JP5279423B2 - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board - Google Patents

Abstract

The photosensitive composition provided in the invention characterized by composing (methyl radical) acrylic ester series adhesive, polymerized compound, neutral photopolymerization initiator, thermalcross-linking agent and compound indicated in following general formula (1) in which X means hydrogen atom or substitute with SigmaMu value higher than -0.22.

Description

  The present invention relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board suitable as a solder resist material for forming an image by laser exposure.

  Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film in which a photosensitive layer is formed by coating a photosensitive composition on a support and drying it has been used. As a method for forming such a permanent pattern, for example, a photosensitive film is laminated on a substrate such as a copper clad laminate on which a permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate is formed. After the exposure, the photosensitive layer is developed to form a pattern, and then subjected to a curing process or the like to form a permanent pattern.

  Up to now, as a photosensitive resin composition useful as a liquid photo solder resist excellent in ultraviolet curability and solder heat resistance, which can form an image by ultraviolet exposure and development with a dilute alkaline aqueous solution after film formation, (a) at least 2 After reacting an epoxy resin containing one terminal epoxy group with 0.8 to 1.2 moles of α / β unsaturated carboxylic acid per epoxy equivalent of the epoxy resin, 0.2 to 1 per epoxy equivalent Compound obtained by reacting with 0.0 mol of polybasic acid anhydride, (b) diluent, (c) sensitizer, (d) 1,3,5-trisglycidyl isocyanuric acid having a melting point of 130 ° C. or lower There has been proposed a photosensitive resin composition comprising an epoxy resin comprising the above, and (d) an epoxy resin curing agent selected from S-triazine compounds such as melamine (see Patent Document 1).

  Although it is known that an S-triazine compound improves plating resistance, Patent Document 1 does not mention storage stability. When plating resistance is improved, there is a problem that storage stability is lowered, and further improvement and development of a photosensitive composition capable of improving plating resistance and achieving both storage stability is desired. It is.

Japanese Patent Laid-Open No. 2-173747

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a photosensitive composition, a photosensitive film, and a photosensitive laminate that can achieve not only developability, hardness, heat resistance, and sensitivity, but also excellent plating resistance and storage stability, which are necessary as a solder resist. An object is to provide a body, a method for forming a permanent pattern, and a printed circuit board.

Means for solving the problems are as follows. That is,
<1> A photosensitive composition comprising a (meth) acrylate binder, a polymerizable compound, a neutral photopolymerization initiator, a thermal crosslinking agent, and a compound represented by the following general formula (1). It is a thing.
However, in said general formula (1), X represents the substituent whose (sigma) m value is -0.22 or more.
<2> In general formula (1), X is substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group, and at least one hydrogen atom. The photosensitive composition according to <1>, which is any of amino groups.
<3> The photosensitive composition according to any one of <1> to <2>, wherein the (meth) acrylate binder is a polymer compound containing an acidic group and an ethylenically unsaturated bond in a side chain.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the polymerizable compound is contained in an amount of 10% by mass or more based on the solid content in the photosensitive composition solid content. is there.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the neutral photopolymerization initiator is an oxime ester photopolymerization initiator.
<6> From the above <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 5>. The photosensitive composition according to any one of 5>.
<7> A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <6> on a support.
<8> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <6> on a substrate.
<9> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <6>.
<10> Exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface of the picture element portion in the light modulation unit are modulated after the light is modulated by the light modulation unit. The method for forming a permanent pattern according to <9>.
<11> The method for forming a permanent pattern according to any one of <9> to <10>, wherein the photosensitive layer is developed after the exposure.
<12> The method for forming a permanent pattern according to <11>, wherein the development of the photosensitive layer is performed after the development.
<13> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of <9> to <12>.

  According to the present invention, it is possible to solve various problems in the prior art, and a photosensitive composition that is compatible with not only developability, hardness, heat resistance, sensitivity, but also excellent plating resistance and storage stability, which is necessary as a solder resist, A photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board can be provided.

(Photosensitive composition)
In the present invention, the photosensitive composition comprises a (meth) acrylate binder, a polymerizable compound, a neutral photopolymerization initiator, a thermal crosslinking agent, and a compound represented by the following general formula (1). It contains, and further contains other components as necessary.
However, in said general formula (1), X represents the substituent whose (sigma) m value is -0.22 or more.

<Compound represented by the general formula (1)>
The compound represented by the general formula (1) is not particularly limited as long as the σm value of X is −0.22 or more in the general formula (1), and may be appropriately selected according to the purpose. However, the σm value of X is preferably −0.21 to 0.8, more preferably −0.07 to 0.7, and particularly preferably −0.07 to 0.6. When the σm value is less than −0.21, storage stability may be deteriorated, and when it exceeds 0.8, stability of the compound may be deteriorated. On the other hand, when the σm value is within the particularly preferable range, it is advantageous in terms of both plating resistance and storage stability.
The σm value in the present invention is a substituent constant defined by Hammett and is described in, for example, “Chemical Review, 1991 (Vol. 91), pages 165-195”.
Moreover, there is no restriction | limiting in particular as addition amount of the compound represented by the said General formula (1) in the said photosensitive composition, Although it can select suitably according to the objective, 0.1 mass part-20 A mass part is preferable, 0.2 mass part-10 mass parts are more preferable, 0.5 mass part-8 mass parts are especially preferable. When the amount of the compound represented by the general formula (1) is less than 0.1 parts by mass, the effect on the plating resistance may be dilute, and when it exceeds 20 parts by mass, the storage stability is deteriorated. In addition, the cured film becomes brittle and the resistance may be inferior. On the other hand, when the amount of the compound represented by the general formula (1) is within the particularly preferable range, it is advantageous in terms of both plating resistance and storage stability.

The X is not particularly limited as long as the σm value is −0.22 or more, and can be appropriately selected according to the purpose. Examples thereof include a hydrogen atom, a halogen atom, and an alkyl group having 1 to 12 carbon atoms. , An aryl group having 6 to 12 carbon atoms in total, an alkenyl group, an amino group substituted with at least one hydrogen, and the like. The alkyl group, aryl group, and aralkyl group may have a substituent. Examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, a hydroxyaryl group, a carboxy group, An ester group, an amide group, a cyano group, a halogen group, a nitro group, and the like are preferable.
Among them, "- Cl", "- CH _3" is, because it can improve the storage stability of the photosensitive composition, preferably.

Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (m-1) to (m-19).

Table 1 shows the σm values of the substituents of the compounds represented by the structural formulas (m-1) to (m-19).

<(Meth) acrylate binder>
As the (meth) acrylate binder, a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain is preferably used.

-High molecular compound containing an acidic group and an ethylenically unsaturated bond in the side chain-
Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and a carboxyl group is preferable from the viewpoint of obtaining raw materials.
The binder includes at least one polymerizable double bond in the molecule, for example, (meth) acryl group such as (meth) acrylate group or (meth) acrylamide group, vinyl ester of carboxylic acid, vinyl ether, allyl. Various polymerizable double bonds such as ether can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound such as a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, or cinnamic acid, or an alicyclic epoxy group. Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having a (meth) acryloyl group (for example, an epoxy group such as cyclohexene oxide in the same molecule). In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. Moreover, the compound etc. which copolymerize cyclic ether group containing polymeric compounds, such as glycidyl methacrylate, and vinyl monomers, such as (meth) acryloyl alkyl ester, and add (meth) acrylic acid to the epoxy group of a side chain, etc. are mentioned. It is done.
Examples of these include Japanese Patent No. 2763775, Japanese Patent Laid-Open No. 3-172301, Japanese Patent Laid-Open No. 2000-232264, and the like.

Among these, the (meth) acrylate binder is obtained by adding a polymerizable compound containing a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) to a part of the acidic group of the polymer compound. And a polymer compound selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to part or all of the cyclic ether group of the polymer compound. In this case, the addition reaction between the acidic group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.
Among these, from the viewpoint of the development stability of the photosensitive composition over time, the (meth) acrylate-based binder contains an aromatic group which may contain a carboxyl group in the side chain and may contain a heterocycle in the side chain, and A polymer compound containing an ethylenically unsaturated bond is preferred.

--Aromatic group which may contain a heterocycle--
Examples of the aromatic group that may include the heterocycle (hereinafter, also simply referred to as “aromatic group”) include, for example, a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, Examples include those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples of the aromatic group include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole. Ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring Group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring Group, purine ring group, pyran ring group, Lysine ring group, a piperazine ring group, an indole ring group, an indolizine ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, a triazine ring group. In these, a hydrocarbon aromatic group is preferable and a phenyl group and a naphthyl group are more preferable.

  The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, A thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and the like, each of which may have a substituent, may be mentioned.

Examples of the alkyl group include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups, and cyclic alkyl groups.
Specific examples of the alkyl group 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, tridecyl group, hexadecyl group. , Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group, 2-norbornyl group and the like. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are preferable.

Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples of such substituents include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups. Group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfo Xyl group, acylthio group, acylamino group, N-a Killacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N '-Alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N ' -Dialkyl-N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N ' -Diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N '-Aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- Alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl Group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group ( -SO 3 _H) and its conjugated base group (referred to as a sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfinamoyl group, N- aryl Sulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N- Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonato group), dialkyl Phosphono group (—PO ₃ (alkyl) ₂ ) (hereinafter “alkyl” means an alkyl group) To do. ), A diarylphosphono group (—PO ₃ (aryl) ₂ ) (hereinafter “aryl” means an aryl group), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphone Group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl)) ) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group _(-OPO 3 H (alkyl)) and its conjugated base group (referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate base (aryl phosphite Hona preparative oxy Group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups.
Specific examples of the aryl group in the substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulphonatophenyl group, phosphonopheny Groups, phosphonium Hona preparative phenyl group.

Specific examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like.
Specific examples of the alkynyl group in the substituent include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of ^{R 01} of the acyl group in the substituents ^(R 01 CO-), a hydrogen atom, an alkyl group described above, and aryl groups.
Among these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups, acyloxy groups Group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group, phosphonatoxy Group, aryl group, alkenyl group and the like are preferable.
In addition, examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group, and examples of the silyl group in the substituent include a trimethylsilyl group.

On the other hand, examples of the alkylene group in the alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. For example, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms are preferable.
Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. In these, a phenyl group and a naphthyl group are preferable.
The alkyl group may have a substituent, and examples of the aryl group having such a substituent (hereinafter sometimes referred to as “substituted aryl group”) include the ring-forming carbon of the above-described aryl group. Examples of the substituent on the atom include a group having a monovalent nonmetallic atomic group other than a hydrogen atom.
As the substituent that the aryl group may have, for example, the above-described alkyl group, substituted alkyl group, and the substituents that the alkyl group may have are preferable.

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples include methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, and 3-butynylphenyl group.

Examples of the alkenyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ )) and the alkynyl group (—C≡C (R ⁰⁵ )) include, for example, R ⁰² , R ⁰³ , R ⁰⁴ , and R ^Examples include a group in which ⁰⁵ is a monovalent nonmetallic atomic group.
Examples of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.

Preferable specific examples of the alkenyl group and alkynyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenyl An ethynyl group etc. are mentioned.
As said heterocyclic group, the pyridyl group illustrated as a substituent of a substituted alkyl group etc. are mentioned, for example.

Examples of the oxy group (R ⁰⁶ O—) include those in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
Examples of such oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N- A diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group and the like are preferable.
Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specific examples of preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxy Ethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy Group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

As the amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) which may contain an amide group, for example, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atoms excluding a hydrogen atom A group consisting of a group is mentioned. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring.
Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N'-alkyl-N'-arylureido group, N', N'-dialkyl-N-alkylureido group, N ', N'- Alkyl-N′-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N ′ -Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group and the like. It is done. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Also, ^{R 07} acylamino group, N- alkylacylamino group, N- arylacylamino group definitive acyl group ^(R 07 CO-) are as defined above. Of these, an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group are more preferable.
Specific examples of preferred amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Examples of the sulfonyl group (R ⁰¹¹ —SO ₂ —) include those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group.
As such a sulfonyl group, for example, an alkylsulfonyl group, an arylsulfonyl group, and the like are preferable. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
Specific examples of the sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, and a chlorophenylsulfonyl group.

As described above, the sulfonate group (—SO ₃ —) means a conjugate base anion group of a sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation.
As such counter cations, generally known ones can be appropriately selected and used. For example, oniums (for example, ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions ^{(e.g., Na +, K +, Ca} 2+, Zn 2+ etc.).

Examples of the carbonyl group (R ⁰¹³ —CO—) include groups in which R ⁰¹³ is a monovalent nonmetallic atomic group.
Examples of such carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group. N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group and the like. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
The carbonyl group is preferably a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, or an N-arylcarbamoyl group. A group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable.
Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N- A methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group and the like are preferable.

Examples of the sulfinyl group (R ⁰¹⁴ —SO—) include those in which R ⁰¹⁴ is a monovalent nonmetallic atomic group.
Examples of such sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N -Diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, etc. are mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, an alkylsulfinyl group and an arylsulfinyl group are preferable.
Preferable examples of the substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, a tolylsulfinyl group and the like.

The phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups. For example, the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphosphono group , Monoalkylphosphono group, monoarylphosphono group and the like are preferable. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred.
More preferred specific examples of the phosphono group include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

The phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) and, as mentioned above, the phosphono group _(-PO 3 _{H 2),} coupled from the first dissociation acid, or the second dissociated acid bases An anionic group is meant. Usually, it is preferable to use it with a counter cation. As such a counter cation, generally known ones can be appropriately selected. For example, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The phosphonato group may be a conjugated base anion group in which one of the phosphono groups is substituted with an organic oxo group. Specific examples thereof include the monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

The aromatic group can be produced by a normal radical polymerization method by using one or more radically polymerizable compounds containing an aromatic group and, if necessary, one or more other radically polymerizable compounds as a copolymerization component. it can.
Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.

As the radically polymerizable compound containing an aromatic group, for example, a compound represented by the general formula (A-1) and a compound represented by the general formula (A-2) are preferable.
However, in said general formula (A-1), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group that may contain a heterocycle.
However, in said general formula (A-2), R < ₁ >, R < ₂ >, R < ₃ > and Ar represent the same meaning as the said general formula (A-1).

The organic group of L is, for example, a polyvalent organic group composed of non-metallic atoms, and includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 oxygen atoms. Those consisting of atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms.
More specifically, examples of the organic group of L include those formed by combining the following structural units, polyvalent naphthalene, polyvalent anthracene and the like.

  The L linking group may have a substituent, and examples of the substituent include the aforementioned halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyano group, amide group, amino group, alkyl group, Examples include alkenyl groups, alkynyl groups, aryl groups, substituted oxy groups, substituted sulfonyl groups, substituted carbonyl groups, substituted sulfinyl groups, sulfo groups, phosphono groups, phosphonato groups, silyl groups, and heterocyclic groups.

In the compound represented by the general formula (A-1) and the compound represented by the general formula (A-2), the general formula (A-1) is preferable in terms of sensitivity. Of the general formula (A-1), those having a linking group are preferable from the viewpoint of stability, and the organic group of L is an alkylene group having 1 to 4 carbon atoms in the non-image area. It is preferable in terms of removability (developability).
The compound represented by the general formula (A-1) is a compound including a structural unit represented by the following general formula (A-3). Moreover, the compound represented by the general formula (A-2) is a compound containing a structural unit of the following general formula (A-4). Among these, the structural unit of the general formula (A-3) is preferable in terms of storage stability.

However, in said general formula (A-3) and general formula (A-4), R < ₁ >, R < ₂ > and R < ₃ > and Ar are said general formula (A-1) and general formula (A-2). Means the same.
In the general formulas (A-3) and (A-4), R ₁ and R ₂ are hydrogen atoms, and R ₃ is a methyl group, from the viewpoint of removal (developability) of non-image areas. preferable.
In addition, L in the general formula (A-3) is preferably an alkylene group having 1 to 4 carbon atoms in terms of removability (developability) of non-image areas.

  The compound represented by the general formula (A-1) or the compound represented by the general formula (A-2) is not particularly limited, and examples thereof include the following exemplary compounds (1) to (30). It is done.

  Among the exemplary compounds (1) to (30), (5), (6), (11), (14), and (28) are preferable, and among these, (5) and (6) are storage stable. Is more preferable from the viewpoints of colorability and developability.

  The content of the aromatic group that may contain a heterocycle in the (meth) acrylate binder is not particularly limited, but when the total structural unit of the polymer compound is 100 mol%, the general formula (A- It is preferable to contain 20 mol% or more of the structural unit represented by 3), and it is more preferable to contain 30 mol% to 45 mol%. When the content is less than 20 mol%, storage stability may be lowered, and when it exceeds 45 mol%, developability may be deteriorated.

--Ethylenically unsaturated bond--
There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by the following general formula (A-5)-(A-7) is preferable.

However, in the general formulas (A-5) to (A-7), R _{1 to} R ₁₁ each independently represents a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ₄ . Z represents an oxygen atom, a sulfur atom, —N—R ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

In the general formula (A-5), as R ₁ , for example, a hydrogen atom or an optionally substituted alkyl group is preferable, and the hydrogen atom or methyl group has high radical reactivity. This is more preferable.
R ₂ and R ₃ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl which may have a substituent. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, such as a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group that may have a substituent and an aryl group that may have a substituent are more preferable because of high radical reactivity.
As R ₄ , for example, an alkyl group which may have a substituent is preferable, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, and an alkoxy group. Examples include carbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like.

In the general formula (A-6), examples of R _{4 to} R ₈ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An alkyl group that may have a group, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, and a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc. are preferable, a hydrogen atom, a carboxyl group , An alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
Examples of the substituent that can be introduced include those listed in the general formula (A-5).

In the general formula (A-7), as R ₉ , for example, a hydrogen atom, an alkyl group which may have a substituent, and the like are preferable, and a hydrogen atom and a methyl group are more preferable because of high radical reactivity.
R ₁₀ and R ₁₁ each independently have, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like are preferable, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.
Here, as the substituent which can be introduced, those exemplified in the general formula (A-5) are exemplified.
Z represents an oxygen atom, a sulfur atom, —NR ₁₃ —, or a phenylene group which may have a substituent. R ₁₃ represents an alkyl group which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

Among the side chain ethylenically unsaturated bonds represented by the general formulas (A-5) to (A-7), those having the general formula (A-5) have high polymerization reactivity and high sensitivity. preferable.
The content of the ethylenically unsaturated bond in the polymer compound is not particularly limited, but is preferably 0.5 meq / g to 3.0 meq / g, more preferably 1.0 meq / g to 3.0 meq / g. 1.5 meq / g to 2.8 meq / g is particularly preferable. When the content is less than 0.5 meq / g, the curing reaction amount is small, so the sensitivity may be low. When the content is more than 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

The method for introducing the ethylenically unsaturated bond represented by the general formula (A-5) into the side chain is not particularly limited. For example, the polymer compound containing a carboxyl group in the side chain and the ethylenically unsaturated bond are not limited. It can be obtained by addition reaction of a compound having a saturated bond and an epoxy group.
The polymer compound containing a carboxyl group in the side chain is usually composed of, for example, one or more radical polymerizable compounds containing a carboxyl group and, if necessary, one or more other radical polymerizable compounds as a copolymerization component. The radical polymerization method includes, for example, suspension polymerization method, solution polymerization method and the like.

The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these. The compounds represented are preferred.
However, in said general formula (A-8), R < ₁ > represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
In the general formula (A-9), _{R 2} represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Of the compound represented by the general formula (A-8) and the compound represented by the general formula (A-9), the compound represented by the general formula (A-8) is preferable, and the general formula (A- In 8), L ₁ is more preferably an alkylene group having 1 to 4 carbon atoms.

The compound represented by the general formula (A-8) or the compound represented by the general formula (A-9) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40). It is done.

  Examples of the radical polymerizable compound containing a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl styrene, and particularly preferred is acrylic acid. And methacrylic acid.

  Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, triphenylphosphine, and the like. The reaction can be carried out in an organic solvent at a reaction temperature of 50 ° C. to 150 ° C. for several hours to several tens of hours.

Although there is no restriction | limiting in particular as a structural unit which has an ethylenically unsaturated bond in the said side chain, For example, the structure represented by the following general formula (A-10), the structure represented by general formula (A-11) And those represented by a mixture thereof are preferred.
However, in said general formula (A-10) and general formula (A-11), Ra-Rc represents a hydrogen atom or monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group that may have a linking group.

  The content of the polymer compound having the structure represented by the general formula (A-10) to the structure represented by the general formula (A-11) is preferably 20 mol% or more, more preferably 20 mol% to 50 mol%, 25 mol% to 45 mol% is particularly preferable. When the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. When the content is more than 50 mol%, the storage stability may be deteriorated.

--Carboxyl group--
The polymer compound of the present invention may have a carboxyl group in order to improve various performances such as non-image area removability.
The carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group.
Examples of the acid group having such radical polymerizability include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
The radical polymerizable compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p -Carboxylstyrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

  The content of the carboxyl group in the (meth) acrylate-based binder is 1.0 meq / g to 4.0 meq / g, and preferably 1.5 meq / g to 3.0 meq / g. If the content is less than 1.0 meq / g, the developability may be insufficient, and if it exceeds 4.0 meq / g, the image strength may be easily damaged by alkaline water development.

In order to improve various performances such as image strength, the polymer compound is preferably copolymerized with another radical polymerizable compound in addition to the radical polymerizable compound described above.
Examples of the other radical polymerizable compound include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.

Specific examples include acrylic acid esters such as alkyl acrylate, methacrylic acid esters such as aryl acrylate and alkyl methacrylate, styrenes such as aryl methacrylate, styrene and alkyl styrene, alkoxy styrene, and halogen styrene.
As the acrylate esters, alkyl groups having 1 to 20 carbon atoms are preferable. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate Octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl Examples include acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.
Examples of the aryl acrylate include phenyl acrylate.

As the methacrylic acid esters, those having 1 to 20 carbon atoms in the alkyl group are preferable. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl. Methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.
Examples of the aryl methacrylate include phenyl methacrylate, cresyl methacrylate, and naphthyl methacrylate.

Examples of the styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, and trifluoromethyl. Styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc. are mentioned.
Examples of the alkoxystyrene include methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, and the like.
Examples of the halogen styrene include chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, and 2-bromo-4-trifluoro. Examples include rumethylstyrene and 4-fluoro-3-trifluoromethylstyrene.
These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

  In the present invention, the solvent used for synthesizing the polymer compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol , Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide Dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These may be used alone or in combination of two or more.

In the present invention, the molecular weight of the polymer compound is preferably 10,000 or more, more preferably 10,000 to 50,000 in terms of mass average molecular weight. When the mass average molecular weight is less than 10,000, the cured film strength may be insufficient, and when it exceeds 50,000, the developability tends to decrease.
In the present invention, the polymer compound may contain an unreacted monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.

  In this invention, a high molecular compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may mix and use another high molecular compound. In this case, the content of the other polymer compound in the polymer compound of the present invention is preferably 50% by mass or less, and more preferably 30% by mass or less.

  The solid content in the photosensitive composition of the (meth) acrylate binder is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass.

  The solid content in the photosensitive composition of the (meth) acrylate binder is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dimethylol tricyclodecane di (meth) acrylate (tricyclodecane dimethanol di (meth) acrylate) and dipenta. An example is erythritol hexaacrylate.

  In the present invention, the “polymerizable compound” does not include a polymerizable compound that can be contained in the binder.

  5 mass%-50 mass% are preferable, and, as for solid content content in the said photosensitive composition solid content of the said polymeric compound, 10 mass%-40 mass% are more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

<Thermal crosslinking agent>
The thermal cross-linking agent is not particularly limited as long as it is a compound that causes a cross-linking reaction by heating, and can be appropriately selected according to the purpose. Curing of the photosensitive layer formed using the photosensitive composition In order to improve the later film strength, for example, an epoxy compound having at least two epoxy groups (oxirane ring) in one molecule (oxirane compound) within at least one molecule in a range that does not adversely affect developability and the like. An oxetane compound having two oxetane rings, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, a melamine derivative, and the like can be used. Among these, an epoxy compound having at least two epoxy groups in one molecule is particularly preferable.

  Examples of the epoxy compound having at least two epoxy groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, odor Phenol novolac type epoxy resin), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. ), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (Naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.” "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin Reaction product of 4-vinylcyclohexene-1-oxide ring-opened polymer with peracetic acid or the like, epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methyl Stilbene liquid crystal epoxy resin, dibenzoyloxybenzene liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP − 0S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

The epoxy group in the epoxy compound having at least two epoxy groups in one molecule may have an alkyl group at the β-position, and an epoxy group in which the β-position is substituted with an alkyl group (more specifically, Are particularly preferably β-alkyl-substituted glycidyl group and the like.
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among them, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the photosensitive composition and from the viewpoint of ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol Carbon number of F, bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate such as 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate, bisphenol A-formal Hydrate polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; dihydroxynaphthalene Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ether of dinaphthol, di-β-alkyl glycidyl ether of binaphthol; poly- of phenol-formaldehyde polycondensate β-alkyl glycidyl ethers; poly-β-alkyl glycidyl ethers of monoalkyl substituted phenol-formaldehyde polycondensates of 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of cresol-formaldehyde polycondensates; xylenol-formaldehyde Poly-β-alkyl glycidyl ethers of dialkyl-substituted phenol-formaldehyde polycondensates having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of condensates; poly-β-alkyl glycidyl ethers of bisphenol A-formaldehyde polycondensates Bisphenol compounds such as poly-β-alkyl glycidyl ethers of formaldehyde polycondensates; poly-β-alkyl glycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; The
Among these, β-alkylglycidyl ether derived from a bisphenol compound represented by the following general formula (C-1) and a polymer obtained from this and epichlorohydrin, and the following general formula (C-2) Poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate represented by
However, in said general formula (C-1), R represents either a hydrogen atom and a C1-C6 alkyl group. n represents an integer of 0 to 20.
However, in said general formula (C-2), R represents either a hydrogen atom and a C1-C6 alkyl group. R ″ represents either a hydrogen atom or CH ₃ , and n represents an integer of 0 to 20.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two epoxy groups (oxirane ring) in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  The skeleton of the epoxy compound is preferably at least one selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a hardly soluble epoxy resin.

  Examples of the epoxy compound having at least two oxetane rings in one molecule include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether. 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) Multifunctionals such as methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof In addition to oxetanes, compounds having an oxetane group and novola Resin, poly (p-hydroxystyrene), cardo type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes and other ether compounds, and other ether compounds. And a copolymer of an unsaturated monomer having an alkyl group and an alkyl (meth) acrylate.

  Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  As content of the said thermal crosslinking agent, 1 mass%-50 mass% are preferable with respect to the total solid in a photosensitive composition, and 3 mass%-30 mass% are more preferable. When the content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, the developability and the exposure sensitivity may be decreased.

<Neutral photopolymerization initiator>
As the photopolymerization initiator, a neutral photopolymerization initiator is used. Moreover, you may contain another photoinitiator as needed.

The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a compound having at least an aromatic group, such as (bis) acylphosphine oxide and esters thereof. , Acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds and esters thereof are more preferred, and are represented by any one of the following general formulas (I) and (II). Particularly preferred is a compound having a partial structure. Two or more neutral photopolymerization initiators may be used in combination.
Examples of the (bis) acylphosphine oxide include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6- Dichlorobenzoylphenylphosphine oxide, 2,6-dimethylmethyoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide and the like.
Examples of the acetophenone compounds include acetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- ( 4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and the like.
Examples of the benzophenone compounds include benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, diphenoxybenzophenone, and the like.
Examples of the benzoin ether compounds include benzoin ethyl ether and benzoin propyl ether.
Examples of the ketal derivative compound include benzyldimethyl ketal.
Examples of the thioxanthone compound include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, and the like.
Examples of the oxime ester compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino Examples include -1-phenylpropan-1-one, and compounds described in JP-A No. 2000-80068 and JP-T No. 2004-534797.

However, in said general formula (I) and (II), Ar represents either an aromatic group or a heterocyclic group. Y ¹ represents any ^one of a hydrogen atom and a monovalent substituent, and Y ² represents any one of an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , and CONY ⁴ Y ^5. . Y ³ , Y ⁴ , and Y ^{5 each} represent an aliphatic group, an aromatic group, or a heterocyclic group. m represents an integer of 1 or more.

Y ¹ is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
Y ² includes an aliphatic group, —CO— (aliphatic group), —CO— (aromatic group), —CO— (heterocyclic group), —CO ₂ — (aliphatic group), —CO _2. - (aromatic group), and -CO ₂ - is preferably any one of (heterocyclic group).
Y ³ and Y ⁴ are preferably either an aliphatic group or an aromatic group.

  The neutral photopolymerization initiator may be a compound in which a plurality of structures represented by the general formula (I) and the general formula (II) are bonded via a linking group.

  In the general formula (I) and the general formula (II), the aliphatic group represents an alkyl group, an alkenyl group, or an alkynyl group, each of which may have a substituent, and the aromatic group is Represents an aryl group or a heterocyclic (heterocyclic) group which may have a substituent. Examples of the monovalent substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, and a hydroxyl group. , An ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group, each representing an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group.

Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl Group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group and fluorenyl group can be mentioned. Among them, a group having any one of phenyl group and naphthyl group is preferable, and a group having naphthyl group is particularly preferable.
In addition, these aromatic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

The heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, and an isothiazole ring. Group, indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, Quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring group, purine ring group, Pyran ring group, piperidine ring group, piperazine ring group, morpholine ring group, India Ring group, indolizine ring group, chromene ring group, cinnoline ring group, acridine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring group , Thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group, and acridine ring group are particularly preferable.
Moreover, these heterocyclic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

  Examples of the monovalent substituent include a halogen atom, an amino group that may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred.

  In addition, the monovalent substituent composed of the nonmetal atom is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.

  Examples of the alkyl group that may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl A group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group Can do. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent nonmetallic atom excluding a hydrogen atom, and preferred examples include a halogen atom (—F, —Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Moyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diary Ru-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl- N-arylcarbamoyl group, al Killsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N— Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N -Alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group ( -PO ₃ H ₂₎ and its conjugated base group (a phosphonato group Be), dialkylphosphono group _(-PO 3 _{(alkyl) 2)} "alkyl = alkyl group, hereinafter the" diarylphosphono group _(-PO 3 _{(aryl) 2)} "aryl = aryl group, hereinafter the" alkyl An arylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as an alkylphosphonato group), a monoarylphosphono group (— PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO) ₃ H _{(alkyl) 2),} diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl ho Suphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (referred to as alkylphosphonatoxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylpheny Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group in the substituent Examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may include an acyl group (R ⁰¹ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, or an aryl group.

The ^{R 01} of the acyl group ^(R 01 CO-), a hydrogen atom, and the alkyl group, and an aryl group. Among these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N are more preferable. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatooxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group , A naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
As the substituted aryl group, those having a group consisting of a monovalent non-metallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group (-C (R ⁰² ) = C (R ⁰³ ) (R ⁰⁴ ) and -C≡C (R ⁰⁵ )) include R ^{A group in which 02} , R ⁰³ , R ⁰⁴ and R ⁰⁵ are monovalent non-metallic atoms can be used.
R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and specific examples thereof are shown in the above examples. Things can be mentioned. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
Specifically, vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group and the like.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁰⁶ O—), a group in which R ⁰⁶ is a group composed of a monovalent nonmetallic atom excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

As the substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Can be used. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, and aryl groups and substituted aryl groups described above. Acylamino group, N-alkylacylamino group, N-arylacylamino ^{R 07} of the base definitive acyl group ^(R 07 CO-) is as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

As described above, the sulfonate group (—SO ₃ ^— ) means a conjugated base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

As the substituted carbonyl group (R ⁰¹³ —CO—), a group in which R ⁰¹³ is a monovalent nonmetallic atom can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), a group in which R ⁰¹⁴ is a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups. Preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonate group (—PO ₃ H ₂ ^— , —PO ₃ H ⁻ ) is a conjugate base anion derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means group. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic hydroxyl group with one organic oxo group among the above-mentioned substituted phosphono groups. Specific examples thereof include the monoalkylphosphono group (—PO ₃ H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

As said neutral photoinitiator, the compound represented by either the following general formula (III) or general formula (IV) is still more preferable.
However, the general formula (III) and the general formula _{(IV), R 101} represents the same meaning as ^{Y 1} in the general formulas (I) and ^{(II), Y 12} is general formulas (I) and This represents the same meaning as Y ² in (II).

As R ₁₀₁ , either a hydrogen atom or an aliphatic group is more preferable, and an aliphatic group having 1 to 10 carbon atoms is particularly preferable.
Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, an octyl group, and an allyl group.
Y ¹² is particularly preferably —CO— (aliphatic group). The aliphatic group in Y ¹² is preferably an aliphatic group having 1 to 10 carbon atoms.
Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group, a benzyl group and the like are preferable.

  Other specific examples of the neutral photopolymerization initiator include compounds disclosed in, for example, JP 2001-233842 A, JP 2004-534797 A, and JP 2002-519732 A And compounds represented by the following structural formulas.

In the structural _formulas, R represents _{n-C 3 H 7, n} -C 8 H 17, camphor, and one of the _{p-CH 3 C 6 H 4} .

In the above structural formula, R represents either nC ₃ H ₇ or p-CH ₃ C ₆ H ₄ .

As the neutral photopolymerization initiator, a neutral photopolymerization initiator represented by the following general formula (V) is also preferably used.
However, in the general formula (V), Y ² and Ar have the same meaning as in the general formulas (I) and (II). m represents an integer of 0 or more. Y ⁵ represents a substituent, and when m is 2 or more, Y ⁵ may be the same or different. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.

Among the neutral photopolymerization initiators represented by the general formula (V), a compound represented by the following general formula (VI) is more preferable, represented by any one of the following general formulas (VII) and (VIII). Particularly preferred are the compounds
In the general formula ^{(VI), Y 2, Y} 5, m, and Ar represent the same meaning as in the general formula (V). X represents either O or S. A represents either a 5- or 6-membered ring.

However, the general formula (VII) and the general formula (VIII), ^{Y 6} may have a substituent, an alkyl group. l represents an integer of 0 to 6. Y ⁷ represents any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group. When l is 2 or more, the Y ⁷ may be the same or different. It may be. X and A represent the same meaning as in general formula (VI).

In the general formulas (V) and (VI), the substituent represented by Y ⁵ is not particularly limited, and examples thereof include alkyl groups, alkoxy groups, aryloxy groups, halogen atoms, sulfonyl groups, acyloxy groups, nitro groups. Group, acylamino group, and the like. Among these, any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group is preferable.

Here, specific examples of the neutral photopolymerization initiator represented by the general formula (V) include compounds represented by the following structural formulas (1) to (54). However, it is not limited to these.

However, in the structural formulas (1) to (54), Me represents a methyl group. Ph represents a phenyl group. Ac represents an acetyl group.

  The content of the neutral photopolymerization initiator is, for example, preferably 0.1% by mass to 15% by mass in terms of solid content, more preferably 0.5% by mass to 10% by mass, and 1.0% by mass to 8.0 mass% is particularly preferable. When the amount is less than 0.1% by mass, the sensitivity is lowered, and it may be difficult to obtain a cured film having sufficient hardness. When the amount is more than 15% by mass, the tackiness when formed into a film is deteriorated. In addition, the cured film may become brittle because Tg is lowered.

-Other photopolymerization initiators-
The other photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. It is preferable that it has photosensitivity to visible light, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and initiates cationic polymerization depending on the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.

  Examples of the other photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thio compounds, ketones. Compounds, acridine compounds, metallocenes and the like. Specific examples include compounds described in JP-A-2005-258431. Among these, ketone compounds and acridine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate. The said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  The solid content in the photosensitive composition of the photopolymerization initiator is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and 0.5% by mass to 15% by mass is particularly preferred.

<Other ingredients>
Examples of the other components include fillers, adhesion promoters, sensitizers, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and other auxiliary agents (for example, Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these, properties such as stability, photographic properties, film physical properties and the like of the intended photosensitive film can be adjusted.

-Filler (inorganic filler)-
The filler (inorganic filler) can improve the surface hardness of the permanent pattern, can keep the coefficient of linear expansion low, and has a function of keeping the dielectric constant and dielectric loss tangent of the cured layer itself low. It can use suitably for the photosensitive composition of this.
There is no restriction | limiting in particular as said filler (inorganic filler), It can select suitably from well-known things, For example, a kaolin, barium sulfate, barium titanate, a silicon oxide powder, a fine powder silicon oxide, a gas phase method Examples thereof include silica, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

The average particle size of the filler (inorganic filler) is preferably less than 3 μm, more preferably 0.1 μm to 2 μm. If the average particle size is 3 μm or more, resolution may be deteriorated due to light scattering.
The addition amount of the filler (inorganic filler) is preferably 5% by mass to 75% by mass, more preferably 8% by mass to 70% by mass, and particularly preferably 10% by mass to 65% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 90% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

Further, organic fine particles can be added as necessary. Suitable organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, it is possible to use an average particle diameter of 0.1-2 .mu.m, oil absorption 100m ² / g~200m ² / g approximately silica, spherical porous fine particles composed of a crosslinked resin.

  Since the filler (inorganic filler) contains particles having an average particle size of 0.1 μm to 2 μm, the permanent pattern was thinned to a thickness of 5 μm to 20 μm as the printed wiring board was made thinner. However, the filler (inorganic filler) particles do not destroy both the front and back surfaces of the permanent pattern. As a result, there is no generation of dendrites in the high acceleration test (HAST), and the permanent pattern has excellent heat resistance and moisture resistance. It can be.

-Adhesion promoter-
In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion promoter can be used for each layer.

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass with respect to all components of the photosensitive layer. Mass% is particularly preferred.

-Sensitizer-
The photosensitive composition may contain a sensitizer.
The sensitizer is used in combination when the photosensitive layer is exposed and developed to improve the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferred.
The sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.).
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
The sensitizer is at least one selected from a condensed ring compound, an aminophenyl ketone compound, a polynuclear aromatic, an acid nucleus, a basic nucleus, and a fluorescent brightener nucleus. It contains seeds and may contain other sensitizers as needed. As the sensitizer, a hetero-fused compound and an aminobenzophenone compound are more preferable in terms of improving sensitivity, and a hetero-fused compound is particularly preferable.

--Condensed ring compound--
Among the above exemplary compounds, hetero-fused ring compounds are preferred as compounds in which an aromatic ring or a heterocyclic ring is fused (fused ring-based compounds). The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are more preferable, and among these, a thioxanthone compound is particularly preferable.
Specific examples of the hetero-fused ketone compound include acridone compounds such as, for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; thioxanthone, Thioxanthone compounds such as isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, QuantacureQTX; 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- ( 1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonyl Bi (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-2002 Coumarin compounds such as coumarin compounds described in JP-A-363209; and the like; The
In addition, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), and the like.

The content of the sensitizer is preferably 0.01% by mass to 4% by mass, more preferably 0.02% by mass to 2% by mass, and 0.05% by mass with respect to the total solid content of the photosensitive composition. % To 1% by mass is particularly preferable.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.

The mass ratio of the sensitizer and the content of the photopolymerization initiator in the photosensitive composition is [(sensitizer) / (photopolymerization initiator)] = 1 / 0.1 to 1/100. It is preferable that the ratio is 1/1 to 1/50.
When the mass ratio of the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may be lowered and the change in sensitivity over time may be deteriorated.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and 0.01% by mass to 1% by mass with respect to the polymerizable compound. % Is particularly preferred.
When the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.

-Plasticizer-
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  The content of the plasticizer is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass with respect to all components of the photosensitive composition, and 1% by mass to 30% by mass. % Is particularly preferred.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel・ Pink B Supra (CI Pigment Red 81), Monastral Asuto Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Blue 64. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content of the color pigment in the photosensitive composition can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation, and varies depending on the type of the color pigment. Generally, 0.01% by mass to 10% by mass is preferable, and 0.05% by mass to 5% by mass is more preferable.

(Photosensitive film)
The photosensitive film of the present invention is obtained by laminating a photosensitive layer made of a photosensitive composition on a support. Preferably, a protective layer is laminated on the photosensitive layer, and other layers such as a cushion layer and an oxygen barrier layer (PC layer) are laminated as necessary.

  There is no restriction | limiting in particular as a form of the said photosensitive film, According to the objective, it can select suitably, For example, the form which has the said photosensitive layer and the said protective layer in this order on the said support body, A form comprising the PC layer, the photosensitive layer, and the protective layer in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective layer in this order on the support. And the like. The photosensitive layer may be a single layer or a plurality of layers.

<Photosensitive layer>
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.
In the exposure process described later, the photosensitive layer modulates the light from the light irradiating means by means of a light modulating means having n picture element portions that receive and emit light from the light irradiating means, and then It is preferable that exposure is performed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface at the portion are arranged.

In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is preferably 100 mJ / cm ² or less, More preferably, it is 70 mJ / cm ² or less. If the minimum energy of light used for the exposure exceeds 100 mJ / cm ² , the tact time becomes long, which is not preferable.

Here, “the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” is so-called development sensitivity, for example, when the photosensitive layer is exposed. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure and the thickness of the cured layer generated by the development process following the exposure.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the thickness of the cured layer and the thickness of the photosensitive layer before the exposure are within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 3 micrometers-100 micrometers are preferable, and 5 micrometers-70 micrometers are more preferable.
As a method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support, and the solution is directly applied. The method of laminating by applying and drying is mentioned.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol etc. Alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, and the like ketones; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy Esters such as propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride Halogenated hydrocarbons such as monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

  In the present invention, the photosensitive layer contains a binder and a polymerizable compound, and is formed of a photosensitive composition containing other components as necessary.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of a synthetic resin and transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2 micrometers-150 micrometers are preferable, 5 micrometers-100 micrometers are more preferable, 8 micrometers-50 micrometers are especially preferable. The support may be a single layer or may have a multilayer structure.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

<Protective layer>
The photosensitive film may form a protective layer on the photosensitive layer.
Examples of the protective layer include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective layer, Although it can select suitably according to the objective, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable.
Examples of the combination of the support and the protective layer (support / protective layer) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective layer. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

The static friction coefficient between the support and the protective layer is preferably 0.3 to 1.4, and more preferably 0.5 to 1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.

  The protective layer may be surface-treated to adjust the adhesion between the protective layer and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective layer. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective layer and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 ° C to 120 ° C.

<Other layers>
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, You may have layers, such as a surface protective layer. These layers may be used alone or in combination of two or more. Further, a protective layer may be provided on the photosensitive layer.

<Method for producing photosensitive film>
The said photosensitive film can be manufactured as follows, for example.
First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution for a photosensitive film.

  As said solvent, the thing similar to the solvent of the said photosensitive composition solution is mentioned.

  Next, the photosensitive composition solution is applied on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.

  Examples of the method for applying the photosensitive composition solution include the methods described above.

  Since the photosensitive film uses the photosensitive composition, it has good plating resistance, storage stability, sensitivity, developability, and adhesion, and a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, Can be suitably used for forming various patterns such as color filters, columns, ribs, spacers, liquid crystal structural members such as spacers, partition walls, etc., and for forming patterns such as holograms, micromachines, and proofs. It can be suitably used for forming a permanent pattern on a substrate.

  In particular, since the thickness of the photosensitive film is uniform, even if the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned when forming the permanent pattern, the high acceleration test (HAST ), Dendrite is not generated, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on the substrate and other layers appropriately selected according to the purpose.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

<Method for producing photosensitive laminate>
Examples of the method for producing the photosensitive laminate include, as a first aspect, a method in which the photosensitive composition is applied to the surface of the substrate and drying, and as a second aspect, at least a photosensitive layer in the photosensitive film. And a method of transferring and laminating at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective layer, it is preferable to peel this protective layer and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  Since the photosensitive film and the photosensitive laminate use the photosensitive composition, plating resistance, storage stability, sensitivity, developability, and adhesion are good, and a high-definition permanent pattern can be efficiently formed. Yes, for forming various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, for manufacturing liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, It can be suitably used for forming a pattern such as a proof, and can be particularly suitably used for forming a permanent pattern on a printed circuit board.

  In particular, since the photosensitive film has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned in the formation of the permanent pattern, in the highly accelerated life test (HAST) Since dendrites are not generated and a high-definition permanent pattern having excellent heat resistance and moisture resistance is obtained, lamination onto a substrate is performed more finely.

(Permanent pattern forming method)
The permanent pattern forming method includes at least an exposure process, and includes other processes such as an appropriately selected development process.
The pattern forming apparatus, which will be clarified through the description of the pattern forming method, includes the photosensitive laminate, and has at least light irradiation means and light modulation means.

<Exposure process>
The exposure step is a step of exposing the photosensitive layer. The materials for the photosensitive layer and the substrate are as described above.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive composition is heated and pressurized on the substrate. It is preferable to carry out with respect to the photosensitive layer in the photosensitive laminate formed by laminating while performing at least one of the above.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The analog exposure is not particularly limited and can be appropriately selected according to the purpose. For example, exposure with a (super) high pressure mercury lamp, xenon lamp, halogen lamp, etc. through a photomask having a predetermined pattern. The method of performing is mentioned.

  The digital exposure is not particularly limited as long as it is performed without using the photomask, and can be appropriately selected according to the purpose. For example, an exposure head including at least a light irradiation unit and a light modulation unit; The exposure head irradiates the photosensitive layer with light emitted from the light irradiation means while modulating at least one of the photosensitive layers according to pattern information by the light modulation means. It is preferable.

  The light source used in the digital exposure is not particularly limited as long as it is a light source that emits ultraviolet to near infrared rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp , Fluorescent lamps for use in halogen lamps and copying machines, or known light sources such as laser light are used. Among these, (ultra) high pressure mercury lamps and laser light are preferable, and laser light is more preferable.

  The (super) high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and has a higher vapor pressure to increase luminous efficiency. Among the emission line spectra, an emission line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of emission line spectra may be used.

The “laser” of the laser beam is an acronym for “Light Amplification by Stimulated Emission of Radiation”. As an apparatus for emitting the laser light, an oscillator and an amplifier that generate monochromatic light having higher coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in a material having an inversion distribution, are preferably used. Can be mentioned.
Examples of the excitation medium for the laser light include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as solid laser, liquid laser, gas laser, and semiconductor laser can be used.
Specifically, examples of the gas laser include an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), and a He—Cd laser (325 nm), and examples of the solid laser include a YAG laser and a YVO ₄ laser (1, 064 nm), YAG laser or YVO ₄ laser, 2nd harmonic (532 nm), 3rd harmonic (355 nm), 4th harmonic (266 nm), a combination of a waveguide wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 400 nm) ), A combination of a waveguide wavelength conversion element and AlGaInP or an AlGaAs semiconductor t (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among these, preferable laser light includes an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) in terms of cost, and a 355 nm laser having high output in terms of productivity.

  The wavelength of the laser beam is, for example, preferably 200 nm to 1,500 nm, more preferably 300 nm to 800 nm, still more preferably 330 nm to 500 nm, and particularly preferably 350 nm to 420 nm.

-Light modulation means-
As the light modulation means, a typical method is a method having n pixel parts and controlling the pixel parts according to the pattern information. Specifically, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect. And liquid crystal light shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. In this state, no light is exposed between the light spots. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By using such exposure heads having the DMD side by side, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed by using a mirror gradation spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another typical method of the light modulation means is a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of plane reflecting surfaces around it. The polygon mirror reflects and irradiates light from the light source onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. Then, an image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. At this time, the scanning time can be shortened by using a plurality of lights from the light source.

  As the light modulation means, in addition, an example of drawing using a polygon mirror described in JP-A-5-150175, a lower part described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet) An example in which a part of the image of the layer is visually acquired, and exposure is performed by aligning the position of the upper layer with the position of the lower layer with an apparatus using a polygon mirror, an example of exposure with the DMD described in JP-A-2004-56080, Example of combination of exposure apparatus provided with polygon mirror described in JP-T-2002-523905, exposure apparatus provided with polygon mirror described in JP-A-2001-255661, DMD, LD, and multiple exposure described in JP-A-2003-50469 An example of an exposure method in which the exposure amount is changed depending on the part of the substrate described in JP-A-2003-156653, Examples such as exposure method for performing a positional deviation adjustment according to an open 2005-43576 publication can be mentioned.

-Light irradiation means-
There is no restriction | limiting in particular as said light irradiation means, ie, the light irradiation method, Although the above-mentioned exposure light source can be selected suitably according to the objective, Two or more light from these light sources is synthesize | combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of composing and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber is preferable.

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition, the Gaussian beam 1 / e ² value is preferably 5 μm to 30 μm, 7 μm to 20 μm is more preferable.
It is preferable to spatially modulate the laser beam according to image data. Therefore, it is preferable to use the DMD which is a spatial light modulator for this purpose.

  Examples of the exposure apparatus having the light modulation means and the light irradiation means are described in, for example, Japanese Patent Application Laid-Open Nos. 2005-222039, 2005-258431, and 2006-30966. However, the exposure apparatus is not limited to this.

<Development process>
The development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weak alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. As said weak alkaline aqueous solution, 0.1 mass%-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

  In the formation of the pattern, for example, a curing process, an etching process, a plating process, and the like may be included. These may be used alone or in combination of two or more.

<Curing process>
When the pattern formation method is a permanent pattern formation method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the development step. It is preferable to provide the hardening process process which processes.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine and the like are preferable. It is mentioned in. Exposure is usually ^{10mJ / cm 2 ~2,000mJ / cm 2} .

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, more preferably 120 ° C to 200 ° C. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
The heating time in the entire surface heating is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater, etc. are mentioned.

  The pattern forming method can be used to form various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure of 405 nm, and has high density and high productivity. It can be suitably used for forming a compatible pattern.

  In the permanent pattern forming method, if the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from impact and bending from the outside. In the case of the interlayer insulating film, for example, it is useful for high-density mounting of semiconductors and components on a multilayer wiring board, a build-up wiring board, and the like.

  Since the permanent pattern forming method uses the photosensitive composition, it is used for forming various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, proofs and the like, and in particular, it can be suitably used for the formation of permanent patterns on printed boards.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
Example 1
-Production of photosensitive film-
On a 16 μm thick polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) as a support, a photosensitive composition solution having the following composition was applied and dried, and a 30 μm thick photosensitive film was formed on the support. A layer was formed. On the photosensitive layer, as a protective layer, a polypropylene film having a thickness of 20 μm (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated to produce a photosensitive film.

Composition of <Photosensitive composition solution> Solution of binder represented by the following formula B-1 ... 37.2 parts by mass A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd. Compound "J-1") ........................... 9.15 parts by mass Represented by the following formula K-1. Compound (manufactured by Daito Chemical Co., Ltd.) ... 0.63 parts by mass DETX (manufactured by Nippon Kayaku Co., Ltd.) ... 0.32 parts by mass (the above-mentioned K- The compound represented by 1 and DETX are hereinafter referred to as a photopolymerization initiator “H-1”, and the composition of “H-1” in the photosensitive composition solution was 0.95 parts by mass.)
A compound represented by the following formula M-1 (manufactured by Tokyo Chemical Industry Co., Ltd.): 1 part by mass Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin. 1 ".) ... 5.00 parts by weight Pigment dispersion (hereinafter referred to as" G-1 ") ... 35.7 parts by weight MegaFuck F- 780F (manufactured by Dainippon Ink Co., Ltd.) 30% by mass methyl ethyl ketone solution ... 0.13 parts by mass Methyl ethyl ketone (solvent) ... 12.0 parts by mass The pigment dispersion is represented by 30 parts by mass of silica (manufactured by Admatechs Co., Ltd., SO-C2) and the following formula B-1. 48.2 parts by weight of binder solution and 0.51 phthalocyanine blue Part, 0.14 parts by weight of anthraquinone yellow pigment (PY24) and 59.0 parts by weight of normal propyl acetate were mixed in advance, and then zirconia with a diameter of 1.0 mm was obtained with a motor mill M-250 (manufactured by Eiger). It was prepared by dispersing for 3 hours at a peripheral speed of 9 m / s using beads.

(Synthesis Example 1)
Synthesis of Binder B-1 90.6 g of 1-methoxy-2-propanol was placed in a 1,000 mL three-necked flask and heated to 90 ° C. under a nitrogen stream. To this, 105.8 g of benzyl methacrylate, 156 g of 1-methoxy-2-propanol in 120.6 g of methacrylic acid, and 7.24 g of 1-methoxy-2-propanol in 50 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Each was added dropwise over 3 hours. After completion of the dropwise addition, the reaction was further continued by heating for 1 hour. Subsequently, 2.00 g of 1-methoxy-2-propanol 20 g solution of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was continued by heating for 3 hours, and then the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (30/70 mol% ratio).
Next, 105.2 g of glycidyl methacrylate and 20 g of 1-methoxy-2-propanol were added to the dropping funnel, and 0.34 g of p-methoxyphenol was added to the flask, and the mixture was stirred and dissolved. After dissolution, 0.82 g of triphenylphosphine was added and heated to 100 ° C., and then glycidyl methacrylate was dropped from the dropping funnel over 1 hour to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 45.8 g of 1-methoxy-2-propanol was added, and a solution of a binder B-1 having an acid value of 121 mgKOH / g, a mass average molecular weight of 31,000 and a solid content of 45% by mass was prepared.

In the compound represented by the formula M-1, the σm value of the chloro group “—Cl” as a substituent is 0.37.

-Lamination on substrate-
The substrate was prepared by subjecting a surface of a copper clad laminate (no through hole, copper thickness: 12 μm) to chemical polishing. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. And a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was prepared.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

<Protective film peelability>
The obtained photosensitive film was cut and wound on a roll having an inner diameter of 4 inches and a length of 220 mm in a roll shape having a width of 200 mm and a length of 80 m. It set to the said vacuum laminator, the peeling test of the protective film was done at room temperature 25 degreeC, and peelability was evaluated visually. The evaluation criteria are as follows. The results are shown in Table 2.
-Evaluation criteria-
○: Peeling at the interface between the protective film and the photosensitive layer was light peeling, and no photosensitive composition remained on the surface of the protective film.
(Triangle | delta): Peeling in the interface of a protective film and a photosensitive layer was medium peeling, generation | occurrence | production of peeling sound and a small amount of photosensitive composition remained on the protective film surface.
X: Peeling at the interface between the protective film and the photosensitive layer was heavy peeling, and the photosensitive composition remained on the surface of the protective film.

The sensitivity of the laminate was evaluated as follows.
<Sensitivity>
The laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). Pattern data of L / S (line / space) = 50 μm / 50 μm was set to 0 on the surface of the photosensitive layer of the obtained laminate using INPREX IP-3000 (manufactured by Fuji Film Co., Ltd., pixel pitch = 1.0 μm). exposed by irradiating light of different light energy from .5MJ / cm ² to 500 mJ / cm ² at ^{2 1/2} times the interval, curing the L / S (line / space) = 50 [mu] m / 50 [mu] m line pattern It was. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spray development was carried out for 2 to 3 times the shortest development time (or 40 to 60 seconds), and the uncured area was dissolved and removed. The line width of the L = 50 μm pattern thus obtained was measured using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 times), and the exposure amount at which the line width was 50 μm was determined with sensitivity (optimal). Exposure amount). The results are shown in Table 2.

<Developability (shortest development time)>
The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. The shorter the shortest development time, the better the developability. The results are shown in Table 2.

<Evaluation of raw preservation>
The laminate was sealed at room temperature (23 ° C., 55% RH) in a moisture-proof bag (cylindrical bag made of black polyethylene, film thickness: 80 μm, water vapor transmission rate: 25 g / m ² · 24 hr or less), then 40 After storing at 0 ° C. for 3 days, the shortest development time is measured by the same method as in the evaluation of the shortest development time, and the value obtained by the evaluation of the shortest development time is stored at t ₀ for 3 days. The value of t ₁ / t ₀ was calculated with the value of the shortest development time at t being t ₁ . The closer the value of t ₁ / t ₀ is to 1, the better the raw storage stability. Table 2 shows the results based on the following evaluation criteria.
A: t ₁ / t ₀ is 1.0 ≦ t ₁ / t ₀ <1.5
◯: t ₁ / t ₀ is 1.5 ≦ t ₁ / t ₀ <2.0
Δ: t ₁ / t ₀ is 2.0 ≦ t ₁ / t ₀ <4.0
X: t ₁ / t ₀ is 4.0 ≦ t ₁ / t ₀

<Evaluation of electroless gold plating resistance>
On the photosensitive layer surface of the laminate prepared in the same manner as the laminate, except that the substrate was a copper-clad laminate (no through-hole, copper thickness 12 μm) subjected to chemical polishing treatment. , INPREX IP-3000 (manufactured by Fuji Film Co., Ltd., pixel pitch = 1.0 μm) was used to form an independent fine line pattern from 30 μm to 1,000 μm at an optimal exposure amount, and after standing at room temperature for 10 minutes The support is peeled off from the photosensitive laminate, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. is applied to the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa, twice the shortest development time. Spray development was performed for 3 times (or 40 seconds to 60 seconds), and uncured areas were dissolved and removed. Thereafter, the entire surface was exposed with an ultrahigh pressure mercury lamp at 200 mJ / cm ² and further subjected to heat treatment (post-baking) at 150 ° C. for 1 hour to form a solder resist pattern (permanent pattern).
--- Electroless gold plating process--
The test substrate on which the solder resist pattern (permanent pattern) is formed is immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 mass% aqueous solution of Metex L-5B) for 3 minutes, and then immersed in running water for 3 minutes. And washed with water.
Next, after immersing in a 14.3% by mass antimony persulfate aqueous solution for 3 minutes at room temperature, after immersing in running water for 3 minutes and washing with water, and further immersing the test substrate in a 10% by mass sulfuric acid aqueous solution at room temperature for 1 minute, It was immersed in running water for 30 seconds to 1 minute and washed with water.
Next, the substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10% by weight aqueous solution of metal plate activator 350) for 7 minutes, then immersed in running water for 3 minutes, and then washed at 85 ° C. with nickel. After dipping in a plating solution (Meltex, Melplate Ni-865M, 20 vol% aqueous solution, pH 4.6) for 20 minutes and performing electroless nickel plating, after dipping in a 10 wt% sulfuric acid aqueous solution at room temperature for 1 minute Then, it was immersed in running water for 30 seconds to 1 minute and washed with water.
Next, the test substrate was immersed in a gold plating solution at 75 ° C. (Okuno Pharmaceutical Co., Ltd., OPC Muden Gold, pH 12-13, thick gold plating 0.3 μm) for 4 minutes, and after electroless gold plating, After immersing in running water for 3 minutes and washing with water, further immersed in warm water at 60 ° C. for 3 minutes, sufficiently washed with water, dried, and an electroless gold-plated test substrate was obtained.
The test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape, and the peeled state of the cured film was determined according to the following criteria. The results are shown in Table 2.
-Evaluation criteria-
◎: No peeling at all ○: No peeling for images with a line width of 50 μm or more △: No peeling for images with a line width of 500 μm or more ×: Even images with a line width of 500 μm or more may be peeled off

(Example 2)
A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the amount of the compound represented by the formula M-1 in the photosensitive composition solution was changed from 1 part by mass to 2 parts by mass. In the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storability, and electroless gold plating resistance was performed. The results are shown in Table 2.

(Example 3)
A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the amount of the compound represented by the formula M-1 in the photosensitive composition solution was changed from 1 part by mass to 5 parts by mass. In the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storability, and electroless gold plating resistance was performed. The results are shown in Table 2.

Example 4
Implementation was carried out except that the compound represented by the formula M-1 in the photosensitive composition solution was a compound represented by the following formula M-2 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, a laminate and a permanent pattern were produced, and in the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storage, and electroless gold plating resistance Went. The results are shown in Table 2.

In the compound represented by the formula M-2, the σm value of the methyl group “—CH ₃ ” as a substituent is −0.07.

(Example 5)
Implementation was performed except that the compound represented by the above formula M-1 in the photosensitive composition solution was a compound represented by the following formula M-3 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, a laminate and a permanent pattern were produced, and in the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storage, and electroless gold plating resistance Went. The results are shown in Table 2.

In the compound represented by the formula M-3, the σm value of the vinyl group “—CHCH ₂ ” as a substituent is −0.1.

(Example 6)
Implementation was performed except that the compound represented by the above formula M-1 in the photosensitive composition solution was a compound represented by the following formula M-4 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, a laminate and a permanent pattern were produced, and in the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storage, and electroless gold plating resistance Went. The results are shown in Table 2.

In the compound represented by the formula M-4, the σm value of the phenyl group “—Ph” as a substituent is 0.06.

(Example 7)
Implementation was performed except that the compound represented by the above formula M-1 in the photosensitive composition solution was a compound represented by the following formula M-5 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, a laminate and a permanent pattern were produced, and in the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storage, and electroless gold plating resistance Went. The results are shown in Table 2.

In the compound represented by the formula M-5, the σm value of the hydrogen atom “—H” as a substituent is 0.

(Example 8)
Implementation was carried out except that the compound represented by the above formula M-1 in the photosensitive composition solution was a compound represented by the following formula M-6 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, a laminate and a permanent pattern were produced, and in the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storage, and electroless gold plating resistance Went. The results are shown in Table 2.

In the compound represented by the formula M-6, the σm value of the amino group “—NHBu” in which one hydrogen atom as a substituent is substituted with a butyl group is −0.21.

Example 9
In the same manner as in Example 1, except that the compound represented by the formula M-1 in the photosensitive composition solution was changed to the compound represented by the following formula M-8, and the addition amount was changed to 2 parts by mass. A body and a permanent pattern were produced, and the protective film peelability, sensitivity, developability (shortest development time), raw shelf life, and electroless gold plating resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Synthesis Example 2)
Synthesis of Compound Represented by Formula M-8 above To a 2,000 L three-necked flask, 500 mL of molten phenol is added and heated to 60 ° C. Thereto, 128 g of dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 98 g of ammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) are added, and the mixture is heated and stirred at 125 ° C. for 8 hours. After cooling to 60 ° C., 1.5 L of 2-propanol was added and stirred, and the solid content was collected by filtration using a Buchner funnel. The fine gray solid collected by filtration was stirred in 2-L of 2-propanol and then collected again by filtration and dried by a blow dryer for 24 hours to obtain 204 g of a guanamine precursor.
To a 500 mL three-necked flask, 11.1 g of guanamine precursor, 12.3 g of ethyl monochloroacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 150 mL of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) are added and stirred with sodium ethoxide. 37.4 g of an ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped. After stirring for 30 minutes, the mixture was heated and stirred at 65 ° C. for 6 hours. After cooling the reaction solution, the content was poured into 1 L of water under stirring, and after stirring for 1 hour, the solid was collected by filtration.
The solid was washed with water and acetone, and then dried with an air dryer to obtain 8.9 g of the compound represented by the formula M-8.

(Example 10)
In the same manner as in Example 1, except that the compound represented by the formula M-1 in the photosensitive composition solution was changed to the compound represented by the following formula M-9 and the addition amount was changed to 2 parts by mass. A body and a permanent pattern were produced, and the protective film peelability, sensitivity, developability (shortest development time), raw shelf life, and electroless gold plating resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Synthesis Example 3)
Synthesis of Compound Represented by Formula M-9 Synthetic Example 2 except that ethyl monochloroacetate was changed to ethyl trifluoroacetate in Synthesis Example 2 (synthesis of compound represented by Formula M-8). The synthesis was performed in the same manner as above to obtain 16.8 g of the compound represented by the formula M-9.

(Example 11)
In the same manner as in Example 1, except that the compound represented by the formula M-1 in the photosensitive composition solution was changed to the compound represented by the following formula M-10 and the addition amount was changed to 2 parts by mass. A body and a permanent pattern were produced, and the protective film peelability, sensitivity, developability (shortest development time), raw shelf life, and electroless gold plating resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Synthesis Example 4)
Synthesis of compound represented by formula M-10 In a 1,000 L three-necked flask, 14.6 g of 2,4-diamino-6-chlorotriazine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.5 g of glycine (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.), 60 g of ethanol and 20 g of water were added, and 8.5 g of a 48% aqueous sodium hydroxide solution was added dropwise with stirring. After dropping, the mixture was heated to 80 ° C. and reacted for 14 hours. The system was cooled, 500 mL of water was added and filtered. When 20 g of acetic acid was added to the obtained filtrate, a solid was precipitated and collected by filtration. The solid was washed with water and acetone, and then dried with an air dryer to obtain 12.6 g of the compound represented by the formula M-10.

(Example 12)
In the same manner as in Example 1, except that the compound represented by the formula M-1 in the photosensitive composition solution was changed to the compound represented by the following formula M-11 and the addition amount was changed to 2 parts by mass. A body and a permanent pattern were produced, and the protective film peelability, sensitivity, developability (shortest development time), raw shelf life, and electroless gold plating resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Synthesis Example 5)
Synthesis of Compound Represented by Formula M-11 above Synthetic Example 2 except that ethyl monochloroacetate was changed to methyl methanesulfonyl acetate in Synthesis Example 2 described above (synthesis of compound represented by Formula M-8 above). The synthesis was performed in the same manner as above to obtain 12.2 g of the compound represented by the formula M-11.

(Example 13)
In the same manner as in Example 1, except that the compound represented by the formula M-1 in the photosensitive composition solution was changed to the compound represented by the following formula M-12, and the addition amount was changed to 2 parts by mass. A body and a permanent pattern were produced, and the protective film peelability, sensitivity, developability (shortest development time), raw shelf life, and electroless gold plating resistance were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Synthesis Example 6)
Synthesis of Compound Represented by Formula M-12 Above Synthesis Example 2 except that ethyl monochloroacetate was changed to ethyl oxalate in Synthesis Example 2 (synthesis of compound represented by Formula M-8 above). Synthesis was carried out in the same manner to obtain 16.2 g of the compound represented by the formula M-12.

(Comparative Example 1)
Implementation was performed except that the compound represented by the formula M-1 in the photosensitive composition solution was a compound represented by the following formula M-7 (manufactured by Tokyo Chemical Industry Co., Ltd.), and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, a laminate and a permanent pattern were produced, and in the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw storage, and electroless gold plating resistance Went. The results are shown in Table 4.

In the compound represented by the formula M-7, the σm value of the amino group “—NH ₂ ” is −0.26.

(Comparative Example 2)
A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the compound represented by the formula M-1 in the photosensitive composition solution was not used, and the protective film was produced in the same manner as in Example 1. The peelability, sensitivity, developability (shortest development time), raw storage stability, and electroless gold plating resistance were evaluated. The results are shown in Table 4.

(Comparative Example 3)
The photopolymerization initiator H-1 in the photosensitive composition solution is replaced with a basic photopolymerization initiator H-2 (IRG.369 (manufactured by Ciba Specialty Chemicals Co., Ltd.)) and represented by the above formula M-1. A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the compound was represented by the above formula M-2 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the addition amount was changed to 2 parts by mass. In the same manner as in Example 1, evaluation of protective film peelability, sensitivity, developability (shortest development time), raw shelf life, and electroless gold plating resistance was performed. The results are shown in Table 4.

(Comparative Example 4)
The binder represented by the formula B-1 in the photosensitive composition solution is replaced with binder B-2 (PR300 (manufactured by Dainippon Ink Co., Ltd.)) which is an epoxy acrylate, and the polymerizable compound J-1 is replaced with the polymerizable compound J. -2 (A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), the thermal cross-linking agent N-1 is replaced with the thermal cross-linking agent N-2 (TEPIC (manufactured by Nissan Chemical Co., Ltd.)), and the photopolymerization initiator H -1 is replaced with a basic photopolymerization initiator H-2 (IRG.369 (manufactured by Ciba Specialty Chemicals)), the compound represented by the formula M-1 is represented by the formula M-2. A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was used and the addition amount was changed to 2 parts by mass. Peelability, sensitivity, developability (shortest Image time), raw storage stability, the evaluation of the electroless gold plating resistance were carried out. The results are shown in Table 4.

(Comparative Example 5)
The binder represented by the formula B-1 in the photosensitive composition solution is replaced with binder B-2 (PR300 (manufactured by Dainippon Ink Co., Ltd.)) which is an epoxy acrylate, and the polymerizable compound J-1 is replaced with the polymerizable compound J. -2 (A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), the thermal cross-linking agent N-1 is replaced with the thermal cross-linking agent N-2 (TEPIC (manufactured by Nissan Chemical Co., Ltd.)), -1 is replaced with a basic photopolymerization initiator H-2 (IRG.369 (manufactured by Ciba Specialty Chemicals)), the compound represented by the formula M-1 is represented by the formula M-7. A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was used and the addition amount was changed to 2 parts by mass. Peelability, sensitivity, developability (shortest Image time), raw storage stability, the evaluation of the electroless gold plating resistance were carried out. The results are shown in Table 4.

From the results of Tables 2 to 4, it was found that in Examples 1 to 13, the protective film peelability, sensitivity, and developability were excellent, and both the raw storability and plating resistance could be improved.
Moreover, in Examples 2 to 4 using an appropriate amount of Compound M-1 or M-2 and Example 13 using an appropriate amount of Compound M-12, it was found that the raw storage stability could be further improved.

Table 5 shows the σm values of the substituents of the compounds represented by Formulas M-1 to M-12 used in the above Examples and Comparative Examples.

Since the photosensitive composition of the present invention can achieve not only developability, hardness, heat resistance, and sensitivity required as a solder resist, but also excellent plating resistance and storage stability, it has particularly high storage stability. It can be suitably used for the required film type solder resist.
Since the photosensitive film of the present invention improves plating resistance and storage stability and can efficiently form a high-definition permanent pattern, various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern It can be suitably used for forming liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., particularly for forming permanent patterns on printed circuit boards. be able to.
Since the pattern forming method of the present invention uses the photosensitive composition, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

Claims (12)

A photosensitive composition comprising a (meth) acrylate binder, a polymerizable compound, a neutral oxime ester photopolymerization initiator, a thermal crosslinking agent, and a compound represented by the following general formula (1): object.
In the general formula (1), X state, and are σm value is -0.22 or more, and a hydrogen atom, a halogen atom, alkyl group having a total carbon number of 1 to 12, wherein the alkyl group having a substituent , aryl group having a total carbon number of 6 to 12, wherein the aryl group having a substituent, an aralkyl group having a substituent, an alkenyl group, at least one amino group wherein a hydrogen has been _{substituted, -CO-NH 2, -CO-} CF ₃ , —CO—Ph (where Ph represents a phenyl group), and —CO—CH ₃ , and the substituent is a hydroxy group, an alkoxy group, an aryloxy group, a mercapto group, or an alkylthio group. , Arylthio group, hydroxyaryl group, carboxy group, ester group, amide group, cyano group, halogen group, and nitro group . In the general formula (1), X represents —Cl and —CH. ₃ The photosensitive composition according to claim 1, which is any one of the following.   The photosensitive composition according to claim 1, wherein the (meth) acrylate binder is a polymer compound containing an acidic group and an ethylenically unsaturated bond in a side chain.   The photosensitive composition according to any one of claims 1 to 3, wherein the polymerizable compound is contained in an amount of 10% by mass or more based on the solid content in the photosensitive composition solid content. The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The photosensitive composition as described. A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a support. A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a substrate. A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to claim 1. The exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of an exit surface of a picture element portion in the light modulation unit after the light is modulated by the light modulation unit. 8. The permanent pattern forming method according to 8. The permanent pattern forming method according to claim 8, wherein the photosensitive layer is developed after the exposure. The method for forming a permanent pattern according to claim 10, wherein the photosensitive layer is cured after development. A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to claim 8.