends (hereinafter, the polycarbonate compound and the polyester compound are sometimes referred to as “(c1) polycarbonate compound” and “( c2) a polyester compound ”) and a diisocyanate compound (hereinafter sometimes referred to as“ (c3) diisocyanate compound ”). In particular, from the viewpoint of improving the appearance of the photocured product, it is preferable to use a urethane compound obtained by reacting (c1) a polycarbonate compound and (c3) a diisocyanate compound.

  (C1) The polycarbonate compound has a structure in which an alkylene group is arranged in the main chain through a carbonate bond, and can be obtained by a known method. For example, when a polycarbonate compound is obtained by a phosgene method, a diol compound and phosgene And react. Examples of the diol compound include diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, erylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2 -Methyl-1,3-butanediol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol, 3,3,5-trimethyl-1 , 6-hexanediol, 2,3,5-trimethyl-pentanediol, 1,6-hexanediol, 1,5-pentanediol, etc., and these may be used alone or in combination of two or more. used. Further, polyol compounds such as trimethylolpropane, trimethylolethane, hexanetriol, heptanetriol, and pentaerythritol may be contained.

  Among the polycarbonate compounds, hexamethylene carbonate represented by the following general formula (7) and pentamethylene represented by the following general formula (8) derived from 1,6-hexanediol and 1,5-pentanediol. Those containing carbonate are preferred.

— (CH ₂ ) ₆ —O—CO—O— (7)
_{- (CH 2) 5 -O-} CO-O- (8)

  The molar ratio of hexamethylene carbonate and pentamethylene carbonate contained in the polycarbonate compound is preferably hexamethylene carbonate / pentamethylene carbonate = 1/9 to 9/1. When this content ratio is out of the above range, the elongation and strength of the photocured product tend to decrease.

  (C2) The polyester compound can be obtained by a known method by polycondensation of a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include aromatic and aliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, and sebacic acid. Examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, neopentyl glycol, diethylene glycol, and triethylene glycol.

  The polycarbonate compound and the polyester compound preferably have a weight average molecular weight (for example, measured by GPC and converted to polystyrene) of 600 to 1,000. If the weight average molecular weight is outside the above range, the elongation and strength of the photocured product tend to decrease.

  (C3) Examples of the diisocyanate compound include an aliphatic diisocyanate compound having a divalent aliphatic group such as an alkylene group, an alicyclic diisocyanate compound having a divalent alicyclic group such as cycloalkylene, and an aromatic diisocyanate. Examples of the compound include these isocyanurate-modified products, carbodiimidization-modified products, and biuret-modified products.

  Examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Examples of the alicyclic diisocyanate compound include isophorone diisocyanate, methylene bis (cyclohexyl) diisocyanate, and 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane. Examples of the aromatic diisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-triene diisocyanate or dimerized polymer of 2,6-triene diisocyanate, (o, p or m)- Xylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate. These are used individually by 1 type or in combination of 2 or more types. Moreover, the isocyanate compound which has 2 or more isocyanate groups, such as a triphenylmethane triisocyanate and a tris (isocyanate phenyl) thiophosphate, may be contained. Among these, an alicyclic diisocyanate compound is preferable and isophorone diisocyanate is more preferable from the viewpoint of achieving a higher level of flexibility and toughness of the photocured product.

  A urethane compound having an isocyanate group at a plurality of terminals (hereinafter sometimes referred to as “(c4) urethane compound”) comprises (c1) a polycarbonate compound and / or (c2) a polyester compound and (c3) a diisocyanate compound. It is obtained by reacting. The (c4) urethane compound preferably has an isocyanate group at both ends. In this case, in the above reaction, the (c3) diisocyanate compound has a total amount of 1 mol of the (c1) polycarbonate compound and (c2) polyester compound. The blending amount is preferably 1.01 to 2.0 mol, and more preferably 1.1 to 2.0 mol. (C3) When the compounding quantity of a diisocyanate compound is less than 1.01 mol or exceeds 2.0 mol, there exists a tendency that the urethane compound which has an isocyanate group in both ends cannot be obtained stably. In the reaction of synthesizing the urethane compound (c4), it is preferable to add dibutyltin dilaurate as a catalyst. The reaction temperature is preferably 60 to 120 ° C. If the temperature is less than 60 ° C, the reaction tends not to proceed sufficiently. If the temperature exceeds 120 ° C, the operation tends to be dangerous due to rapid heat generation.

  A compound having a hydroxyl group and an ethylenically unsaturated group in the molecule (hereinafter referred to as “(c5) hydroxyl group-containing ethylenically unsaturated compound), which can be used in the reaction to obtain the compound (C1) by reacting with the urethane compound. Examples of the “compound”) include compounds having a hydroxyl group and a (meth) acryloyl group in the molecule. Examples of such compounds include hydroxy (meth) acrylates, caprolactone adducts or alkylene oxide adducts thereof, ester compounds of polyhydric alcohols such as glycerin and (meth) acrylic acid, and glycidyl (meth) arylate acrylic acid. Examples include adducts.

  Examples of the hydroxy (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples of these caprolactone adducts include hydroxyethyl (meth) acrylate / caprolactone adduct, hydroxypropyl (meth) acrylate / caprolactone adduct, and hydroxybutyl (meth) acrylate / caprolactone adduct. Examples of the adduct include hydroxyethyl (meth) acrylate / alkylene oxide adduct, hydroxypropyl (meth) acrylate / propylene oxide adduct, and hydroxyethyl (meth) acrylate / butylene oxide adduct. Examples of ester compounds include glycerin mono (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane mono (meth) acrylate, and ditrimethylolpropane. Examples include tri (meth) acrylate, di (meth) acrylate of an ethylene oxide adduct of trimethylolpropane, and di (meth) acrylate of a propylene oxide adduct of trimethylolpropane. These are used individually by 1 type or in combination of 2 or more types.

  The (C1) compound is obtained by subjecting (c4) urethane compound to (c5) hydroxyl group-containing ethylenically unsaturated compound. In such an addition reaction, it is preferable that the amount of (c5) the hydroxyl group-containing ethylenically unsaturated compound is 2.0 to 2.4 mol relative to 1 mol of (c4) urethane compound. (C5) When the amount of the hydroxyl group-containing ethylenically unsaturated compound is less than 2.0 mol, the photopolymerization tends to be insufficient, and when it exceeds 2.4 mol, the elongation of the photocured product and There is a tendency for strength to decrease. The above addition reaction is preferably performed in the presence of, for example, p-methoxyphenol, di-t-butyl-hydroxy-toluene, etc. In addition, it is preferable to add dibutyltin dilaurate as a catalyst. The reaction temperature is preferably 60 to 90 ° C. When the temperature is lower than 60 ° C., the reaction tends not to proceed sufficiently. When the temperature exceeds 90 ° C., gelation tends to occur due to rapid heat generation. The end point of the reaction may be, for example, the time when the isocyanate group disappears in the infrared absorption spectrum.

  When producing the photosensitive resin composition which concerns on this embodiment, although the weight average molecular weights of (C1) compound are 1000-20000, it is preferable that it is 3000-20000, and it is more preferable that it is 3500-10000, More preferably, it is 4000-8000. If the weight average molecular weight is less than 1,000, the plating resistance of the photocured product becomes insufficient, and the flexibility and the flexibility decrease due to insufficient elongation and strength of the photocured product. There exists a tendency and when it exceeds 20000, there exists a tendency for compatibility with the above-mentioned (A) component to fall.

  (C1) A compound may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Examples of the available (C1) compound include UF-8001G, UF-8003M, UF-TCB-50, UF-TC4-55 (manufactured by Kyoeisha Chemical Co., Ltd., trade name), and hyaloid 9082-95. (Trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The content ratio of the component (C1) in the photosensitive resin composition of the present invention is preferably 30 to 90% by mass, preferably 40 to 80% by mass, based on the total component (C). More preferably, it is more preferably 50 to 70% by mass. By containing the compound (C1) in the above ratio, the flexibility of the cured film can be further improved.

  The component (C) may contain other photopolymerizable compounds in addition to the compound (C1). As another photopolymerizable compound, a bisphenol A (meth) acrylate compound is preferable. Although there is no restriction | limiting in particular, From a viewpoint which improves the photosensitivity and resolution of the photosensitive resin composition among bisphenol A type | system | group (meth) acrylate compounds, it is a compound represented, for example by following General formula (9). It is more preferable.

In the general formula (9), R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = A positive integer chosen to be 4-40.

  Examples of Y and Z include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. Among these, Y and Z are preferably an ethylene group or a propylene group, and more preferably an ethylene group.

  For p and q, the value of p + q is preferably 6 to 34, more preferably 8 to 30, further preferably 8 to 28, particularly preferably 8 to 20, 16 is very preferable, and 8 to 12 is most preferable. If the value of p + q is less than 4, the compatibility with the component (A) tends to be reduced. If p + q exceeds 40, the hydrophilic property of the permanent mask resist obtained by exposing and developing the photosensitive resin composition. Tends to increase and the water absorption rate tends to increase.

  The aromatic ring in the general formula (9) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, and 1 to 10 carbon atoms. Alkylamino group, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, allyl group, hydroxyl group, hydroxyalkyl having 1 to 20 carbon atoms Group, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, acyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 1 to 20 carbon atoms , An alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a heterocyclic ring Group containing, and aryl groups substituted with these substituents. In addition, these substituents may form a condensed ring. Moreover, the hydrogen atom in these substituents may be substituted with a halogen atom or the like. In addition, when the aromatic ring in the general formula (9) has two or more substituents, they may be the same or different.

  Examples of the compound represented by the general formula (9) include bisphenol A (meth) acrylate compounds. Specifically, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, and the like.

  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) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, and 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like. These can be used alone or in combination of two or more.

  2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name) or BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.). , Trade name) is available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) Is possible.

  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) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, and 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These can 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.

  In addition, it is preferable that the content rate of (C) component in the photosensitive resin composition of this invention is 20-70 mass% in the ratio of solid content on the basis of the whole photosensitive resin composition, and is 30-60 mass. % Is more preferable, and it is more preferable that it is 35-55 mass%. If this ratio is less than 20% by mass, the photosensitivity tends to be insufficient, and if it exceeds 70% by mass, the photocured product tends to become brittle.

  (D) A black pigment is a component which provides desired visible light absorptivity to the permanent mask resist to be formed. Examples of the (D) black pigment used in the present invention include carbon black, lamp black, bone black, graphite, iron black, copper chromium black, copper iron manganese black, titanium black, cobalt iron chromium black, and oxidation. Examples include ruthenium. Among these, as for the carbon black, commercially available products such as MHI Black # 220 (manufactured by Mikuni Dye Co., Ltd., trade name) can be obtained as a dispersion.

  In addition, it is preferable that the content rate of (D) component in the photosensitive resin composition of this invention is 0.01-5 mass% in the ratio of solid content on the basis of the whole photosensitive resin composition, and is 0.00. It is more preferable that it is 1-3 mass%, and it is further more preferable that it is 0.5-1.5 mass%. When this proportion is less than 0.01% by mass, a necessary hue tends not to be obtained, and when it exceeds 5% by mass, the photocurability of the photosensitive resin composition tends to be lowered.

  The photosensitive resin composition according to the present embodiment preferably contains a blocked isocyanate compound in addition to the components (A) to (D) from the viewpoint of improving the reliability of the permanent mask resist. Among the blocked isocyanate compounds, it is more preferable to contain a compound having two or more divalent groups represented by the following general formula (10) in the molecule. Permanent mask which is further excellent in flexibility, plating resistance, heat resistance and chemical resistance by containing a block isocyanate compound having two or more divalent groups represented by the following general formula (10) in the molecule A photosensitive resin composition capable of forming a resist can be obtained.

また、ブロックイソシアネート化合物は、永久マスクレジストの電気絶縁性を向上する観点から、分子内に、芳香環及び下記一般式（１１）で表される３価の基の一方又は双方を含むことが好ましい。

The blocked isocyanate compound preferably contains one or both of an aromatic ring and a trivalent group represented by the following general formula (11) in the molecule from the viewpoint of improving the electrical insulation of the permanent mask resist. .

  A thermosetting component such as a melamine resin, a dye, a pigment, a plasticizer, a stabilizer, and the like can be added to the photosensitive resin composition according to the present embodiment as necessary.

  In addition, the photosensitive resin composition of the present invention may be, for example, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl cellosolve, and ethyl cellosolve, if necessary. Dissolve in ether solvents, chlorinated hydrocarbon solvents such as dichloromethane and chloroform, solvents such as toluene, N, N-dimethylformamide, or mixed solvents and apply as a solution with a solid content of about 30 to 60% by mass. can do.

  Next, the photosensitive element of the present invention will be described. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support 10, a photosensitive layer 20 provided on the support 10, and a protective film 30 provided on the photosensitive layer 20.

  The photosensitive layer 20 is a layer made of the above-described photosensitive resin composition of the present invention. The photosensitive layer 20 is prepared by dissolving the photosensitive resin composition of the present invention in the above solvent or mixed solvent to obtain a solution having a solid content of about 30 to 60% by mass, and then uniformly coating the solution on the support 10. Preferably formed.

  Further, the thickness of the photosensitive layer 20 is usually set by the thickness of the wiring pattern, but is preferably 10 to 100 μm in thickness after drying after removing the solvent by heating and / or hot air blowing, More preferably, it is 20-60 micrometers, and it is further more preferable that it is 25-50 micrometers. If the thickness is less than 10 μm, the cured film tends to be broken or the followability to the unevenness of the substrate surface tends to deteriorate, and if it exceeds 100 μm, the flexibility of the photocured product tends to decrease.

  Examples of the support 10 included in the photosensitive element 1 include polymer films made of polyethylene terephthalate, polypropylene, polyethylene, polyester, and the like. Among these, polyethylene terephthalate is preferable.

  The thickness of the support 10 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. If the thickness is less than 5 μm, the covering property tends to decrease, and if it exceeds 100 μm, the resolution tends to decrease.

  When used as the photosensitive element 1, the protective film 30 preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and still more preferably 15 to 25 μm. When the thickness is less than 5 μm, the protective film 30 tends to be easily broken during lamination, and when it exceeds 30 μm, the cost tends to be inferior.

  The photosensitive element 1 thus obtained can be stored, for example, in the form of a flat plate as it is, or on a cylindrical core or the like, and stored in a roll form. Note that the photosensitive element 1 does not necessarily have the protective film 30 described above, and may have a two-layer structure of the support 10 and the photosensitive layer 20.

  In addition, since the support 10 and the protective film 30 must be removable from the photosensitive layer 20 later, it is preferable that the support 10 and the protective film 30 have not been subjected to a surface treatment that makes removal impossible. The treatment other than the surface treatment is not particularly limited, and for example, the support 10 and the protective film 30 may be subjected to antistatic treatment as necessary.

  The photosensitive element 1 is suitably used for forming a resist pattern on a substrate such as a circuit forming substrate. In this case, for example, the resist pattern is formed by removing the protective film 30 from the photosensitive element 1 and laminating the photosensitive element 1 on the circuit forming substrate so that the photosensitive layer 20 is adjacent to the circuit forming substrate. By a method comprising a laminating step, an exposure step of irradiating a predetermined portion of the photosensitive layer 20 with actinic rays to form a photocured portion on the photosensitive layer 20, and a developing step of removing the photosensitive layer 20 other than the photocured portion. ,It is formed.

  Here, the circuit forming substrate includes an insulating layer and a conductor layer (made of an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, and stainless steel) formed on the insulating layer. Refers to the substrate.

  In the lamination step, for example, the photosensitive layer 20 is laminated by a method of pressure-bonding to the circuit forming substrate while heating. The atmosphere during the lamination is not particularly limited, but the lamination is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually the surface of the conductor layer of the circuit forming substrate, but may be a surface other than the conductor layer. The heating temperature of the photosensitive layer 20 is preferably 90 to 130 ° C., the pressing pressure is preferably 0.2 to 1.0 MPa, and the ambient atmospheric pressure is more preferably 4000 Pa (30 mmHg) or less. Further, if the photosensitive layer 20 is heated to 90 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance. However, in order to further improve the stackability, the circuit forming substrate is preliminarily processed. Heat treatment can also be performed.

  In the exposure step, a predetermined portion of the photosensitive layer 20 is irradiated with actinic rays to form a photocured portion. Examples of the method for forming the photocured portion include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork. At this time, when the support 10 is transparent, the support 10 may be irradiated with actinic rays while being laminated. When the support 10 is opaque, the photosensitive layer 20 is irradiated with actinic rays after removing it.

  As the light source of actinic light, 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, a xenon lamp, or the like that can effectively emit ultraviolet rays can be used. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can also be used.

  After the exposure, if the support 10 is present on the photosensitive layer 20, the support 10 is removed and then developed by removing the photosensitive layer 20 other than the photocured portion using an alkaline aqueous solution. A pattern is formed (development process). In the development process, development is performed by a known method such as spraying, rocking dipping, brushing, scraping, or the like, using an alkaline aqueous solution corresponding to the photosensitive resin composition. When an alkaline aqueous solution is used as a developer, it is safe and stable, and operability is good.

  Examples of the base of the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium and potassium, alkali carbonates such as lithium, sodium and potassium carbonates or bicarbonates, potassium phosphate, sodium phosphate and the like. And alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. Of these, an aqueous solution of sodium carbonate is preferred.

  The pH of the alkaline aqueous solution is preferably 9-11. The development temperature may be adjusted according to the developability of the photosensitive layer. A small amount of an organic solvent or the like can be added to the alkaline aqueous solution in order to accelerate the surface active agent, antifoaming agent, and development.

  The resist pattern obtained by the above-described forming method is preferably used for forming a flexible resin layer on a film-like substrate, and used as a permanent mask formed on a film-like substrate. More preferably.

For example, when used as an FPC cover lay (permanent mask resist), after the above development process is completed, UV irradiation or heating with a high-pressure mercury lamp is performed for the purpose of improving solder heat resistance, chemical resistance, etc. as the FPC cover lay. It is preferable to carry out. When irradiating with ultraviolet rays, the irradiation amount is adjusted to, for example, an irradiation amount of about 0.2 to 10 J / cm ² . When heating a resist pattern, it is preferable to heat for about 15 to 90 minutes in the range of about 100 to 170 ° C. Both ultraviolet irradiation and heating may be performed. In this case, ultraviolet irradiation and heating may be performed simultaneously, or after either one is performed, the other may be performed. When performing ultraviolet irradiation and heating simultaneously, it is more preferable to heat to 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.

  The flexible printed wiring board on which the coverlay having the desired performance is formed in this way is mounted on a device such as a camera after components such as LSI are mounted (soldered).

  FIG. 2 is a schematic cross-sectional view showing a cross-sectional shape of a resist pattern formed on an FPC substrate. FIG. 2 shows a permanent mask resist 60 having a predetermined pattern provided on an FPC substrate including a base material 40 and a copper foil 50 provided on the base material 40. As shown in FIG. 2, the permanent mask resist 60 is formed on both the base material 40 and the copper foil 50. However, if the curability of the bottom of the photosensitive layer is insufficient, a developer is applied to the uncured portion. Therefore, after development, the line width 200 at the bottom of the resist shown in FIG. 2 becomes smaller than the line width 100 at the top of the resist, and the resist bottom is chipped. On the other hand, if the photosensitive resin composition of the present invention is used to form a black permanent mask resist having a predetermined pattern, the line width at the bottom of the resist even when the photosensitive layer is thickened. It is possible to form a permanent mask resist having a good shape with 200 being 80% or more with respect to the line width 100 of the upper part of the resist.

  The photosensitive resin composition of the present invention includes a black permanent mask resist, a plasma display panel (PDP), a field emission display (FED), a liquid crystal display device (LCD), a fluorescent display device, an image transmission device, a hybrid It can be applied as a photosensitive resin composition for forming a structural support (spacer, rib, partition wall, etc.) having a thickness of, for example, about 5 to 200 μm in an integrated circuit or the like.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Examples 1-3 and Comparative Examples 1-5)
(Preparation of photosensitive resin composition)
As components (A), (C), (D) and other components, the components shown in Table 1 were prepared.

  CCR-1171H in Table 1 is a compound obtained by reacting a cresol novolac type epoxy resin and a vinyl group-containing monocarboxylic acid represented by the above general formula (3) with a polybasic acid anhydride. It is an acid-modified vinyl group-containing epoxy resin obtained by reaction.

Further, the weight average molecular weights of the components (A) and (C) were measured by gel permeation chromatography (GPC) and calculated by a calibration curve using standard polystyrene. The measurement conditions by GPC are shown below.
Column: Gelpack GL-R440 + GL-R450 + GL-R400M
Flow rate: 2.05 mL / min
Concentration: 120 mg / 5 mL
Injection volume: 200 μL
Eluent: THF

  As the component (B), the components shown in Table 2 were prepared.

  In Table 2, the component (B1) is a compound represented by the following general formula (14), and the component (B2) is a compound represented by the following general formula (15). Moreover, (B3) and (B4) component are compounds which do not correspond to any of the said General formula (1) and the said General formula (2).

  The components (A), (C), (D) and other components shown in Table 1 and the components (B) shown in Table 2 were mixed at the ratios shown in Tables 1 and 3 to prepare a mixed solution. In addition, the compounding quantity in Table 3 shows the compounding quantity of solid content (weight part).

(Production of photosensitive element)
The prepared mixed solution is uniformly coated on a polyethylene terephthalate film (thickness: 25 μm) as a support, dried for 5 minutes using a 100 ° C. hot air circulating dryer to remove the solvent, and photosensitive. A photosensitive layer made of a resin composition was formed. The thickness of the photosensitive layer after drying was 40 μm.

  Next, a polyethylene film (thickness: 20 μm) is bonded as a protective film on the main surface of the photosensitive layer (the surface opposite to the side in contact with the support), and the photosensitive resin composition is bonded to the support. A photosensitive element having a structure sandwiched between protective films was obtained.

(Preparation of permanent mask resist)
The copper surface of a substrate for FPC (trade name: F30VC125RC11, manufactured by Nikkan Kogyo Co., Ltd.) in which a 35 μm thick copper foil was laminated on a polyimide substrate was polished with an abrasive brush, washed with water and dried.

Next, using a vacuum pressure laminator (model MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), the photosensitive element is placed on the copper surface of the FPC substrate, and the polyethylene film which is a protective film from the photosensitive element. After peeling off, the photosensitive layer was laminated to face the substrate. The lamination conditions were a molding temperature of 60 ° C., a molding pressure of 0.4 MPa (4 kgf / cm ² ), a vacuum time and a pressurization time of 20 seconds each.

The laminated sample with the photosensitive element laminated is cooled to 23 ° C. and allowed to stand for 1 hour or longer. Then, a 21-step tablet of a stove is brought into close contact with the photosensitive layer side of the laminated sample, and an exposure machine (Oak Manufacturing Co., Ltd.). (Manufactured by HMW-201GX)), exposure was performed with an energy amount of 400 mJ / cm ² .

  The exposed laminated sample was allowed to stand at room temperature for 30 minutes, and then subjected to spray development at 30 ° C. for 90 seconds using a 1% by mass aqueous sodium carbonate solution to remove unexposed portions. Next, heat treatment was performed at 160 ° C. for 1 hour to obtain an evaluation laminate in which a permanent mask resist (coverlay) was formed on the FPC substrate.

  The following evaluation was performed using the laminated sample and the laminate for evaluation. The evaluation results are collectively shown in Table 4.

[Evaluation of adhesion]
A phototool having a wiring pattern with a line width / space width of 30/400 to 200/400 (unit: μm) is closely attached to the laminated sample obtained above as a stove 21-step tablet and a negative for adhesive evaluation. Then, the exposure was carried out with an energy amount of 400 mJ / cm ^{2 using} an exposure machine (HMW-201GX type manufactured by Oak Manufacturing Co., Ltd.).

  The exposed laminated sample was allowed to stand at room temperature for 30 minutes, and then subjected to spray development at 30 ° C. for 90 seconds using a 1% by mass aqueous sodium carbonate solution, thereby removing unexposed portions and evaluating adhesion. The adhesion value is the smallest value of the line width (μm) remaining without being peeled off by the development process. The smaller the adhesion value, the higher the adhesion.

[Evaluation of resist shape]
FIG. 2 is a schematic cross-sectional view showing a cross-sectional shape of a resist pattern formed on an FPC substrate. If the curability at the bottom of the photosensitive layer is insufficient, the developer enters the uncured portion, so that after development, the line width 200 at the bottom of the resist shown in FIG. 2 becomes smaller than the line width 100 at the top of the resist. , Chipping occurs at the bottom of the resist.

  Exposure and development are performed under the same conditions as in the evaluation of adhesion, and the resist shapes (line width: 100 μm) on the copper foil and polyimide base material of the FPC substrate are respectively S-made by Hitachi, Ltd. Observation was made using a 2100A scanning electron microscope, and the resist shape (on the copper foil and on the substrate) was evaluated according to the following criteria. “○” indicates that the line width at the bottom of the resist is 90 to 120% with respect to the line width at the top of the resist, and the line width at the bottom of the resist is 80% or more and less than 90% with respect to the line width at the top of the resist. The line width at the bottom of the resist is less than 80% of the line width at the top of the resist, and the mark is “x”. Those having an evaluation of “◯” and “Δ” can be judged to be at a practical level.

[Evaluation of flexibility]
By visually observing the occurrence of cracks in the permanent mask resist layer when the laminate for evaluation is immersed in a solder bath at 260 ° C. for 10 seconds and subjected to solder treatment, and then folded 180 ° by goby folding. The flexibility was evaluated. The case where crack generation was not confirmed was evaluated as “good”, and the case where crack generation was confirmed was evaluated as “bad”.

[Evaluation of chemical resistance]
After the FPC substrate on which the permanent mask resist is formed is immersed in a chemical at room temperature, that is, 2N-HCl or 2N-NaOH aqueous solution for 15 minutes, respectively, to the interface between the FPC substrate and the permanent mask resist at the opening of the permanent mask resist pattern The chemical penetration was evaluated by visually observing the occurrence of chemical penetration and resist floating. A sample having no soaking and floating at the interface was evaluated as “good”, and a sample having soaking and floating at the interface was evaluated as “bad”.

[Evaluation of plating resistance]
Using the above evaluation laminate, the following electroless nickel / gold plating was applied to the surface of the FPC substrate on which the permanent mask resist was formed. Electroless nickel / gold plating includes degreasing process (5 minutes immersion), water washing process, soft etching process (2 minutes immersion), water washing process, pickling process (3 minutes immersion), water washing process, pre-dip process (90 seconds immersion) ), Electroless nickel plating step (23 minutes treatment), water washing step, electroless gold plating step (15 minutes treatment), water washing step, and drying step. In addition, the material used for each process of electroless nickel / gold plating is as follows.
Degreasing process: PC-455 (manufactured by Meltex, trade name) 25% by weight aqueous solution soft etching process: ammonium persulfate 150 g / L aqueous solution pickling process: 5% by volume sulfuric acid aqueous solution electroless nickel plating process: NIMDEN NPF-2 (Product name, manufactured by Uemura Kogyo Co., Ltd.)
Electroless gold plating process: Goblite TIG-10 (trade name, manufactured by Uemura Kogyo Co., Ltd.)

  Immediately after the drying process, cello tape (registered trademark) is applied to the surface of the FPC substrate on which electroless nickel / gold plating has been applied, and then peeled off vertically (90 ° peel-off test) to remove the permanent mask resist. The plating resistance (peeling) was evaluated by visually observing the presence or absence of. The case where the permanent mask resist was not peeled was evaluated as “good”, and the case where the permanent mask resist was peeled was evaluated as “bad”.

  Further, when gold plating is stripped at the interface between the FPC substrate and the permanent mask resist, the deposited gold plating is observed at the interface. After the electroless nickel / gold plating, the interface was observed with an optical microscope through a permanent mask resist, and the plating resistance (boring) was evaluated. Those without gold plating were evaluated as “good”, and those with gold plating were evaluated as “bad”.

[Evaluation of resolution]
A phototool using the above laminated sample and having a wiring pattern with a line width / space width of 30/30 to 200/200 (unit: μm) as a 21-step tablet of a stower and a negative for resolution evaluation on the laminated sample Was exposed to light with an energy amount of 400 mJ / cm ^{2 using} an exposure machine (HMW-201GX type manufactured by Oak Manufacturing Co., Ltd.).

  Next, the exposed laminated sample was allowed to stand at room temperature for 30 minutes, and then spray-developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 90 seconds, and the unexposed area was removed to evaluate the resolution. The resolution value is the smallest value among the space widths (μm) in which the unexposed portions can be completely removed by the development process. The smaller the resolution value, the better the resolution.

[Evaluation of trackability]
Photosensitive film for etching with a resist thickness of 20 μm (manufactured by Hitachi Chemical Co., Ltd., trade name: H-Y920) is copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: E-67, copper foil thickness: 18 μm) ) And sprayed with a cupric chloride etchant (2 mol / liter, CuCl ₂ , 2N-HCl aqueous solution, 50 ° C.) at a pressure of 0.2 MPa (2 kgf / cm ² ) for 100 seconds. The copper on the laminate not protected by the resist was dissolved. Further, a stripping solution (3 mass% NaOH aqueous solution, 45 ° C.) is sprayed at a pressure of 0.2 MPa (2 kgf / cm ² ) to strip the resist pattern on the copper clad laminate, and the line width / space width = 100 / A printed wiring board on which a 100 μm copper line was formed was produced.

Next, the polyethylene film as a protective film is peeled off from the produced photosensitive element, and the photosensitive layer on the photosensitive element is formed using a vacuum pressure laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.). The photosensitive film was laminated on the printed wiring board toward the surface on which the copper line of the printed wiring board was formed. In this case, the laminator was held under a reduced pressure of 4 × 10 ⁴ Pa or less for 30 seconds, and then performed under conditions of a molding temperature of 70 ° C., a molding pressure of 0.4 MPa (4 kgf / cm ² ), and a pressurization time of 30 seconds.

  After lamination, the interface between the printed wiring board and the photosensitive layer laminated on the printed wiring board was observed with an optical microscope, and the followability was evaluated. The case where no air void was confirmed at the interface was evaluated as “good”, and the case where air void was confirmed at the interface was evaluated as “bad”.

  As is apparent from Table 4, even when the photosensitive layer had the black pigment and the photosensitive layer was thickened, the photosensitive resin composition of the present invention was sufficient to the bottom of the photosensitive layer. Photocurability can be obtained, and a black permanent mask resist having a good resist shape and sufficient adhesion can be formed on a printed wiring board. Moreover, according to the photosensitive resin composition of the present invention, a black permanent mask resist excellent in flexibility, chemical resistance, plating resistance, resolution, and followability to the substrate can be formed.

  In addition, in Examples 1 and 2 in which the weight of the solid content of the component (B1) is 0.5 times and 1 times the weight of the solid content of the component (B2), the weight of the solid content of the component (B1) Compared to Example 3 which is twice the weight of the solid content of the component (B2), the resist shape on the substrate tends to be excellent.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive film of this invention. It is a schematic cross section which shows the cross-sectional shape of the resist pattern formed on the board | substrate for FPC.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 20 ... Photosensitive layer, 30 ... Protective film, 40 ... Base material, 50 ... Copper foil, 60 ... Permanent mask resist, 100 ... Line width of resist upper part, 200 ... Bottom of resist Line width.

Claims (4)

A photosensitive resin composition used for forming a permanent mask resist on a printed wiring board,
A binder polymer containing (A) (A1) an acid-modified vinyl group-containing epoxy resin and (A2) an acrylic resin,
(B) (B1) a photopolymerization initiator containing a compound represented by the following general formula (1) and (B2) a compound represented by the following general formula (2),
(C) a photopolymerizable compound having an ethylenically unsaturated group, and
(D) a black pigment,
Containing a photosensitive resin composition.

[In General Formula (1), each of R ¹ and R ² independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a carboxyl group. R < ³ > -R < ⁵ > shows a hydrogen atom or a C1-C6 alkyl group each independently, k shows the integer of 0-4, l shows the integer of 0-5. A plurality of R ¹ and R ² may be the same or different. ]

[In General Formula (2), R ⁶ and R ⁷ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a carboxyl group. R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n each independently represents an integer of 0 to 5. A plurality of R ⁶ and R ⁷ may be the same or different. ]   (C) The photopolymerizable compound which has an ethylenically unsaturated group contains the compound of the weight average molecular weight 1000-20000 which has a urethane bond and an ethylenically unsaturated group in (C1) molecule | numerator. Resin composition.   A photosensitive element provided with a support body and the photosensitive layer which consists of a photosensitive resin composition of Claim 1 or 2 formed on this support body. A permanent mask resist obtained by curing the photosensitive resin composition according to claim 1 by light irradiation.

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