JP2006030765A - Photosensitive resin composition, photosensitive element using it, method for manufacturing resist pattern, and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition superior in resolution, adhesion, tent reliability and scum property, and to provide a photosensitive element using it, a method for manufacturing a resist pattern, and a method for manufacturing a printed wiring board. <P>SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerization compound, and (C) a photo initiator. (B) components contain the photopolymerization compound having at least three polymerizable ethylene unsaturated couplings in a molecule expressed by general formula (I) and the photopolymerization compound having at least two polymerizable ethylene unsaturated couplings, an ethylene glycol chain, and a propylene glycol chain in a molecule. Wherein, R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>denote each independently a hydrogen atom or methyl group, l, m and n are independently positive integers, and (l+m+n) is equal to 3-30. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

  Conventionally, in the field of printed wiring board production, as a resist material used for etching, plating and the like, a photosensitive resin composition and a photosensitive element obtained by using a support and a protective film are widely used. The printed wiring board is formed by laminating a photosensitive element on a copper substrate, exposing the pattern, removing the unexposed portion with a developer, performing etching or plating, and forming a pattern. It is manufactured by a method of peeling off from above.

  As a developing solution for removing the unexposed portion, an alkali developing type using a sodium hydrogen carbonate aqueous solution or the like has become mainstream, and the developing solution usually has an ability to dissolve a layer of the photosensitive resin composition to some extent. Any photosensitive resin composition can be dissolved or dispersed in the developer during development.

  With recent increases in the density of printed wiring boards, the contact area between the copper substrate and the patterned photosensitive resin composition layer is reduced, so that the photosensitive resin composition and the photosensitive element can be developed, etched or etched. In the plating process, excellent adhesive strength, mechanical strength, chemical resistance, flexibility and the like are required, and resolution and adhesion are required. In the tenting method, tent reliability is also required with respect to irregular formation of through holes, narrowing of through hole lands, and the like.

  Patent Document 1 includes a binder polymer having a carboxyl group, a photopolymerization initiator, and a photopolymerizable compound having at least one polymerizable ethylenically unsaturated compound in the molecule, and the photopolymerizable compound component is linear. A photosensitive resin composition containing urethane acrylate and γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate and a photosensitive element using the same are disclosed. Although this photosensitive resin composition and photosensitive element are excellent in plating resistance and adhesion, tent reliability and scum properties were not so good.

  Patent Document 2 discloses an acrylate compound having a single polyethylene glycol chain and an acrylate compound having a single polypropylene glycol chain. Although the acrylate compound having a single polyethylene glycol chain has improved releasability, it has a problem that problems such as deterioration in resist shape and tent reliability occur because the hydrophilicity is too high. In addition, an acrylate compound having a single polypropylene glycol chain has good flexibility, but does not improve resolution, is easily separated with an alkaline developer, and has a scum that causes a short circuit or disconnection when attached to a substrate. There was a problem of many occurrences.

  Furthermore, Patent Document 3 discloses a photosensitive resin composition containing an ethylenically unsaturated compound in which both a polyethylene glycol chain and a polypropylene glycol chain are incorporated in one molecule as an attempt to solve the above-mentioned problem. The photosensitive element used is disclosed. However, although the photosensitive resin composition and the photosensitive element have improved the above problems, satisfactory characteristics with respect to resolution and scum properties have not necessarily been obtained.

Japanese Patent Laid-Open No. 7-128551 JP-A-5-232699 JP 2004-4635 A

  An object of the present invention is to provide a photosensitive resin composition excellent in resolution, adhesion, tent reliability and scum, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board. is there.

  The present invention is a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the component (B) is represented by the following general formula (I): A photopolymerizable compound having at least three polymerizable ethylenically unsaturated bonds in the molecule represented and a photopolymerization having at least two polymerizable ethylenically unsaturated bonds, an ethylene glycol chain and a propylene glycol chain in the molecule The present invention relates to a photosensitive resin composition containing a photosensitive compound.

（一般式（Ｉ）中、Ｒ_１、Ｒ_２及びＲ_３は各々独立に水素原子又はメチル基を示し、ｌ、ｍ、及びｎは各々独立に正の整数であり、ｌ＋ｍ＋ｎは３〜３０である。）
また、前記分子内に少なくとも２つの重合可能なエチレン性不飽和結合、エチレングリコール鎖及びプロピレングリコール鎖を有する光重合性化合物が、下記一般式（II）、一般式（III）又は一般式（IＶ）で表される化合物であることが好ましい。

(In the general formula (I), R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a methyl group, l, m and n are each independently a positive integer, and l + m + n is 3 to 30. is there.)
The photopolymerizable compound having at least two polymerizable ethylenically unsaturated bonds, ethylene glycol chain and propylene glycol chain in the molecule is represented by the following general formula (II), general formula (III) or general formula (IV It is preferable that it is a compound represented by this.

（一般式（II）中、Ｒ_４及びＲ_５は各々独立に水素原子又は炭素数１〜３のアルキル基を示し、ｍ_１、ｍ_２及びｎ_１は各々独立に正の整数であり、ｍ_１＋ｍ_２及びｎ_１は各々独立に１〜３０であり、―(Ｃ_３Ｈ_６Ｏ)―は ―(ＣＨ_２ＣＨ(ＣＨ_３)―Ｏ)― 又は ―(ＣＨ_２ＣＨ_２ＣＨ_２―Ｏ)― である。）

(In General Formula (II), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m ₁ , m ₂ and n ₁ are each independently a positive integer, ₁ + m ₂ and n ₁ are each independently 1 to 30, and — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O )-

（一般式（III）中、Ｒ_４及びＲ_５は各々独立に水素原子又は炭素数１〜３のアルキル基を示し、ｍ_３、ｎ_２及びｎ_３は各々独立に正の整数であり、ｍ_３及びｎ_２＋ｎ_３は各々独立に１〜３０であり、―(Ｃ_３Ｈ_６Ｏ)―は ―(ＣＨ_２ＣＨ(ＣＨ_３)―Ｏ)― 又は ―(ＣＨ_２ＣＨ_２ＣＨ_２―Ｏ)― である。）

(In General Formula (III), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m ₃ , n ₂ and n ₃ are each independently a positive integer, ₃ and n ₂ + n ₃ are each independently 1 to 30, and — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O )-

（一般式（IＶ）中、Ｒ_４及びＲ_５は各々独立に水素原子又は炭素数１〜３のアルキル基を示し、ｍ_４及びｎ_４は各々独立に１〜３０の整数であり、―(Ｃ_３Ｈ_６Ｏ)― は ―(ＣＨ_２ＣＨ(ＣＨ_３)―Ｏ)― 又は ―(ＣＨ_２ＣＨ_２ＣＨ_２―Ｏ)― である。）

(In the general formula (IV), R ₄ and R ₅ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m ₄ and n ₄ each independently represents an integer of 1 to 30; C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O) —.)

  From the viewpoint of adhesion and developer resistance, it is preferable that the (A) binder polymer contains styrene or a styrene derivative as a copolymerization component.

  Moreover, it is preferable that (B) component contains the bisphenol A type (meth) acrylate compound further represented by the following general formula (V).

（一般式（Ｖ）中、Ｒ_６及びＲ_７は各々独立に水素原子又はメチル基を示し、Ｘ及びＹは各々独立に炭素数２〜６のアルキレン基を示し、ｐ及びｑは各々独立に正の整数であり、ｐ＋ｑは２〜４０である。）

(In General Formula (V), R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q each independently represent (It is a positive integer, and p + q is 2 to 40.)

  From the viewpoint of adhesion and sensitivity, it is preferable that the (C) photopolymerization initiator contains a 2,4,5-triarylimidazole dimer.

  Moreover, the compounding quantity of (A) component, (B) component, and (C) component is 40-80 weight part of (A) component with respect to 100 weight part of total amounts of (A) component and (B) component, ( The component (B) is preferably 20 to 60 parts by weight and the component (C) is preferably 0.1 to 20 parts by weight.

  Moreover, this invention relates to the photosensitive element formed by apply | coating and drying the said photosensitive resin composition on a support body.

  Further, the present invention provides a photosensitive element comprising a photosensitive film obtained by coating and drying the photosensitive resin composition on a support, and further laminating a protective film so as to be in contact with the layer of the photosensitive resin composition opposite to the support. About.

  In the present invention, the photosensitive element is laminated on the circuit forming substrate so that the layer of the photosensitive resin composition is in close contact, irradiated with actinic rays in an image form, and the exposed portion is photocured, The present invention relates to a method for producing a resist pattern, wherein unexposed portions are removed by development.

  The present invention also relates to a method for manufacturing a printed wiring board, wherein the circuit forming substrate on which the resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

  The photosensitive resin composition of the present invention, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board have excellent effects of improving resolution, adhesion, tent reliability, and scum properties. Play.

Hereinafter, the present invention will be described in detail.
In the present invention, (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.

  The (A) binder polymer in the present invention is not particularly limited, and examples thereof include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. . From the viewpoint of alkali developability, an acrylic resin is preferable. These are used alone or in combination of two or more.

  The weight average molecular weight of the (A) binder polymer is preferably 20,000 to 300,000, and more preferably 40,000 to 150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long. However, the weight average molecular weight and the number average molecular weight in the present invention are measured by gel permeation chromatography, and values converted to standard polystyrene are used.

  The (A) binder polymer preferably has a dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 6.0, and more preferably 1.0 to 3.0. When the degree of dispersion exceeds 6.0, the adhesion and resolution tend to decrease.

  The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl, and the like. -Esters of vinyl alcohol such as n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, ( (Meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylic acid esters such as 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic Acid, α-bromo (me ) Acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid, α-cyanocinnamic Examples thereof include polymerizable monomers having a carboxyl group such as acid, itaconic acid, crotonic acid and propiolic acid, and maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate. As said (meth) acrylic-acid alkylester, the compound etc. which the hydroxyl group, the epoxy group, the halogen group, etc. substituted to the compound represented by the following general formula (VI), the alkyl group of these compounds, etc. are mentioned, for example.

（一般式（ＶI）中、Ｒ_８は水素原子又はメチル基を示し、Ｒ_９は炭素数１〜１２のアルキル基を示す）

(In the general formula (VI), R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents an alkyl group having 1 to 12 carbon atoms)

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ₉ in the general formula (VI) include, for example, 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 structural isomers thereof can be mentioned. Examples of the monomer represented by the general formula (VI) 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, (meth) acrylic acid dodecyl ester and the like. These are used alone or in combination of two or more.

  The (A) binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability, for example, radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. Can be manufactured. The binder polymer (A) preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of adhesion and developer resistance.

  From the viewpoint of adhesion and developer resistance, the styrene or styrene derivative is preferably included as a copolymerization component in an amount of 0.1 to 30% by weight, more preferably 1 to 28% by weight, and more preferably 1.5 to 27%. It is particularly preferable to contain the content by weight. If this content is less than 0.1% by weight, the adhesion tends to be inferior, and if it exceeds 30% by weight, the peel piece tends to be large and the peel time tends to be long.

  These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. A binder polymer etc. are mentioned.

  The acid value of the (A) binder polymer is preferably 100 to 500 mgKOH / g, and more preferably 100 to 300 mgKOH / g. When the acid value is less than 100 mgKOH / g, the development time tends to be long, and when it exceeds 500 mgKOH / g, the developer resistance of the photocured resist tends to be lowered.

  In the present invention, the photopolymerizable compound (B) is a photopolymerizable compound having at least three polymerizable ethylenically unsaturated bonds in the molecule represented by the general formula (I) and at least two polymerizable molecules in the molecule. A photopolymerizable compound having an ethylenically unsaturated bond, an ethylene glycol chain and a propylene glycol chain.

In the photopolymerizable compound having at least three polymerizable ethylenically unsaturated bonds in the molecule represented by the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a methyl group. , L, m, and n are each independently a positive integer. In addition, l + m + n is 3 to 30, preferably 6 to 29, more preferably 9 to 28, particularly preferably 12 to 27, and preferably 15 to 27 from the viewpoint of resolution. Is highly preferred. When l + m + n exceeds 30, the adhesion tends to decrease.

Specific examples of the compound represented by the general formula (I) include a vinyl compound in which R _1, R ₂ and R ₃ are methyl groups and 1 + m + n = 21 (average value) (Hitachi Chemical Industry Co., Ltd.) Product name TMPT21E) and the like.

  The photopolymerizable compound having at least two polymerizable ethylenically unsaturated bonds, an ethylene glycol chain and a propylene glycol chain in the molecule may be the above general formula (II), general formula (III) or general formula (IV It is preferable that it is a compound represented by this.

In the compound represented by the general formula (II), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m ₁ , m ₂ and n ₁ are each independently And m ₁ + m ₂ and n ₁ are each independently 1 to 30, and — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O) —.

In the compound represented by the general formula (III), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m ₃ , n ₂ and n ₃ are Each independently a positive integer, m ₃ and n ₂ + n ₃ are each independently 1-30, — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — Or — (CH ₂ CH ₂ CH ₂ —O) —.

In the compound represented by the general formula (IV), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m ₄ and n ₄ each independently It is an integer of 1 to 30, and — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O) —.

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ₄ and R ₅ in the general formula (II), general formula (III), or general formula (IV) include, for example, a methyl group, an ethyl group, and n-propyl. Group, isopropyl group and the like.

The total number of repeating ethylene glycol chains (m ₁ + m ₂ , m ₃ and m ₄ ) in the general formula (II), general formula (III) or general formula (IV) is an integer of 1 to 30 each independently. It is preferably an integer of 1 to 10, more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8. If the number of repetitions exceeds 30, the resist shape and tent reliability tend to deteriorate.

The total number of repeating propylene glycol chains (n ₁ , n ₂ + n ₃ and n ₄ ) in the general formula (II), general formula (III) or general formula (IV) is each independently an integer of 1 to 30. , Preferably an integer of 5 to 20, more preferably an integer of 8 to 16, and particularly preferably an integer of 10 to 14. If the number of repetitions exceeds 30, scum tends to occur.

Specific examples of the compound represented by the general formula (II) include, for example, vinyl having R ₄ = R ₅ = methyl group, m ₁ + m ₂ = 4 (average value), and n ₁ = 12 (average value). A compound (product name FA-023M, manufactured by Hitachi Chemical Co., Ltd.) and the like. Specific examples of the compound represented by the general formula (III) include, for example, vinyl having R ₄ = R ₅ = methyl group, m ₃ = 6 (average value), and n ₂ + n ₃ = 12 (average value). A compound (product name FA-024M, manufactured by Hitachi Chemical Co., Ltd.) and the like. Specific examples of the compound represented by the general formula (IV) include, for example, a vinyl compound (R ₄ = R ₅ = methyl group, m ₄ = 1 (average value), n ₄ = 9 (average value)) Shin-Nakamura Chemical Co., Ltd. product name NK ester HEMA-9P). These may be used alone or in combination of two or more.

  Examples of the photopolymerizable compound (B) other than the above include bisphenol A (meth) acrylate compounds. As said bisphenol A type (meth) acrylate compound, the compound represented by the said general formula (V) is preferable.

R ₆ and R ₇ in the general formula (V) are each independently a hydrogen atom or a methyl group, and preferably a methyl group. X and Y in the general formula (V) are each independently an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. In the general formula (V), p and q are each independently a positive integer, p + q is 2 to 40, and preferably 6 to 34 from the viewpoint of compatibility with the component (A). More preferably, it is -30, It is further more preferable that it is 8-28, It is especially preferable that it is 8-20, It is very preferable that it is 8-16, It is very preferable that it is 8-12. When p + q exceeds 40, the hydrophilicity increases, the resist image tends to be peeled off during development, and the plating resistance against solder plating or the like tends to decrease.

  Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. From the viewpoints of resolution and plating resistance, an ethylene group and an isopropylene group are exemplified. Groups are preferred.

  Moreover, the aromatic ring in the general formula (V) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 10 carbon atoms. Group, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, carbon A C1-C10 alkyl mercapto group, an allyl group, a hydroxyl group, a C1-C20 hydroxyalkyl group, a carboxyl group, a C1-C10 carboxyalkyl group, and a C1-C10 alkyl group. An acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, and an alkyl group having 2 to 10 carbon atoms. Alkenyl group, N- alkylcarbamoyl group or a group containing a heterocyclic ring having 2 to 10 carbon atoms, an aryl group substituted by these substituents. The above substituents may form a condensed ring. Moreover, the hydrogen atom in these substituents may be substituted with the above substituents such as a halogen atom. When the number of substituents is 2 or more, each of the two or more substituents may be the same or different.

  Examples of the bisphenol A-based (meth) acrylate compound represented by the general formula (V) include 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) acryloxy) And polyethoxypolypropoxy) phenyl) propane.

  Examples of the 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-((meta ) 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) acryloxynonane) Xyl) 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)) (Acryloxytetradecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) Etc. 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). 4- (methacryloxypentadecaethoxy) phenyl) is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These may be used alone or in combination of two or more.

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

  Other than the compound represented by the general formula (I), other than the compound represented by the general formula (II), general formula (III) or general formula (IV) and other than the bisphenol A-based (meth) acrylate compound As the photopolymerizable compound (B), for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, and an α, β-unsaturated carboxylic acid with a compound containing a glycidyl group. Compound obtained, urethane monomer such as (meth) acrylate compound having urethane bond, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) Examples include acryloyloxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, and EO-modified nonylphenyl (meth) acrylate. Moreover, you may use together the photopolymerizable compound which has one polymerizable ethylenically unsaturated bond in a molecule | numerator. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the 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 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is done.

  Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

  Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl, and the like.

  Examples of the urethane monomer include a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO / PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. Examples of the EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Examples of the EO / PO-modified urethane di (meth) acrylate include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).

  Examples of the (C) photopolymerization initiator in the present invention include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone. 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2 Aromatic ketones such as morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1- Quinones such as loloanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, Benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole Dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9, 9'-acridinyl) heptane and other acridine derivatives, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. Further, 2,4,5-triarylimidazole dimer is preferable from the viewpoint of adhesion and sensitivity. These are used alone or in combination of two or more.

  The blending amount of the (A) binder polymer is preferably 40 to 80 parts by weight and more preferably 45 to 70 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). preferable. If this blending amount is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating properties tend to be inferior, and if it exceeds 80 parts by weight, the photosensitivity tends to be insufficient. .

  The blending amount of the (B) photopolymerizable compound is preferably 20 to 60 parts by weight, and preferably 30 to 60 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). Is more preferable. If the blending amount is less than 20 parts by weight, the tent reliability tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to become brittle.

  The amount of the compound represented by the general formula (I), which is one of the components in the (B) photopolymerizable compound, is preferably 3 to 50% by weight in the component (B). More preferably, it is -20% by weight. If the blending amount is less than 3% by weight, the scum property tends to deteriorate, and if it exceeds 50% by weight, the photocured product tends to become brittle.

  (B) Formulation of a photopolymerizable compound having at least two polymerizable ethylenically unsaturated bonds, both an ethylene glycol chain and a propylene glycol chain in the molecule, which is one of the components in the photopolymerizable compound. The amount is preferably 5 to 50% by weight, more preferably 10 to 30% by weight in the component (B). If the blending amount is less than 5% by weight, the tent reliability tends to be inferior, and if it exceeds 50% by weight, the photocured product tends to become brittle.

  The blending amount of the photopolymerization initiator (C) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and is 0.2 to 10 parts by weight. More preferably, it is a part. If the blending amount is less than 0.1 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be.

  In addition, the photosensitive resin composition of the present invention includes, if necessary, dyes such as malachite green, photochromic agents such as tribromophenyl sulfone and leuco crystal violet, thermochromic inhibitors, p-toluenesulfonamide and the like. Plasticizers, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, etc. (A) and ( B) About 0.01 to 20 parts by weight can be contained per 100 parts by weight of the total component. These are used alone or in combination of two or more.

  If necessary, the photosensitive resin composition of the present invention may be a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. And can be applied as a solution having a solid content of about 30 to 60% by weight.

  The photosensitive resin composition of the present invention is preferably applied as a liquid resist on a metal surface and dried, and then coated with a protective film as necessary, or used in the form of a photosensitive element. Although there is no restriction | limiting in particular as said metal, For example, iron-type alloys, such as copper, copper-type alloy, nickel, chromium, iron, stainless steel, etc. are mentioned. The metal is preferably copper, a copper-based alloy, or an iron-based alloy from the viewpoint of adhesion to a resist and electron conductivity.

  Moreover, although the thickness of the layer of the said photosensitive resin composition changes with uses, it is preferable that it is 1-100 micrometers in thickness after drying, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the adhesive force and resolution tend to decrease.

  Further, the transmittance of the layer of the photosensitive resin composition with respect to ultraviolet rays having a wavelength of 365 nm is preferably 5 to 75%, more preferably 7 to 60%, and particularly preferably 10 to 40%. preferable. If the transmittance is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior. The transmittance can be measured with a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer (product name, manufactured by Hitachi, Ltd.).

  When used as the photosensitive element, the support preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and particularly preferably 10 to 16 μm. If the thickness is less than 5 μm, the layer of the photosensitive resin composition tends to be broken when the support is peeled off before development, and if it exceeds 25 μm, the resolution tends to be lowered.

  The haze of the support is preferably 0.001 to 5.0, more preferably 0.001 to 2.0, and particularly preferably 0.01 to 1.8. When this haze exceeds 2.0, the resolution tends to decrease. The haze is measured according to JIS K 7105, and can be measured with a commercially available turbidimeter such as NDH-1001DP (manufactured by Nippon Denshoku Industries Co., Ltd., product name).

  Examples of the support include heat-resistant and solvent-resistant polymer films such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

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

  The tensile strength in the film longitudinal direction of the protective film is preferably 13 MPa or more, more preferably 13 to 100 MPa, particularly preferably 14 to 100 MPa, and very preferably 15 to 100 MPa. 16 to 100 MPa is extremely preferable. If the tensile strength is less than 13 MPa, the protective film tends to be broken during lamination.

  The tensile strength in the film width direction of the protective film is preferably 9 MPa or more, more preferably 9 to 100 MPa, particularly preferably 10 to 100 MPa, and very preferably 11 to 100 MPa. It is very preferably 12 to 100 MPa. If the tensile strength is less than 9 MPa, the protective film tends to be broken during lamination.

  The tensile strength can be measured according to JIS C 2318-1997 (5.3.3). For example, a commercial tensile strength tester such as Tensilon (product name, manufactured by Toyo Baldwin Co., Ltd.). Measurement is possible.

  Examples of the first protective film include polymer films such as polyethylene and polypropylene.

  In addition, since these support and protective film must be removable from the layer of the photosensitive resin composition later, they must be subjected to a surface treatment that makes removal impossible. There is no particular limitation, and processing may be performed as necessary. Furthermore, these supports and protective films may be subjected to antistatic treatment as necessary.

  The photosensitive element having two layers of the support and the photosensitive resin composition layer thus obtained, and the photosensitive element having three layers of the support, the photosensitive resin composition layer and the protective film, For example, the protective film is further laminated as it is or on the other surface of the photosensitive resin composition layer, wound around a cylindrical core and stored. In addition, it is preferable to wind up in this case so that a support body may become the outermost side. From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element, and it is more preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance.

  Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

When producing a resist pattern using the photosensitive element, for example, when the protective film is present, after the protective film is removed, the layer of the photosensitive resin composition is heated to form a circuit. Examples of the method include laminating by pressure bonding to a substrate, and the laminating is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C., and the pressure bonding pressure is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. In addition, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance. It is also possible to pre-heat the substrate.

  The layer of the photosensitive resin composition thus completed is irradiated with actinic rays in an image form through a negative or positive mask pattern called an artwork. Under the present circumstances, when the support body which exists on the layer of the photosensitive resin composition is transparent, you may irradiate actinic light as it is, and when opaque, it is preferable to remove. Examples of the active light source include known light sources that effectively emit ultraviolet rays, such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, and xenon lamps. In addition, those that effectively emit visible light, such as a photographic flood bulb and a solar lamp, can be used.

  Next, after the exposure, when a support is present on the layer of the photosensitive resin composition, after removing the support, the unexposed portion is removed and developed by wet development, dry development, etc. Manufacture a pattern. In the case of wet development, development is performed by a known method such as spraying, rocking immersion, brushing, scraping, or the like, using a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. To do. The developer is preferably a safe and stable developer with good operability, such as an alkaline aqueous solution. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used. Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, A dilute solution of 0.1 to 5% by weight sodium tetraborate is preferred. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the layer of the photosensitive resin composition. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  The aqueous developer comprises water or an alkaline aqueous solution and one or more organic solvents. Examples of the alkaline substance include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine and the like can be mentioned. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono And butyl ether. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by weight, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by weight in order to prevent ignition. Moreover, you may use together 2 or more types of image development methods as needed. Examples of the development method include a dip method, a battle method, a spray method, brushing, and slapping. A high pressure spray method is preferable from the viewpoint of resolution.

As the treatment after development, the resist pattern may be further cured and used by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary.

  For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide-based etching solution, etc. can be used. It is preferable to use a ferric chloride solution.

  When a printed wiring board is produced using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, and hard Examples thereof include gold plating such as gold plating and soft gold plating. Next, the resist pattern can be peeled with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by weight sodium hydroxide aqueous solution, a 1 to 10% by weight potassium hydroxide aqueous solution and the like are used. Examples of the peeling method include a dipping method and a spray method, and the dipping method and the spray method may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

Hereinafter, the present invention will be described with reference to examples.
(Examples 1-3 and Comparative Examples 1-6)
The components (A), (C), color former, dye, solvent, and plasticizer shown in Table 1 were mixed at the weights shown in the same table to obtain a solution.

なお、上記共重合体の重量平均分子量はゲルパーミエーションクロマトグラフィーにより測定し、標準ポリスチレン換算した値を使用したものである。ゲルパーミエーションクロマトグラフィーの条件は以下に示す。

In addition, the weight average molecular weight of the said copolymer is measured by gel permeation chromatography, and uses the value converted into standard polystyrene. The conditions for gel permeation chromatography are shown below.

Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) (product name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: Room temperature Flow rate: 2.05 ml / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

  Next, the component (B) shown in Table 2 was dissolved in the obtained solution by the weight shown in the same table to obtain a solution of the photosensitive resin composition.

＊１：一般式（Ｉ）において、Ｒ_１＝Ｒ_２＝Ｒ_３＝メチル基で、ｌ＋ｍ＋ｎ＝２１（平均値）であるビニル化合物（日立化成工業（株）製、製品名）
＊２：一般式（II）において、Ｒ_４＝Ｒ_５＝メチル基、ｍ_１＋ｍ_２＝４（平均値）、 ｎ_１＝１２（平均値）であるビニル化合物（日立化成工業（株）製、製品名）
＊３：一般式（III）において、Ｒ_４＝Ｒ_５＝メチル基、ｍ_３＝６（平均値）、ｎ_２＋ｎ_３＝１２（平均値）であるビニル化合物（日立化成工業（株）製、製品名）
＊４：２，２−ビス（４−（メタクリロキシペンタエトキシ）フェニル）プロパン（新中村化学工業（株）製、製品名）
＊５：ポリプロピレングリコールジアクリレート（プロピレングリコール鎖の繰り返し単位は６〜７）（新中村化学工業（株）製、製品名）

* 1: Vinyl compound (product name) manufactured by Hitachi Chemical Co., Ltd., wherein R ₁ = R ₂ = R ₃ = methyl group and 1 + m + n = 21 (average value) in general formula (I)
* 2: In general formula (II), R ₄ = R ₅ = methyl group, m ₁ + m ₂ = 4 (average value), n ₁ = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd.) ,product name)
* 3: A vinyl compound (manufactured by Hitachi Chemical Co., Ltd.) in which R ₄ = R ₅ = methyl group, m ₃ = 6 (average value), n ₂ + n ₃ = 12 (average value) in the general formula (III) ,product name)
* 4: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 5: Polypropylene glycol diacrylate (repeat unit of propylene glycol chain is 6-7) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

  Next, the obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (haze: 1.7%, product name: GS-16, manufactured by Teijin Limited), and 100 ° C. After drying with a hot air convection dryer for 10 minutes, a polyethylene protective film (tensile strength in the film longitudinal direction: 16 MPa, tensile strength in the film width direction: 12 MPa, manufactured by Tamapoli Co., Ltd., product name NF-15) A protected photosensitive element was obtained. The film thickness after drying of the layer of the photosensitive resin composition was 20 μm.

  On the other hand, the copper surface of a copper-clad laminate (product name: MCL-E-61, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, is a brush equivalent to # 600. Polishing using a polishing machine (manufactured by Sankei Co., Ltd.), washing with water, drying with an air flow, heating the obtained copper-clad laminate to 80 ° C., and the photosensitive resin on the copper surface The layer of the composition was laminated at a speed of 3 m / min using a 120 ° C. heat roll while peeling off the protective film.

  Next, a photo tool having a stove 21-step tablet as a negative, and a photo tool having a wiring pattern having a line width / space width of 6/6 to 47/47 (unit: μm) as a negative for resolution evaluation A phototool having a wiring pattern with a line width / space width of 6/400 to 47/400 (unit: μm) was placed on the test piece as a negative for evaluating the properties. Then, using an exposure machine HMW-201 (product name, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp, 21 stages of the stofer when sprayed with a 1 wt% sodium carbonate aqueous solution for 40 seconds at 30 ° C. The exposure was performed with an energy amount such that the number of remaining step steps of the step tablet was 7.0, and development was performed by the above developing method. Here, the resolution was evaluated based on the smallest value of the line width that did not peel off by the development process and had no resist residue between the resist patterns. The smaller the numerical value, the better the resolution evaluation. Further, the adhesion was evaluated by the smallest value of the line width without any line chipping, peeling or twisting due to development processing. The smaller the numerical value, the better the evaluation of adhesion.

Also, a copper-clad laminate having a length and width of 250 × 200 mm and a thickness of 1.6 mm and 100 through-holes with a diameter of 6 mmφ were used as a base material, and the photosensitive resin composition was used as the base material. The film was laminated to a thickness of 20 μm after drying, exposed at 70 mJ / cm ² , and developed at 30 ° C. using a 1 wt% sodium carbonate aqueous solution for 40 seconds. Next, a cylindrical probe having an insertion diameter of 1.5 mmφ was introduced into the center of the layer of the cured photosensitive resin composition on the through hole at a speed of 2.0 m / min. Made from the point where the bottom surface of the cylindrical probe and the layer of the photosensitive resin composition are in contact with each other as the strength and extensibility of the layer of the photosensitive resin composition. The approach distance of the columnar probe was measured. The larger the values of tent strength and tent elongation, the better the tent reliability.

For the scum property, only 0.2 m ² of the photosensitive resin composition layer of the obtained photosensitive element was taken out, added to a 1.0 wt% sodium carbonate aqueous solution, and stirred at 30 ° C. for 2 hours with a stirrer. Propylene-based antifoaming agent (manufactured by Hitachi Chemical Co., Ltd., product name: CF-900) was added so as to be 0.1% by weight, stirred for 30 minutes and left to stand for a day and night. Was observed.
A: No occurrence of scum O: Some occurrence of scum ×: Many occurrences of scum The results are summarized in Table 3.

  As is apparent from Table 3, Examples 1 to 3 are excellent in resolution, adhesion, tent reliability, and scum properties.

It is a tent reliability evaluation method in the embodiment of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Cylindrical probe: Insertion diameter 1.5mmphi, 2 ... Insertion speed: 2.0m / min, 3 ... Photosensitive resin composition layer: Thickness 20micrometer, 4 ... Through hole: Diameter 6mmphi, 5 …… Through hole substrate: 1.6mm thickness

Claims (10)

(A) A photosensitive resin composition containing a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the component (B) is represented by the following general formula (I) A photopolymerizable compound having at least three polymerizable ethylenically unsaturated bonds in the molecule and a photopolymerizable compound having at least two polymerizable ethylenically unsaturated bonds, an ethylene glycol chain and a propylene glycol chain in the molecule; A photosensitive resin composition comprising:

(In the general formula (I), R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a methyl group, l, m and n are each independently a positive integer, and l + m + n is 3 to 30. is there.) The photopolymerizable compound having at least two polymerizable ethylenically unsaturated bonds, ethylene glycol chain and propylene glycol chain in the molecule is represented by the following general formula (II), general formula (III) or general formula (IV) The photosensitive resin composition of Claim 1 which is a compound represented by these.

(In General Formula (II), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m ₁ , m ₂ and n ₁ are each independently a positive integer, ₁ + m ₂ and n ₁ are each independently 1 to 30, and — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O )-

(In General Formula (III), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m ₃ , n ₂ and n ₃ are each independently a positive integer, ₃ and n ₂ + n ₃ are each independently 1 to 30, and — (C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O )-

(In the general formula (IV), R ₄ and R ₅ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m ₄ and n ₄ each independently represents an integer of 1 to 30; C ₃ H ₆ O) — is — (CH ₂ CH (CH ₃ ) —O) — or — (CH ₂ CH ₂ CH ₂ —O) —.) (A) The photosensitive resin composition of Claim 1 or 2 whose binder polymer is a compound which contains styrene or a styrene derivative as a copolymerization component. The photosensitive resin composition of any one of Claims 1-3 in which (B) component contains the bisphenol A type (meth) acrylate compound further represented by the following general formula (V).

(In General Formula (V), R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q each independently represent (It is a positive integer, and p + q is 2 to 40.) (C) The photosensitive resin composition of any one of Claims 1-4 in which a photoinitiator contains a 2,4,5-triaryl imidazole dimer. Component (A), component (B) and component (C) are blended in amounts of 100 to parts by weight of component (A) and component (B), and (A) component is 40 to 80 parts by weight, (B) The photosensitive resin composition according to any one of claims 1 to 5, wherein the component is 20 to 60 parts by weight and the component (C) is 0.1 to 20 parts by weight. The photosensitive element formed by apply | coating and drying the photosensitive resin composition of any one of Claims 1-6 on a support body. The photosensitive resin composition according to any one of claims 1 to 6 is applied and dried on a support, and further a protective film is laminated so as to be in contact with the layer of the photosensitive resin composition opposite to the support. A photosensitive element. The photosensitive element according to claim 7 or 8 is laminated so that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate, irradiated with actinic rays in an image form, and the exposed portion is photocured, A method for producing a resist pattern in which unexposed portions are removed by development. A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern has been produced by the method for producing a resist pattern according to claim 9.

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