JP5129680B2 - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board - Google Patents

Description

  The present invention relates to a photosensitive composition having high sensitivity and good developability in which a polymerizable compound can be efficiently polymerized in a short time, and a photosensitive film, a photosensitive laminate, and a permanent pattern using the photosensitive composition. The present invention relates to a forming method and a printed circuit board.

  The solder resist is used for the purpose of preventing a solder bridge and protecting a circuit when soldering a component to a printed wiring board, and requires various characteristics such as adhesion, chemical resistance, and electrical characteristics. In recent years, in the printed wiring board manufacturing industry, there has been a demand for weight reduction of printed wiring boards and higher density of conductor circuits, and in response to this, development can be performed with a photosensitive composition for forming a photographic development type solder resist, particularly an alkaline aqueous solution. Photosensitive compositions have been developed and used (see, for example, Patent Document 1).

  Formation of a photosensitive layer using such a photosensitive composition for forming a photographic development type solder resist is performed by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, or the like. Coating process to coat the entire surface of the substrate, temporary drying process to volatilize the organic solvent to enable contact exposure, exposure process to cool and contact exposure, development process to remove unexposed areas by development, sufficient coating properties Requires a heat curing step to obtain. Among these processes, the exposure process is an extremely sensible process in which the negative film is exchanged depending on the type of the printed wiring board, aligned, vacuumed, and exposed. Therefore, the shortening of the exposure process is a major factor for improving productivity and reducing the price, and the high sensitivity of the photosensitive composition for forming a solder resist greatly contributes to shortening the exposure process. It is desired to increase the sensitivity of the photosensitive composition for resist formation.

  In order to realize such a demand for higher sensitivity, certain oxime ester derivatives and certain dithioalkylene compounds are useful as photopolymerization initiators that generate active radicals by the action of light and initiate monomer polymerization. It is known (see Patent Documents 2 to 6).

  However, in order to achieve higher sensitivity, if the addition amount of the oxime ester derivative and the dithioalkylene compound is increased, the developability changes with the lapse of 24 hours or more after lamination, the resolution is lowered, and development residue is generated. There is a problem that it is likely to occur, and the immediate improvement is desired at present.

JP-A-1-141904 JP 60-166306 A JP 2001-233842 A JP 2000-80068 A JP 2005-182004 A Japanese Patent No. 2632069

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is a photosensitivity having high sensitivity and good developability in which active radicals are generated by irradiation with energy rays, particularly light, to efficiently initiate polymerization, and a polymerizable compound can be efficiently polymerized in a short time. It aims at providing the photosensitive composition, the photosensitive film using this photosensitive composition, the photosensitive laminated body, the permanent pattern formation method, and a printed circuit board.

Means for solving the problems are as follows. That is,
<1> It contains at least a binder, a polymerizable compound, a thermosetting compound, a photopolymerization initiator, and a sensitizer.
The polymerizable compound contains at least one selected from methacrylate compounds,
The photopolymerization initiator is a compound represented by the following general formula (A-1),
The photosensitive composition is characterized in that the sensitizer is a compound represented by the following general formula (B-1).
However, in the general formula (A-1), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and the R ¹ may be further substituted with a substituent. R ² represents any of a hydrogen atom, an alkyl group, and a cyano group, Ar represents either an aromatic ring or a heteroaromatic ring, and Ar and R ² are bonded to each other to form a ring. May be. n represents 0 or 1.
However, in the general formula (B-1), R ⁶ and R ⁷ may be the same as or different from each other, and represent any one of an alkyl group, an aryl group, and an alkenyl group, R ⁶ and R ⁷ may form a ring made of a nonmetallic element together with the sulfur atom to which they are bonded, and these may be further substituted with a substituent. G ¹ and G ² may be the same or different from each other, and may be a hydrogen atom, a cyano group, a carbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, Any one of an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group, wherein G ¹ and G ² are merocyanine dyes composed of a nonmetallic atom together with carbon atoms to which each is bonded, and an acidic nucleus May be used, and these may be further substituted with a substituent. However, either G ¹ or G ^{2 represents} any of a carbonyl group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group. p represents any integer of 0-2.
<2> The photosensitive composition according to <1>, wherein the compound represented by the general formula (A-1) is a compound represented by the following general formula (A-2).
However, in the general formula (A-2), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, which may be further substituted with a substituent. R ³ represents any one of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, a nitro group, and an acylamino group. m represents an integer of 0 or more, and when m is 2 or more, the R ^{3 s} may be the same as or different from each other, and may be linked to each other to form a ring. . Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of a 5-membered ring, a 6-membered ring, and a 7-membered ring, and these may be further substituted with a substituent. X represents either an oxygen atom or a sulfur atom.
<3> The photosensitive property according to <2>, wherein the compound represented by the general formula (A-2) is a compound represented by any one of the following general formulas (A-3) and (A-4). It is a composition.
However, in the general formula (A-3) and (A-4), R ⁴ represents any of an alkyl group, and alkyl group, wherein R ⁴ may be further substituted with a substituent . R ⁵ represents any one of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, a nitro group, and an acylamino group. l represents an integer of 0 to 6, and when l is 2 or more, the R ^{5 s} may be the same or different from each other, and may be connected to each other to form a ring. Good. A represents either a 5-membered ring or a 6-membered ring, and these may be further substituted with a substituent. X represents either an oxygen atom or a sulfur atom.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the compound represented by the general formula (B-1) is a compound represented by the following general formula (B-2). It is.
However, in the general formula (B-2), R ⁸ and R ⁹ may be the same as or different from each other, and may be a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a halogen atom. R ⁸ and R ⁹ may be bonded to each other to form an aromatic ring, and at least one of an alkyl group, an alkyloxy group, and a halogen atom is further formed on the aromatic ring. You may have. R ¹⁰ and R ¹¹ may be the same as or different from each other, and each represents a hydrogen atom, an alkyl group, or an aryl group. Y represents either an oxygen atom or a sulfur atom.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the thermosetting compound is an epoxy compound having two or more epoxy groups in one molecule.
<6> At least one epoxy compound having two or more epoxy groups in one molecule is selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a hardly soluble epoxy resin It is the photosensitive composition as described in said <5>.
<7> The photosensitive composition according to any one of <1> to <6>, further including at least one of an inorganic filler and an organic filler.
<8> A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <7> on a support.
<9> A photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <7> on a substrate.
<10> A method for forming a permanent pattern, comprising exposing the photosensitive layer formed of the photosensitive composition according to any one of <1> to <7>.
<11> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <10>.

  According to the present invention, conventional problems can be solved, an active radical is generated by irradiation with energy rays, particularly light, and polymerization is efficiently started, and a polymerizable compound can be efficiently polymerized in a short time. There can be provided a photosensitive composition having high sensitivity and good developability, and a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed board using the photosensitive composition.

  The photosensitive composition of the present invention contains at least a binder, a polymerizable compound, a thermosetting compound, a photopolymerization initiator, and a sensitizer, and further contains other components as necessary. Become.

<Binder>
The binder is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. The binder may be used alone or in combination of two or more.
There is no restriction | limiting in particular as a mass average molecular weight of the said binder, Although it can select suitably according to the objective, For example, it is preferable that it is 10,000-100,000, and 10,000-50,000 are more. preferable. 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.

As the binder, for example, a carboxyl group-containing resin having one or more carboxyl groups in one molecule (hereinafter sometimes referred to as “carboxyl group-containing resin”) is suitable.
The carboxyl group-containing resin is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
The carboxyl group-containing resin is not particularly limited as long as it has one or more carboxyl groups in one molecule, but a carboxyl group and a polymerizable unsaturated double bond are contained in one molecule. , Each preferably has at least one. Examples of the unsaturated double bond include various polymerizable double bonds such as acrylic group (for example, (meth) acrylate group, (meth) acrylamide group, etc.), vinyl ester of carboxylic acid, vinyl ether, allyl ether and the like. It is done. As such a carboxyl group-containing resin having at least one carboxyl group and polymerizable unsaturated double bond in one molecule, more specifically, an acrylic resin containing a carboxyl group, Cyclic ether group-containing polymerizable compounds (for example, glycidyl acrylate; glycidyl methacrylate; glycidyl esters of unsaturated fatty acids such as cinnamic acid; compounds having an alicyclic epoxy group (for example, cyclohexene oxide) and a (meth) acryloyl group; Etc.) are added. In addition, compounds obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing a carboxyl group and a hydroxyl group are also included.
Examples of these compounds include compounds described in Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-232264, and the like.

Among these compounds, as the carboxyl group-containing resin, among the compounds described above, a polymerizable compound containing a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) is added to a part of the carboxyl group. More preferably, the polymer is selected from those obtained by adding a carboxyl group-containing polymerizable compound to some or all of the cyclic ether groups. At this time, the addition reaction between the carboxyl group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.
Among these, from the viewpoint of development stability of the photosensitive composition over time, the carboxyl group-containing resin includes a carboxyl group, an aromatic group that may contain a heterocyclic ring, and an ethylenically unsaturated bond in the side chain. The inclusion is preferred.

-Carboxyl group-
The carboxyl group can be produced by a normal radical polymerization method using at least one radical polymerizable compound having an acid group and, if necessary, at least one other radical polymerizable compound as a copolymerization component. Examples of the polymerization method include suspension polymerization method and solution polymerization method.
Examples of the acid group possessed by such a radical polymerizable compound 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 individually by 1 type and may use 2 or more types together.

The carboxyl group content in the carboxyl group-containing resin is preferably 1.0 to 4.0 meq / g, and more preferably 1.5 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.
Here, the carboxyl group content (meq / g) can be measured by neutralization titration using sodium hydroxide.

-Aromatic group which may contain a heterocycle-
Examples of the aromatic group that may contain the heterocycle (hereinafter also referred to as “aromatic group”) include, for example, a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a benzene ring. And those in which a 5-membered unsaturated ring forms 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, such as a triazine ring group. Among 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 aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, and the like, each of which may have a substituent, may be mentioned.

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

Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Specific examples of such substituents include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, and alkyldithio groups. , Aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyl Oxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group , Arylsulfoxy group, acylthio 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 ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N ' -Diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl -N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl- N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo Group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonato group) ), A dialkylphosphono group (—PO ₃ (alkyl) ₂ ) (hereinafter “alkyl” is an alkyl group) Means. ), A diarylphosphono group (—PO ₃ (aryl) ₂ ) (hereinafter “aryl” means an aryl group), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphone Group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl)) ) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group _(-OPO 3 H (alkyl)) and its conjugated base group (referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate base (aryl phosphite Hona preparative oxy Group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group as a substituent that the alkyl group may have include the aforementioned alkyl groups.

  Specific examples of the aryl group as the substituent which the alkyl group may have include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a chlorophenyl group, Methylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetyl Aminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatof Group, phosphono phenyl group, such as phosphate Hona preparative phenyl group.

  Specific examples of the alkenyl group as a substituent that the alkyl group may have include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group.

  Specific examples of the alkynyl group as a substituent that the alkyl group may have include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.

Examples of the acyl group (R ⁰¹ CO—) as a substituent that the alkyl group may have include those in which R ⁰¹ is any one of a hydrogen atom, the aforementioned alkyl group, and an aryl group. It is done.

  Specific examples of the heterocyclic group as a substituent that the alkyl group may have include a pyridyl group, a piperidinyl group, and the silyl group in the substituent includes a trimethylsilyl group.

Examples of the oxy group (R ⁰² O—) as a substituent that the alkyl group may have include those in which R ⁰² 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. Further, examples of the acyl group (R ⁰³ CO—) in the acyloxy group include those in which R ⁰³ 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 more preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, a phosphonatooxy group.

Examples of the sulfonyl group (R ⁰⁴ —SO ₂ —) as a substituent that the alkyl group may have include a group in which R ⁰⁴ is 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.

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

Examples of the carbonyl group (R ⁰⁵ —CO—) as a substituent that the alkyl group may have include those in which R ⁰⁵ 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.
The carbonyl group is preferably a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, or an N-arylcarbamoyl group. A group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable.
Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, aryloxycarbonyl 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 ⁰⁶ —SO—) as a substituent that the alkyl group may have include those in which R ⁰⁶ 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.
Specific examples of the substituted sulfinyl group include hexylsulfinyl group, benzylsulfinyl group, tolylsulfinyl group and the like.

The phosphono group as a substituent that the alkyl group may have means one in which one or two of the hydroxyl groups on the phosphono group are substituted with another organic oxo group. 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—) as a substituent that the alkyl group may have is the acid first of the phosphono group (—PO ₃ H ₂ ) as described above. It means a conjugated base anion group derived from dissociation or acid second dissociation. Usually, it is preferable to use it with a counter cation. As such a counter cation, generally known ones can be appropriately selected. For example, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).
The phosphonato group may be a conjugated base anion group 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)).

  Among these substituents that the alkyl group may have, a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N -Alkylcarbamoyl group, 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-aryls Famoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho A nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group and the like are preferable.

  Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkyl 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 N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxy Carbonylmethyl 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- (phosphonophene) 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.

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

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

Examples of the alkenyl group or alkynyl group as a substituent that the aromatic group may have include, for example, any one or two hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above. And a divalent or trivalent organic residue, for example, a straight-chain alkenyl group or alkynyl group having 1 to 12 carbon atoms, or a branched structure having 3 to 12 carbon atoms. Are preferably an alkenyl group or alkynyl group, a cyclic alkenyl group or alkynyl group having 5 to 10 carbon atoms.
Examples of the alkenyl group (—C (R ⁰⁷ ) ═C (R ⁰⁸ ) (R ⁰⁹ )) and the alkynyl group (—C≡C (R ⁰¹⁰ )) include, for example, R ⁰⁷ , R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ is a group composed of a monovalent nonmetallic atomic group.
Examples of R ⁰⁷ , R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.

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

Examples of the amino group (R ⁰¹¹ NH—, (R ⁰¹² ) (R ⁰¹³ ) N—) that may contain a substituent as the substituent that the aromatic group may have include, for example, R ⁰¹¹ , R ⁰¹² and R ⁰¹³ may be a group consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom. R ⁰¹² and R ⁰¹³ 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 03} acylamino group, N- alkylacylamino group, N- arylacylamino group definitive acyl group ^(R 03 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.

The method for introducing the aromatic group into the side chain is not particularly limited. For example, the polymer containing a carboxyl group in the side chain described above and one or more radically polymerizable compounds containing an aromatic group, As needed, it can manufacture by the normal radical polymerization method with 1 or more types of 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 either an organic group or a single bond. Ar represents an aromatic group that may include 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).
When the compound represented by the general formula (a-1) is polymerized, it becomes a polymer including a structural unit represented by the following general formula (a-3). Moreover, the compound represented by the said general formula (a-2) becomes a polymer containing the structural unit of the following general formula (a-4). Among these, the polymer containing the structural unit of the general formula (a-4) is preferable from the viewpoint of storage stability.

However, in the general formulas (a-3) and (a-4), R ₁ , R ₂ , R ₃ , L, and Ar have the same meanings as the general formulas (a-1) and (a-2). Represents.
In the general formulas (a-3) and (a-4), R ₁ and R ₂ are preferably hydrogen atoms, and R ₃ is preferably a methyl group, from the viewpoint of removability (developability) of the non-image area.
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 a non-image area.

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

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

  The content of the aromatic group that may contain a heterocycle in the carboxyl group-containing resin is not particularly limited, but when the total structural unit of the carboxyl group-containing resin is 100 mol%, the general formula (a-3) ) Is preferably contained in an amount of 20 mol% or more, more preferably 30 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 either of the following general formula (a-5)-(a-7) Is preferred.

In the general formula (a-5) ~ (a -7), R 1 ~R 11 independently represents a hydrogen atom, 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 alkyl group which may have a substituent 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, a hydrogen atom, an alkyl group which may have a substituent, and the like are 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), R _{4 to} R ₈ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, or a nitro group. , A cyano group, 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, substituted An alkylamino group which may have a 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.
Examples of the substituent that can be introduced include those listed in the general formula (a-5).

In the general formula (a-7), R ₉ is preferably, for example, a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group 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 ethylenically unsaturated bonds represented by the general formulas (a-5) to (a-7), the ethylenically unsaturated bond represented by the general formula (a-5) has high polymerization reactivity. Sensitivity is increased, which is more preferable.
Although there is no restriction | limiting in particular as content in the said carboxyl group containing resin of the said ethylenically unsaturated bond, 0.5-3.0 meq / g is preferable, 1.0-3.0 meq / g is more preferable, 1 0.5 to 2.8 meq / g is particularly preferable. When the content is less than 0.5 meq / g, the curing reaction amount is small, so the sensitivity may be low. When the content is more than 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

  The method for introducing the ethylenically unsaturated bond represented by the general formula (a-5) into the side chain is not particularly limited. For example, the polymer containing a carboxyl group in the side chain described above and the ethylenically unsaturated bond are not limited. It can be obtained by addition reaction with a compound having a saturated bond and an epoxy group.

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 any one of the following general formulas (a-8) and (a-9) Is preferred.
However, in said general formula (a-8), R < ₁ > represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
In the general formula (a-9), _{R 2} represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Of the compound represented by the general formula (a-8) and the compound represented by the general formula (a-9), the compound represented by the general formula (a-8) is preferable, and the general formula (a- In 8), L ₁ is more preferably an alkylene group having 1 to 4 carbon atoms.

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

  Specific 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, and triphenyl. The reaction can be performed by reacting phosphine or the like in an organic solvent at a reaction temperature of 50 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 structural unit represented by the following general formula (a-10), represented by general formula (a-11) Structural units and structural units synthesized by mixing these are preferred.
However, in said general formula (a-10) and (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 structural unit represented by the general formula (a-10) to the structural unit represented by the general formula (a-11) is not particularly limited, but the total structural unit of the carboxyl group-containing resin is 100 mol%. In this case, 20 mol% or more is preferable, 20 to 50 mol% is more preferable, and 25 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.

The carboxyl group-containing resin is preferably copolymerized with another radical polymerizable compound in addition to the above-described radical polymerizable compound for the purpose of improving various performances such as image strength.
Examples of the other radical polymerizable compound include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.

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

Examples of the styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, and trifluoromethyl. 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-. Examples thereof include trifluoromethyl styrene and 4-fluoro-3-trifluoromethyl styrene.
These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

  The solvent used for synthesizing the carboxyl group-containing resin 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 Examples include sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These may be used alone or in combination of two or more.

  The carboxyl group-containing resin may contain an unreacted monomer. In this case, the content of the monomer in the carboxyl group-containing resin is preferably 15% by mass or less.

The said carboxyl group containing resin may be used individually by 1 type, and may mix and use 2 or more types.
As content of the said carboxyl group containing resin, 5 mass%-80 mass% are preferable with respect to the total solid in a photosensitive composition, and 10 mass%-70 mass% are more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

<Polymerizable compound>
The polymerizable compound contains at least one selected from methacrylate compounds. The polymerizable compound may be either low molecular weight (monomer) or high molecular weight (oligomer), but preferably has a low molecular weight. The methacrylate compound may be monofunctional or polyfunctional.

There is no restriction | limiting in particular as said methacrylate compound, According to the objective, it can select suitably, For example, a trimethylol propane trimethacrylate (NK ester TMPT, Shin-Nakamura Chemical Co., Ltd.), neopentyl glycol dimethacrylate (NK ester NPG). , Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (NK ester DCP, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol methacrylate (NK ester HD-N, Shin-Nakamura Chemical Co., Ltd.) , Diethylene glycol dimethacrylate (NK ester 2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (NK ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polypropylene glycol # 400 dimethacrylate (NK ester) PG, Shin-Nakamura Chemical Co., Ltd.), and the like. These may be used individually by 1 type and may use 2 or more types together.
5 mass%-50 mass% are preferable with respect to the solid component of the said photosensitive composition, and, as for content of the methacrylate compound as the said photopolymerizable compound, 10 mass%-35 mass% are more preferable. When the content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and when it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. It is not preferable.

As said polymeric compound, other polymeric compounds may be included as needed besides the said methacrylate compound.
The other polymerizable compound preferably has at least one ethylenic double bond.
Examples of the monomer having one ethylenic double bond include alkyl acrylate, hydroxyalkyl acrylate, amino acrylate; alkyl methacrylate, hydroxyalkyl methacrylate, amino methacrylate (for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2 -Ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, etc.); vinyl esters such as silicone acrylate, acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl acetate; isobutyl Vinyl ethers such as vinyl ether; styrene, alkyl-styrene, halo-styrene, N-vinylpyrrolidone, salt Vinyl, vinylidene chloride, and the like.

  Examples of the monomer having two or more ethylenic double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, neoprene glycol diacrylate, hexamethylene glycol diacrylate, diacrylate of bisphenol A, 4,4 '-Bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate (DPHA), vinyl acrylate, divinylbenzene, divinyl succinate, phthalate Examples include diallyl acid, triallyl phosphate, triallyl isocyanurate, and tris (2-acryloylethyl) isocyanurate.

Examples of the oligomer having at least one ethylenic double bond include acrylated epoxy resins; acrylates, polyesters having vinyl ether groups, polyesters having epoxy groups; polyurethanes, polyethers, and the like. Also included are unsaturated polyester resins produced from maleic acid, phthalic acid, and one or more diols and having a molecular weight of 500 to 3,000. Furthermore, oligomers of vinyl ether; maleic acid-terminated oligomers having a main chain of polyester, polyurethane, polyether, polyvinyl ether and epoxy; These may be used individually by 1 type and may use 2 or more types together.
Among these, a combination of an oligomer having a vinyl ether group and a polymer described in WO90 / 01512, a copolymer of vinyl ether and a monomer functionalized with maleic acid, and the like are preferable. . The oligomer is sometimes referred to as a prepolymer.
Among these, an ester of an ethylenically unsaturated carboxylic acid and a polyol or polyepoxide, a polymer having an ethylenically unsaturated group in the main chain or in a side chain group (for example, unsaturated polyester, polyamide, polyurethane, or these A copolymer, a copolymer having a (meth) acryl group in the side chain group, and the like are particularly preferable.

  Examples of the ethylenically unsaturated carboxylic acid include unsaturated fatty acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, linolenic acid, and oleic acid. Among these, acrylic acid and methacrylic acid are particularly preferable.

<Thermosetting compound>
The thermosetting compound (thermal crosslinking agent) is not particularly limited as long as it is a compound that undergoes a crosslinking reaction by heating, and can be appropriately selected according to the purpose, but is formed using the photosensitive composition. In order to improve the film strength of the photosensitive layer after curing, for example, an epoxy compound (oxirane compound) having at least two epoxy groups (oxirane ring) in one molecule within a range that does not adversely affect developability and the like An oxetane compound having at least two oxetane rings in one molecule can be used. Among these, an epoxy compound having at least two epoxy groups in one molecule is particularly preferable.

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

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

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

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

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

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

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

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

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

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

<Photopolymerization initiator>
The photosensitive composition of the present invention contains an oxime compound as a photopolymerization initiator and, if necessary, a conventionally known photopolymerization initiator other than the oxime compound.

-Oxime compounds-
The oxime compound used in the present invention is represented by the following general formula (A-1).
However, in the general formula (A-1), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group.
There is no restriction | limiting in particular as said acyl group, According to the objective, it can select suitably, For example, an aliphatic acyl group, an aromatic acyl group, a heteroaromatic acyl group, etc. are mentioned.
There is no restriction | limiting in particular as the total carbon number of the said acyl group, Although it can select suitably according to the objective, 2-30 are preferable, 2-20 are more preferable, and 2-16 are still more preferable.
The acyl group may be further substituted with a substituent, and examples of the substituent include an alkyloxy group, an aryloxy group, and a halogen atom.
The acyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group , Decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl group, phenoxyacetyl group, 2ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group Group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group, acryloyl group, and the like.

The alkyloxycarbonyl group is not particularly limited and may be appropriately selected depending on the purpose.
There is no restriction | limiting in particular as total carbon number of the said alkyloxycarbonyl group, Although it can select suitably according to the objective, 2-30 are preferable, 2-20 are more preferable, and 2-16 are still more preferable.
The alkyloxycarbonyl group may be further substituted with a substituent, and examples of the substituent include an alkyloxy group and a halogen atom.
Specific examples of the alkyloxycarbonyl group are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyl Examples thereof include an oxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, and an ethoxyethoxycarbonyl group.

The aryloxycarbonyl group is not particularly limited and may be appropriately selected depending on the purpose.
There is no restriction | limiting in particular as total carbon number of the said aryloxycarbonyl group, Although it can select suitably according to the objective, 7-30 are preferable, 7-20 are more preferable, and 7-16 are still more preferable.
The aryloxycarbonyl group may be further substituted with a substituent, and examples of the substituent include an alkyloxy group and a halogen atom.
Specific examples of the aryloxycarbonyl group are not particularly limited and may be appropriately selected depending on the purpose. For example, phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5- Examples thereof include a diethoxyphenoxycarbonyl group, a parachlorophenoxycarbonyl group, a paranitrophenoxycarbonyl group, a paracyanophenoxycarbonyl group, and the like.

In the general formula (A-1), R ² represents a hydrogen atom, an alkyl group, or a cyano group.
There is no restriction | limiting in particular as said alkyl group, According to the objective, it can select suitably, For example, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a tertiary octyl group etc. are mentioned.

In General Formula (A-1), Ar represents either an aromatic ring or a heteroaromatic ring.
There is no restriction | limiting in particular as said aromatic ring, According to the objective, it can select suitably, For example, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned.
The heteroaromatic ring is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a pyrrole ring, an indole ring, a benzofuran ring, and a benzothiophene ring.

n represents an integer of 0 (zero) or 1, and Ar and R ² may be connected to each other to form a ring.

Among the oxime compounds represented by the general formula (A-1), a compound represented by the following general formula (A-2) is preferable in terms of excellent sensitivity.
However, in the general formula (A-2), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, which may be further substituted with a substituent. R ³ represents any one of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, a nitro group, and an acylamino group. m represents an integer of 0 or more, and when m represents an integer of 2 or more, the R ^{3 s} may be the same as or different from each other, and are connected to each other to form a ring. Also good. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of a 5-membered ring, a 6-membered ring, and a 7-membered ring, and these may be further substituted with a substituent. X represents either an oxygen atom or a sulfur atom.
The details of R ¹ and Ar are the same as those in the general formula (A-1).
There is no restriction | limiting in particular as said acyl group, According to the objective, it can select suitably, For example, an aliphatic acyl group, an aromatic acyl group, a heteroaromatic acyl group, etc. are mentioned.
There is no restriction | limiting in particular as the total carbon number of the said acyl group, Although it can select suitably according to the objective, 2-30 are preferable, 2-20 are more preferable, and 2-16 are still more preferable.
The acyl group may be further substituted with a substituent, and examples of the substituent include an alkyloxy group, an aryloxy group, and a halogen atom.
Specific examples of the acyl group are not particularly limited and may be appropriately selected depending on the purpose. For example, acetyl group, 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, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, Examples thereof include 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group, acryloyl group, and the like.

The alkyloxycarbonyl group is not particularly limited and may be appropriately selected depending on the purpose.
There is no restriction | limiting in particular as total carbon number of the said alkyloxycarbonyl group, Although it can select suitably according to the objective, 2-30 are preferable, 2-20 are more preferable, and 2-16 are still more preferable.
The alkyloxycarbonyl group may be further substituted with a substituent, and examples of the substituent include an alkoxy group and a halogen atom.
Specific examples of the alkyloxycarbonyl group are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyl Examples thereof include an oxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, and an ethoxyethoxycarbonyl group.

The aryloxycarbonyl group is not particularly limited and may be appropriately selected depending on the purpose.
There is no restriction | limiting in particular as total carbon number of the said aryloxycarbonyl group, Although it can select suitably according to the objective, 7-30 are preferable, 7-20 are more preferable, and 7-16 are still more preferable.
The aryloxycarbonyl group may be further substituted with a substituent, and examples of the substituent include an alkoxy group and a halogen atom.
Specific examples of the aryloxycarbonyl group are not particularly limited and may be appropriately selected depending on the purpose. For example, phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5- Examples thereof include a diethoxyphenoxycarbonyl group, a parachlorophenoxycarbonyl group, a paranitrophenoxycarbonyl group, a paracyanophenoxycarbonyl group, and the like.

In the general formula (A-2), each R ³ independently represents an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, a nitro group, or an acylamino group. Represents either.
There is no restriction | limiting in particular as said alkyl group, According to the objective, it can select suitably, For example, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a tertiary octyl group etc. are mentioned.
There is no restriction | limiting in particular as said alkyloxy group, According to the objective, it can select suitably, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned.
There is no restriction | limiting in particular as said aryloxy group, According to the objective, it can select suitably, For example, a benzyloxy group, a phenoxy group, 4-chlorophenoxy group, 4-methylphenoxy group, etc. are mentioned.
The alkylthio group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methylthio group, a butylthio group, an octylthio group, and a dodecylthio group.
The aryllthio group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a benzylthio group, a phenylthio group, and a 4-methylphenylthio group.
There is no restriction | limiting in particular as said halogen atom, According to the objective, it can select suitably, For example, a chloro group, a bromo group, an iodo group etc. are mentioned.
The alkyloxycarbonyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
The acylamino group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methylcarbonylamino group, an ethylcarbonylamino group, and a benzenecarbonylamino group.

In the general formula (A-2), m represents any integer of 0 or more, and can be appropriately selected depending on the structure of Ar.
When m represents any integer of 2 or more, the R ^{3 s} may be the same as or different from each other, and may be connected to each other to form a ring. When R ³ is connected to each other to form a ring, specific examples of the oxime compound represented by the general formula (A-2) include compounds represented by the following structural formulas. The aromatic ring represented by Ar including the formed ring structure portion may further have a substituent, and the substituent is the same as R ³ described above. X represents any of —CH ₂ —, an oxygen atom, and a sulfur atom.
In the structural formula, Y and Z each represent CH ₂ , —O—, —S—, and —NR—, and R represents a hydrogen atom or an alkyl group.

In General Formula (A-2), Ar represents either an aromatic ring or a heteroaromatic ring.
There is no restriction | limiting in particular as said aromatic ring, According to the objective, it can select suitably, For example, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned.
The heteroaromatic ring is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a pyrrole ring, an indole ring, a benzofuran ring, and a benzothiophene ring.

In the general formula (A-2), A represents a 5-membered ring, a 6-membered ring, or a 7-membered ring.
The 5-membered ring, the 6-membered ring, or the 7-membered ring is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably formed by a ring-forming substituent. Examples of the ring-forming substituent include alkylene, alkenylene, alkynylene and the like. These ring-forming substituents may be used alone or in combination of two or more, and may have a hetero atom such as an oxygen atom or a sulfur atom.
The 5-membered ring, the 6-membered ring, and the 7-membered ring may be further substituted with a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkyloxy group, an aryloxy group, A halogen atom, and the like.
Among these, the A is preferably any of the 5-membered ring and the 6-membered ring from the viewpoint of excellent sensitivity.

Among the oxime compounds represented by the general formula (A-2), a compound represented by any one of the following general formulas (A-3) and (A-4) is more preferable in terms of excellent sensitivity.

However, in the general formula (A-3) and ^{(A-4), R} 4 represents any of an alkyl group, and an alkyloxy group.
There is no restriction | limiting in particular as said alkyl group, According to the objective, it can select suitably.
The alkyl group may be further substituted with a substituent, and examples of the substituent include an alkyloxy group and a halogen atom.
Specific examples of the alkyl group are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Among these, a methyl group, an ethyl group, and a propyl group are preferable in terms of excellent sensitivity.

There is no restriction | limiting in particular as said alkyloxy group, According to the objective, it can select suitably.
The alkyloxy group may be further substituted with a substituent, and examples of the substituent include an alkyloxy group and a halogen atom.
Specific examples of the alkyloxy group are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

In the general formulas (A-3) and (A-4), each R ⁵ independently represents an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, or nitro. Represents either a group or an acylamino group.
The details of the alkyl group, the alkyloxy group, the aryloxy group, the alkylthio group, the arylthio group, the halogen atom, the alkyloxycarbonyl group, the nitro group, and the acylamino group are as described in the general formula ( In A-1), the alkyl group represented by R ² , the alkyloxy group, the aryloxy group, the alkylthio group, the arylthio group, the halogen atom, the alkyloxycarbonyl group, the nitro group, and the The same as the details of the acylamino group.
Among these, examples of the R ^5, from the viewpoint of excellent absorption efficiency, the alkyl group, the arylthio group, the halogen atom is preferable.

In said general formula (A-3) and (A-4), l represents the integer in any one of 0-6. Among these, it is preferable that it is an integer in any one of 0-2 at the point of synthetic suitability.
When l represents any integer of 2 or more, the R ^{5 s} may be the same as or different from each other, and may be connected to each other to form a ring.

In the general formulas (A-3) and (A-4), A represents either a 5-membered ring or a 6-membered ring, and these may be further substituted with a substituent.
The details of the 5-membered ring and the 6-membered ring are the same as the details of the 5-membered ring and the 6-membered ring represented by A in the general formula (A-2).
Among these, as said A, it is preferable that it is a 5-membered ring at the point which is excellent in a sensitivity.

In the general formulas (A-3) and (A-4), X represents —CH ₂ —, an oxygen atom, or a sulfur atom.

Specific examples of the oxime compound represented by at least one of the general formulas (A-1), (A-2), (A-3), and (A-4) include the following structural formulas (1) to ( 26), but the present invention is not limited to these.
However, in said structural formula (1)-(26), Me represents a methyl group and Ph represents a phenyl group. The structural formulas (24) to (26) are IRGACURE OXE01, IRGACURE OXE02, and CGI325 manufactured by CIBA.

-Conventionally known photopolymerization initiator-
Examples of the photopolymerization initiator include camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, such as α-hydroxycycloalkyl phenyl ketone or 2-hydroxy-2-methyl-1-phenylpropanone, dialkyloxyacetophenone. , Α-hydroxy- or α-amino-acetophenone, such as (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4-aroyl- 1,3-dioxolane, benzoin alkyl ethers and benzyl ketals (eg, dimethylbenzyl ketal), phenylglyoxal esters and derivatives thereof, dimeric phenylglyoxal esters, di- Cetyl, perester (for example, benzophenone tetracarboxylic acid perester described in EP 126,541), monoacylphosphine oxide (for example, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, bis Acylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxide), halomethyltriazine (for example, 2- [2- (4-methoxyphenyl) vinyl] -4,6-bistrichloromethyl [1 , 3,5] Tria 2- (4-methoxyphenyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2- (3,4-dimethoxyphenyl) -4,6-bistrichloromethyl [1,3, 5] Triazine, 2-methyl-4,6-bistrichloromethyl [1,3,5] triazine, 2- (4-N, N-di (ethoxycarbonylmethylaminophenyl) -4,6-bis (trichloromethyl) ) [1,3,5] triazine, 2- (4-methoxynaphthyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2- (1,3-benzodioxol-5-yl) -4 , 6-bistrichloromethyl [1,3,5] triazine, 2- [2- [4- (pentyloxy) phenyl] ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2 -(3-Methyl-2-furanyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (5-methyl-2-furanyl) ethenyl] -4,6- Bistrichloromethyl [1,3,5] triazine, 2- [2- (2,4-dimethoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- ( 2-methoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (4-isopropyloxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3 , 5] triazine, 2- [2- (3-chloro-4-methoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2-bromo-4-N, N-di (et Cycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2-chloro-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6 -Bistrichloromethyl [1,3,5] triazine, 2- [3-bromo-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] Triazine, 2- [3-chloro-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine); Buhr, R.A. Dammel and C.D. Lindley, Polym. Mater. Sci. Eng. 61,269 (1989), other halomethyltriazines described in European Patent No. 0222788, etc .; described in US Pat. No. 4,371,606, US Pat. No. 4,371,607, etc. A halomethyloxazole photoinitiator; A. 1,2-disulfones as described in Bartmann, Synthesis 5,490 (1993), etc .; hexaarylbisimidazoles, and hexaarylbisimidazole / co-initiator systems (eg, 2-mercaptobenzthiazole, ferrocenium compounds); titanocene (eg, , Bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyrylphenyl) titanium combined with o-chlorohexaphenyl-bisimidazole), and the like.

Examples of the conventionally known photopolymerization initiator further include a cationic photoinitiator and a peroxide compound (for example, benzoyl peroxide, U.S. Pat. No. 4,950,581, column 19, lines 17-25). And the like, U.S. Pat. No. 4,950,581, column 18, line 60 to column 19, line 10, aromatic sulfonium, phosphonium or iodonium salts, cyclopentadienyl- Arene-iron (II) complex salts (for example, (η ⁶ -isopropylbenzene) (η ⁵ -cyclopentadienyl) -iron (II) hexafluorophosphate), oxime sulfone described in European Patent No. 780,729 Acid esters, and the like. Examples thereof include pyridinium and (iso) quinolinium salts described in European Patent Nos. 497,531 and 441,232.

  The content of the photopolymerization initiator is preferably 0.01% by mass to 25% by mass, more preferably 0.01% by mass to 10% by mass with respect to the solid content of the photosensitive composition. 01 mass%-5 mass% are still more preferable. The said content means the sum total of all these photoinitiators, when using together a conventionally well-known photoinitiator.

<Sensitizer>
The sensitizer is represented by the following general formula (B-1).
However, in said general formula (B-1), R < ⁶ > and R < ⁷ > represents either an alkyl group, an aryl group, and an alkenyl group each independently.
There is no restriction | limiting in particular as said alkyl group, Although it can select suitably according to the objective, For example, C1-C10 alkyl groups, such as a methyl group and an ethyl group, etc. are preferable.
The alkyl group may be further substituted with a substituent. Examples of the substituent include a hydroxy group, a cyano group, an alkyloxy group (for example, methoxy group, ethoxy group, etc.), and a halogen atom (for example, Chloro group, bromo group, etc.), carboxyl group, carboalkyloxy group, sulfonyl group, phenyl group, aryl group (eg, p-nitrophenyl group), vinyl group, methylvinyl group, cinnamyl group, and the like. .

The aryl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a phenyl group, a naphthyl group, and the like are preferable.
The aryl group may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, a hydroxy group, a cyano group, and an alkyloxy group having 1 to 10 carbon atoms (for example, Methoxy group, ethoxy group, etc.), halogen atom (for example, chloro group, bromo group, etc.), carboxyl group, carboalkyloxy group, sulfonyl group, and the like.

There is no restriction | limiting in particular as said alkenyl group, Although it can select suitably according to the objective, For example, a vinyl group etc. are preferable.
The alkenyl group may be further substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 18 carbon atoms. May be further substituted with an alkyl group having 1 to 10 carbon atoms such as a methyl group.

R ⁶ and R ⁷ may form a ring made of a nonmetallic element together with the sulfur atom to which each is bonded. The ring is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a 5-membered ring, a 6-membered ring, a 5-membered ring condensed with an aromatic ring, or an aromatic ring condensed A 6-membered ring.
The ring may be further substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group, a substituted alkyl group, a substituted aryl group, a hydroxy group, a cyano group, an alkyloxy group, a halogen atom, A carboxyl group, a carboalkyloxy group, a sulfonyl group, etc. are mentioned.

  In the general formula (B-1), p represents 0 or 1.

In the general formula (B-1), G ¹ and G ² are each independently a hydrogen atom, cyano group, carbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkylthio group, arylthio group, alkyl It represents any of a sulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group. However, either G ¹ or G ^{2 represents} any one of a carbonyl group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group. Represent.
The alkyl group in the alkyloxycarbonyl group, the alkylthio group, the alkylsulfonyl group, and the fluoroalkylsulfonyl group is not particularly limited and may be appropriately selected depending on the intended purpose. 10 alkyl groups and the like are preferable.
There is no restriction | limiting in particular as an aryl group in the said aryloxycarbonyl group, the said arylthio group, and the said arylsulfonyl group, Although it can select suitably according to the objective, For example, a phenyl group, a naphthyl group, etc. are preferable.
Examples of the acyl group (—COR) include those in which R is any one of an alkyl group, an aryl group, and an alkylaryl group. There is no restriction | limiting in particular as an alkyl group in this aryl group and this alkylaryl group, Although it can select suitably according to the objective, For example, a C1-C10 alkyl group etc. are preferable. There is no restriction | limiting in particular as an aryl group, Although it can select suitably according to the objective, For example, a phenyl group, a naphthyl group, etc. are preferable.
The alkyl group and aryl group may be further substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, a hydroxy group, a cyano group, and an alkyl having 1 to 10 carbon atoms. Examples thereof include an oxy group, a halogen atom, a carboxyl group, a carboalkyloxy group, a sulfonyl group, a sulfoalkyloxy group, an aryl group having 6 to 18 carbon atoms, an acyl group, a vinyl group, and a cinnamyl group.

Further, G ¹ and G ² may form a ring used as an acidic nucleus in a merocyanine dye composed of a non-metal atom together with the carbon atom to which each is bonded. There is no restriction | limiting in particular as a ring used as an acidic nucleus with this merocyanine pigment | dye, According to the objective, it can select suitably, For example, the following (a)-(t) etc. are mentioned.
(A) 1,3-dicarbonyl nucleus (for example, 1,3-indandione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione ,Such)
(B) a pyrazolinone nucleus [for example, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3-methyl-2- Pyrazolin-5-one, etc.]
(C) isoxazolinone nucleus (for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc.)
(D) Oxindole nucleus (eg 1-alkyl-2,3-dihydro-2-oxindole)
(E) 2,4,6-triketohexahydropyrimidine nucleus [for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl; 1,3-dialkyl compounds such as 1,3-diethyl and 1,3-dibutyl; 1,3-diphenyl, 1,3 -1,3-diaryl compounds such as di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl); 1-alkyl-3-aryl compounds such as 1-ethyl-3-phenyl, etc. Can be]
(F) 2-thio-2,4-thiazolidinedione nucleus (for example, rhodanine and derivatives thereof) Examples of the derivative include 3-alkylrhodanine such as 3-ethylrhodanine and 3-allylrhodanine; -3-aryl rhodanine such as phenyl sudanine, etc.)
(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione) nucleus (for example, 2-ethyl-2-thio-2,4-oxazolidinedione, etc.) )
(H) thianaphthenone nucleus [eg, 3 (2H) -thianaphthenone, 3 (2H) -thianaphthenone-1,1-dioxide, etc.]
(I) 2-thio-2,5-thiazolidinedione nucleus (for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.)
(J) 2,4-thiazolidinedione nucleus (for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.)
(K) Thiazolidinone nucleus (for example, 4-thiazolidinone, 3-ethyl-4-thiazolidinone, etc.)
(L) 4-thiazolinone nucleus (for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one, etc.)
(M) 2-Imino-2-oxozoline-4-one (coagulant hydantoin) nucleus (n) 2,4-imidazolidinedione (hydantoin) nucleus (for example, 2,4-imidazolidinedione, 3-ethyl-2, 4-imidazolidinedione, etc.)
(O) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus (eg, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidine) Dione etc.)
(P) 2-imidazolin-5-one nucleus (for example, 2-n-propyl-mercapto-2-imidazolin-5-one)
(Q) Furan-5-one nucleus (r) 4-hydroxy-2 (1H) -quinolinone nucleus or 4-hydroxy-2 (1H) -pyridinone nucleus [for example, N-methyl-4-hydroxy-2 (1H)- Quinolinone, Nn-butyl-4-hydroxy-2 (1H) -quinolinone, N-methyl-4-hydroxy-2 (1H) -pyridinone, etc.]
(S) a 4-hydroxy-2H-pyran-2-one nucleus optionally substituted with a substituent or a thioindoxyl nucleus optionally substituted with a 4-hydroxycoumarin nucleus (t) substituent (for example, 5 -Methylthioindoxyl etc.)

Among the sensitizers represented by the general formula (B-1), a compound represented by the following general formula (B-2) is preferable from the viewpoint of curing sensitivity.
However, in said general formula (B-2), R < ⁸ > and R < ⁹ > represents either a hydrogen atom, an alkyl group, an aryl group, an acyl group, and a halogen atom each independently. R ⁸ and R ⁹ may be bonded to each other to form an aromatic ring, and may further have at least one of an alkyl group, an alkyloxy group, and a halogen atom on the aromatic ring. Good.

In the general formula (B-2), R ¹⁰ and R ¹¹ each independently represent any of a hydrogen atom, an alkyl group, and an aryl group. Y represents an oxygen atom or a sulfur atom.
There is no restriction | limiting in particular as said alkyl group, Although it can select suitably according to the objective, For example, an ethyl group, a butyl group, etc. are preferable.
There is no restriction | limiting in particular as said aryl group, Although it can select suitably according to the objective, For example, a phenyl group etc. are preferable.

Specific examples of the sensitizer represented by at least one of the general formulas (B-1) and (B-2) include the following Exemplified Compound Nos. 1-No. However, the present invention is not limited to these examples.
However, in the structural formula, t-Bu represents a tert-butyl group. Ph represents a phenyl group. Et represents an ethyl group.

  There is no restriction | limiting in particular as content of the said sensitizer, Although it can select suitably according to the objective, 0.01 mass%-50 mass% are preferable with respect to the said polymeric compound, 0.1 The mass% to 20 mass% is more preferable.

<Inorganic filler and organic filler>
The inorganic 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 Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle size of the inorganic filler is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic filler, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned.
Further, silica having an average particle diameter of 0.01 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  As content of at least any one of the said inorganic filler and an organic filler, 1-60 mass% is preferable with respect to the total solid of the said photosensitive composition. When the content is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced. When the content exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

<Other ingredients>
Examples of the other components include epoxy curing accelerators, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and further adhesion promoters to the substrate surface and others. Auxiliary agents (for example, conductive particles, fillers, 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 properties of the intended photosensitive film can be adjusted.

-Epoxy curing accelerator-
In the photosensitive composition of the present invention, a known epoxy curing accelerator can be used to accelerate thermal curing of the thermosetting compound (thermal crosslinking agent). Examples of the epoxy curing accelerator include amine compounds (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 derivative bicyclic amidine compounds and salts thereof (eg , Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl)- -Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino- 6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric 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 curing accelerator is not particularly limited as long as it can accelerate the reaction between the thermal crosslinking agent or these and a carboxyl group, and other compounds capable of promoting thermal curing other than those described above. May be used.
As for solid content in the said photosensitive composition solid content of the said epoxy hardening accelerator, 0.01 mass%-15 mass% are preferable.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive composition.
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, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

As content of the said thermal polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound in the said photosensitive composition, 0.005-2 mass% is more preferable, 0.01- 1% by mass is particularly preferred.
When the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.

-Plasticizer-
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer formed by the photosensitive composition.
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 Dioctyl acid, etc .; glycols such as polyethylene glycol and polypropylene glycol are listed.

  As content of the said plasticizer, 0.1 mass%-50 mass% are preferable with respect to the total solid of the said photosensitive composition, 0.5 mass%-40 mass% are more preferable, 1 mass% -30 mass% is still more preferable.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. 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 content of the color pigment can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer at the time of forming a permanent pattern, and varies depending on the type of the color pigment. 0.01-10 mass% is preferable with respect to the total solid of an adhesive composition, and 0.05-5 mass% is more preferable.

-Adhesion promoter-
In order to improve the adhesion between the layers, or the adhesion between the photosensitive layer composed of the photosensitive composition and the photosensitive film using the photosensitive composition, the layers are known. A so-called adhesion promoter can be used.

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

  The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass with respect to the total solid content of the photosensitive composition. 1% by mass to 5% by mass is particularly preferable.

  The photosensitive composition of the present invention is excellent in sensitivity, resolution, and storage stability, and can efficiently form a high-definition permanent pattern. For this reason, it can be widely used for forming permanent patterns such as printed wiring boards, display members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for forming.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the photosensitive composition of the present invention formed on the support, and if necessary, such as a thermoplastic resin layer. It is preferable to have other layers.

<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 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 still more 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.

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention.
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 0.1 to 200 mJ / cm ² . Preferably, it is 0.2 to 100 mJ / cm ² , more preferably 0.5 to 50 mJ / cm ² , and particularly preferably 1 to 30 mJ / cm ² .
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 200 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

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

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

<Protective film>
The photosensitive film may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective film, 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 still more preferable.
Examples of the combination of the support and the protective film (support / protective film) 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 film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
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 film may be surface-treated in order to adjust the adhesion between the protective film 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 film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying it at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 ° C to 120 ° C.

<Other layers>
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen 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. Moreover, you may have a protective film on the said photosensitive layer.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or lower, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less, which are soluble in an alkaline solution. In addition, even in an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance so that a substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  Further, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. By setting such an interlayer adhesive force, only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. can do. In addition, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl Examples thereof include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. A copolymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and may be appropriately selected depending on the intended purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. With such an interlayer adhesive strength, the support and the cushion layer are peeled off from the photosensitive film, and after the photosensitive layer is exposed, the photosensitive layer can be developed using an alkaline developer. . Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer are peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer. .

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

The ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 60% by mass to 90% by mass, More preferably, 80% by mass is more preferable, and 65% by mass to 80% by mass is particularly preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. Production of the photosensitive film may be difficult.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5 micrometers-50 micrometers are preferable, 10 micrometers-50 micrometers are more preferable, and 15 micrometers-40 micrometers are especially preferable.
If the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Such a problem may occur.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed with polyvinyl alcohol as a main component, and preferably has a thickness of about 0.5 μm to 5 μm.

[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.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include spraying, roll coating, spin coating, slit coating, and extrusion coating. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
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.

The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape.
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. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

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

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

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, at least in the photosensitive film of the present invention. Examples of the method include transferring and laminating the photosensitive layer while performing 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 a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  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 film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton KK, VP130) , Hitachi Chemical Co., Ltd., HLM-V570).

  Since the photosensitive film and the photosensitive laminate of the present invention use the photosensitive composition of the present invention, the photosensitive film and the photosensitive laminate have high sensitivity and high resolution, sensitivity over time, film curability, and thermal shock resistance. Good, high-definition permanent patterns can be efficiently formed, for various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, color filters, pillar materials, rib materials, spacers, It can be suitably used for the production of liquid crystal structural members such as partition walls, pattern formation for holograms, micromachines, proofs, and the like, and in particular, it can be suitably used for permanent pattern formation on printed circuit boards.

  In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, the high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

(Pattern forming apparatus and permanent pattern forming method)
The pattern forming apparatus of the present invention includes the photosensitive layer and includes at least light irradiation means and light modulation means.

The permanent pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer of this invention. The photosensitive layer and substrate material of the present invention 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 depending on 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 halogen lamps and copiers, 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 sealed in a quartz glass tube or the like, and has a higher vapor pressure and higher 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 higher coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in a material having an inversion distribution, are preferably used. Can be mentioned.
Examples of the excitation medium for the laser light include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as solid laser, liquid laser, gas laser, and semiconductor laser can be used.
Specifically, examples of the gas laser include an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), and a He—Cd laser (325 nm), and examples of the solid laser include a YAG laser and a YVO ₄ laser (1, 064 nm), YAG laser or YVO ₄ laser, 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 type wavelength conversion element and an AlGaInP or AlGaAs semiconductor (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among these, a suitable laser beam 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; Spatial Light Modulator), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect, Examples thereof include a liquid crystal optical shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. In this state, no light is exposed between the light spots. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By using such exposure heads having the DMD side by side, it is possible to deal with substrates of various widths.
In the DMD, the luminance 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, described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet). An example in which a part of the image of the lower 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. Exposure with DMD described in JP-A-2004-56080 An exposure apparatus provided with a polygon mirror described in JP-T-2002-523905, an exposure apparatus provided with a polygon mirror described in JP-A-2001-255661, DMD and LD described in JP-A-2003-50469 The exposure amount is changed depending on the combination of multiple exposures and the portion of the substrate described in Japanese Patent Application Laid-Open No. 2003-156853 Examples of optical methods, etc. Examples of an exposure method for performing a positional deviation adjustment described in JP 2005-43576 and the like.

-Light irradiation means-
The light irradiation means, that is, the light irradiation method is not particularly limited, and the above-described exposure light source can be appropriately selected according to the purpose. Two or more light beams from these light sources are combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

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

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition, the Gaussian beam 1 / e ² value is preferably 5 μm to 30 μm, 7 μm to 20 μm is more preferable.
In the present invention, it is preferable to spatially modulate laser light 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 modulating unit and the light irradiating unit are described in JP-A-2005-222039, JP-A-2005-258431, JP-A-2006-30966, and the like. However, the exposure apparatus in the present invention 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, weakly 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.

The pH of the weak alkaline aqueous solution is, for example, preferably 8-12, more preferably 9-11. 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 25 ° C. to 40 ° C., for example.

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

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

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

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

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

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

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Synthesis Example 1)
-Synthesis of polymer compound 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. A 159 g solution of 1-methoxy-2-propanol in which 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.) were 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 into a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added, stirred and dissolved. 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. 1-Methoxy-2-propanol was added to prepare a solution of polymer compound 1 represented by the following structural formula having a solid content of 30% by mass.
It was 15,000 as a result of measuring the mass mean molecular weight of the obtained high molecular compound 1 by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.
Moreover, the acid value per solid content was 2.2 meq / g from the titration using sodium hydroxide.
Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.
<Polymer Compound 1>
However, in the polymer compound 1, * 1 represents a mixture of the structure represented by the following structural formula (a) and the structure represented by (b) (mixing ratio is unknown).

Example 1
<Preparation of photosensitive composition>
-Preparation of dispersion-
The dispersion was prepared by previously mixing the following components and then dispersing the mixture for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm using a Motor Mill M-200 (manufactured by Eiger).
Silica (manufactured by Admatechs Co., Ltd., Admafine SO-C2) 22 parts by mass Thermosetting accelerator (dicyandiamide) 0.26 parts by mass HELIOGEN BLUE D7086 (manufactured by BASF) 0 .40 parts by mass-PALIOTOL YELLOW D0960 (manufactured by BASF) ... 0.11 parts by mass-Polymer compound 1 of Synthesis Example 1 (solid content of 45 mass% in 1-methoxy-2-propanol solution)- 35 parts by mass n-propyl acetate 43 parts by mass

Next, each of the following components was mixed with 38 parts by mass of the dispersion (after filtration) to prepare a photosensitive composition solution.
[Each component of the photosensitive composition solution]
Polymer compound 1 of Synthesis Example 1 (solid content of 45% by mass in 1-methoxy-2-propanol solution) 40 parts by mass Polymerizable compound 1 (dipentaerythritol hexaacrylate; DPHA) 4.8 parts by mass Polymerizable compound 2 (NK ester NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8 parts by mass
-Thermosetting compound represented by the following structural formula (Toto Kasei Co., Ltd., Epototo YDF-170, epoxy equivalent 170 g / eq) ... 5.3 parts by mass
However, n is 0, 70% or more.
-Photopolymerization initiator represented by the following formula 10 0.82 parts by mass
-Sensitizer represented by the following formula (Exemplary Compound No. 33): 0.06 parts by mass
In the formula, Me represents a methyl group, and Et represents an ethyl group.
・ Fluorosurfactant (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc., 30% by mass 2-butanone solution) 0.2 mass part ・ Methyl ethyl ketone 10 mass parts

-Production of photosensitive film-
The obtained photosensitive composition solution was applied with a bar coater onto a PET (polyethylene terephthalate) film (Toray Industries, Inc., 16FB50) having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as a support, and hot air at 80 ° C. It dried in the circulation type dryer, and formed the 30-micrometer-thick photosensitive layer. Next, a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated as a protective film on the photosensitive layer by lamination to produce a photosensitive film.

-Preparation of photosensitive laminate-
Next, a chemical polishing treatment was performed on the surface of the base material, that is, a copper-clad laminate (no through hole, copper thickness: 12 μm) on which a wiring was formed as a printed board. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The laminating conditions were a vacuuming time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 10 seconds.

<Evaluation of sensitivity>
The laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). On the surface of the photosensitive layer of the obtained laminate, INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm) was used, and 500 mJ / at intervals of 0.5 mJ / cm ² to 2 ^1/2 times. Exposure was performed by irradiating light having different light energy amounts up to cm ^2, and a pattern of L / S = 50/50 (μm / μm) was cured. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spray development for twice the minimum development time, dissolve and remove the uncured region, measure the line width of the pattern L / S = 50/50 (μm / μm), and the line width is 50 μm The optimal exposure amount was determined as The results are shown in Table 1.

<Evaluation of resolution>
The laminates after 2 hours and 24 hours from lamination were allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. Using the INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm) on the photosensitive layer surface of the obtained laminate, round hole pattern data in 10 μm increments from 40 μm to 400 μm in diameter is optimal. Irradiation was performed with an exposure amount, and pattern exposure of each hole diameter was performed. After standing at room temperature for 10 minutes, in the same manner as in the evaluation of the shortest development time, spray development was performed twice as long as the shortest development time obtained by the above method to dissolve and remove uncured regions. . The surface of the cured resin pattern thus obtained was observed with an optical microscope, and the minimum round hole diameter free from abnormalities such as tsumari and twist in the cured resin pattern was defined as the resolution. The results of resolution after 2 hours and 24 hours after lamination are shown in Table 1. The smaller the numerical value, the better the resolution.

(Example 2)
Photosensitive in the same manner as in Example 1, except that the polymerizable compounds 1 and 2 in Example 1 were changed to 9.6 parts by mass of the polymerizable compound 1 (NK ester NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.). A composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
Example 1 is the same as Example 1 except that polymerizable compound 2 (NK ester NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.) is changed to polymerizable compound 2 (NK ester TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.). Thus, a photosensitive composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Photosensitive in the same manner as in Example 1, except that the polymerizable compounds 1 and 2 in Example 1 were changed to 9.6 parts by mass of the polymerizable compound 1 (NK ester TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.). A composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
Photosensitive in the same manner as in Example 1, except that the polymerizable compounds 1 and 2 in Example 1 were changed to 9.6 parts by mass of the polymerizable compound 1 (NK ester DCP, Shin-Nakamura Chemical Co., Ltd.). A composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
In Example 1, the photosensitive composition was prepared like Example 1 except having changed the sensitizer into 0.40 mass part of diethyl thioxanthone.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1, except that the polymerizable compounds 1 and 2 were changed to 9.6 parts by mass of the polymerizable compound 1 (dipentaerythritol hexaacrylate). .
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, except that the polymerizable compounds 1 and 2 were changed to 9.6 parts by mass of the polymerizable compound 1 (NK ester A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), in the same manner as in Example 1, A photosensitive composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
In Example 1, except that the polymerizable compounds 1 and 2 were changed to 9.6 parts by mass of the polymerizable compound 1 (NK ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), in the same manner as in Example 1, A photosensitive composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
In Example 1, except that the polymerizable compounds 1 and 2 were changed to 9.6 parts by mass of the polymerizable compound 1 (NK ester A-NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.), in the same manner as in Example 1, A photosensitive composition was prepared.
Using each of the obtained photosensitive compositions, the sensitivity and the resolution after 2 hours and 24 hours after lamination were evaluated in the same manner as in Example 1. The results are shown in Table 1.

  Since the photosensitive composition and photosensitive film of the present invention are excellent in sensitivity and laminating and resolution after 24 hours, and can efficiently form high-definition patterns, such as protective films, interlayer insulating films, solder resist patterns, etc. It can be widely used for various pattern formation, printed circuit boards, color filters and column materials, rib materials, spacers, display members such as partition walls, holograms, micromachines, proofs, and other permanent patterns. It can be suitably used for pattern formation.

Claims (10)

It contains at least a binder, a polymerizable compound, a thermosetting compound, a photopolymerization initiator, and a sensitizer,
The polymerizable compound contains at least one selected from methacrylate compounds,
The photopolymerization initiator is a compound represented by the following general formula (A-1),
The said sensitizer is a compound represented by the following general formula (B-1), The photosensitive composition characterized by the above-mentioned.
However, in the general formula (A-1), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and the R ¹ may be further substituted with a substituent. R ² represents any of a hydrogen atom, an alkyl group, and a cyano group, Ar represents either an aromatic ring or a heteroaromatic ring, and Ar and R ² are bonded to each other to form a ring. May be. n represents 0 or 1.
However, in the general formula (B-1), R ⁶ and R ⁷ may be the same as or different from each other, and represent any one of an alkyl group, an aryl group, and an alkenyl group, R ⁶ and R ⁷ may form a ring made of a nonmetallic element together with the sulfur atom to which they are bonded, and these may be further substituted with a substituent. G ¹ and G ² may be the same or different from each other, and may be a hydrogen atom, a cyano group, a carbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, Any one of an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group, wherein G ¹ and G ² are merocyanine dyes composed of a nonmetallic atom together with carbon atoms to which each is bonded, and an acidic nucleus May be used, and these may be further substituted with a substituent. However, either G ¹ or G ^{2 represents} any of a carbonyl group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group. p represents 0 or 1. The photosensitive composition according to claim 1, wherein the compound represented by the general formula (A-1) is a compound represented by the following general formula (A-2).
However, in the general formula (A-2), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, which may be further substituted with a substituent. R ³ represents any one of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, a nitro group, and an acylamino group. m represents an integer of 0 or more, and when m is 2 or more, the R ^{3 s} may be the same as or different from each other, and may be linked to each other to form a ring. . Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of a 5-membered ring, a 6-membered ring, and a 7-membered ring, and these may be further substituted with a substituent. X represents either an oxygen atom or a sulfur atom. The photosensitive composition according to claim 2, wherein the compound represented by the general formula (A-2) is a compound represented by any one of the following general formulas (A-3) and (A-4).
However, in the general formula (A-3) and (A-4), R ⁴ represents any of an alkyl group, and alkyl group, wherein R ⁴ may be further substituted with a substituent . R ⁵ represents any one of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, an alkyloxycarbonyl group, a nitro group, and an acylamino group. l represents an integer of 0 to 6, and when l is 2 or more, the R ^{5 s} may be the same or different from each other, and may be connected to each other to form a ring. Good. A represents either a 5-membered ring or a 6-membered ring, and these may be further substituted with a substituent. X represents either an oxygen atom or a sulfur atom. The photosensitive composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (B-1) is a compound represented by the following general formula (B-2).
However, in the general formula (B-2), R ⁸ and R ⁹ may be the same as or different from each other, and may be a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a halogen atom. R ⁸ and R ⁹ may be bonded to each other to form an aromatic ring, and at least one of an alkyl group, an alkyloxy group, and a halogen atom is further formed on the aromatic ring. You may have. R ¹⁰ and R ¹¹ may be the same as or different from each other, and each represents a hydrogen atom, an alkyl group, or an aryl group. Y represents either an oxygen atom or a sulfur atom.   The photosensitive composition according to any one of claims 1 to 4, wherein the thermosetting compound is an epoxy compound having two or more epoxy groups in one molecule.   Furthermore, the photosensitive composition in any one of Claim 1 to 5 containing at least any one of an inorganic filler and an organic filler.   A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to claim 1 on a support.   A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to claim 1 on a substrate.   A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to claim 1.   A printed circuit board comprising a permanent pattern formed by the method for forming a permanent pattern according to claim 9.