JP2009186510A - Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity, excellent raw stock preservability, and high reliability in insulation, and to provide a photosensitive film, a photosensitive laminate, a method for forming permanent pattern, and a printed wiring board. <P>SOLUTION: This photosensitive composition contains binder, polymeric compound, oxime derivative, and ion adsorbent. Preferably, the ion adsorbent is zirconium phosphate, and the oxime derivative is the compound represented by formula, wherein R<SP>1</SP>denotes any one of acyl group which may have hydrogen atom and substituent, alkoxycarbonyl group, and allyl oxycarbonyl group, R<SP>2</SP>denotes any one of halogen atom, alkyl group, allyl group, alkyloxy group, allyloxy group, alkylthio group, allylthio group, and amino group respectively and independently, m denotes an integer of 0-4, wherein when m is 2 or more, it may connect mutually to form a ring, and A denotes any one of 4, 5, 6, and 7-membered rings. <P>COPYRIGHT: (C)2009,JPO&INPIT

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.

As the photosensitive composition for forming the solder resist, for example, there is a photosensitive composition containing an ion adsorbent such as antimony pentoxide hydrate (see Patent Document 1).
Moreover, an oxime compound is known as a polymerization initiator of a highly sensitive photosensitive composition. (See Patent Document 2).

  Today, it is desired to provide a photosensitive composition or the like that has sufficient sensitivity for digital imaging (DI) exposure, excellent raw storage stability, and further excellent insulation reliability.

JP 2000-159859 A JP 2007-231000 A

  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 aims to provide a photosensitive composition, a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed circuit board that have high sensitivity and excellent raw storage stability and high insulation reliability. And

Means for solving the above problems are as follows. That is,
<1> A photosensitive composition comprising a binder, a polymerizable compound, an oxime derivative, and an ion adsorbent.
<2> The photosensitive composition according to <1>, wherein the ion adsorbent contains zirconium phosphate.
<3> The photosensitive composition according to <1> or <2>, further including a filler.
<4> The photosensitive composition according to any one of <1> to <3>, further including a thermal crosslinking agent.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the oxime derivative is represented by the following general formula (1).
However, in said general formula (1), R < ¹ > represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is respectively independently. , A halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings.
<6> The photosensitive composition according to <5>, wherein the oxime derivative is represented by the following general formula (2).
However, in said general formula (2), R < ¹ > represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is respectively independently. , A halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group, and m represents an integer of 0 to 4. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3.
<7> The photosensitive resin composition according to <5>, wherein the oxime derivative is represented by any one of the following general formulas (3) and (4).
However, the general formula (3) and (4), R ¹ represents a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, and represents either an aryloxycarbonyl group, R ² is Each independently represents a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amino group, and m represents an integer of 0-4. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3.
<8> In the general formulas (2), (3), and (4), X is any one of O and S, 1 is any one of 1 and 2, and R ¹ has a substituent. The photosensitive composition according to <6> or <7>, wherein the photosensitive composition is any one of an acyl group and an alkoxycarbonyl group.
<9> The photosensitive composition according to any one of <1> to <5>, wherein the polymerizable compound has a weight average I / O value of 0.5 or less.
<10> A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <9> on a support.
<11> A photosensitive laminate having a photosensitive layer made of the photosensitive composition according to any one of <1> to <9> on a support on a substrate.
<12> 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 <9>.
<13> Exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The method for forming a permanent pattern according to <12>.
<14> The method for forming a permanent pattern according to <12> or <13>, wherein the photosensitive layer is developed after the exposure.
<15> The method for forming a permanent pattern according to <12>, wherein the development of the photosensitive layer is performed after the development.
<16> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of <12> and <15>.

  According to the present invention, the conventional problems can be solved, and the photosensitive composition, the photosensitive film, the photosensitive laminate, the permanent pattern forming method, which have high sensitivity and excellent raw storage stability and high insulation reliability, And a printed circuit board.

[Photosensitive composition]
The photosensitive composition contains a binder, a polymerizable compound, an oxime derivative, and an ion adsorbent, preferably contains a filler and a thermal crosslinking agent, and further contains other components as necessary.

(binder)
As the binder, a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain, an epoxy acrylate compound, or the like is preferably used, and among these, an acidic group and an ethylenically unsaturated bond are included in the side chain. A polymer compound is particularly 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.
In addition, as the binder, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester of carboxylic acid, a vinyl ether, an allyl ether, etc. Various polymerizable double bonds 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, 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 (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. In addition, examples include compounds obtained by copolymerizing a cyclic ether group-containing polymerizable compound such as glycidyl methacrylate and a vinyl monomer such as (meth) acryloyl alkyl ester and adding (meth) acrylic acid to the side chain epoxy group. 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 binder is obtained by adding a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) -containing polymerizable compound to a part of the acidic group of the polymer compound, and the polymer compound It is more preferable that the polymer compound is selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to a part or all of the cyclic ether group. 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 them, from the viewpoint of development stability of the photosensitive composition over time, the binder is a polymer compound containing an aromatic group which may contain a carboxyl group and a heterocycle in the side chain, and an ethylenically unsaturated bond in the side chain. Is preferred.

--Aromatic group which may contain a heterocycle--
Examples of the aromatic group that may contain 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 thereof 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, are exemplified.

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 ( Referred to as -SO ₃ H) and its conjugated base group (a sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfide Inamo yl 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, (referred to as phosphonato group) N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group, dialkylphosphono group _{(-PO 3 (alkyl) 2)} ( hereinafter, "alkyl" is to mean an alkyl group . ), Diaryl phosphono group _{(-PO 3 (aryl) 2)} ( hereinafter, "aryl" means an aryl group.), Alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphonates 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 a 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 phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, and fluorenyl groups. 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. The thing which has group which consists of monovalent nonmetallic atomic groups other than a hydrogen atom as a substituent on an atom is mentioned.
As the substituent that the aryl group may have, for example, those described above as the substituent that the alkyl group, the substituted alkyl group, and 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 ^A group in which ⁰⁵ is a group composed of a monovalent non-metallic atomic group is exemplified.
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-mentioned 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, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, a phosphonooxy group, a 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 as the previous example. 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 (For example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ and the} like).

Examples of the carbonyl group (R ⁰¹³ —CO—) include those in which R ⁰¹³ is a group composed of 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.
As the carbonyl group, a formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group are preferable. 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 one in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo group, 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 counter cations, 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 obtained by substituting one organic oxo group in the phosphono 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 an ordinary 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. .
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 formula (A-3) and general formula (A-4), R ₁ and R ₂ are hydrogen atoms, and R ₃ is a methyl group, from the viewpoint of removability (developability) of non-image areas. preferable.
Further, 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 the heterocyclic ring in the binder is not particularly limited, but is represented by the general formula (A-3) when the total structural unit of the polymer compound is 100 mol%. It is preferable to contain 20 mol% or more of structural units, and more preferably 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 lowered.

--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 a hydrogen atom or a 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 of introducing the ethylenically unsaturated bond represented by the general formula (A-5) into the side chain is not particularly limited, but for example, a polymer compound containing a carboxyl group in the side chain and ethylenically unsaturated It can be obtained by addition reaction of a compound having a 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 radically polymerizable compounds containing a carboxyl group and, if necessary, one or more other radically 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, but for example, a compound represented by the following general formula (A-8) and a general formula (A-9) 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- Also 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. Examples thereof include 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 alone or in combination of two or more.

  The content of the carboxyl group in the 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 compounds 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 thereof 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 Examples include 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. Examples thereof include styrene, ethoxymethyl styrene, acetoxymethyl styrene and the like.
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.

<Epoxy acrylate compound>
The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained, for example, by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.

  Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; NISSAN CHEMICAL INDUSTRY CO., LTD. "ALALDITE PT810; Ciba Specialty Chemicals" etc.), bisphenol A 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 phenol novolac type epoxy resin, glycidylamine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane), hydantoy Type epoxy resin, cycloaliphatic 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 (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals”, etc.), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Co., Ltd., etc.); a polyphenol compound obtained by a condensation reaction of a phenol compound such as phenol, o-cresol, naphthol and an aromatic aldehyde having a phenolic hydroxyl group; D Reaction product with chlorohydrin; Reaction product of polyphenol compound obtained by addition reaction of phenol compound with diolefin compound such as divinylbenzene and dicyclopentadiene and epichlorohydrin; Ring-opening polymerization product of 4-vinylcyclohexene-1-oxide Epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy resin obtained by glycidyl etherification of one kind selected from phenol and cresol and p-hydroxybenzaldehyde condensate; bis (glycidyloxyphenyl) fluore Bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of carboxyl group-containing monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, Acrylic acid dimer; in addition, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride; halogen Examples thereof include reaction products with carboxylic acid compounds, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Further, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1. Kyoeisha Yushi Chemical Co., Ltd. HOA-MP and HOA-MS, Osaka Organic Chemical Industry Co., Ltd. biscoat # 2100, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, Maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride , Phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride , Dibasic acid anhydrides such as chlorendic anhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride Acids, polybasic acid anhydrides such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid and the like can also be used. These may be used individually by 1 type and may use 2 or more types together.
Each is reacted in order to obtain an epoxy acrylate, and the ratio of reacting them is 0.8 to 1.2 equivalents of carboxyl groups of the carboxyl group-containing monomer, preferably 1 equivalent of epoxy groups of the polyfunctional epoxy compound. Is 0.9-1.1 equivalent, 0.1-1.0 equivalent of polybasic acid anhydride, preferably 0.3-1.0 equivalent.

  Also, compounds obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 can be used as the epoxy acrylate of the present invention.

  The molecular weight of the epoxy acrylate compound is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described later. If it exceeds 1,000, developability may deteriorate. Also, synthesis of the resin becomes difficult.

  5-80 mass% is preferable and, as for solid content content in the said photosensitive composition of the said binder, 10-70 mass% is more preferable.

  The solid content of the binder in the photosensitive composition 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)
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, It is preferable that the weight average of I / O value is 0.50 or less.
Examples of the polymerizable compound include tricyclodecane dimethanol diacrylate (I / O value: 0.428), tricyclodecane dimethanol dimethacrylate (I / O value: 0.385), trimethylolpropane trimethacrylate (I / O value: 0.517), neopentyl glycol diacrylate (I / O value: 0.564), 1,10-decanediol diacrylate (I / O value: 0.388), 1,6-hexanediol Diacrylate (I / O value: 0.443), 1,9-nonanediol diacrylate (I / O value: 0.413), neopentyl glycol dimethacrylate (I / O value: 0.477), 1, 9-nonanediol dimethacrylate (I / O value: 0.365), etc.

The I / O value is a value that organically handles the polarity of various organic compounds, also called (inorganic value) / (organic value), and is a functional group contribution method that sets parameters for each functional group. One. As the I / O value, in detail, an organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, No. 1-16 (1954); Volume 10, No. 719-725 (1957); Fragrance Journal No. 34, No. 97-111 (1979); Fragrance Journal No. 50, No. 79-82 (1981); etc. In the literature.
The concept of the I / O value is a straight line in which the properties of a compound are divided into an organic group representing a covalent bond and an inorganic group representing an ionic bond, and all organic compounds are named as an organic axis and an inorganic axis. Each point on the coordinates is shown.
The inorganic value is obtained by quantifying the magnitude of the influence on the boiling point of various substituents and bonds of an organic compound, based on the hydroxyl group. Specifically, when the distance between the boiling point curve of the linear alcohol and the boiling point curve of the linear paraffin is about 100 ° C., the influence of one hydroxyl group is set to 100 as a numerical value. Based on this numerical value, the value obtained by quantifying the influence on the boiling point of various substituents or various bonds is the inorganic value of the substituent that the organic compound has. For example, the inorganic value of the —COOH group is 150, and the inorganic value of the double bond is 2. Therefore, the inorganic value of a certain organic compound means the sum of inorganic values such as various substituents and bonds of the compound.
The organic value is determined based on the influence of the methylene group in the molecule as a unit and the boiling point of the carbon atom representing the methylene group. That is, since the average value of the boiling point increase due to addition of one carbon in the vicinity of 5 to 10 carbon atoms of the linear saturated hydrocarbon compound is 20 ° C., the organic value of one carbon atom is set to 20 on the basis of this. Based on this, the value obtained by quantifying the influence on the boiling point of various substituents and bonds is the organic value. For example, the organic value of a nitro group (—NO ₂ ) is 70.
The closer the I / O value is to 0, the more non-polar (hydrophobic and organic) organic compounds are, and the larger the I / O value is, the more polar (hydrophilic and inorganic) organic compounds are. Show.
The weight average of the I / O values is, for example, the I / O value when the polymerizable compound A is used in a mixture of a polymerizable compound in a ratio of a wt% and B in a ratio of b wt% (a + b = 100). Weight average = (I / O value of A × a / 100 + I / O value of B × b / 100).
Hereinafter, an example of a method for calculating the I / O value will be described.

  The I / O value of pentaerythritol tetraacrylate is obtained by calculating the inorganic value and the organic value by the following method, and calculating the following formula: (inorganic value) / (organic value).

  Since pentaerythritol tetraacrylate has 17 carbon atoms, the organic value of pentaerythritol tetraacrylate is calculated to be 20 (organic value of carbon atoms) × 17 (number of carbon atoms) = 340.

  The inorganic value of pentaerythritol tetraacrylate is that pentaerythritol tetraacrylate has four carboxyl groups and four double bonds, so the inorganic value of pentaerythritol tetraacrylate is 60 (inorganic value of ester group) × 4 (number of ester groups) +2 (inorganic value of double bond) × 4 (number of double bonds) = 248

  Therefore, it can be seen that the I / O value of pentaerythritol tetraacrylate is 248 (inorganic value of the copolymer) / 340 (organic value of the copolymer) = 0.729.

  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.

(Oxime derivatives)
The oxime derivative is represented by the following general formula (1).
However, in said general formula (1), R < ¹ > represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is respectively independently. , A halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings.
In the oxime derivative, it has excellent storage stability and high sensitivity, and by adding the oxime derivative, it has excellent storage stability without causing polymerization during storage, and is easy to handle. An active radical is generated by irradiation of light to efficiently initiate polymerization, and a highly sensitive polymerizable composition capable of efficiently polymerizing the polymerizable compound in a short time is obtained.

The oxime derivative is more preferably an oxime derivative represented by the following general formula (2).
However, in said general formula (2), R < ¹ > represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is respectively independently. , A halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group, and m represents an integer of 0 to 4. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3.

The oxime derivative is more preferably an oxime derivative represented by any one of the following general formulas (3) and (4).
However, the general formula (3) and (4), R ¹ represents a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, and represents either an aryloxycarbonyl group, R ² is Each independently represents a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amino group, and m represents an integer of 0-4. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3.

In the oxime derivative according to any one of the general formulas (2) to (4), in the general formulas (2), (3), and (4), X is any one of O and S, and l is It is either 1 or 2, and R ¹ is preferably either an acyl group which may have a substituent or an alkoxycarbonyl group.

In the general formulas (1), (2), (3) and (4), R ¹ is any ^one of a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group. It is.
The acyl group may be any of aliphatic, aromatic and heterocyclic rings. Those having 2 to 30 carbon atoms are preferred, those having 2 to 20 carbon atoms are more preferred, and those having 2 to 16 carbon atoms are particularly preferred. The acyl group may further have a substituent. As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.
The acyl group may have a substituent, for example, acetyl group, n-propanoyl group, i-propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group. , Decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, toluenecarbonyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl Group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group, acryloyl group and the like.

  The alkyloxycarbonyl group may have a substituent, preferably has 2 to 30 carbon atoms, more preferably has 2 to 20 carbon atoms, and more preferably has 2 to 16 carbon atoms. Particularly preferred. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. Is mentioned.

  The aryloxycarbonyl group may have a substituent and is preferably an alkoxycarbonyl group having a total carbon number of 7 to 30, more preferably a total carbon number of 7 to 20, and a total carbon number of 7 to 16. Is particularly preferred. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

In the general formulas (1), (2), (3) and (4), each R ² is independently a halogen atom, alkyl group, aryl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group. group, and include any of the amino groups, in particular, aliphatic, aromatic, heteroaromatic, halogen ^{atom, -OR 3, -SR 3, -NR} 3 R 4 can be mentioned. R ³ and R ⁴ may be connected to each other to form a ring. R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heteroaromatic group. When m is 2 or more and are connected to each other to form a ring, each of R ² independently may form a ring, and a ring is formed via at least one of R ³ and R ^4. Also good.

In the case of forming a ring via the substituent R ² , the following structures are exemplified.
In the structural formula, Y and Z represent any one of CH ₂ , —O—, —S—, and —NR—.

  As an alkyl group, you may have a substituent and a C1-C18 thing is preferable, and a C1-C10 thing is especially preferable. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group, n -An octyl group, t-octyl group, and n-decyl group are mentioned.

  The aryl group may have a substituent and preferably has a total carbon number of 6 to 20, particularly preferably a total carbon number of 6 to 12. Examples of such an alkyl group include a phenyl group, a biphenyl group, a naphthyl group, a chlorophenyl group, and a methoxyphenyl group.

  As an alkyloxy group, you may have a substituent and a C1-C18 thing is preferable, and a C1-C12 thing is especially preferable. Such alkyloxy groups include methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, t-butyloxy, 2-ethylhexyloxy, n-decyloxy, phenethyloxy Group and phenoxyethoxy group.

  The aryloxy group may have a substituent and preferably has 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples of such an aryloxy group include a phenoxy group, a naphthyloxy group, a chlorophenyloxy group, and a methoxyphenyloxy group.

  As an alkylthio group, you may have a substituent and a C1-C18 thing is preferable, and a C1-C12 thing is especially preferable. Examples of such an alkylthio group include a methylthio group, an ethylthio group, an i-propylthio group, an n-butylthio group, an n-octylthio group, an n-dodecylthio group, and a 2-ethylhexylthio group.

  As the arylthio group, those having 6 to 20 carbon atoms are preferable, and those having 6 to 12 carbon atoms are particularly preferable. Examples of such an arylthio group include a phenylthio group, a tolylthio group, a chlorophenylthio group, and an ethoxycarbonylphenylthio group.

As the amino group, at least one of an alkyl group and an aryl group may be substituted, and those having 1 to 20 carbon atoms are preferable, and those having 1 to 12 carbon atoms are particularly preferable. Examples of such an amino group include —NH ₂ group, diethylamino group, diphenylamino group, and methylphenylamino group.

Specific examples of the aliphatic group, aromatic group, and heteroaromatic group of R ² , R ³ , and R ⁴ include the same groups as those described above for R ¹ .

Specific examples of the oxime derivatives represented by the general formulas (1) to (4) include compounds represented by the following structural formulas (1) to (52), but the present invention is limited to these. It is not something.

The oxime derivative can be identified by measuring a ¹ H-NMR spectrum and a UV-vis absorption spectrum.

(Method for producing oxime derivative)
As a method for producing the oxime derivative, a corresponding oxime compound (hereinafter referred to as a material oxime compound) which is a starting material of the oxime derivative and an acyl chloride or anhydride are present in the presence of a base (eg, triethylamine, pyridine). And can be easily synthesized by reacting in an inert solvent such as THF, DMF, and acetonitrile, or in a basic solvent such as pyridine. As said reaction temperature, -10-60 degreeC is preferable.
Further, by using chloroformate, alkylsulfonyl chloride, and arylsulfonyl chloride as the acyl chloride, various corresponding oxime ester compounds can be synthesized.

  As a method for synthesizing a material oxime compound used as a starting material in producing the oxime derivative, a standard chemistry textbook (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) It can be obtained by various methods described in monographs (eg, SR Sandler & W. Karo, Organic functional group preparations, Vol. 3, Academic Press).

As a particularly preferable synthesis method of the material oxime compound, for example, a method of reacting an aldehyde or ketone with hydroxylamine or a salt thereof in a polar solvent such as ethanol or ethanol water can be mentioned. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and that the base can be added at the beginning of the reaction or continuously during the reaction.
A basic solvent such as pyridine can also be used as the base and / or solvent or cosolvent.
The reaction temperature is generally preferably the reflux temperature of the mixture, that is, about 60 to 120 ° C.

Other preferred methods of synthesizing the material oxime compounds include nitrosation of “active” methylene groups with nitrous acid or alkyl nitrites. See, for example, Organic Synthesis coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp. 199 and 840 and alkaline conditions such as those described in Organic Synthesis coll. Vol. V, pp. 32 and 373, coll. Vol. III, pp. 191 and 513, coll. Vol. II, pp. Both acidic conditions as described in 202, 204 and 363 are suitable for the synthesis of material oxime compounds used as starting materials in the present invention.
The nitrous acid is usually produced from sodium nitrite.
Examples of the alkyl nitrite include methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.

  The oxime ester group may exist in two types of configuration (Z) or (E). The isomers may be separated by conventional methods, or the isomer mixture may be used as it is as a photoinitiating seed. Therefore, the oxime derivative may be a mixture of isomers on the configuration of the compounds of the structural formulas (1) to (52).

  The oxime derivative is excellent in storage stability and has high sensitivity, and when added to the polymerizable composition, it has excellent storage stability without causing polymerization during storage. An active radical is generated to initiate polymerization efficiently, and a highly sensitive polymerizable composition capable of efficiently polymerizing the polymerizable compound in a short time can be obtained. Therefore, the oxime derivative is used as a radical generator as a printing ink, transparent finishing material, powder coating material, building marking or road marking, photo reproduction method, holographic recording material, image recording method, organic solvent or aqueous alkali. Production of developable printing plate, sun curable coating material for production of screen printing mask, dental filling composition, adhesive, pressure sensitive adhesive, laminating resin, liquid and film etching resist, solder resist, It can be used by adding to electroplating resists, permanent resists, printed circuit boards, optically configurable dielectrics for electronic circuits, and the like. In addition, materials for various display applications, materials for forming structures in the manufacturing process of plasma display panels and electroluminescent display devices, color filters, optical switches, optical gratings (interference gratings), optical circuit manufacturing materials, mass curing (transparent UV curing in molds) or stereolithographic techniques for the production of three-dimensional articles, composite materials such as styrenic polyester, other thick-layer composition production materials, electronic components and integrated circuit coatings or It can be used as a resist for sealing, a material for forming an optical fiber, a coating material for producing an optical lens, and the like. Furthermore, it can also be used for the manufacture of medical devices, aids, implants, and gels having thermotropic properties. In particular, it can be suitably used for the photosensitive composition of the present invention.

  The oxime derivative can be used as an initiator for emulsion polymerization, pearl polymerization, and suspension polymerization. Moreover, you may use additionally as a polymerization initiator for fixing the regular state of the monomer and oligomer of a liquid crystal as an initiator for fixing a dye to an organic material.

(Ion adsorbent)
The ion adsorbent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include zirconium phosphate, antimony pentoxide hydrate, antimony trioxide, and hydrotalcites. In the present invention, it is particularly preferable to use zirconium phosphate from the viewpoint of insulation reliability.
Examples of commercially available ion adsorbents include IXE-100, IXE700F (manufactured by Toagosei Co., Ltd.), and DHA-4A-2 (manufactured by Kyowa Interface Science Co., Ltd.).
The ion adsorbents may be used alone or in combination of two or more.

(Filler)
The filler is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous silica , Crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like.
The filler may be used alone or in combination of two or more.

The average particle size of the filler is preferably less than 3 μm, and 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 amount of the filler added is preferably 5% by mass to 75% by mass, more preferably 8% by mass to 70% by mass, and still more preferably 10% by mass to 65% by mass. If the addition amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently reduced. The film quality becomes brittle, and when a wiring is formed using a permanent pattern, the function as a protective film for the wiring may be impaired.

As the filler, it is also possible to add organic fine particles 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, and spherical porous particles comprising a crosslinked resin.

  Since the filler contains particles having an average particle size of 0.1 μm to 2 μm, even if the permanent pattern is thinned to a thickness of 5 μm to 20 μm as the printed wiring board is thinned, the filler The front and back surfaces of the permanent pattern are not cross-linked, and as a result, no ion migration occurs even in a high acceleration test (HAST), and a permanent pattern excellent in heat resistance and moisture resistance can be obtained.

(Thermal crosslinking agent)
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, developability, etc. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.

  The epoxy compound having at least two oxirane groups in one molecule is not particularly limited and may be appropriately selected depending on the intended purpose. For example, bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin Co., Ltd.) Or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC: manufactured by Nissan Chemical Industries”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy Resin, novolac epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, halogenated epoxy resin (for example Low brominated epoxy resin, highly halogenated epoxy resin, brominated phenol novolac type epoxy resin, etc.), 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) ), Glycidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester) ) Hydantoin type epoxy resin, cycloaliphatic epoxy resin (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “ GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries Ltd., etc.), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac 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 Fats (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 Chemical Co., Ltd.”), phenol compounds, Epoxidized reaction product of polyphenol compound obtained by addition reaction with diolefin compound such as divinylbenzene and dicyclopentadiene and epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid , Epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin , Binaphthyl type liquid crystal epoxy tree , Azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin, bis (glycidyloxy) Phenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used. A compound containing an epoxy group substituted with a group (more specifically, a β-alkyl-substituted glycidyl group or the like) is particularly preferable.
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 ratio of the glycidyl group is preferably 30% or more, more preferably 40% or more, and still more 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 these, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the photosensitive composition and 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 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 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate and the like, and C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formalde De 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; 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 ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate 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 (D-1) and a polymer obtained from this and epichlorohydrin, and the following general formula (D-2) Poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate represented by
However, in said general formula (D-1), R represents either a hydrogen atom or a C1-C6 alkyl group. n represents an integer of 0 to 20.
However, in said general formula (D-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 0-20.
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 oxirane rings 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 bisphenol type epoxy resins, novolac type epoxy resins, alicyclic group-containing type epoxy resins, and poorly soluble epoxy resins.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, 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) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds with hydroxyl group resins such as silsesquioxane, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

Further, in order to promote the thermal curing of the epoxy compound or the oxetane compound, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N , N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives Cyclic amidine compounds or salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl) Midazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S- Triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric An acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
The solid content in the solid content of the photosensitive composition of the epoxy compound, the oxetane compound, and a compound capable of accelerating thermal curing between these and the carboxylic acid is usually preferably 0.01% by mass to 15% by mass. .

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like. In addition, as a commercial item of the said polyisocyanate compound, BL317 (made by Sumitomo Bayer Urethane Co., Ltd.) etc. are mentioned, for example.

Furthermore, for the purpose of improving the storage stability, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec). -Butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, Methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. 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.

  The solid content in the photosensitive composition solid content of the thermal crosslinking agent is preferably 1% by mass to 50% by mass, and more preferably 3% by mass to 30% by mass. When the solid 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 lowered.

(Other ingredients)
Examples of the other components include thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and further adhesion promoters and other auxiliaries (for example, conductivity) to the substrate surface. Particles, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. By appropriately containing these, properties such as the stability, photographic properties, and film physical properties of the intended photosensitive film can be adjusted.

<Thermal polymerization inhibitor>
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 more preferable. 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.

<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 exemplified compounds, hetero-fused compounds are preferred as compounds in which an aromatic ring or a heterocycle is condensed (condensed 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. As said hetero condensed ring type compound, a hetero condensed ring type ketone compound is mentioned, for example. 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 an acridone compound 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-2002-363209 Coumarin compounds such as coumarin compounds described in Japanese Patent Publication No.
Also 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 (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squalium (for example, 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 the content exceeds 4% by mass, the shape of the pattern may be deteriorated.

The mass ratio between the sensitizer and the photopolymerization initiator content in the photosensitive composition is [(sensitizer) / (oxime derivative)] = 1 / 0.1 to 1/100. Is preferable, and it is more preferable that it 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.

<Plasticizer>
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 more preferable.

<Coloring 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 (C.I. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), C.I. I. Pigment Yellow 55, Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), carbon, C.I. 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: 3, 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. Pigment blue 64 and the like. 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.

<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, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, Amino group-containing benzotriazole, silane coupling agent and the like can be mentioned.

  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.

(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 elements for receiving and emitting 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 in 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 exposure amount 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. However, a film thickness measuring device, a surface roughness measuring device (for example, Surfcom) 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 to the photosensitive layer. The method of laminating | stacking by apply | coating 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 purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like, it is directly applied to the support. 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, a polymerizable compound, an oxime derivative, and an ion adsorbent, and is formed of a photosensitive composition containing other components as necessary. The

<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 discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

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. For example, a cushion layer, an oxygen barrier 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, sensitivity, developability, and adhesion, 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 various pattern formation, color filter, pillar material, rib material, spacer, production of liquid crystal structural members such as spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for forming a permanent pattern.

  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 member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and may be appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having an uneven 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 of applying the photosensitive composition 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, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is 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, the sensitivity, developability, and adhesion are good, and a high-definition permanent pattern can be efficiently formed. For the formation of various patterns such as insulating films and permanent patterns such as solder resist patterns, for the production of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, for the formation of patterns such as holograms, micromachines, and proofs In particular, it can be 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.

“Laser” of the laser light 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 a higher coherence and directivity by amplification and oscillation of light waves using a phenomenon of stimulated emission that occurs in a material having an inversion distribution is 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, Ar ion lasers (364 nm, 351 nm), Kr ion lasers (356 nm, 351 nm), and He—Cd lasers (325 nm) can be cited as gas lasers, and YAG lasers, YVO ₄ lasers (1, 1, 064 nm), YAG laser or YVO ₄ laser, second harmonic (532 nm), third harmonic (355 nm), fourth 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, suitable 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 a 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 which 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. If the light spot is not exposed between the light spots, the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction. 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 according to the purpose. From the viewpoint of the resolution of the dark color separation partition wall, 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 alkaline aqueous 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 forming method is a permanent pattern forming 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 developing step. It is preferable to provide the hardening process process which performs a process.
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 whole 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 without departing from the gist thereof. Unless otherwise specified, “part” is based on mass.

[Example 1]
(Manufacture 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 28 μm thick photosensitive layer was formed on the support. 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 the following binder 1: 100 parts by mass Tricyclodecane diacrylate (trade name: NK ester A-DCP)
(C-1, I / O value = 0.428) ········ 18 parts by mass Photopolymerization initiator represented by the following formula A-1 ··· ··· 1.0 part by mass Sensitizer represented by the following formula S-1 ······· 0.7 parts by mass Epototo YDF170 (epoxy equivalent 170 g / Eq., Manufactured by Tohto Kasei Co., Ltd., bisphenol F epoxy resin) ... 8.9 parts by weight Dicyandiamide ... ········ 0.5 parts by weight Pigment dispersion ···················· 80.21 parts by weight MegaFuck F-780F ( 30% by weight methyl ethyl ketone solution of Dainippon Ink Co., Ltd .... 0.2 parts by weight IXE-10 1: 1 (mass ratio) mixture of 0 (manufactured by Toagosei) and IXE-700F (manufactured by Toagosei) 4.0 mass Part

<< Synthesis of Binder 1 >>
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 3.0 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 38 g of 1-methoxy-2-propanol was added to prepare a solution of binder 1 having an acid value of 112 mgKOH / g, a weight average molecular weight of 15,000 and a solid content of 30% by weight.

  The pigment dispersion is 30 parts by weight of barium sulfate (B30 manufactured by Sakai Chemical Co., Ltd.), 50 parts by weight of the binder 1 solution, 0.16 parts by weight of phthalocyanine blue, and anthraquinone yellow pigment (PV24) 0. 0.07 part by mass was mixed in advance, and then dispersed with a motor mill M-250 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm at a wind speed of 9 m / s for 3 hours.

<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.

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. And spray development for 2 to 3 times the shortest development time (or 40 to 60 seconds) to dissolve and remove uncured regions. 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 1.

<Development and curing process>
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 at a pressure of 0.15 MPa for 60 seconds to dissolve uncured regions. Removed. Thereafter, it was washed with water and dried to form a permanent pattern.

<Evaluation of insulation reliability 1 (Condition 1)>
The substrate was prepared in the same manner as the method for forming a permanent pattern except that a copper-clad laminate having a copper thickness of 12 μm was used to form a wiring in a comb shape so that line / space = 50 μm / 50 μm. The permanent pattern was subjected to a high-speed accelerated life test (HAST test) to evaluate dendrite and insulation resistance (Ω). In the HAST test, a high-acceleration tester is used, and the insulation resistance (Ω) of the conductor bump is measured under the same conditions after applying a voltage of 10 V for 200 hours in an atmosphere where the temperature of the electronic component module is 130 ° C. and the relative humidity is 85%. Then, dendrite observation of the conductor bump was performed and evaluated as follows. The results are shown in Table 1.
〔Evaluation criteria〕
◎: No change in wiring ○: No dendrite is seen but anode wiring is slightly changed △: No dendrite is seen but anode wiring is difficult to see ×: Dendrite is present

<Insulation reliability evaluation 2 (Condition 2)>
The substrate was prepared in the same manner as the method for forming a permanent pattern except that a copper-clad laminate having a copper thickness of 12 μm was used to form a wiring in a comb shape so that line / space = 50 μm / 50 μm. The permanent pattern was subjected to a high-speed accelerated life test (HAST test) to evaluate dendrite and insulation resistance (Ω). In the HAST test, the insulation resistance (Ω) of the conductor bumps was measured under the same conditions after applying a voltage of 50V for 200 hours in an atmosphere where the temperature was 130 ° C and the relative humidity was 85% using a high acceleration tester. Then, dendrite observation of the conductor bump was performed and evaluated as follows. The results are shown in Table 1.
〔Evaluation criteria〕
◎: No change in wiring ○: No dendrite is seen but anode wiring is slightly changed △: Dendrite is not seen but anode wiring is difficult to see ×: Dendrite is present

<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 . However, to fill in the "×" if the photosensitive layer even if the 60 seconds spray development at the time t ₁ measured can not be removed. The closer the obtained value is to 1, the better the raw storage stability. The results are shown in Table 1.

[Example 2]
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the ion adsorbent was changed to B-2, and sensitivity and insulation reliability (Condition 1 and Condition 2) were produced in the same manner as in Example 1. ) And raw storage stability were evaluated. The results are shown in Table 1. The ion adsorbent B-2 is a 1: 1 (mass ratio) mixture of IXE-100 (manufactured by Toagosei Co., Ltd.) and DHA-4A-2 (manufactured by Kyowa Interface Chemical Co., Ltd.).

Example 3
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the ion adsorbent was changed to B-3, and sensitivity and insulation reliability (Condition 1 and Condition 2) were produced in the same manner as in Example 1. ) And raw storage stability were evaluated. The results are shown in Table 1. The ion adsorbent B-3 is DHA-4A-2 (manufactured by Kyowa Interface Chemical Co., Ltd.).

Example 4
A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the polymerizable compound was replaced with C-2, and the sensitivity and insulation reliability (Condition 1 and Condition 2) were produced in the same manner as in Example 1. ) And raw storage stability were evaluated. The results are shown in Table 1. The polymerizable compound C-2 is tricyclodecane dimethanol dimethacrylate. The I / O value of the polymerizable compound C-2 is 0.385.

Example 5
A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the polymerizable compound was replaced with C-3, and the sensitivity and insulation reliability (Condition 1 and Condition 2) were produced in the same manner as in Example 1. ) And raw storage stability were evaluated. The results are shown in Table 1. The polymerizable compound C-3 is trimethylolpropane trimethacrylate. The I / O value of the polymerizable compound C-3 is 0.517.

Example 6
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the oxime derivative (initiator) was changed to A-2, and in the same manner as in Example 1, sensitivity, insulation reliability (conditions) 1 and condition 2) and evaluation of raw preservation were performed. The results are shown in Table 1. The oxime derivative A-2 is represented by the following formula A-2.

Example 7
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the oxime derivative (initiator) was changed to A-3, and in the same manner as in Example 1, sensitivity, insulation reliability (conditions) 1 and condition 2) and evaluation of raw preservation were performed. The results are shown in Table 1. The oxime derivative A-3 is Irgacure 250 (manufactured by Ciba Specialty Chemicals).

Example 8
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the oxime derivative (initiator) was replaced with A-4, and in the same manner as in Example 1, sensitivity, insulation reliability (conditions) 1 and condition 2) and evaluation of raw preservation were performed. The results are shown in Table 1. The oxime derivative A-4 is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

Example 9
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the ion adsorbent was changed to B-4 and the polymerizable compound was changed to C-3. Insulation reliability (conditions 1 and 2) and raw storage stability were evaluated. The results are shown in Table 1. The ion adsorbent B-4 is antimony pentoxide hydrate. The polymerizable compound C-3 is the same as that used in Example 5.

Example 10
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the ion adsorbent was changed to B-5 and the polymerizable compound was changed to C-3. Insulation reliability (conditions 1 and 2) and raw storage stability were evaluated. The results are shown in Table 1. The ion adsorbent B-5 is antimony trioxide. The polymerizable compound C-3 is the same as that used in Example 5.

[Comparative Example 1]
A laminated body and a permanent pattern were produced in the same manner as in Example 1 except that the polymerizable compound was changed to C-3 without using an ion adsorbent. The properties (conditions 1 and 2) and raw storage stability were evaluated. The results are shown in Table 1. The polymerizable compound C-3 is the same as that used in Example 5.

Since the photosensitive film of the present invention maintains developability and improves insulation reliability and can efficiently form a high-definition permanent pattern, a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern Can be suitably used for the formation of various patterns such as color filters, pillar materials, rib materials, spacers, spacers and other liquid crystal structural members, holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on printed circuit boards. Can be suitably used.
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 (16)

  A photosensitive composition comprising a binder, a polymerizable compound, an oxime derivative, and an ion adsorbent.   The photosensitive composition according to claim 1, wherein the ion adsorbent contains zirconium phosphate.   The photosensitive composition of Claim 1 or 2 which further contains a filler.   The photosensitive composition in any one of Claim 1 to 3 which further contains a thermal crosslinking agent. The photosensitive composition according to any one of claims 1 to 4, wherein the oxime derivative is represented by the following general formula (1).
However, in said general formula (1), R < ¹ > represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is respectively independently. , A halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings. The photosensitive composition of Claim 5 by which an oxime derivative is represented by following General formula (2).
However, in said general formula (2), R < ¹ > represents either a hydrogen atom, the acyl group which may have a substituent, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is respectively independently. , A halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group, and m represents an integer of 0 to 4. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3. The photosensitive resin composition according to claim 5, wherein the oxime derivative is represented by any one of the following general formulas (3) and (4).
However, the general formula (3) and (4), R ¹ represents a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, and represents either an aryloxycarbonyl group, R ² is Each independently represents a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amino group, and m represents an integer of 0-4. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3. In the general formulas (2), (3) and (4), X is either O or S, 1 is any one of 1 and 2, and R ¹ has a substituent. The oxime derivative according to claim 6 or 7, which is any one of a good acyl group and an alkoxycarbonyl group.   The photosensitive composition according to claim 1, wherein the polymerizable compound has an I / O value weight average of 0.5 or less.   A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to claim 1 on a support.   A photosensitive laminate comprising a support and a photosensitive layer made of 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 aberration due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. 12. The permanent pattern forming method according to 12.   The method for forming a permanent pattern according to claim 12 or 13, wherein the photosensitive layer is developed after the exposure.   The permanent pattern forming method according to claim 12, wherein after the development, the photosensitive layer is cured.   A printed circuit board, wherein a permanent pattern is formed by the method for forming a permanent pattern according to claim 12.