TW200941138A - Photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern, and printed board - Google Patents

Abstract

The photosensitive resin composition of the present invention is characterized in comprising binder, polymeric compound, oxime derivative, and ion adsorbent. Preferably the ion adsorbent is an aspect comprising zirconium phosphate, the photosensitive composition is an aspect further comprising filler, the photosensitive composition is an aspect further comprising heat crosslinking agent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, a photosensitive film, and a photosensitive property suitable for use as a solder resist material for image formation by laser exposure. A laminate, a permanent pattern forming method, and a printed substrate. [Prior Art] In the prior art, when a permanent pattern such as a solder resist is formed, a photosensitive film obtained by applying a photosensitive composition on a support and drying to form a photosensitive layer is used. In the method of forming such a permanent pattern, for example, a photosensitive film is laminated on a substrate such as a copper clad laminate in which a permanent pattern is formed to form a laminate, and the photosensitive layer of the laminate is exposed. After exposure, the photosensitive layer is developed to form a pattern, followed by a hardening treatment or the like to form a permanent pattern. The photosensitive composition for forming the solder resist is, for example, a photosensitive composition containing an ion adsorbent such as ruthenium pentoxide hydrate (see JP-A-2000-1 59859). Further, a polymerization initiator of a highly sensitive photosensitive composition is known as an anthracene derivative (refer to JP-A-2007-23 1 000). At present, it is desired to provide a photosensitive composition having sufficient sensitivity to digital image (DI) exposure and excellent activity retention, and an excellent insulating property. SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to solve the above various problems and achieve the following objects. That is, the object of the present invention is to provide a photosensitive composition having high sensitivity and active storage stability and high insulation reliability, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed substrate. The means for solving the above problems is as follows: <1> A photosensitive composition comprising a binder, a polymerizable compound, an anthracene derivative, and an ion adsorbent. &lt;2&gt; The photosensitive composition of &lt;1&gt;, wherein the ion adsorbent contains phosphoric acid. &lt;3&gt; The photosensitive composition according to the above &lt;1&gt; or &lt;2&gt;, further containing a dip. The photosensitive composition according to any one of the above-mentioned <1> to <3>, which further contains a thermal crosslinking agent. The photosensitive composition of any one of the above-mentioned <1> to <4>, wherein the 肟 derivative system is represented by the following formula (1),

In the above formula (1), R1 represents a hydrogen atom, a mercapto group which may have a substituent, an alkoxycarbonyl group and an aryloxycarbonyl group, and R2 each independently represents Any of a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a thiol group, an arylthio group, and an amine group. The m system represents an integer of 〇4, and when two or more, it may be linked to each other to form a ring. The A series indicates any of the 4, 5, 6 and 7-member rings. &lt;6&gt; The photosensitive composition of the above &lt;5&gt; wherein the anthracene derivative is represented by the following formula (2), .200941138 Formula (2) ❹

In the above formula (2), R1 represents a hydrogen atom, a mercapto group which may have a substituent, an alkoxycarbonyl group and an aryloxycarbonyl group, and R2 each independently represents a halogen atom or an alkyl group. Any of an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group and an amine group, and m represents an integer of 0 to 4. The X system represents the CH2, 0, and 8. The 丨 indicates an integer from 1 to 3. &lt;7&gt; The photosensitive composition of the above &lt;5 &gt; wherein the anthracene derivative is represented by any one of the following general formulae (3) and (4)

In the above formulae (3) and (4), R1 represents a hydrogen atom, or a substituent which may have a substituent, an anthracene group, and an aryloxy anthracene group. The halogen atom, the aryl group, the aryl group, the alkoxy group, the aryloxy group, the alkylthio group, the arylthio group and the amine group 'm) represent an integer of 0 to 4. The X system indicates any of CH2, Ο and S. The 1 series represents the integer of 1 to 3 .200941138. &lt;8&gt; The photosensitive composition of the above &lt;6&gt; or &lt;7&gt;, wherein, in the general formulae (2), (3) and (4), X represents either Ο or S, 1 series In any of 1 and 2, R1 represents any of an alkyl group and an alkoxycarbonyl group which may have a substituent. The photosensitive composition of any one of the above-mentioned <1> to <5>, wherein the weight average of the I/O値 of the polymerizable compound is 〇.5 or less. &lt;10&gt; A photosensitive film comprising a photosensitive layer composed of the photosensitive composition according to any one of the above items <1> to <9> on the support. &lt;11&gt; A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to any one of the above items <1> to <9>. &lt;12&gt; A method of forming a permanent pattern, which comprises at least exposing a photosensitive layer formed using the photosensitive composition according to any one of &lt;1&gt; to &lt;9&gt;&lt;13&gt; The permanent pattern forming method according to the above &lt;12&gt;, wherein the exposure is performed by a microlens array formed by arranging microlenses having an aspherical surface capable of correcting light rays by means of light modulation After the modulation, there is a variation due to deformation of the exit surface of the drawing portion of the light modulation means. &lt;14&gt; The permanent pattern forming method of &lt;12&gt; or &lt;13&gt;, wherein the exposure of the photosensitive layer is performed after exposure. &lt;15&gt; The method of forming a permanent pattern according to the above &lt;12&gt;, wherein after the development is performed, the hardening treatment of the photosensitive layer is performed. &lt;16&gt; A printed circuit board characterized in that the permanent pattern is formed in accordance with the permanent pattern forming method of any one of the above &lt;12&gt; to &lt;15&gt;. According to the present invention, it is possible to provide a photosensitive composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and the like, which have high sensitivity and excellent storage stability, and have high insulation reliability. Printed substrate. [Embodiment] [Photosensitive composition] The photosensitive composition contains a binder, a polymerizable compound, an anthracene derivative, and an ion adsorbent, and preferably contains a binder, a thermal crosslinking agent, and further contains other components as necessary. (Binder) The above-mentioned binder can be suitably used as a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain, an epoxy acrylate compound, etc., among which an acid group and an ethyl group are used in the side chain. A polymer compound having an unsaturated bond is particularly preferred. - A polymer compound having an acidic group and an ethylenically unsaturated bond in the side chain - The acidic group may, for example, be a carboxyl group, a phosphoric acid group or a sulfonic acid group, and a carboxyl group is preferred because the raw material is easily obtained. Further, as the binder, at least one polymerizable double bond in the molecule, for example, an acryloyl group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester of a carboxylic acid, or a vinyl ether can be used. Various polymerizable double bonds such as allyl ether. More specifically, the acidic group may be an acrylic resin containing a carboxyl group, and a polymerizable compound containing a cyclic ether group, for example, an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate or cinnamic acid may be added. Glycidyl ester, or an epoxy group-containing polycondensate having an alicyclic epoxy group (for example, an epoxy group such as cyclohexene oxide in the same molecule) and a (meth) acrylonitrile group. 200941138 A compound obtained by synthesizing a compound or the like. In addition, a compound obtained by adding a polymerizable compound containing an isocyanate group such as ethyl isocyanate (meth)acrylate to an acrylic resin containing an acidic group and a hydroxyl group, and an acrylic resin containing an anhydride group may be added. A compound obtained by adding a polymerizable compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate is added. Further, a copolymerizable compound containing a cyclic ether such as glycidyl methacrylate may be copolymerized with a vinyl monomer such as (meth) propylene sulfoxide to add (meth)acrylic acid. A compound obtained by an epoxy group of a side chain or the like. In the above-mentioned, the binder is selected from a cyclic ether group (for example, in a partial structure), etc., in the above-mentioned adhesives, etc. A polymerizable compound having an epoxy group or an oxetane group is added to one part of the acidic group of the polymer compound, and a carboxyl group-containing polymerizable compound is added to the ring of the polymer compound. A polymer compound of any one or all of the ether groups is more preferable. In this case, the addition reaction of the acid group with the compound having a cyclic ether group is preferably carried out in the presence of a catalyst, and particularly preferably the catalyst is selected from the group consisting of an acidic compound and a neutral compound. In the case of the development stability of the photosensitive composition over time, the binder contains a polymer compound which may also contain a carboxyl group and a hetero ring in the side chain, and a polymer compound which contains an ethylenic unsaturated bond in the side chain. It is better. - an aromatic group which may also contain a heterocyclic ring - may also contain a heterocyclic aromatic group (hereinafter also referred to simply as "aromatic group"), and examples thereof include a benzene ring and two to three benzene rings. The fused ring is formed, .200941138 The benzene ring and the 5-membered unsaturated ring form a thick ring. Specific examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a benzopyrrole group, a benzofuran ring group, a benzothiophene group, and a pyridyl group. Pyrazole ring group, isoxazole ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzisothiazole ring group, imidazole ring group, indazole ring group, thiazole ring group , benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, thiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, hydrazine ring group, pyrimidine ring group, pyridine ring Base, argon ring group, quinazoline ring group, quinoxaline ring group, indole cyclopropyl ring group, phenanthridine ring group, indazole ring group, indole ring group, pyrancycloyl group, piperidinyl group, piperazine Cultivating ring group, anthracene ring group, D ring fluorene ring group, chromene ring group, croup ring group, acridine ring group, morphine ring group, tetrazolium ring group, three tillage ring group, etc. . Among these, a hydrocarbon aromatic group is preferred, and a phenyl group or a naphthyl group is more preferred. The aromatic group may have a substituent, and examples of the substituent include a halogen atom, an amine group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a decyl group, and the like. A nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, etc. which each may have a substituent. The alkyl group may, for example, be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group or a cyclic alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group, and a thirteen group. Hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, methylbutyl, isohexyl, 2-ethyl Hexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl 200941138, 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 preferred. The substituent which may have an alkyl group, for example, may be a group composed of a monovalent non-metal atomic group other than hydrogen, and examples of such a substituent include a halogen atom (-F, -Br, -Cl, - I), hydroxy, alkoxy, aryloxy, decyl, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamino, N,N-dialkylamine , N-arylamino, N,N-diarylamino, N-alkylindenyl-N-arylamino, decyloxy, aminomethyl methoxy, N-alkylaminomethyl methoxy , N-arylaminomethyl methoxy, N,N-dialkylaminomethyl methoxy, hydrazine, fluorenyl-diarylaminomethyl methoxy, hydrazine-alkyl-hydrazine-arylamine Methyl methoxy, alkyl 'alkyl sulfoxy group, aryl sulfoxy group, acylthio group, guanylamino group, n-alkyl guanylamino group, N · aryl Alkylamino, ureido, Ν'-alkylureido, N',N,-dialkylureido, Ν'-arylureido, N',N,-diarylureido, Ν'-alkyl- Ν'-arylureido, N-alkylureido, N-arylureido, Ν'-alkyl- oxime-alkylurea, Ν'-alkyl-oxime-arylureido, oxime, oxime, - Dialkyl-indole-alkylurea Ν',Ν'·Dialkyl-fluorene-arylureido' Ν,-aryl-Ν-alkylureido, fluorene,-aryl-fluorene-arylureido, Ν', Ν'-diaryl- Ν-alkylureido, Ν', Ν'-diaryl-fluorene-arylureido, Ν'-alkyl-oxime-aryl-oxime-alkylurea, Ν'-alkyl-oxime, -aryl - anthracene-arylurea group, alkoxycarbamoylamino group, aryloxycarbamoylamino group, fluorenyl-alkyl-hydrazine-alkoxycarbenylamino group, fluorenyl-alkyl-fluorene-aryloxycarbazide Amino, fluorene-aryl-fluorenyl-alkoxycarbenylamine, fluorenyl-aryl-fluorene-aryloxycarbenylamine, indolyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxy Carbonyl, aminomethyl decyl, fluorenyl-alkylaminomethyl fluorenyl, fluorene, fluorenyl-dialkylaminomethyl fluorenyl, fluorenyl-arylaminomethyl fluorenyl, -10-200941138 N, N-di Arylaminomethyl indenyl, N-alkyl-N-arylaminomethylindenyl, alkylsulfinic acid, arylsulfinic acid, alkylsulfonyl, arylsulfonyl, sulfonate Acid group (-SChH) and its conjugate base (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, amine sulfinyl group, N-alkylamine sulfinyl group , N,N-dialkylamine sulfinylene, N_arylamine Indenyl, N,N-diarylamine sulfinyl, N-alkyl-N-arylamine sulfinyl, amine sulfonyl, N-alkylamine sulfonyl, N,N-di Alkylamine sulfonyl, N-arylamine sulfonyl, anthracene, fluorene diarylamine sulfonyl, N-alkyl-N-arylsulfonyl, phosphonic acid (-P〇3H2 And its conjugated thiol group (hereinafter referred to as phosphonate group), dialkylphosphonic acid group (-P03 (alky 1) 2) (hereinafter, "aikyl" means alkyl group), diarylphosphonic acid group (-P03 (ary 1) 2) (hereinafter, "aryi" means aryl), alkyl arylphosphonic acid (-P〇3 (alky) (aryl), monoalkylphosphonic acid group ( -P〇3 (alkyl)) and its conjugated base (hereinafter referred to as alkylphosphonate), monoarylphosphonate (-P03H (aryl)) and its conjugated base (hereinafter referred to as aryl) Phosphonate), phosphinomethoxy (-OPOsH2) and its conjugated base (hereinafter referred to as phosphonateoxy), dialkylphosphoniumoxy (-〇P〇3 (alkyl) 2), diaryl Alkylphosphonium oxy (-0P03 (aryl) 2), alkyl aryl phosphinomethoxy (_OP 〇 3 (alkyl) (aryl), monoalkyl phosphinooxy (-〇p〇 3H (alkyl) And conjugated bases (hereinafter referred to as alkylphosphonic acids) Oxyl group), monoarylphosphonium oxy group (-〇p〇3H(aryl)) and conjugated base (hereinafter referred to as arylphosphonateoxy group), cyano group, nitro group, aryl group, alkenyl group , alkynyl, heterocyclic, decyl and the like. Specific examples of the alkyl group of the substituent include the above alkyl group. Specific examples of the aryl group of the above substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a decyl group, a cumyl group, a chlorophenyl group, and a bromine group. 200941138 phenyl group, chloro group Phenyl, hydroxyphenyl 'methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzamidine phenyl, methylthiophenyl, phenylthio Phenyl, methylaminophenyl, dimethylaminophenyl, acetaminophen phenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, presentoxycarbonylphenyl, N- Phenylaminopyristylphenyl, cyanophenyl, sulfonylphenyl, sulfonylphenyl, phosphonicphenyl and phosphophenyl. The alkenyl group of the above substituent may, for example, be an ethyl thiophene group, a 1-propylidene group, a 1-butenyl group, a cinnamyl group or a 2-chloro-1-vinyl group. The alkynyl group in the above substituent may, for example, be an ethynyl group, a 1-propynyl group, a 1-butynyl group or a trimethyldecyl ethynyl group. R&lt;)1 of the fluorenyl group (rQ1c〇-) of the above substituent may, for example, be a hydrogen atom, an alkyl group or an aryl group as described above. Among these substituents, a halogen atom (-F, _Br, _C1, _1), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, an N,N-diamine group , methoxy, N-alkylaminomethyl methoxy, arylaminomethyl methoxy, acid amine, methionyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxy fluorenyl, hydrazine Aminomethyl fluorenyl, N-alkylaminomethyl fluorenyl, anthracene, fluorene dialkylaminomethyl aryl, fluorenyl-arylaminomethyl fluorenyl, fluorenyl-alkyl-hydrazine-arylamino Mercapto, sulfonate, sulfonate, sulfonyl, hydrazine-alkylamine sulfonyl, hydrazine, hydrazine-dialkylamine sulfonyl, fluorene-arylamine sulfonyl, decane Base-fluorene-arylsulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkylphosphonic acid, alkylphosphonic acid, monoarylphosphine An acid group, an arylphosphonate group, a phosphinomethoxy group, a phosphonate group, an aryl group, an alkenyl group or the like is preferred. In addition, examples of the heterocyclic group of the above-mentioned substituent include a pyridyl group, a piperidine-12-.200941138 group, and the like. The alkyl group of the above substituent may, for example, be a trimethyldecyl group. On the other hand, the alkyl group of the alkyl group may, for example, be one which removes any one of hydrogen atoms from the alkyl group having 1 to 20 carbon atoms and becomes a divalent organic residue, for example, carbon. A linear form of 1 to 12 atoms, a branched form having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are preferred. Specific examples of the substituted alkyl group by a combination of such a substituent and an alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, and a methoxy group. Methyl, isopropoxymethyl, butoxymethyl, second butoxybutyl, methoxyethoxyethyl, aryloxymethyl, phenoxymethyl, methylthiomethyl ,toluylthiomethyl, pyridylmethyl, tetramethylpiperidinylmethyl, N-ethinyltetramethylpiperidinylmethyl, trimethyldecylmethyl, methoxyethyl 'B Aminoethyl 'diethylaminopropyl, morpholinyl propyl, ethoxymethyloxy, benzhydryloxymethyl, N-cyclohexylaminomethyloxyethyl, N-phenylamine Methyl methoxyethyl, acetaminoethyl, N-methylbenzimidyl propyl, 2-sided oxyethyl, 2-sided oxypropyl, carboxypropyl, methoxycarbonyl , aryloxycarbonylbutyl, chlorophenoxycarbonylmethyl, aminomethylmethylmethyl, N-methylaminomethylmethyl, N,N-dipropylaminocarboxamide , N-(methoxyphenyl)aminocarbamidoethyl, N-methyl-N-(sulfophenyl)amino Mercaptomethyl, sulfonate butyl, sulfonyl butyl, acesulfonyl butyl, N-ethylamine sulfonylmethyl, N,N-dipropylamine sulfonylpropyl, N _Tolylamine sulfonylpropyl, N-methyl-N-(phosphonophenyl)amine sulfonyl octyl, phosphonic butyl, phosphonic hexyl, diethylphosphonyl butyl , diphenylo-o-propyl, methylphosphonic butyl, methyl ortho-butyl, tolylphosphonic hexyl, tolylphosphonate, -13- 200941138 phosphinomethoxypropyl, Phosphonate oxybutyl, benzyl, phenethyl, α-methylbenzyl, 1-methyl-1-phenylethyl, p-methylbenzyl, cinnamyl, allyl, 1-propenyl Methyl, 2-butenyl, 2-methylallyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3-butynyl, and the like. Examples of the aryl group include a benzene ring, two to three benzene rings to form a fused ring, a benzene ring and a 5-membered unsaturated ring to form a fused ring. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, an anthracenyl group, a fluorenyl group and the like. Among these, a phenyl group or a naphthyl group is preferred. The alkyl group may have a substituent, and such a substituted aryl group (hereinafter also referred to as a "substituted aryl group"), for example, a substituent on the ring-forming carbon atom of the aryl group may be exemplified. A base composed of a monovalent non-metal atomic group other than a hydrogen atom. The substituent which the aryl group may have, for example, the above-mentioned alkyl group or substituted alkyl group, which is preferably a substituent which the above-mentioned alkyl group may have, is preferably a preferred specific example of the above substituted aryl group, and may be exemplified. Phenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxy Phenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, two Ethylaminophenyl, porphyrin phenyl, ethoxylated phenyl, benzhydryloxyphenyl, N-cyclohexylaminomethyloxyphenyl, N-anilinylmethyloxyphenyl, B Nonylaminophenyl, N-methylbenzhydrylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, aryloxycarbonylphenyl, chlorophenoxycarbonylphenyl, aminoguanidine Phenylphenyl, N-methylaminocarbamiphenyl, N,N-dipropylaminocarbamyl • 14 · 200941138 Phenyl, N-(methoxyphenyl)aminoformamidobenzene Base, N_methyl-N-(sulfonic acid phenyl Aminomethylphenyl phenyl, sulfonyl phenyl, phosphonate phenyl, sulfonyl phenyl, N-ethylamine sulfonyl phenyl, N-N-dipropylamine sulfonyl phenyl , N-tolylamine sulfonylphenyl, N-methyl_N_(phosphonophenyl)amine sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, diethylphosphonic acid Phenyl, diphenylphosphonylphenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonic phenyl, allyl phenyl, 1-propenylmethylphenyl, 2-butenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propenylphenyl, 2-butynylphenyl and 3- Butyl phenyl and the like. The above alkenyl group (-C(R02) = C(R03)(R04)) and alkynyl group (-C3C(R05)) may, for example, be ΙΙΰ2, RQ3, RQ4 and R〇5 are monovalent non-metals. The base of the atomic group. Examples of the RG2, RG3, and RG4 include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples of these may be mentioned as examples. Among these, a hydrogen atom, a sulfonium atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group or a cyclic alkyl group is preferred. Preferable specific examples of the above alkenyl group and alkynyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, a 1-hexenyl group, a 1-octenyl group, and a 1-methyl group. -1-propenyl, 2-methyl-1-propenyl, 2-methyl-1-butenyl, 2-phenyl-1-vinyl, 2-chloro-1-vinyl, ethyl fast radical, 1-propynyl, 丨-butynyl, phenylethynyl and the like. The above heterocyclic group may, for example, be a pyridyl group of the substituent -15-200941138 which is a substituted alkyl group. The oxy group (RG60-) is exemplified by a non-metal atomic group other than a hydrogen atom. Such an oxy group is, for example, an alkoxy group, an aryloxy group, a decyloxy group, an aminomethyl methoxy group, an N-alkylaminomethyl methoxy group, an N-arylaminomethyl methoxy group, N, N. -dialkylaminomethyl methoxy, N,N-diarylaminomethyl methoxy, Ν-alkyl-fluorene-arylaminomethyl methoxy 'alkyl sulfoxyl group An arylthiooxy group, a phosphinyloxy group, a phosphonic acid group or the like is preferred. 〇 w The alkyl group and the aryl group are exemplified by the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. Further, in the fluorenyloxy group (rG7co·;), R〇7 may, for example, be an alkyl group, a substituted alkyl group, an aryl group or an aryl group as exemplified in the above examples. Among these substituents, an alkoxy group, an aryloxy group, a decyloxy group or an arylthio group is more preferred. Specific examples of the preferred oxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, and a benzyl group. Allyloxy, phenethyloxy, carboxyethyloxy, methoxycarbonyl^

❹ C-oxyl, ethoxycarbonylethyloxy, methoxyethoxy, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, taste Ethyloxy, morpholinepropoxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xylyloxy, decyloxy, cumyloxy, A Oxyphenoxy, ethoxyphenoxy, chlorophenoxy, bromophenoxy, ethoxycarbonyl, benzhydryloxy, naphthyloxy, phenylsulfonyloxy, phosphinomethoxy, Phosphonic acid group and the like. The amine group which may also contain a mercapto group (RG8NH-, (RM^rO^n-) may, for example, -16 - 200941138, for example, RM, and RG1() are a base composed of a non-metal atom group other than a hydrogen atom. Further, RM may be bonded to 115 to form a ring. The aforementioned amine group may, for example, be an N-alkylamino group, an N,N-dialkylamino group, an N-arylamino group, an anthracene or a fluorene-diarylamine. , N-alkyl-N-arylamino, decylamino, N-alkylnonylamino, fluorene-aryl decylamino, ureido, Ν'·alkylureido, Ν', Ν'- Alkylureido, Ν'-arylureido, Ν', Ν'-diarylureido, Ν'·alkyl-Ν'-arylureido' Ν-alkylureido, Ν-arylureido, Ν'- Alkyl-oxime-alkylureido, Ν'-alkyl-oxime-arylureido, Ν', Ν'-dialkyl-oxime-alkylurea, Ν'-alkyl-Ν'-arylureido, Ν',Ν'-Dialkyl-oxime-alkylureido, Ν', Ν'-dialkyl-Ν'-arylureido, Ν'-aryl-oxime-alkylureido, Ν'-aryl -Ν-arylureido, Ν', Ν'-diaryl-fluorenyl-alkylurea, Ν', Ν'-diaryl-fluorene-arylureido, Ν'·alkyl-Ν'-aryl -Ν-alkylureido, hydrazine, -alkyl-Ν'-aryl-hydrazine-arylureido, alkoxycarbenamine , aryloxycarbaguanyl, fluorenyl-alkyl-hydrazine-alkoxycarbenylamine, fluorenyl-alkyl-fluorene-aryloxycarbenylamine, fluorene-aryl-hydrazine-alkoxy carbon An amidino group, a fluorenyl-aryl-fluorene-aryloxycarbenylamino group, etc. Examples of the alkyl group and the aryl group include the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. The R" group of the fluorenyl group, the fluorenyl-alkylamino group, and the fluorenyl group of the fluorenyl-aryloxy group (R^CO-) is as described above. Among these, the oxime-homoamine group, N, N a dialkylamino group, an N-arylamino group, a decylamino group is more preferable. Specific examples of a preferred amine group include a methylamino group, an ethylamino group, a diethylamino group, a morpholinyl group, a piperidinyl group, Pyrrolidinyl group, anilino group, benzylideneamine group, ethylamino group, etc. The sulfonyl group (Reil-S〇2.) is, for example, a group in which V11 is composed of a monovalent non-metal atomic group. Such a sulfonyl group is preferably, for example, an alkylsulfonyl group, an arylsulfonyl group or the like. -17- 200941138 The alkyl group and the aryl group may be exemplified by the above-mentioned alkyl group, substituted group, and aryl group. And a substituted aryl group. Specific examples of the above sulfonyl group include butyl sulfonyl 'phenyl sulfonyl group, chlorobenzene The above-mentioned sulfonate group (_S〇3-) is as defined above, and means that the conjugated base anion group of the sulfonic acid group (-S03H) is usually used together with the relative cation. The relative cation can be appropriately selected from those generally known, such as guns (e.g., ammonium, anthraquinone, scaly, iron iodide, ruthenium, etc.), metal ions (e.g., Na+, K+, Ca2+, Zn2+). The carbonyl group (R^U-CO-) may, for example, be a base of R*113 which is composed of a monovalent non-goldic atomic group. Examples of such a carbonyl group include a decyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethyl fluorenyl group, an N-alkylaminocarbamyl group, and an N,N-dialkylamine. A fluorenyl group, an N-arylaminomethyl fluorenyl group, an N,N-diarylaminomethyl fluorenyl group, an N-alkyl-fluorene'-arylaminocarbamyl group, and the like. The alkyl group and the aryl group may be exemplified by the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. The aforementioned carbonyl group is a fluorenyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aminomethyl fluorenyl group, a fluorenyl-alkylaminomethyl fluorenyl group, an anthracene, a fluorenyl-dialkylaminocarbamyl group. Further, a fluorenyl-arylaminomethyl fluorenyl group is preferred, and a fluorenyl group, a fluorenyl group, an alkoxycarbonyl group or an aryloxycarbonyl group is more preferred. Specific examples of the above carbonyl group may be exemplified by a methyl group, an ethyl fluorenyl group, a benzhydryl group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an aryloxycarbonyl group, and a -18-200941138 methylaminophenylvinyl group. Alkylcarbonyl, methoxycarbonylmethoxycarbonyl, N-methylaminomethylmercapto, N-phenylaminocarbamimidyl, N,N-diethylaminomethylguanidinyl, morpholinecarbonyl, and the like. The sulfinyl group (RQ14-SO-) may be a group in which R^14 is composed of a monovalent non-metal atomic group. Examples of such a sulfinyl group include an alkylsulfinyl group, an aryl sulfonate group, an amine sulfinylene group, an N-alkylamine sulfinylene group, and an N,N-dialkylamine sulfinic acid. An anthracenyl group, an N-arylamine sulfinyl group, an N,N-diarylamine sulfinyl group, an N-alkyl-N-arylamine sulfinyl group, and the like. The alkyl group and the aryl group may be mentioned as an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Among these, an alkylsulfinyl group or an arylsulfinyl group is preferred. Specific examples of the above substituted sulfinyl group may, for example, be a hexylsulfinyl group, a benzylsulfinyl group or a tolylsulfinyl group. The above phosphonic acid group means that one to two of the hydroxyl groups on the phosphonic acid group are substituted by another organic sideoxy group, for example, the aforementioned dialkylphosphonic acid group, diarylphosphonic acid group, or alkane. A arylphosphonic acid group, a monoalkylphosphonic acid group, a monoarylphosphonic acid group or the like is preferred. Among these, a dialkylphosphonic acid group or a diarylphosphonic acid group is more preferred. More preferable examples of the phosphonic acid group include a diethylphosphonic acid group, a dibutylphosphonic acid group, a diphenylphosphonic acid group and the like. The aforementioned tartaryl group (-Ρ〇3Η2-, -Ρ03Η-) is as defined above, and means an conjugated base anion group derived from an acid of a phosphonic acid group (-P〇3H2) or a second dissociated acid. It is usually preferred to use it together with a relative cation. Such a relative cation can be appropriately selected from those generally known, for example, various guns (for example, ammonium-19-200941138, anthraquinone, scaly, iodine, sorghum, etc.) metal ions (for example, Na+, K+, Ca2+, Zn2+, etc.). The above phosphonic acid group may be a conjugated base anion group in which a hydroxyl group is substituted by an organic side oxy group in a phosphonic acid group, and specific examples thereof include the aforementioned monoalkyl squaric acid group (-P).共3H(alkyl), a conjugated base of a monoarylphosphonic acid group (-P03H(aryl)). Ο

The aromatic group can be produced by a usual radical polymerization method by using one or more aromatic group-containing radical polymerizable compounds and one or more other radical polymerizable compounds which are required as a copolymerization component. The radical polymerization method is usually, for example, a suspension polymerization method or a solution polymerization method. The aromatic group-containing radically polymerizable compound is preferably a compound represented by the formula (A-1) or a compound represented by the formula (A-2).

Ri Ra

I I Q·- General formula (A-1) In the above formula (A-1), Ri, R2 and R3 each represent a hydrogen atom or a monovalent organic group. The L system represents an organic group and is not acceptable. The Ar system represents an aromatic group which may also contain a hetero ring.

In the above formula (A-2), b, R2, R3 and Ar are synonymous with the above formula (A-1). -20- 200941138 The organic group of the above L is, for example, a polyvalent organic group composed of a non-metal atom, and may be exemplified by 1 to 60 carbon atoms, hydrazine to 10 nitrogen atoms, and 0 to 50 oxygen atoms. More specifically, the organic group of L may be a combination of the following structural units, polyvalent naphthalene, polyvalent hydrazine, or the like.

ten

•δ— 〇

0-I+-J k Η

The linking group of L may have a substituent, and the above substituent may, for example, be a halogen atom, a hydroxyl group, a carboxyl group, a sulfonate group, a nitro group, a cyano group, a decylamino group, an amine group, an alkyl group, an alkenyl group or an alkyne group. A aryl group, an aryl group, a substituted oxy group, a substituted sulfonyl group, a substituted carbonyl group, a substituted sulfinyl group, a sulfonic acid group, a phosphonic acid group, a phosphonic acid group, a decyl group, or a heterocyclic group. The compound represented by the above formula (A-1) and the compound represented by the above formula (a-2) are preferably in the form of sensitivity (A·1). Further, among the above-mentioned general formula (A-1), in terms of stability, it is preferable to have a linking group, and the organic group of the above -21 to 200941138 L is not removable (developing property) of the non-image portion. In other words, an alkylene group having a carbon number of 1 to 4 is preferred. The compound represented by the above formula (A-1) is a compound containing a structural unit of the following formula (A-3). Further, the compound represented by the above formula (A_2) is a compound containing a structural unit of the following formula (A-4). Among them, in terms of preservation stability, the structural unit of the formula (A-3) is preferred. 〇

General formula (A-3)

In the above formula (A-3) and formula (Α·4), r2, r3 and Ar are represented by the above formula (A-1) and formula (α·2). (Synonymous) In the above-mentioned general formula (Α-3) and general formula (Α-4), in terms of the removability (developability) of the non-image portion, Ri and R2 are hydrogen atoms, and R3 is preferably a methyl group. L' of the above formula (A-3) is preferably an alkylene group having 1 to 4 carbon atoms in terms of the removability (developability) of the non-image portion. The compound represented by the above formula (A-1) or the compound represented by the formula (2) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (3). -22- 200941138 0(1)

(10)

(Π)

(4)

(12)

(13) Ο φ)

(14)

乂 S&lt;CHjCH20

(15)

&quot;^Oj-Ct^CHaO (16) -23- 200941138 ¢17) ch3

m ,c〇r-

¢25)

¢29)

Among the above-exemplified compounds (1) to (30), SiCC is preferably (5), (6), (11) and (28), and in terms of storage stability and development properties. , and (6) is better. The aromatic group may further contain a heterocyclic ring, and the binder is not particularly limited, and the total structural unit of the polymer compound is 1 and (14) is (5): the content is 00%-24-.200941138% by volume. The structural unit represented by the above formula (A-3) is preferably contained in an amount of 20 mol% or more, and more preferably 30 mol% to 45 mol% or more. When the content is less than 20 mol%, there is a case where the storage stability is lowered, and when the content is more than ο mol%, the development property is lowered. - Ethylene unsaturated bond - The ethylenic unsaturated bond is not particularly limited, and is preferably, for example, those represented by the following formulas (A-5) to (A-7). © 1

General formula (A - 5 ) R* ^ - Y*C~Cs C Formula (A-6) (% ftjf - 2 - Cr C Formula (A-7) wherein the above formula (A-5) is In (A-7), RpRu each independently represents a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom or -N-R4. The Z system represents an oxygen atom, a sulfur atom, -N- R4, or a phenyl group. R4 represents a hydrogen atom or a monovalent organic group. In the formula (A-5), R! is each independently and, for example, a hydrogen atom, an alkyl group which may have a substituent, etc., because The radical reactivity is high, and a hydrogen atom or a methyl group is more preferable. -25-200941138 The above R·2 and R3 are each independently and may, for example, be a hydrogen atom, a halogen atom, an amine group, a carboxyl group or an alkoxycarbonyl group. a sulfonic acid group '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, or The amine group having a substituent, the arylamine group which may have a substituent, the alkylsulfonyl group which may have a substituent, the arylsulfonyl group which may have a substituent, etc., because the radical reactivity is high' 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. The above IU is preferably an alkyl group which may have a substituent, etc., because of reactivity with a radical. Preferably, the hydrogen group is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or the like. Here, examples of the substituent which can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, and an aromatic group. An oxy group, a halogen atom, an amine group, an alkylamino group, an arylamine group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a decylamino group, an alkylsulfonyl group, an arylsulfonyl group, etc. (A-6), iU to R8 are, for example, a hydrogen atom, a halogen atom, an amine group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, or 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 group which may have a substituent, an arylamine group which may have a substituent, It may preferably be an alkylsulfonyl group having a substituent, an arylsulfonyl group having a substituent, etc., and a hydrogen atom or a carboxyl group. The oxycarbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are more preferable. The above-mentioned substituent which can be introduced can be exemplified by the above formula (A-5) -26-200941138 In the above formula (A-7), R9 is, for example, a hydrogen atom or an alkyl group which may have a substituent, and is preferably a hydrogen atom or a methyl group because of a high radical reactivity. The above R1() And Ru each independently and, for example, a hydrogen atom, a halogen atom, an amine group, a dialkylamine group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, an alkyl group which may have a substituent, or An aryl group having a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamine group which may have a substituent, an arylamine group which may have a substituent, or may have The alkylsulfonyl group of the substituent, the arylsulfonyl group which may have a substituent, etc. are preferable because the radical is highly reactive, and a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or an alkyl group which may have a substituent Further, an aryl group which may have a substituent is more preferable. Here, the substituent which can be introduced can be exemplified by the above formula (A-5). The above Z system represents an oxygen atom, a sulfur atom, -Nh 3- or a pendant phenyl group which may have a substituent. R13 represents an alkyl group or the like which may have a substituent, and is preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group because of its high radical reactivity. Among the side chain ethylenically unsaturated bonds represented by the above formulas (A-5) to (A-7), the sensitivity is high because of the high polymerization reaction, and the formula (Α·5) is more preferable. The content of the aforementioned unsaturated bond in the above polymer compound is not particularly limited to 〇_5meq/g to 3.0 meq/g, more preferably 1.0 meq/g to 3.0 meq/g, and i.5 meq/g. ~2.8meq/g is especially good. When the above content is less than 0.5 meq/g, since the amount of hardening reaction is small, there is a case where the sensitivity is low, and when it is more than 3. Omeq/g, there is a case where the stability of storage is deteriorated. The above content (meq/g) can be measured by, for example, iodine titration. The method of introducing the ethylenic unsaturated bond represented by the above formula (A-5) in the side chain is not particularly limited, and for example, a polymer compound having a carboxyl group in a side chain and an ethylenically unsaturated bond and an epoxy can be used. The compound is obtained by addition reaction of a compound.

The polymer compound having a carboxyl group in the side chain can be, for example, one or more kinds of other radical polymerizable compounds containing a carboxyl group and one or more other radical polymerizable compounds which are required to be a copolymerization component. Manufactured by free radical polymerization. The radical polymerization method is usually, for example, a suspension polymerization method or a solution polymerization method. The compound having an ethylenic unsaturated bond and an epoxy group is not particularly limited as long as it has such a compound, and for example, a compound represented by the following formula (A-8) and a compound represented by the formula (A-9) are good. ❹

Η General formula (A-8) wherein, in the above formula (A-8), Ri represents a hydrogen atom or a methyl group. Ll represents an organic group.

In the above formula (A-9), R2 represents a hydrogen atom or a methyl group. L2 represents an organic group. The W system represents an aliphatic hydrocarbon group of 4 to 7 membered rings. The compound represented by the above formula (A-8) and the compound of the formula (A-9); in the compound -28-.200941138, the compound represented by the formula (A-8) is preferred, The formula (Α·8) 'is more preferably an alkyl group having 1 to 4 carbon atoms. The compound represented by the formula (A-8) or the compound of the formula (A-9) is not particularly limited, and examples thereof include the following exemplified compounds (3 1) to (40).

The radically polymerizable compound containing a carboxyl group is, for example, a silicic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid or p-carboxystyrene, and particularly preferred is acrylic acid. Methyl propyl acid and so on. -29- 200941138 The reaction system for introducing the aforementioned side chain can be, for example, a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride. The fourth-order ammonium salt, pyridine, triphenylphosphine oxide or the like is used as a catalyst in an organic solvent at a reaction temperature of 50 ° C to 150 ° C for several hours to several tens of hours. The structural unit having an ethylenic unsaturated bond in the side chain is not particularly limited, and is, for example, a structure represented by the following formula (A-10), a structure represented by the formula (A·11), and a structure in which the structures are mixed. It is better. 〇 r?-?T c-ch2 RbC-O-CHsr CH-Lf^O-C Ο 0Η h General formula (A-10)

RaRc 13⁄4

Oh General Formula (A-1) In the above formula (A-10) and formula (A-11), Ra to RC represents a hydrogen atom or a monovalent organic group. The 1 line represents a hydrogen atom or a methyl group. The ^ system indicates an organic group which may also have a linking group. The structure represented by the above formula (A-10) or the structure represented by the formula (A-11) is preferably 20 mol% or more, and 20 mol% to 5 mol%, based on the content of the polymer compound. More preferably, it is particularly good at 2 5 m% to 4 5 m%. When the content is less than 20 mol%, the case where the amount of hardening reaction is small and the case where the sensitivity is low is more than 50 mol%, the storage stability may be deteriorated. -Carboxyl group - The polymer compound of the present invention may have a carboxyl group in order to improve various properties such as non-image portion removability. -30- 200941138 The above carboxyl group can be imparted to the above polymer compound by copolymerizing it with an organic compound having an oxy group. The acid group having such a radical polymerizable property may, for example, be a sulfonic acid or a phosphoric acid group, and particularly preferably a carboxylic acid. The radically polymerizable compound having a carboxyl group is not appropriately selected according to the purpose, and examples thereof include acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic ethylene. Among these, acrylic acid, A The base acrylate is preferably used alone or in combination of two. The carboxyl group is preferably used in an amount of from 1.0 meq/g to 1.5 meq/g to 3.0 meq/g. When the content is less than 1. The property is insufficient, and when it is more than 4.0 meq/g, the image strength which is easily damaged may be impaired. In order to enhance various properties such as image strength, it is preferred to copolymerize other radical polymerizable compounds in addition to the above-mentioned radical polymerizable compound. The other radical polymerizable compound may, for example, be a free ester of an acid ester, a methacrylate or a styrene. Specific examples thereof include methacrylate aryl esters such as alkyl acrylates and methacrylate aryl esters such as alkyl methacrylates; styrenes such as styrene and alkylstyrene; and halogen-containing styrenes. The acrylates are polymerized by a group of, for example, a carbon number of an alkyl group. For example, a carboxylic acid is particularly limited, and an acid, a methacrylic acid, a p-carboxybenzene, or a p-carboxylic acid phenylene is used. -4 . Omeq/g * When imaging with Omeq/g to an alkali water-developing polymer compound, it is selected, for example, from a propylene-based polymerizable ester, acrylic acid, methacrylic styrene, 〜 20 is preferred, -31-200941138, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, acrylic acid · third octyl ester, Chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, neopentyl alcohol monoacrylate, glycidyl acrylate, benzyl acrylate , methoxybenzyl acrylate, decyl acrylate, tetrahydrofurfuryl acrylate, and the like. The acryl aryl ester may, for example, be phenyl acrylate or the like. The methacrylates are preferably those in which the carbon atom of the alkyl group is from 1 to 20, and examples thereof include methyl methacrylate, ethyl methacrylate, propyl acrylate, and isopropyl methacrylate. Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methyl. chlorobenzyl acrylate, octyl acrylate, 4-hydroxybutyl methacrylate methacrylate 5-hydroxypentyl ester, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, methacrylic acid methacrylate Ester, decyl methacrylate, tetrahydrofurfuryl methacrylate, and the like.前述 The aryl methacrylate may, for example, be phenyl methacrylate, cresyl methacrylate or naphthyl methacrylate. Examples of the styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, and hexyl styrene. Cyclohexylstyrene, mercaptostyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethoxymethylmethylstyrene, and the like. The alkoxystyrene may, for example, be methoxystyrene, 4-methoxy-32-.200941138--3-methylstyrene, dimethoxystyrene or the like. The halogen styrene may, for example, be chlorostyrene, dichlorobenzenetrichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene styrene, iodine styrene, fluorostyrene, trifluorostyrene, 2 - bromo-methylstyrene, 4-fluoro-3-trifluoromethylstyrene, and the like. These radically polymerizable compounds may be used alone or in combination of two or more. In the present invention, the solvent used in the synthesis of the polymer compound is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include dichlorocyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, and B. Glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyacetic acid. 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-di Methylamine, N,N-dimethylacetamide, dimethylhydrazine, toluene, methyl lactate, ethyl lactate, and the like. These may be used alone or in combination of two or more. In the present invention, the molecular weight of the polymer compound is preferably 10,000 or more, more preferably 10,000 to 50,000. When the average molecular weight is less than 10,000, the film strength tends to be low when the strength of the cured film is less than 50,000. Further, in the present invention, a non-monomer may be contained in the polymer compound. In this case, the monomer is preferably 15% by mass or less based on the polymer compound. In the present invention, the polymer compound may be used singly or in combination of two or more. Further, other polymer compounds may be mixed, and ethylene, and monobromo-tetrafluoro may be used in combination with no specific amount of ethylene, butanol, ethyl ester, methyl ethyl phthalate, and a mixture of molecular weights, and the amount of the reaction. It can be mixed and used. In the above-mentioned other polymer compound, the content of the polymer compound of the present invention is preferably 5% by mass or less, and more preferably 3% by mass or less. &lt;Epoxy acrylate compound&gt; The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated bond and a carboxyl group in the molecule. Such a compound can be obtained, for example, by a method in which a polyfunctional epoxy compound is reacted with a carboxyl group-containing monomer, and a polybasic acid anhydride is further added. For example, the above-mentioned polyfunctional epoxy compound may, for example, be a bixylenol type or a bisphenol type epoxy resin ("YX4000; manufactured by JAPAN EPOXY RESINS Co., Ltd."), or a mixture thereof, or an isomeric isocyanate skeleton. Heterocyclic epoxy resin ("TEPIC; manufactured by Nissan Chemical Industry Co., Ltd.", "ARALDITE PT810; manufactured by CIBA SPECIALTY CHEMICALS"), bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated phenol novolak type epoxy resin, epoxy acrylamide type epoxy Resin (for example, tetraepoxypropyldiaminediphenylmethane, etc.), hydantoin epoxy resin alicyclic epoxy resin, trishydroxyphenylmethane epoxy resin, bisphenol A novolac type ring Oxygen resin, tetraphenol ethane type epoxy resin, butyl citrate resin, tetra-glycidyl dimethyl phenol ethane resin, naphthalene-containing epoxy resin ("ESN-190, ESN-360" ; Nippon Steel Chemical Co., Ltd., "HP-4032, EXA-4750, EXA-4700; Epoxy resin having a dicyclopentadiene skeleton ("HP-7200, HP-7200H; Dainippon Ink Chemical Industry Co., Ltd. -34-200941138"), etc., by the Japan Ink Chemical Industry Co., Ltd. a polyphenol compound obtained by a condensation reaction between a phenol compound such as phenol, o-cresol or naphthol and an aromatic aldehyde having a phenolic hydroxyl group, and a reaction product with epichlorohydrin; a phenol compound and divinylbenzene or dicyclopentane a polyphenol compound obtained by an addition reaction of a diene compound such as a diene, and a reaction product with epichlorohydrin; a ring-opening polymer of 4-vinylcyclohexene-1-oxide using a ring of peracetic acid or the like Oxidized one; heterocyclic epoxy resin such as triglycidyl isocyanate; epoxy methacrylate copolymerized epoxy resin ("CP-50S, CP-50M; Nippon Oil and Fats Co., Ltd. a copolymerized epoxy resin of cyclohexylm-butyleneimine and glycidyl methacrylate; a condensate selected from the group consisting of phenol and cresol and p-hydroxybenzamide Epoxy resin obtained by etherification of epoxy propyl; double (glycidoxy The phenyl group-based adamantane type epoxy resin, etc. These may be used alone or in combination of two or more. Examples of the carboxyl group-containing monomer include (meth)acrylic acid and vinylbenzoic acid. Maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano cinnamic acid, acrylic acid dimer; and others (A An addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl acrylate with a cyclic acid anhydride such as maleic anhydride, decanoic anhydride or cyclohexane dicarboxylic anhydride; and a reaction with a halogen-containing carboxylic acid compound The product, ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. In addition, the commercial products can use ARONIX Μ-5300, Μ-5400 'Μ5500 and Μ-5600 made by East Asia Synthetic Chemical Industry Co., Ltd., ΝΚ ESTER CB-1 and CBX-1 made by Shin-Nakamura Chemical Industry Co., Ltd. ΗΟΑ-ΜΡ and HOA-MS manufactured by Kyoeisha Chemical Industry Co., Ltd., -35-.200941138 818&lt;: 〇八丁#2 100, manufactured by Osaka Organic Chemical Industry Co., Ltd. These may be used alone or in combination of two or more. Further, examples of the polybasic acid anhydride include succinic anhydride, methyl benzoic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, and dodecyl succinic anhydride. , nonenyl succinic anhydride, cis-succinic anhydride, methyl maleic anhydride, 2,3-dimethyl maleic anhydride, 2-chlorobutane-anhydride, 2,3-chlorochloride Dibutyl dianhydride, brominated dianhydride, itaconic anhydride, citraconic anhydride, cis-aconitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, six Hydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, chlorendic anhydride and 5-(2) 1,2. Bis-oxytetrahydrofuranyl)-3-methyl-3-cyclohexan-1,2-diresin anhydride, etc. Dibasic anhydrides can also be used 1,2,4-benzenetricarboxylic anhydride, coke honey A polybasic acid anhydride such as petroic anhydride or 3,3',4,4'-diphenyl ketone tetracarboxylic acid. These may be used alone or in combination of two or more. The respective groups are reacted in order to obtain an epoxy acrylate such that the ratio of the reactions is based on the epoxy group of 1 equivalent of the polyfunctional epoxy compound, and the carboxyl group of the carboxyl group-containing monomer is 〇8 to 1.2 equivalents to 0.9. It is preferably 1.1 equivalents, and the polybasic acid anhydride is 0.1 to 1.0 equivalent, preferably 0.3 to 1.0 equivalent. Further, an epoxy acrylate having an anthracene skeleton (a compound having no carboxyl group) and a compound obtained by adding an acid anhydride described in JP-A No. 5-7 0 528 can also be used as the epoxy of the present invention. Acrylate. The epoxy acrylate compound preferably has a molecular weight of 1,000 to 1,000,000 and more preferably 2,000 to 50,000. When the molecular weight is less than 1,000, -36-.200941138 may have a strong adhesiveness on the surface of the photosensitive layer, and after the photosensitive layer is hardened as described later, the film may become brittle or the surface hardness may be deteriorated, and may be more than 100,000. When there is a case where the imaging performance is deteriorated. Moreover, the synthesis of the resin also becomes difficult. The content of the solid content of the above-mentioned binder in the photosensitive composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. The content of the solid content of the above-mentioned binder in the photosensitive composition is preferably 5 to 80% by mass, more preferably 1 to 70% by mass. When the content of the solid component is less than 5% by mass, the film strength tends to be deteriorated, and the adhesiveness of the surface V of the photosensitive layer is deteriorated. When the content is more than 80% by mass, the exposure sensitivity may be lowered. (Polymerizable compound) The polymerizable compound is not particularly limited, and may be appropriately selected according to the purpose, and the weight of the I/O値 is preferably 0.50 or less. The polymerizable compound is tricyclodecane dimethanol diacrylate (I/O 値: 0.428), tricyclodecane dimethanol dimethacrylate (I/O 値: 0.385), trihydroxyl-propane trimethyl Acrylate (I/O値: 0.517), neopentyl glycol diacrylate (I/O値: 0.564), 1,10-decanediol diacrylate (I/O 値: 0.388), 1, 6-hexanediol diacrylate (I/O 値·· 0.443), 1,9·nonanediol diacrylate (I/O値: 0.413), neopentyl glycol dimethacrylate (I/O)値:0.477), 1,9-nonanediol dimethacrylate (I/O 値: 0.3 6 5), etc.

The above-mentioned I/O lanthanum is also known as the polarity of various organic compounds of (inorganic 値)/(organic 値), and is treated organically, and is a functional group contribution to the parameter setting of each functional group. One of the laws. In detail, the aforementioned I/O -37-200941138 is in the organic memorial map (Katata Satoshi, San Gong Publishing (1 984)); KUMAMOTO PHARMACEUTICAL BULLETIN (Journal of Medicine), No. 1, Item 1 to 16 (1954) ); Chemistry, Vol. 11, No. 10, No. 719-725 (1957); FRA GRACE JOURNAL (Aromatic Journal), No. 34, No. 97-111 (1979); FRAGRACE JOURNAL ), the 50th issue, the 79th to 82nd (1981) and other documents are described in detail. The entanglement of the above I/O値 distinguishes the properties of the compound into an organic group representing a covalent bond bond and an inorganic group representing an ionic bond, and positions all the organic compounds in the name organic axis and none. Each point on the straight-line coordinates of the crankshaft is not shown. The inorganic lanthanum is obtained by varying the influence of various substituents or bonds of the organic compound on the boiling point and using a hydroxyl group as a reference. Specifically, since the distance between the boiling point curve of the linear alcohol and the boiling point curve of the linear paraffin is about 100 ° C when it is obtained in the vicinity of the carbon number of 5, the influence of one hydroxyl group is determined to be 100, based on the number of In this case, the inorganic enthalpy of the substituent of the fluorene-based organic compound obtained by decomposing the influence of various hydrazine substituents or various kinds of bonds on the boiling point. For example, the inorganic enthalpy of the -COOH group is 150, and the inorganic enthalpy of the double bond is 2. Therefore, the inorganic lanthanide of an organic compound means the sum of inorganic ruthenium of various substituents or bonds which the compound has. The above-mentioned organic oxime means a ruthenium which is defined by the influence of the influence of the carbon atom representing the methylene group on the boiling point in units of methylene groups in the molecule. That is, since the linear saturated hydrocarbon compound increases the average 値20 ° C of the boiling point of one carbon atom of -38 to 200941138 near the carbon number of 5 to 10 0, the organic enthalpy of one carbon atom is used as a reference. The formula is 20, and based on this, the influence of various substituents or bonds on the boiling point is made into an organic enthalpy. For example, the nitro (-N02) organic enthalpy is 70. The closer the I/O 接近 is to 0, the non-polar (hydrophobic, organic) organic compound is shown. When it is larger, it exhibits an organic compound having a polarity (hydrophilic, inorganic). In addition, the weight average of the I/O値 is, for example, when the polymerizable compound A is mixed with a polymerizable compound in a ratio of a 〇 wt% and B b wt% (a + b = 100), and the weight of the I/O 値The average = (I I / O 値 xa / 100 + B I / O 値 xb / 100) to calculate. Hereinafter, an example of the calculation method of the aforementioned I/O値 will be described. The I/O system of pentaerythritol tetraacrylate was calculated by the following method and calculated by calculation (inorganic enthalpy) / (organic enthalpy). Since pentaerythritol tetraacrylate has 17 carbon atoms, the organic enthalpy of neopentyltetraol tetraacrylate can be calculated as follows, that is, 20 (organic 値 of carbon source) x 1 7 (carbon) Atomic number) = 340. Inorganic lanthanide of pentaerythritol tetraacrylate Since neopentyltetraol tetraacrylate has 4 carboxyl groups and 4 double bonds, the intrinsic enthalpy of neopentyltetraol tetraacrylate is 60 (ester-based inorganic値)) 4 (number of ester groups) + 2 (inorganic enthalpy of double bond) Χ 4 (number of double bonds) = 248. From this, it was found that the I/O 新 of pentaerythritol tetraacrylate was 248 (inorganic enthalpy of the above copolymer) / 340 (organic enthalpy of the above copolymer) = 0.729. Further, the "polymerizable compound" of the present invention does not contain the polymerizable compound contained in the binder -39-200941138. The content of the solid content of the polymerizable compound in the photosensitive composition is preferably 5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass. When the content of the solid content is less than 5% by mass, there is a problem that the developing property is deteriorated and the exposure sensitivity is lowered. When the content is more than 50% by mass, the adhesion of the photosensitive layer becomes strong, which is not preferable. . (Anthracene Derivative) The above anthracene derivative is represented by the following formula (1).

In the above formula (1), R1 represents a hydrogen atom, a mercapto group which may have a substituent, an alkoxycarbonyl group and an aryloxycarbonyl group, and R2 each independently represents a halogen atom or an alkyl group. , aryl, alkoxy, aryloxy, thiol, thiol and amine. The m series is not an integer of 0 to 4, and when it is 2 or more, it may be linked to each other to form a ring. Line A indicates any of the 4, 5, 6 and 7 member rings. The anthracene derivative is excellent in stability and high sensitivity, and by adding the anthracene derivative, it is excellent in preservation stability without polymerization, and is easy to handle 'activating by energy rays, particularly irradiation light. The polymerization is started efficiently by radicals, and the polymerizable compound can be efficiently polymerized in a short time to obtain a highly sensitive polymerizable composition. Further, the anthracene derivative of the above formula (2) is more preferably an anthracene derivative. -40- 200941138

In the above formula (2), R1 represents a hydrogen atom, a sulfhydryl group which may have a substituent, an alkoxycarbonyl group and an aryloxycarbonyl group, and R2 each Each of a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group and an amine group is independently represented, and m represents an integer of 0 to 4. The X system indicates any of CH2, 〇, and S. The 1 line represents an integer of 1 to 3. Further, the anthracene derivative is more preferably an anthracene derivative represented by any one of the following general formulae (3) and (4).

General formula (3)

In the above formulae (3) and (4), R1 represents a hydrogen atom, or an alkyl group, an alkoxycarbonyl group or an aryloxycarbonyl group which may have a substituent, and R2 each independently represents Any one of a halogen atom, an alkyl group, an aryl group, an alkoxy 'aryloxy group, an alkylthio group, an arylthio group and an amine group' m represents an integer of 0 to 4. The X system indicates any one of CH2, 〇, and S. The 1 series represents an integer of 1 to 3. -41-200941138 The anthracene derivative described in any one of the above (2) to (4), wherein X is Ο and S in the general formulae (2), (3) and (4), 1 is 1 or 2, and R1 is preferably any of an anthracenyl group and an alkoxycarbonyl group which may have a substituent. In the above formulae (1), (2), (3) and (4), R1 may have any one of a substituent group, an alkoxycarbonyl group and an aryloxycarbonyl group. The thiol group may be any of an aliphatic, an aromatic, and a heterocyclic ring. It is preferable that the total carbon number is 2 to 30, and the total carbon number is 2 to 20, and the total carbon number is 2 to 16. The aforementioned fluorenyl group may further have a substituent. The substituent is preferably an alkoxy group, an aryloxy group or a halogen atom. The mercapto group may have a substituent, and examples thereof include an ethyl fluorenyl group, a n-propyl fluorenyl group, an isopropenyl group, a methyl propyl fluorenyl group, a butyl fluorenyl group, a trimethyl ethenyl group, a hexyl fluorenyl group, and a cyclohexane carbonyl group. , octyl, decyl, dodecyl fluorenyl, octadecyl fluorenyl, benzylcarbonyl, phenoxyethyl hydrazino, 2-ethylhexyl decyl, chloroethyl benzyl benzyl thiol, toluene carbonyl , p-methoxybenzhydryl, 2,5-dibutoxybenzylidene, 1-naphthylfluorenyl, 2-naphthylfluorenyl, pyridylcarbonyl, methacrylinyl, acrylonitrile, and the like. The alkoxycarbonyl group may have a substituent, preferably having a total carbon number of 2 to 30, more preferably 2 to 20 in total carbon, and particularly preferably 2 to 16 in total carbon. The alkoxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, an aryloxycarbonyl group, an octyloxycarbonyl group, or twelve. Alkoxycarbonyl, ethoxyethoxycarbonyl. The aryloxycarbonyl group may have a substituent, preferably an aryloxy carbon group having a total carbon number of 7 to 30, more preferably a total carbon number of 7 to 20, and a total carbon number of 7 to i6 -42 to 200941138. It is especially good. Examples of such an aryloxycarbonyl group include a phenoxy mineral group, an oxycarbonyl group, a p-methoxyphenoxycarbonyl group, a 2,5-diethoxyphenoxy group, a p-chlorophenoxycarbonyl group, and a p-nitrobenzene group. Phenoxy group, p-cyanobenzenecarbonyl. In the above formulae (1), (2), (3) and (4), the 'r2 groups are each independently a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a thiol group and Any of the amine groups may, in particular, be an aliphatic, aromatic aromatic, halogen atom, -OR3, -SR3 or -nr3r4. R3 and R4 can also be joined to form a ring. Further, the r4 system independently represents hydrogen or an aliphatic group, an aromatic group or a heteroaromatic group. When m is the upper side and is connected to each other to form a ring, the independent R2 may be a ring or may form a ring through at least either of R3 and R4. When the ring is formed by the above-mentioned substituent R2, the following knots can be exemplified. 2-Naphthalene γμι Suspend The oxy group can be formed by argon and heteroatoms.

In the above structural formula, 'y and z are each of CH2, -〇-, -s-;g. The alkyl group may have a substituent, and it is preferably one having a total carbon number of from 1 to 18, and particularly preferably having a carbon number of from 1 to ί. Such an alkyl group may, for example, be a methyl group, a propylidene group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, a third fluorene-NR- group, a total group, a fluorenyl group, a -43-.200941138 n-hexyl group. , Zheng Xinji, third octyl, and ruthenium. The aryl group may have a substituent ', preferably 6 to 20 in total carbon number', and is particularly preferably a total carbon number of 6 to 12. Examples of such an aryl group include a phenyl group, a biphenyl group, a naphthyl group, a chlorophenyl group, and a methoxyphenyl group. The alkoxy group may have a substituent, and it is preferably one having a total carbon number of from 1 to 18, and particularly preferably having a total carbon number of from 1 to 12. The alkoxy group may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a third butoxy group, a 2-ethylhexyloxy group or a n-decyloxy group. Phenylethyloxy, phenoxyethoxy. The aryloxy group may have a substituent, and it is preferably a total carbon number of 6 to 20, which is particularly preferably a total carbon number of 6 to 12. Examples of such an aryloxy group include a phenoxy group, a naphthyloxy group, a chlorophenoxy group, and a methoxyphenoxy group. The alkylthio group may have a substituent, and preferably has a total carbon number of from 1 to 18, and is particularly preferably a total carbon number of from 1 to 12. Examples of such an alkylthio group include a methylthio group, an ethylthio group, an isopropylthio group, a n-butylthio group, a n-octylthio group, a n-dodecylthio group, and a 2-ethylhexylthio group. The arylthio group may have a substituent, and it is preferably a total carbon number of 6 to 20, and particularly preferably a total carbon number of 6 to 12. Examples of such an arylthio group include a phenylthio group, a toluenethio group, a chlorophenylthio group, and an ethoxycarbonylphenylthio group. The amine group may have a substituent, and may be substituted by at least one of an alkyl group and an aryl group, preferably having a total carbon number of 1 to 2 0, and particularly preferably having a total carbon number of 1 to 12. Examples of such an amine group include a -NH2 group, a diethylamino group, a diphenylamino group, and a methylanilino group. Specific examples of the aliphatic group, the aromatic group and the heteroaromatic group of R2, R3 and R4 are the same as those of the above R1. -44-.200941138 Specific examples of the anthracene derivatives represented by the above formulas (1) to (4) include the compounds represented by the following structural formulae (1) to (52), but the present invention is not limited thereto. Wait. ❹

-45- 200941138

Structural formula (1)

Structural formula (2)

Structural formula (4)

Structural formula (5)

Structural formula (6)

Structural formula (7) Structural formula (8)

Structural formula (11) Structural formula (12)

Structural formula (13) Structural formula (14) Structural formula (15) Structural formula (16) Structural formula (17) Structural formula (18)

妒OAG structural formula (19) structural formula (20) structural formula (21) structural formula (22)

, QA&lt;!

Structural formula (23) Structural formula (24) Structural formula (25) Structural formula (26) Structural formula (27) Structural formula (28)

Structural formula (29) Structural formula (30) Structural formula (31) Structural formula (32) Structural formula (33) Structural formula (34) -46- 200941138 m

Structural formula (35) Structural formula (36) Structural formula (37) Structural formula (38) Structural formula (39) ^.oJLo.p*, |f ο γΟΗ

Fiber type (40) weave type (41) structure type (42) type (43) fiber type (44) structure type (45)

Structural formula (46) Structural formula (47) Structural formula (48) Structural formula (49) Structural formula (5 (〇 structural formula ¢ 51) Structural formula (52) Further, the anthracene derivative can be measured by 1H-NMR spectrum, Identification by UV-vis absorption spectroscopy (manufacturing method of anthracene derivative) The above-described method for producing an anthracene derivative is obtained by using an anthracene derivative (hereinafter referred to as a material indole derivative) and a crucible of a starting material corresponding to an anthracene derivative. The chloride or anhydride is easily synthesized in the presence of a base (for example, diethylamine or pyridine) in an inert solvent such as THF, DMF or acetonitrile or an alkaline solvent such as pyridine. The reaction temperature is preferably -10·'60 ° C. Further, by using chloroformate, alkylsulfonium chloride or arylsulfonium chloride as the above-mentioned ruthenium chloride, various corresponding oxime ester compounds can be synthesized. The method for synthesizing the hydrazine derivative used in the production of the hydrazine derivative can be carried out in standard chemistry textbooks (for example, J. March, Advanced Organic Chemistry, 4th edition, -47- • 200941138)

Wiley InterSCience, 992), or a variety of methods described in specialized research papers (eg, SR Sanler &amp; W. Karo, Organic functional group preparations, Vol. 3, Academic Press). Come and get. The above-mentioned material hydrazine derivative may be, for example, a method of reacting an aldehyde or a ketone with a hydroxylamine or a salt thereof in a polar solvent such as ethanol or ethanol water. At this time, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. The reaction rate is pH-dependent, and it is known that bases can be continuously added at the beginning of the reaction or during the reaction. It is also possible to use an inert solvent such as pyridine as a base and/or a solvent or a solubilizing agent. The above reaction temperature is usually preferably from the reflux temperature of the mixture, i.e., about 60 to 120 ° C. Other preferred synthesis methods of the above-mentioned material hydrazine derivative include a nitrosylation method using an "active" methylene group of nitrous acid or an alkyl nitrite. For example, in Organic Syntheses coll. Vol. VI (J. ® Wiley &amp; Sons, New York, 1 988), pp. 199 and 840, and for example in Organic Syntheses coll· Vol· ρρ · 32 and 3 73, coll. Vol. Ill, pp. 191 and 513, coll. Vol. II, pp. 202, 204 and 3 63 are both acidic conditions suitable for synthesis in the present invention as a starting point The material used for the material is a hydrazine derivative. The above nitrous acid is usually produced by sodium nitrite. The aforementioned alkyl nitrite may, for example, be methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite. -48- 200941138 The base of the above oxime ester may also be present in two types of stereoscopic configurations (z) or (E). The isomers can be isolated according to a usual method, and the isomer mixture can also be used as a raw material for photoinitiation. Therefore, the anthracene derivative may be a mixture of isomers in a stereo configuration of the compounds of the above structural formulas (1) to (52). Since the above anthracene derivative is excellent in storage stability and high sensitivity, by adding In the polymerizable composition, the storage stability is excellent, and the storage stability is excellent without storage, and the polymerization is efficiently started by the energy ray, particularly the illuminating light ray, and the polymerizable compound is efficiently polymerized. It is possible to efficiently polymerize in a short time to obtain a highly sensitive polymerizable composition. Therefore, the anthracene derivative can be used as a radical generator and added to printing inks, transparent processing materials, powder coating materials, building markings or guide markings, photo copying methods, holographic recording materials, and portrait recordings. Manufacturing method, printing original plate capable of using organic solvent or water-based enamel development, solar hardening coating material for producing screen printing mask, dental enamel filling composition, adhesive, pressure-sensitive adhesive, laminated layer Resin, liquid enthalpy and film-like etching photoresist, solder resist, plating resist, permanent resist, printed circuit board, or light-constituting dielectric for electronic circuits are used. Moreover, it can be used for various materials for use, materials for forming structures in a plasma display panel or an electroluminescence display device, color light sheets, optical switches, optical lattices (interference lattices), optical circuits A material for manufacturing, a large amount of hardening (UV curing using a mold for transparent molding), a material for manufacturing a three-dimensional article according to a stereolithography method, a composite material such as styrene-based polyester, and a material for manufacturing other thick layer compositions , electronic components and laminated electric-49 - 200941138 Road anti-uranium agent for coating or sealing, fiber forming material, coating material for optical lens manufacturing, etc. Moreover, it can also be used in the manufacture of medical devices, auxiliary devices, and graft materials to produce gels having thermal properties. In particular, the photosensitive composition of the present invention can be suitably used. Further, the anthracene derivative can be used as an initiator for emulsion polymerization, particulate polymerization, or suspension polymerization. Further, a polymerization initiator which is a regular state of a monomer or an oligomer for fixing a liquid, and an initiator for fixing a dye to an organic material may be used in addition. 〇 (Ion Adsorbent) The ion adsorbent is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include zirconium phosphate, ruthenium pentoxide hydrate, antimony trioxide, hydrotalcite, and the like. In the present invention, it is particularly preferable to use chromium phosphate from the viewpoint of insulation reliability. For example, IXE-1 〇〇, IXE-700F (above, manufactured by Toagosei Co., Ltd.), and DHA-4A-2 (manufactured by Kyowa Interface Science Co., Ltd.) can be used. ^ The ion adsorbent may be used singly or in combination of two or more. (Digest) The above-mentioned dip is not particularly limited, and can be appropriately selected from well-known materials. For example, kaolin, barium sulfate 'barium titanate, oxidized sand powder, fine powdered cerium oxide, gas phase cerium oxide, amorphous oxidized chopping, crystalline cerium oxide, molten cerium oxide, spherical two Antimony oxide, talc, clay, magnesium carbonate, calcium carbonate, alumina, hydrazine, mica, and the like. -50- 200941138 This material can be used singly or in combination of two or more. The average particle size of the aforementioned dip is preferably less than 3 μm, more preferably 〇1 μm to 2 μm. When the average particle diameter is 3 μm or more, the resolution may be deteriorated due to light irradiation. The amount of the above-mentioned kneaded material is preferably 5% by mass to 7.5 mass%, more preferably 8% by mass to 70% by mass, even more preferably 1% by mass to 65% by mass. When the amount of addition is less than 5% by mass, the linear expansion coefficient may not be sufficiently lowered. When the amount is more than 90% by mass, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film becomes brittle and is formed by using a permanent pattern. When wiring, there is a case where the function as a protective film for wiring is impaired. The aforementioned dip can also add organic microparticles as necessary. The organic fine particles of the appropriate type are not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include a melamine resin, a benzoguanamine resin, and a crosslinked polystyrene resin. A spherical porous fine particle composed of a ceria or a cross-linking resin having an average particle diameter of 0.1 μm to 2 μm, an oil absorption of 100 m 2 /g to 200 m 2 /g, or the like can be used. Since the above-mentioned tanning material contains particles having an average particle diameter of 0.1 μm to 2 μm, even if the permanent pattern is thinned to a thickness of 5 μm to 20 μm as the printed wiring substrate is thinned, the tanning material will not be permanently The surface of the back of the pattern is cross-linked on both sides, and as a result, no ion migration in the acceleration test (HAST) can be used as a permanent pattern excellent in heat resistance and moisture resistance. (Thermal cross-linking agent) The thermal cross-linking agent is not particularly limited, and can be appropriately selected according to the purpose of the film layer formed by the hardening of the photosensitive layer formed by the use of the photosensitive film-51-200941138. The range in which the image or the like adversely affects, for example, an epoxy compound having at least two ethylene oxide groups in one molecule and an oxetane having at least two oxetanyl groups in one molecule can be used. Alkane compound. The epoxy compound having at least two ethylene oxide groups in one molecule is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include a bixylenol type or a bisphenol type epoxy resin ("YX4000; Heterocyclic epoxy resin having a heterotrimeric phthalocyanate skeleton, etc. ("TEPIC; manufactured by Nissan Chemical Industries, Ltd.", "ARALDITEPT810; manufactured by CIBA SPECIALTY CHEMICALS Co., Ltd.) , etc.), bisphenol A type epoxy resin, novolak 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 novolak type epoxy resin, halogenated phenol novolak type epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolak type epoxy resin, etc.), Allyl-containing bisphenol A type epoxy resin, trisphenol methane type epoxy tree 0 ¥ fat, diphenyl dimethanol type epoxy resin, phenol extended biphenyl type epoxy resin, dicyclopentadiene type Epoxy resin ("HP-7200, HP-72 00H; manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy propylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diepoxypropyl aniline, triepoxypropylamino group) Phenol, etc., propylene glycol ester type epoxy resin (diglycidyl citrate, diglycidyl adipate, diglycidyl hexahydrophthalate, di- diglycidyl ester, etc.) Epoxy resin, cycloaliphatic epoxy resin (3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane carboxylate, adipic acid bis(3,4-epoxy) Cyclohexyl-52-200941138 base ester, dicyclopentadiene diepoxide, "GT-300, GT-400, ZEHPE3150; manufactured by DAICEL Chemical Industry Co., Ltd.", etc., quinone imine type alicyclic ring Oxygen resin, trishydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenol ethane type epoxy resin, butyl phthalate resin, tetra-glycidyl dimethyl phenol group Ethane resin, naphthalene-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, 4-functional naphthalene type epoxy resin (commercial product "ESN-190" ESN-3 60; manufactured by Nippon Steel Chemical Co., Ltd., "HP·4032, EXA-4750' Ο EXA-4700; manufactured by Otsuka Ink Chemical Industry Co., Ltd.", etc., by phenol compound and divinylbenzene or a polyphenol compound obtained by an addition reaction of a diolefin compound such as dicyclopentadiene or a reaction product with epichlorohydrin; a peracetic acid using a ring-opening polymer of 4-vinylcyclohexene-1-oxide Epoxidized one; epoxy resin having a linear phosphorus-containing structure' epoxy resin having a ring-shaped phosphorus structure, α-methyl bottom type liquid crystal epoxy resin, and diphenyl styrene oxybenzene type liquid crystal ring Oxygen resin, azophenyl liquid crystal epoxy resin, methylimine phenyl liquid crystal epoxy resin, naphthalene liquid crystal epoxy resin, V哄 type epoxy resin, epoxy methacrylate copolymerization Epoxy resin CP-50S 'CP-50M; made by Nippon Oil & Fat Co., Ltd.), copolymerized epoxy resin of cyclohexyl cis-butyl amide and glycidyl methacrylate; Epoxy resin made of one kind of cresol and p-hydroxybenzamide condensate Glycidyloxyphenyl) adamantane type epoxy resins and the like homes. These may be used alone or in combination of two or more. Further, in addition to the above epoxy compound having at least two epoxy groups in one molecule, it is also possible to use at least -53 to 200941138 in one molecule and two epoxy groups having an alkyl group at the β position. The epoxy compound of the group is particularly preferably a compound containing an epoxy group in which the p position is substituted with an alkyl group (more specifically, a β-alkyl-substituted epoxypropyl group or the like). The epoxy compound containing at least an epoxy group having an alkyl group at the β position may be one or more epoxy groups contained in one molecule, all of which may be a fluorenyl-alkyl-substituted epoxy propyl group, or may be at least One epoxy group is a β-alkyl substituted epoxypropyl group. The epoxy compound containing an epoxy group having an alkyl group at the β position, and the total epoxy resin in the total amount of the epoxy compound contained in the photosensitive composition, from the viewpoint of storage stability at room temperature The ratio of the fluorene-substituted alkyl group in the group is preferably 30% or more, more preferably 40% or more, and more preferably 5% or more. The β-alkyl substituted epoxypropyl group is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include β·methyl epoxypropyl group, β·ethyl epoxypropyl group, and β-propyl epoxy group. Among the above, from the viewpoint of enhancing the storage stability of the photosensitive composition and the ease of synthesis, among them, propyl-methyl epoxypropyl group It is better. The above epoxy compound containing an epoxy group having an alkyl group at the β position is preferably, for example, an epoxide derived from a polyvalent fluorene compound and a fluorene-terminated epihalohydrin. The β-alkyl epihalohydrin is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include β-methylepichlorohydrin, β-methylepibromohydrin, and β-methylepifluorohydrin. _Methyl epihalohydrin; β-ethyl epihalohydrin such as ethyl epichlorohydrin, ethyl ethyl bromide, β-ethyl epifluorohydrin, etc.; Ρ-propyl epigas alcohol '-54- .200941138 propyl Β-propyl epihalohydrin such as epibromohydrin or β-propyl epifluorohydrin; ρ-butyl such as β-butylepichlorohydrin, β-butyleprobromohydrin or β-butylepifluorohydrin Epihalohydrin and the like. Among these, a β-methyl epihalohydrin is preferred from the viewpoint of reactivity with the polyhydric phenol and fluidity. When the polyhydric phenol compound is a compound containing two or more aromatic hydroxy groups in one molecule, it is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include bisphenol A, bisphenol F, and bisphenol S. Biphenol compound, biphenol compound such as biphenol or tetramethylbiphenol, naphthol compound such as dihydroxyphthalenyl or bisphthol, phenol novolak resin such as phenol-formaldehyde polycondensate, cresol-formaldehyde polycondensation a carbon number of 1 to 10, a monoalkyl-substituted phenol-formaldehyde polycondensate, a xylenol-formaldehyde polycondensate, etc., a carbon number of 1 to 10, a dialkyl-substituted phenol-formaldehyde polycondensate, and a bisphenol A-formaldehyde A bisphenol compound-formaldehyde polycondensate such as a polycondensate, a copolycondensate of phenol and a monoalkyl-substituted phenol having 1 to 10 carbon atoms, and a polymerized adduct of a phenol compound and divinylbenzene. Among these, in order to improve fluidity and preserve stability, the bisphenol compound is preferred. ® The above epoxy compound containing an epoxy group having an alkyl group at the β position may, for example, be a di-β-alkylepoxypropyl ether of bisphenolphthalein or a di-β-alkylepoxypropyl group of bisphenol F. Di-β-alkylepoxypropyl ether of bisphenol compound such as di-β-alkylepoxypropyl ether of bisphenol S; di-β-alkylepoxypropyl ether of biphenol, four Di-β-alkylepoxypropyl ether of a biphenol compound such as di-β-alkylepoxypropyl ether of methylbiphenol; di-β-alkylepoxypropyl ether of dihydroxynaphthalene, a naphthol compound such as a naphthol compound such as a di-β-alkylepoxypropyl ether; a poly-β-alkylepoxypropyl acid of a phenol formaldehyde polycondensate; A-55- 200941138 poly-β-alkylepoxypropyl ether of phenol formaldehyde polycondensate, poly-β-alkylepoxypropyl ether of monoalkyl-substituted phenol formaldehyde polycondensate of carbon number 1~10; xylenol-formaldehyde Poly-β-alkylepoxypropyl ether of a polycondensate, poly-fluorene-alkylepoxypropyl ether of a dialkyl-substituted phenol-formaldehyde polycondensate having a carbon number of 1 to 10; bisphenol oxime-formaldehyde polycondensate Bisphenol compound such as poly-β-alkylepoxypropyl ether Poly-β-alkylepoxypropyl ether of a polymer; poly-β-alkylepoxypropyl ether of a polymerized adduct of a phenol compound and divinylbenzene. Among these, a bisphenol compound represented by the following formula (D-1), and a β-alkyl epoxidized ether derived from a polymer obtained by using it with epichlorohydrin or the like, and the following The poly-ρ-alkyl epoxy ether of the phenol compound-formaldehyde polycondensate represented by the formula (D-2) is preferred.

0-CH2-CH-CH 0Η

0 Ο-ΟΗ^-^Α R General formula (D-1) ❹

Any of the alkyl groups. The η system represents 〇 Formula (D-2) R represents a hydrogen atom and an integer of -20 carbon atoms. 1 to 6 R represents a hydrogen atom and a carbon number of 1 to 6 wherein R of the above-mentioned general formula (D-2) represents either a hydrogen atom or CH3, and η represents 0 to 20 The integer. -56-200941138 These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used singly or in combination of two or more. Further, an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β position may be used in combination. The skeleton of the epoxy compound is preferably at least one selected from the group consisting of a bisphenol type epoxy resin, a novolak type epoxy resin, an alicyclic type epoxy resin, and a poorly soluble epoxy resin. The oxetane compound may, for example, be bis[(3-methyl-3-oxonium®cyclobutanemethoxy)methyl]ether or bis[(3-ethyl-3-oxocycle). Butyryl methoxy)methyl]ether, 1,4-bis[3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[3-ethyl 3-oxetanylmethoxy)methyl]benzene, (3-methyl-3.oxetanyl)methyl acrylate, acrylic acid (3-ethyl-3-oxetane) Alkyl)methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or such Polyfunctional oxetane such as oligomer or copolymer, and other compounds having an oxetane group, a novolac resin, a poly(p-hydroxystyrene), or a Caro type An ether compound such as a phenol having a hydroxyl group such as a bisphenol, a calixarene, a calix resorcinarene or a silsesquioxane, and an oxygen compound A copolymer of an unsaturated monomer of a cyclobutane ring and an alkyl (meth)acrylate, and the like. Further, in order to promote thermal hardening of the aforementioned epoxy compound or the aforementioned oxetane compound, for example, an amine compound (for example, dicyanodiamine, benzyldimethylamine, 4-(dimethylamino)-N may be used. , N-dimethylbenzylamine, 4-methoxy-N,M-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), 4-grade ammonium chloride compound 57· 200941138 (for example, diethylbenzylammonium chloride or the like), a blocked isocyanate compound (for example, dimethylamine, etc.), an imidazole derivative bicyclic guanidine compound or a salt thereof (for example, imiline, 2-methylimidazole, 2 -ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2·cyanoethyl) &gt;-2-ethyl-4-methylimidazole, etc.), a phosphorus compound (for example, triphenyl phthalate), a guanamine compound (for example, melamine, guanamine, acetamide, benzoguanamine, etc.) , S-tripper derivative (for example, 2,4-diamino-6-methylpropenylethyl-8-tripper, 2-vinyl-2,4-diamino-8-tripper, 2-vinyl-4,6-diamine®-based-S-three-pile, iso-cyanuric acid adduct, 2,4-diamino-6- The above-mentioned epoxy resin compound or the above-mentioned oxa compound may be used alone or in combination of two or more. The curing catalyst of the cyclobutane compound or the compound capable of promoting the reaction with the carboxyl group is not particularly limited, and a compound capable of promoting thermal curing other than the above may be used. The epoxy compound and the oxygen heterocycle described above can be promoted. The content of the solid content of the butane compound and the thermosetting compound with the carboxylic acid in the photosensitive composition solid® component is usually 0.01% by mass to 15% by mass. Further, the above-mentioned thermal crosslinking agent can be used. The polyisocyanate compound described in JP-A-5-9407, which may be derived from an aliphatic, cyclic aliphatic or aromatic substituted aliphatic compound containing at least two isocyanate groups. Specifically, 2 Functional isocyanates (for example, a mixture of 1,3-diisocyanate and 1,4-diisocyanate), 2,4- and 2,6-diisocyanate, 1,3- And 1,4-diisocyanatobenzene Ester, bis(4-isocyanate-phenyl)methane, bis(4-isocyanatecyclohexyl)methane, iso-58- 200941138 phorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene di Isocyanate or the like), a polyfunctional alcohol such as a bifunctional isocyanate and trimethylolpropane, neopentyl alcohol or glycerin; an alkylene oxide adduct of the polyfunctional alcohol; and an adduct of the bifunctional isocyanate; A cyclic trimer such as methyl diisocyanate or hexamethylene-1,6-diisocyanate or a derivative thereof, etc. Further, a commercial product of the polyisocyanate compound may, for example, be BL3 17 (Sumitomo BAYER URETHANE) Company system) and so on. Further, for the purpose of improving the preservability and the like, a compound obtained by reacting an isocyanate group of the above-mentioned polyisocyanate and a derivative thereof with a blocking agent can also be used. Examples of the isocyanate group blocking agent include alcohols (for example, isopropyl alcohol, ternary butanol, etc.), indoleamines (for example, ε-caprolactam, etc.), and phenols (for example, phenol, A). Phenol, p-tert-butylphenol, p-tert-butylphenylhydrazine, p-second amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxy compound (for example, 3-hydroxypyridine, 8- Hydroxyquinoline, etc., active methylene compound (for example, dialkyl malonate, methyl ethyl ketone oxime, acetyl ketone, alkyl acetoacetate oxime, acetamidine, cyclohexanone oxime) and many more. In addition to the above, a compound having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used. Further, the melamine derivative can be used as the thermal crosslinking agent. The melamine derivative may, for example, be methylol melamine or alkylated hydroxymethyl tripoly fluoroamine (methyl group, ethyl group, butyl group or the like). A compound obtained by etherification). These may be used alone or in combination of two or more. The -59-200941138 is a good foundation for the body of the body. The six layers of the film are fixed, medium-hard or good for the amine-hard cyanide surface. hydroxyl. The content of the solid content of the thermal crosslinking agent in the solid content of the photosensitive composition is preferably 1% by mass to 50% by mass, and preferably 3% by mass to 30% by mass. % is better. When the content of the solid content is less than 1% by mass, the film strength of the cured film is not observed to be improved, and when it is more than 50% by mass, the image forming property may be lowered or the exposure sensitivity may be lowered. ® (Other Ingredients) The above other components may, for example, be a thermal polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye), or the like, and may be used in combination with a surface of a substrate. For example, conductive particles, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, and the like. By appropriately including these, the properties of the target photosensitive film, such as stability, photographic properties, and film properties, can be adjusted. &lt;Thermal polymerization inhibitor&gt; The above-mentioned thermal polymerization inhibitor may, for example, be 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol, gallic phenol, 2-hydroxyl group Diphenyl ketone, 4-methoxy-2-hydroxydiphenyl ketone, cuprous chloride, thiophene, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4 -cresol, 2,2,-methylenebis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper A compounding agent with an organic chelating agent, methyl urate and a thiophene trap, a nitroso compound, a nitroso compound, and a chelating agent for hydrazine 1. -60-.200941138 The content of the thermal polymerization inhibitor is preferably from 0. 01% by mass to 5% by mass, more preferably from 0.05% by mass to 2% by mass, based on the polymerizable compound. · 〇 1% by mass to 1% by mass is more preferable. When the content is less than 0.001% by mass, the stability at the time of storage may be lowered. When the content is more than 5% by mass, the sensitivity to the active energy ray may be lowered. &lt;Sensitizer&gt; The photosensitive composition may further contain a sensitizer. From the viewpoint of exposing and developing the photosensitive layer, after the exposure and development, the thickness of the exposed portion of the photosensitive layer is not changed to enhance the minimum energy (sensitivity) of the pre-recorded light, The agent is particularly preferred for use. The sensitizer can be appropriately selected in combination with the above-described light irradiation means (for example, visible light or ultraviolet light, visible light laser, etc.). The sensitizer is excited by an active energy ray and can generate free radicals by interacting with other substances (for example, a radical generator, an acid generator, etc.) (for example, energy movement, electron movement, etc.). Useful groups such as acid. V The sensitizer contains at least one selected from the group consisting of a condensed ring compound, an aminophenyl ketone compound, a polynuclear aromatic compound, an acid nucleus, a basic nucleus, and a fluorescent whitening agent nucleus. It may also contain other sensitizers as necessary. The sensitizer is preferably a heterocyclic ring compound or an aminodiphenyl ketone compound, and is particularly preferably a heterocyclic ring compound. • A condensed ring compound— Among the above-exemplified compounds, a compound obtained by condensing an aromatic ring or a heterocyclic ring (condensed ring compound) is preferably a heterocyclic ring compound. The above heterocyclic ring .200941138 condensed ring compound means a polycyclic compound having a hetero element in the ring. Among the above rings, a nitrogen atom is preferred. The above heterocyclic ring compound may, for example, be a heterocyclic ketone compound. Among the above-mentioned heterocyclic ketone compounds, an acridone compound and a thioxanthone compound are more preferable, and among these, a thioxanthone compound is particularly preferable. Specific examples of the heterocyclic ketone compound include an acridone compound such as acridone, chloroacridone, N-methyl UT ketone or N-butyl UT ketone; thioxanthone and isopropyl Thiophenone compounds such as thioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxy thioxanthone, Quantacure QTX, etc.; 3-(2-benzofurancarbenyl) )-7-diethylamino coumarin, 3 (2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-diethyl Amino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylamidobenzylidene)-7-di Ethyl coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethylaminocoumarin), 3 -benzimidyl-7-methoxycoumarin, 3-(2·furanyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamyl)- 7. Diethylamine coumarin, 7-methyl ethoxy-3-(3-pyridylcarbonyl) coumarin, 3-benzylidene-5,7-dipropoxycoumarin, 7 -benzotriazol-2-yl-coumarin, 7-diethylamino-4-methylcoumarin, again, The incense described in Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A coumarin or the like such as a soybean compound. Further, well-known polynuclear aromatics (for example, perylene, tri-ortylene), xanthene (for example, luciferin, eosin, red algae-62-200941138 erythrosine, if Danming B, rose red), anthocyanins (for example, phthalocyanine, thiocarbocyanine, oxacarbon cyanine), procyanidins (such as procyanidins, carbon anthocyanins) ), tidal farming (eg, sulfur only, methylene blue, toluidine blue), terpenoids (eg, sputum), snails (eg, shark guns), and the like. The content of the sensitizer is preferably 0.01% by mass to 4% by mass, more preferably 0.02% by mass to 2% by mass, and preferably 0.05% by mass to 1% by mass based on the total solid content of the photosensitive composition. Very good. 〇 ❹ When the content is less than 0.01% by mass, the sensitivity may be lowered. When the content is more than 4% by mass, the shape of the pattern may be deteriorated. The mass ratio of the sensitizer to the photopolymerization initiator in the photosensitive composition is preferably [(sensitizer) / (deuterium derivative)] = 1/0.1 to 1/100, and is 1/ 1 to 1/50 is better. When the mass ratio of the content of the sensitizer to the content of the photopolymerization initiator is outside the above range, there is a case where the sensitivity is lowered and the temporal change in sensitivity is deteriorated. &lt;Plasticizer&gt; The aforementioned plasticizer may, for example, be dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate or dicyclohexyl phthalate. , tridecyl citrate, butyl benzyl citrate, diisononyl phthalate, diphenyl phthalate, diallyl citrate, octyl octyl phthalate, etc.; triethylene glycol Diacetate, tetraethylene glycol diacetate, dimethylethylene citrate, ethyl decyl ethyl glycolate, methyl decyl ethyl glycolate, butyl decyl butyl Glycol esters such as glycolic acid esters and triethylene glycol dicaprylate; phosphates such as tris-63-200941138 toluene ester and triphenyl phosphate; 4-toluenesulfonamide, benzene-expansion amine, Amidoxime such as N-n-butylbenzenesulfonamide or N-n-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, sebacic acid Aliphatic dibasic acid esters such as dioctyl phthalate dioctyl phthalate, dioctyl sebacate, dibutyl maleate, etc.: triethyl citrate, tributyl citrate, triglyceride Oxime ester, butyl laurate, 4,5-diepoxycyclohexane a glycol such as di-octyl diacrylate or polyethylene glycol or polypropylene glycol. The content of the plasticizer in the total composition of the photosensitive composition is preferably from 0.1% by mass to 50% by mass, preferably from 0.5% by mass to 40% by mass, and from 1% by mass to 30% by mass. The mass % is better. &lt;Coloring Pigment&gt; The coloring pigment is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include Victoria Pure Blue-BO (C.1.42595), Auramine (C.1.41000), and fat-soluble black. HB (C.1.26 1 50), Monolite yellow GT (C.I_ Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), CI Pigment Yellow 55, Permanent Yellow HR (CI Pigment Yellow) 83), Yong® Long Curd FBB (CI Pigment Red 146), Hoster Perm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fast Pink B Super (CI · Pigment Red 81), Monaster (M'onastral) Fast Blue (CI Pigment Blue 15), Mono Wright Strong Black B (CI Pigment Black 1), Carbon Black, CI Pigment Red 97, CI Pigment Red 122 , CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI·Pigment Green 36, CI Pigment Blue 15: 1, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, -64 - 200941138 CI Pigment Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and the like. These may be used alone or in combination of two or more. A dye which is appropriately selected from known dyes according to the purpose can be used. The content of the solid content of the coloring pigment in the photosensitive composition can be determined in consideration of the exposure strength, resolution, and the like of the photosensitive layer when a permanent pattern is formed, and is usually 0.01% by mass depending on the type of the coloring pigment. 10% by mass is preferred, and 〇.5% by mass to 5% by mass is more preferably. &lt;Adhesion Promoter&gt; 〇 In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a so-called adhesion promoter which is well known can be used for each layer. The adhesion promoters described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Specific examples thereof include benzimidazole, benzopyrene, benzothiazepine, 2-sulfenylbenzimidazole, 2-sulfenylbenzopyrene, 2-sulfenylbenzothiazepine, and 2-flavor Phenylmethyl-5-phenyl-oxadiazol-2-thione, 5-amino-3-glyphosylmethyl-thiadiazole-2-thione, 2-mercapto-5-methylthio Thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like. The content of the above-mentioned adhesion promoter relative to the total composition of the photosensitive layer is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and more preferably 0.1% by mass. 5% by mass is particularly good. (Photosensitive film) The photosensitive film of the present invention is composed of a photosensitive layer composed of a photosensitive composition in a support volume layer. It is preferable that a protective layer is laminated on the photosensitive layer, and -65-200941138 is preferable, and another layer such as a buffer layer or an oxygen barrier layer (PC layer) may be laminated as necessary. The form of the photosensitive film is not particularly limited, and For example, the support layer may have a configuration in which the photosensitive layer and the protective layer are provided in this order, and the support layer has the PC layer, the photosensitive layer, and the protective layer in this order. And a configuration in which the buffer layer, the PC layer, the photosensitive layer, and the protective layer are provided in this order. Further, the photosensitive layer may be a single layer or a plurality of layers. &lt;Photosensitive layer&gt; The photosensitive layer is not particularly limited in position at which the photosensitive film is provided, and can be appropriately selected according to the purpose, and is usually laminated on the support. In the exposure process described later, the light-receiving means having n drawing portions receives light emitted from the light-irradiating means and emits the light, and after the light from the light-irradiating means is modulated, the photosensitive layer is used. Preferably, the microlens of the microlens array is exposed to light, and the microlens has an aspherical surface which is capable of correcting deformation of the exit surface of the drawing portion after the light is modulated by the optical modulation means. deviation. When the photosensitive layer is exposed and developed, the minimum energy of the light used for exposure is not made before the exposure and development of the photosensitive layer is changed to 100 mJ/cm 2 or less. 70mJ/cxn2 or less is better. When the minimum energy of the light used for the foregoing exposure is more than 100 mJ/cm2, it is not preferable because the adhesive time is increased. -66- 200941138 Here, "the minimum energy of the light used for exposure before the thickness of the exposed portion of the photosensitive layer is changed after the exposure and development" means the so-called development sensitivity, for example, The relationship (sensitivity curve) of the energy (exposure amount) used for the above-described exposure at the time of exposing the photosensitive layer to the thickness of the hard coat layer formed by the development process with the above-described exposure is shown. The thickness of the hardened layer gradually increases with the exposure amount, and is then substantially the same as the thickness of the photosensitive layer before the exposure, and is substantially constant. The aforementioned development sensitivity is obtained by reading the thickness of the hardened layer to a minimum amount of exposure at a certain time. Here, when the thickness of the curing agent and the thickness of the photosensitive layer before the exposure are within ±1 μm, the thickness of the hard coat layer may be regarded as not being changed by exposure and development. The method of measuring the thickness of the hard coat layer and the photosensitive layer before the exposure is not particularly limited, and can be appropriately selected according to the purpose, and a film thickness measuring device and a surface roughness measuring machine (for example, 0 to SURFCOM) can be used. Measured by 1400D (manufactured by Tokyo Seimitsu Co., Ltd.). The thickness of the photosensitive layer is not particularly limited and can be appropriately selected depending on the purpose, and is preferably, for example, 3 μm to 100 μm, more preferably 5 μm to 70 μm. In the method for forming the photosensitive layer, the photosensitive composition of the present invention is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution, and the solution is directly coated on the support, and by A method of drying it to laminate. -67-200941138 The solvent of the photosensitive composition is not particularly limited, and may be appropriately selected, and examples thereof include alkane such as methanol, ethanol, n-propanol, n-butanol, second butanol or n-hexanol; Ethyl acetate, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc., ethyl butyl acetate, n-amyl acetate, methyl acetonate, dimethyl propyl citrate, ethyl benzoate And aromatic hydrocarbons such as benzene, xylene, benzene, and ethylbenzene such as methoxypropyl acetate; ethylene tetrachloride, chloroform, 1,1,1-trichloroethane, dichloromethane, and monochlorobenzene. ® hydrocarbons; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethyl ether, 1-methoxy-2-propanol; dimethyl hydrazine, diamine, dimethyl sub-grinding, Ring and other mills. These may be used alone or in combination of two or more. Further, a method of applying the well-known interface to the above-mentioned coating may be added, and the method of coating may be carried out according to the purpose, and may be directly applied to, for example, a spin coater, a slit coater, a die coater, a curtain coater, or the like. The former method. 〇 The drying conditions are different depending on the type of each component and the solvent, and are usually in the range of 60 ° C to 110 ° C, and 30 seconds to 15 in the present invention. The photosensitive layer contains a binder and a polymerization value. It is composed of a derivative and an ion adsorbent, and may be formed in accordance with a photosensitive composition having other components. &lt;Support&gt; The support is not particularly limited, and can be selected according to the purpose, so that the photosensitive layer can be peeled off, and the light transmittance can be sufficient according to the alcohol, isopropyl, methyl ethyl ketone; ethyl acetate; Esters; halogenated diols such as methyl carbahydrate, trichloroethylene, etc., may also be used as an agent. The appropriate applicator and the roller are used to coat the support with a ratio of about h clock. The three compounds, preferably, are preferably selected from -68 to 200941138, and are preferably better in surface smoothness. The support is preferably made of a synthetic resin and is transparent, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, and poly. (meth)acrylic acid alkyl ester, poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamine , plastic polyimide film, polyvinyl chloride-vinyl acetate copolymer, polytetrahydrofuran, polytrichloroethylene, cellulose film, nylon film, etc. 'In these, polyethylene terephthalate It is especially good. These may be used alone or in combination of two or more. The thickness of the aforementioned support is not particularly limited and can be appropriately selected depending on the purpose, for example, preferably 2 μm to 150 μm, more preferably 5 μm to 1 μm, and particularly preferably 8 μm to 50 μm. The support may be a single layer or may have a multilayer structure. The shape of the support body is not particularly limited, and can be appropriately selected according to the purpose, and is preferably a long strip shape. The length of the long strip-shaped support is not particularly limited, and may be, for example, a length of 10 to 20,000 meters. &lt;Protective layer&gt; The photosensitive film may be formed on the photosensitive layer to form a protective layer. The protective layer is, for example, a paper obtained by laminating paper, polyethylene or polypropylene, and the like, and a polyethylene film or a polypropylene film is preferable. The thickness of the protective layer is not particularly limited, and can be locally selected according to the purpose, for example, preferably from 5 μm to 100 μm, preferably from 8 μm to 50 μm, and from 1 μm to 30 μm. Very good. The combination of the support and the protective layer (support/protective layer) may, for example, be polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyvinyl chloride/cellophane, polyphthalate. Amine/polypropylene, polyethylene terephthalate/polyethylene terephthalate, and the like. Further, by processing at least one of the support and the protective layer, the layer adhesion can be adjusted. The surface treatment of the support may be applied to increase the adhesion to the photosensitive layer, and examples thereof include a primer coating layer, a corona discharge treatment, a flame treatment, an ultraviolet irradiation treatment, a high-frequency irradiation treatment, and a glow discharge. Irradiation treatment, active plasma treatment, laser irradiation treatment, and the like. Further, the static friction coefficient of the support body and the protective layer is preferably 0.3 to 1.4, more preferably 0.5 to 1.2. When the static friction coefficient is less than 0.3, since it is too slippery, a winding offset may occur in the form of a roll, and when it is more than 1.4, it may be difficult to take up a good roll. The photosensitive film is preferably wound up in a cylindrical core and wound up in a roll shape and stored in a roll shape. The length of the long photosensitive film is not particularly limited, and can be appropriately selected, for example, from 10 meters to 20,000 meters. Further, it is also possible to carry out slitting processing in a manner that is easy for the user to use, and to wind up the elongated body of 100 to 1,000 meters into a roll shape. Further, at this time, it is preferable to wind up the support so as to be the outermost side. Further, the roll-shaped photosensitive film may be cut into a sheet shape. From the viewpoint of protecting the end face during storage and preventing the edge from melting, it is preferable to provide a separator (especially those having moisture resistance and desiccant) on the end surface of -70-.200941138. Moreover, it is preferred that the bale is made of a material having a low moisture permeability. In order to adjust the adhesion between the protective layer and the photosensitive layer, the protective layer may be surface-treated. The surface treatment can be formed, for example, on the surface of the protective layer by an undercoat layer composed of polyorganosiloxane, fluorinated polyolefin, polyvinyl fluoride or polyvinyl alcohol. The undercoat layer is formed by applying the coating liquid of the polymer onto the surface of the protective layer and drying it at 30 ° C to 150 ° C for 1 minute to 30 minutes. The above-mentioned drying temperature is particularly preferably 50 ° C to 120 ° C. &lt;Other Layers&gt; The other layer of the photosensitive film is not particularly limited, and may be appropriately selected according to the purpose, and may have, for example, a buffer layer, an oxygen barrier layer (PC layer), a release layer, and an adhesive layer. a layer of a light absorbing layer, a surface protective layer, or the like. The layers may have one layer alone or two or more layers. Further, a protective layer may be provided on the photosensitive layer. &lt;Method for Producing Photosensitive Film&gt; 前述 The photosensitive film can be produced, for example, as follows. First, a photosensitive composition solution for a photosensitive film is prepared by dissolving, emulsifying or dispersing a material contained in the photosensitive composition in water or a solvent. The solvent is the same as the solvent of the photosensitive composition solution. Next, the photosensitive composition solution is applied onto the support and dried to form a photosensitive layer. A photosensitive film can be produced. -71- 200941138 The method of applying the photosensitive composition solution is as described above. In the photosensitive film, the photosensitive composition is excellent in plating resistance, sensitivity, developability, and adhesion, and can be suitably used for a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern. For the formation of liquid crystal structural members such as various pattern forming, color filters, pillars, ribs, spacers, partition walls, etc., holograms, micro-machines, proofs, etc. It is suitable for permanent pattern formation for use in printed substrates. In particular, since the thickness of the film of the photosensitive film is uniform, even when a permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, a high acceleration test (HAST) is performed. Further, dendrites are not produced, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained, so that the substrate can be laminated more finely. (Photosensitive Laminate) The photosensitive layered system has at least the above-mentioned photosensitive layer on the substrate, and is formed by appropriately arranging other layers appropriately selected according to the purpose. &lt;Substrate&gt; The substrate to be processed to form the photosensitive layer or the transferable body to which at least the photosensitive layer of the photosensitive film of the present invention is transferred is not particularly limited, and can be appropriately selected according to the purpose, and can be optionally used, for example. The surface having a high surface smoothness to the uneven surface is selected. The plate-shaped substrate is preferably a substrate. Specifically, a substrate (printing substrate) for producing a printed wiring board, a glass plate (such as soda lime glass), a synthetic resin-72- ‘200941138 film, paper, a metal plate, or the like can be given. &lt;Manufacturing Method of Photosensitive Laminates&gt; The method for producing the photosensitive laminate is a method in which the photosensitive composition is applied onto the substrate and dried, and the photosensitive film is at least a first aspect, and at least the photosensitive film is used. A method of laminating at least one of heating and pressurization of the photosensitive layer is used as the second aspect. In the method for producing a photosensitive laminate according to the first aspect, the photosensitive composition is applied and dried on the substrate to form a photosensitive layer. The coating and drying method is not particularly limited, and can be appropriately selected according to the purpose, and for example, the photosensitive composition is prepared by dissolving, emulsifying or dispersing the photosensitive composition in water or a solvent, and preparing the solution. A method of directly coating the surface of the aforementioned substrate and laminating it by drying it. The coating method and the drying conditions are not particularly limited, and can be appropriately selected according to the purpose, and can be carried out by the same method and strip as the user of the photosensitive film. In the method for producing a photosensitive laminate according to the second aspect, the photosensitive film of the present invention is laminated on at least one of the surface of the substrate by heating or pressing. Further, when the photosensitive film has the protective layer, it is preferable to remove the protective layer and to superimpose the photosensitive layer on the substrate. The heating temperature is not particularly limited and can be appropriately selected according to the purpose, and is preferably, for example, 15 to 180 ° C and 60 to 140. (The pressure is not particularly limited, and may be appropriately selected according to the purpose - 73 - 200941138, for example, preferably 0.1 to 1.0 MPa, preferably 0.2 to 0.8 MPa.) The device of at least one of the devices is not particularly limited, and can be appropriately selected according to the purpose. For example, a laminating machine (for example, 'VP VP-II manufactured by Daisei LAMINATOR Co., Ltd., VP130 manufactured by NICHIGO-MORTON Co., Ltd.) can be suitably used. In the photosensitive film and the photosensitive layered system, the photosensitive composition is excellent in sensitivity, developability, and adhesion, and a high-precision permanent pattern can be formed with high efficiency. It can be suitably used for a protective film or an interlayer insulating film. Liquid crystals such as various patterns such as permanent patterns such as solder resist patterns, color filters, pillars, ribs, spacers, partition walls, etc. Manufacture of structural members, holograms, micromachines, For forming a pattern such as proof, etc., it is particularly suitable for use in forming a permanent pattern of a printed substrate. In particular, the film of the photosensitive film is Uniform thickness, even when forming a permanent pattern, even if the permanent pattern (protective film, interlayer insulating film, ¥ solder resist, etc.) is thinned, 'the dendritic crystal will not be produced in the height accelerated durability test (HAST) (dendrite), since a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained, it can be laminated more finely on a substrate. (Permanent pattern forming method) The permanent pattern forming method includes at least an exposure process and includes Further, other processes such as a development process can be appropriately selected. Further, by the description of the pattern forming method, it is possible to clearly understand that the image forming apparatus of Fig. 74-200941138 includes the photosensitive laminated body and has at least light irradiation means and light modulation. [Exposure Process] The exposure process is a process for exposing the photosensitive layer. The material of the photosensitive layer and the substrate is as described above. The object to be exposed is not particularly limited as long as it is the photosensitive layer, and can be followed. The purpose is appropriately selected, for example, as described above, preferably for the photosensitive layer in the photosensitive laminate. The photosensitive layering system is formed by laminating at least one of the photosensitive film on the substrate while heating or pressurizing the film. The exposure is not particularly limited, and may be appropriately selected according to the purpose, and may be digitally exposed. The analog exposure is preferably a digital exposure. The analog exposure is not particularly limited, and can be appropriately selected according to the purpose, and for example, a photomask having a predetermined pattern can be used, and a (super) high pressure mercury lamp can be used. , Xenon lamps, halogen lamps, etc. to expose the method.

D The digital exposure is not particularly limited as long as it is not used, and can be appropriately selected according to the purpose, for example, at least one of an exposure unit including at least a light irradiation means and a light modulation means, and the photosensitive layer. While moving, the light emitted from the light irradiation means is preferably irradiated with the photosensitive layer from the exposure head by using the light modulation means and changing the pattern information. The light source used for the above-mentioned digital exposure is not particularly limited as long as it emits a light source that emits ultraviolet light to infrared light, and can be appropriately selected according to the purpose - for example, (super) high pressure mercury lamp, xenon lamp, carbon arc. A fluorescent tube such as a lamp or a photocopier or a well-known light source such as laser light is preferable, and among these, (ultra) high pressure mercury lamp and laser light are preferable, and laser light is more preferable. (Super) high-pressure mercury lamp is a discharge lamp in which mercury is sealed in a quartz glass tube or the like, and the vapor pressure of mercury is set to sorghum to improve luminous efficiency. In the bright line spectrum, an ND filter or the like can be used, and only an open line spectrum of one wavelength can be used, and a light having a complex open line spectrum can also be used. The "laser" of the aforementioned laser light is a capital letter of Light Amplification by © Stimulated Emission of Radiation. The device for emitting the aforementioned laser light can be suitably used for the phenomenon of induced emission caused by a substance having a reversed distribution, and the monochromatic light having stronger interference and directivity is produced by amplification and oscillation of light waves. Oscillator and Amplifier The excitation medium of the above-mentioned laser light includes crystal, glass, liquid 'color material, gas, etc., from which well-known lasers such as solid laser, liquid laser, gas laser, semiconductor laser, etc. can be used. 》 ^ Specifically, gas lasers can be Ar ion laser (3 64 nm, 351 nm), Kr ion laser (356 nm, 351 nm), He-Cd laser (325 nm) The solid-state laser can be represented by a YAG laser, a YV〇4 laser (1, 〇64 nm), a 丫80 laser or a 乂04 laser with a 2x wave (532 nm) and a 3x wave ( 3 55 nm), 4 times wave (266 nm), combination of guided wave type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 400 nm), guided wave type wavelength conversion element and AlGalnP or AlGaAs semiconductor t The combination (300 nm ~ 350 nm), AlGaInN (350 nm ~ 470 nm) and so on. Among these, '-76-.200941138 In terms of cost, the preferred laser light can be AlGalnN semiconductor laser (commercially available InGaN-based semiconductor laser 3 75 nm or 405 nm), in terms of productivity. For example, a 355 nm laser with high output can be cited. The wavelength of the aforementioned laser light is preferably, for example, 200 nm to 1,500 nm, preferably 300 nm to 800 nm, and more preferably 330 nm to 500 nm, and 350 nm to 420 nm. Nano is especially good. - Light Modulation means - A representative method of the above-described light modulation means is a method of having n drawing parts and controlling the drawing part in accordance with the pattern information. Specifically, a digital micromirror device (DMD) or a MEMS (Micro Electro Mechanical Systems) type spatial light modulation device (SLM; Spacial Light Modulator) may be cited, and electro-optical The effect is to modulate the transmitted optical element (PLZT element), liquid crystal light shutter (FLC), and the like. Among these, a DMD can be cited. When the DMD is used, the light from the light source is irradiated onto the DMD by a suitable optical system®, and the reflected light from each of the two-dimensional arrays of the DMD is passed through a respective optical system or the like on the photosensitive layer to form two An image of a light spot arranged in a dimension. In this state, although the light spot and the light spot are not exposed, the full exposure of the photosensitive layer can be performed by moving the image of the two-dimensionally arranged light spot in a slightly inclined direction with respect to the two-dimensional array direction. . The DMD can form an image pattern by controlling the angle of each mirror and ON-OFF controlling the light spot. By arranging an exposure head having such a DMD, it is possible to correspond to a wide variety of substrates. -77- 200941138 In the DMD described above, although the brightness of the above-mentioned light spot is only 2 gray scales of 〇N or OFF, when the mirror gray scale type spatial modulation element is used, 256 gray scale exposure can be performed. Further, it is preferable that the optical modulation means has a pattern signal generating means for generating a control signal based on the formed pattern information. In this case, the optical modulation means modulates the light according to a control signal generated by the pattern signal generating means. The control signal is not particularly limited, and can be appropriately selected according to the purpose, and for example, a digital signal can be cited. On the other hand, another representative method of the optical modulation means may be a method using a polygon mirror. Here, a polygon mirror is a rotating member having a series of planar reflecting surfaces around it. Although the polygon mirror reflects light from the light source and illuminates the photosensitive layer, the spot of the reflected light is scanned by the rotation of the plane mirror. With respect to the scanning direction, the photosensitive layer on the substrate can be fully exposed by moving the substrate at right angles. Moreover, the image pattern can be formed by controlling the intensity of the light from the light source on on-off or by intermediate adjustment by an appropriate method. At this time, the scanning time can be shortened by making the light rays from the light source into a plurality of stripes. In addition to the above-described optical modulation means, an example of the polygon mirror described in Japanese Laid-Open Patent Publication No. Hei 5-150175 is also known, and it is described in Japanese Laid-Open Patent Publication No. 2004-523101 (International Publication No. 2002/039793 pamphlet). A part of the image of the lower layer is visually obtained, and the position of the layer is aligned with the position of the lower layer by means of a device using a polygon mirror, which is disclosed in Japanese Patent Application Publication No. 2004-56080. An example of the exposure of the DMD; the exposure apparatus provided with the polygon mirror of the Unexamined-Japanese-Patent No. 2002-523905; the exposure apparatus provided with the polygon mirror of the Unexamined-Japanese-Patent No. 2001-255661. An example of an exposure method in which an exposure amount is changed in accordance with a portion of a substrate described in Japanese Laid-Open Patent Publication No. 2003- 1 56853, and an adjustment position shift described in JP-A-200-5-4 3 5 76 Examples of exposure methods, and the like. In the light irradiation means, the light irradiation method is not particularly limited, and the exposure light source can be appropriately selected according to the purpose to synthesize two or more. It is preferable to irradiate light from the light sources, which is particularly suitable. A laser beam (combined laser light) obtained by combining two or more rays of light is irradiated. The method of irradiating the combined laser light is not particularly limited, and can be appropriately selected according to the purpose, and it is preferable to condense the laser light irradiated from the plurality of laser light sources by a plurality of laser light sources and multimode optical fibers. The method of combining the optical system of the multimode optical fiber to form a combined laser light and irradiating it. The diameter of the aforementioned laser beam is not particularly limited and can be appropriately selected according to the purpose. From the resolution of the rich color wall, the ι/e2 of the Gaussian beam is preferably 5 μm to 30 μm to 7 μm. ~20 microns is better. It is preferable to modulate the aforementioned laser light according to the image data space. Therefore, for this purpose, it is preferable to use the aforementioned DMD of the spatial light modulation element. In the above-mentioned apparatus, the apparatus described in the above-mentioned Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. However, the above exposure apparatus is not limited to this. &lt;Developing Process&gt; The above-described image development is carried out by removing the unexposed portion of the photosensitive layer. The method of removing the uncured region is not particularly limited, and can be appropriately selected for the purpose of 0, and examples thereof include a method of removing using a developing solution. The developing solution is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include an alkaline aqueous solution, a water-based developing solution, and an organic solvent. Among them, a weakly alkaline aqueous solution is preferred. The alkali component of the weakly alkaline aqueous solution may, for example, be lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate or potassium phosphate. , sodium citrate, potassium glutamate, borax, and the like. The pH of the aforementioned weakly alkaline aqueous solution is preferably, for example, about 8 to 12, more preferably about 9 to 11. The weakly alkaline aqueous solution may, for example, be a 0.1% by mass to 5% by mass aqueous sodium carbonate solution or a potassium carbonate aqueous solution. The temperature of the developing solution can be appropriately selected in accordance with the developability of the photosensitive layer, and is preferably, for example, about 25 ° C to 40 ° C. The above-mentioned developing solution may also be used in combination with a surfactant, an antifoaming agent 'organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethyleneamine, sulphate, triethanolamine). Or an organic solvent (for example, an alcohol, a ketone, an ester, an ether, a guanamine, a lactone) or the like for promoting development. Further, the developing liquid may be a water-based developing liquid obtained by mixing water or an aqueous hydrazine solution with an organic solvent, or may be an organic solvent alone. The formation of the aforementioned pattern may, for example, also include a hardening treatment process, an etching process, a mineralizing process, and the like. One type may be used alone or two or more types may be used in combination. &lt;Hardening treatment process&gt; The method of forming the pattern is a permanent pattern forming method of forming a permanent pattern such as a protective film, an interlayer insulating film, or a solder resist pattern, or a permanent pattern of a color photosensitive composition. It is preferred to have a stearic acid stearic acid process for the photosensitive layer after the above-mentioned developing process. The stearic acid process is not particularly limited, and can be appropriately selected according to the purpose, and may be, for example, a full exposure treatment or a total heat treatment. The method of the overall exposure treatment may be, for example, a method of performing overall exposure on the layered body in which the permanent pattern is formed after the development. By the overall exposure, the curing of the resin in the photosensitive composition forming the photosensitive layer can be promoted, and the surface of the permanent pattern can be hardened. The apparatus for performing the above-described overall exposure is not particularly limited, and can be appropriately selected according to the purpose, and a UV exposure machine such as an ultrahigh pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine, or the like can be suitably used. The exposure amount is usually from 10 mJ/cm 2 to 2,000 mJ/cm 2 . The overall heat treatment method may be a method of heating the entire laminate on which the permanent pattern is formed after the development. By this overall heating, the film thickness of the surface of the aforementioned permanent pattern can be increased. -81 - .200941138 The heating temperature for the above-mentioned overall heating is preferably from 120 ° C to 250 ° C, more preferably from 120 ° C to 200 ° C. When the heating temperature is less than 120 °C, the film strength may not be increased by heat treatment. When the temperature is higher than 25 °C, the resin in the photosensitive composition is decomposed and the film quality is slightly brittle. The heating time for the above-mentioned overall heating is preferably from 10 minutes to 120 minutes, more preferably from 15 minutes to 60 minutes. The apparatus for performing the above-described overall heating is not particularly limited, and can be appropriately selected according to the purpose of the known device, and examples thereof include a dry oven, a hot plate, and an IR heater. In the direct drawing using a laser exposure of 40 5 nm, the formation method of the aforementioned pattern can be used for the formation of various patterns which must be prevented from being lowered in sensitivity of the photosensitive layer due to oxygen, and can be suitably used for high density. The formation of a pattern of high productivity. In the permanent pattern forming method described above, when 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 or bending from the outside, particularly in the case of the interlayer insulating film. For example, it is useful for high-density packaging semiconductors or components such as multilayer wiring boards or assembly wiring boards. Since the permanent pattern forming method uses the photosensitive composition, it can be suitably used for various pattern formations such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar, and a rib. The production of a liquid crystal structural member such as a spacer or a partition wall, the production of a hologram, a micromachine, a sample, and the like can be suitably used for forming a permanent pattern of -82 to 200941138 for a printed circuit board. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not intended to be limited thereto, and is not limited to the following examples. Further, as long as it is not specifically notified in advance, "parts" are mass standards. [Example 1] (Manufacture of photosensitive film)

On the polyethylene terephthalate film crucible (manufactured by TORAY Co., Ltd., 16FB50) having a thickness of 16 μm as a support, a photosensitive composition solution composed of the following composition was applied and dried. A photosensitive layer having a thickness of 28 μm was formed on the support. A photosensitive film was produced by using a polypropylene film (manufactured by Oji Paper Co., Ltd., ALFAN E-200) having a thickness of 20 μm on the photosensitive layer as a protective layer. &lt;Photosensitive composition solvent&gt; Composition of the following adhesive-1: 1 part by mass of tricyclodecane diacrylate (trade name: NK ESTER A-DCP) (C-1, I/O 値 = 0.428) ........ 18 parts by mass of the photopolymerization initiator represented by the following formula A-1: 1.0 part by mass of the following formula S-1 Show sensitizer....... 〇_7 parts by mass of EPOTOHTO YDF170 (epoxy equivalent 170g / eq. Dongdu Chemical Co., Ltd., bisphenol F-based epoxy resin)........ 8.9 parts by mass of dicyanodiamine....... 0.5 parts by mass of pigment dispersion............. 80.21 parts by mass of MEGAFAC F-78 0F (large 30% by mass of A-83 - 200941138 base ethyl ketone solution made by Nippon Ink Co., Ltd. 0.2 parts by mass of IXE-100 (manufactured by Toagosei Co., Ltd.) and IXE-700F (manufactured by Toagos Corporation) 1:1 (mass ratio) mixture....... 4.0 parts by mass

S-1 &lt;&lt;Synthesis of Adhesive-1&gt;&gt; In a 1,000 ml three-necked flask, 159 g of 1-methoxy-2-propanol was added and heated to 85 ° C under a nitrogen stream. Here, a solution of 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) in 159 g of 1-methoxy-2-propanol was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further heated for 5 hours to cause a reaction. Then, the heating was stopped to obtain a copolymer of benzyl methacrylate/methacrylic acid (30/70 mol%). Next, 120.0 g of the above polymer solution was transferred to a 300 ml three-necked flask', and 16.6 g of glycidyl methacrylate and 16.16 g of p-methoxyphenol were added and stirred and dissolved. After the dissolution, 3.0 g of triphenylphosphine was added and heated to 1 ° C to carry out an addition reaction. After confirming that the glycidyl methacrylate has disappeared using gas chromatography -84 - 200941138, stop heating. 38 g of methoxy-2-propanol was added to prepare a solution of the binder-1 having an acid value of 112 mgKOH/g, a mass average molecular weight of 15,000, and a solid content of 30% by mass. Further, the pigment dispersion liquid is previously mixed with 30 parts by mass of barium sulfate (B30 manufactured by Seiko Chemical Co., Ltd.), 50 parts by mass of the solution of the binder-1, 0.16 parts by mass of phthalocyanine blue, and 0.07 parts by mass of an anthraquinone yellow pigment. After (PV24), it was prepared by using MOTOR MILL M-250 (manufactured by Eiger Co., Ltd.) and using zirconium particles having a diameter of 1.0 mm, and dispersing at a wind speed of 9 m/s for 3 hours. &lt;Laminating in a substrate&gt; The base system was prepared by applying a chemical honing treatment to a surface of a copper clad laminate (without via holes and a copper thickness of 12 μm). On the copper-clad laminate, a vacuum laminator (NICHIGO-MORTON Co., Ltd., VP130) was used to peel off the photosensitive film while the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Laying the layer to obtain the copper-clad laminate, the photosensitive layer, and the aforementioned poly-paraic acid B

The D-diester film (support) is a laminate. The pressure-bonding conditions are a vacuum suction time of 40 seconds, a pressure-bonding temperature of 70 ° C, a pressure-bonding pressure of 〇. 2 MPa, and a pressurization time of 1 sec. The laminate was subjected to sensitivity evaluation as follows. &lt;Sensitivity&gt; The laminate was allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. On the surface of the photosensitive layer of the obtained laminate, INPREX IP-3000 (manufactured by Fujifilm Co., Ltd., pixel pitch = 1.0 μm) was used, and L/S (line -85 - 200941138 / gap) = 50 μm / 50 μm The pattern data was exposed by irradiating light of different light energies from 0.5 mJ/cm 2 to 500 mJ/cm 2 at intervals of 2 1/2 times to harden the L/S (line/gap) = 50 μm / 50 μm line pattern. After standing at room temperature for 1 minute, the support was peeled off from the photosensitive laminate, and the photosensitive layer on the copper-clad laminate was used in a comprehensive manner 3 (TC 1% by mass aqueous sodium carbonate solution and spray pressure) 0.15 MPa, spray imaging was performed 2 to 3 times (or 40 to 60 seconds) of the shortest development time to remove the unhardened area. Using a laser microscope (VK·9500, manufactured by KEYENCE, Inc.; objective lens 50 times) The measurement was as follows: The line width of the obtained L = 50 μm pattern was measured, and the exposure amount of the line width of 50 μm was taken as the sensitivity (optimum exposure amount). The results are shown in Table 1. &lt;Development and Hardening treatment&gt; A polyethylene terephthalate film (support) was peeled off from the laminate, and the photosensitive layer was entirely sprayed with a 1% by mass aqueous sodium carbonate solution at 30 ° C and sprayed at a spray pressure of 0.15 MPa for 60 seconds. Then, the uncured region is removed. Then, it is washed with water and dried to form a permanent pattern. <Evaluation of Insulation Reliability 1 (Condition 1)&gt; ® For a substrate thickness other than the above, a copper thickness of 12 μm is used. Copper clad laminate with line/gap = 50 microns / 50 microns A permanent pattern produced in the same manner as the method of forming the permanent pattern described above was formed in the form of a comb, and a high-speed accelerated durability test (HAST test) was performed to evaluate a dendrite and an insulation resistance (Ω). The HAST test uses a high-acceleration tester to measure the insulation resistance (Ω) of the conductor bump under the same conditions after applying a voltage of 10 V for 200 hours in an environment of a temperature of 130 ° C and a relative humidity of 85%. Subsequently, the dendritic crystals of the conductor bumps were observed and evaluated as follows. The results are shown in Table 1. [Evaluation criteria] ◎: The wiring was completely unchanged 〇: although no dendrites were observed Crystal, but the anode wiring slightly changed. Δ: Although no dendritic crystals were observed, the anode wiring was difficult to recognize X: dendritic crystals &lt; evaluation of insulation reliability 2 (condition 2)&gt; In the same manner as the method of forming the permanent pattern, the copper-clad laminate having a copper thickness of 12 μm is formed by comb-forming a wire with a line/gap=50 μm/50 μm. Permanent pattern for high speed accelerated durability test (HAST test) and evaluation of dendrites and insulation resistance (Ω). HAST test with high acceleration tester, electronic components at temperature 1 30 ° In an environment where the relative humidity is 8 5%, after applying a voltage of 50 V for 200 hours, the insulation resistance (Ω) of the conductor bump is measured under the same conditions, and then the dendritic crystal of the conductor bump is observed and as follows The results are shown in Table 1. [Evaluation Criteria] ◎: The wiring was completely unchanged. 树: Although no dendritic crystals were observed, the anode wiring slightly changed. Δ: Although no dendritic crystals were observed, the anode wiring was difficult. Identification X: Dendritic crystals &lt;Evaluation of activity preservability&gt; The laminate was sealed at a room temperature (23 ° C, 55% RH) in a moisture-proof bag (black polyethylene tubular bag, film thickness) : 80 μm, water vapor transmission rate: -87-200941138 25 g/m 2 ·24 hours or less), after storing at 40 ° C for 3 days, the above method was measured in the same manner as the evaluation of the shortest development time described above. The shortest imaging time will be in front The enthalpy obtained by the evaluation of the shortest development time is U, and the 最 of the shortest development time after 3 days is stored as tl, and n of n/to is calculated. However, in the case of U measurement, even if the photosensitive layer could not be removed even if the image was sprayed for 60 seconds, "x" was recorded. The closer the obtained enthalpy is to 1, the more excellent the activity preservability. The results are shown in Table 1. [Example 2] 积 In the same manner as in Example 1, except that the ion adsorbent was changed to B-2, the laminate and the permanent pattern were produced, and the sensitivity and insulation reliability were evaluated in the same manner as in Example 1. 1 and condition 2), and active preservation. The results are shown in Table 1. Further, the ion adsorbent B-2 is a mixture of 1 : 1 (mass ratio) of 1XE-100 (manufactured by Toray Synthetic Co., Ltd.) and DHA-4A-2 (manufactured by Kyowa Interface Chemical Co., Ltd.). [Example 3] A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the ion adsorbent was changed to B-3, and sensitivity and insulation reliability were evaluated in the same manner as in Example 1. 1 and condition 2), and active storage. The results are shown in Table 1. Further, the ion adsorbent B-3 is DHA-4A-2 (manufactured by Kyowa Interface Chemical Co., Ltd.). [Example 4] A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the polymerizable compound was changed to C 2 , and sensitivity and insulation reliability were evaluated in the same manner as in Example 1 (Condition 1 and conditions) 2), and active insurance -88- 200941138 deposit. The results are shown in Table 1. Further, the polymerizable compound C_2 is brothel-methanol-methyl propyl vinegar. The polymerizable compound C 2 値 was 0.385. [Example 5] In addition to changing the polymerizable compound to C-3, the laminate and the permanent pattern were produced in the same manner as in Example 1, and the sensitivity and insulation reliability were evaluated in the same manner as in Example 1 (Condition 1 and Condition 2). And existence. The results are shown in Table 1. Further, the polymerizable compound C-3 0 methylpropane trimethacrylate. The polymerizable compound C-3 was 0.5 17 . [Example 6] In addition to the change of the anthracene derivative (initiator) to A-2, the laminate and the permanent pattern were produced in the same manner as in the culture, and the sensitivity and insulation reliability were evaluated in the first example (conditions). 1 and condition 2), preservation. The results are shown in Table 1. Further, the anthracene derivative A-2 is shown in the lower wing.

The tricyclic I/O example 1 is similarly activated. The trihydroxyl I/O is the same as in the first embodiment and the active form A-2.

A - 2 [Example 7] A laminate and a permanent pattern were produced in the same manner as 1 except that the anthracene derivative (initiator) was changed to A-3, and -89- was the same as in Example 1 of Example 1. 200941138 Conducted to evaluate sensitivity, insulation reliability (Condition 1 and Condition 2), and active storage. The results are shown in Table 1. Further, the anthracene derivative A-3 is IRGACURE 250 (manufactured by CIBA SPECIALTY CHEMICALS). [Example 8] A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the anthracene derivative (initiator) was changed to A-4, and sensitivity and insulation reliability were evaluated in the same manner as in Example 1. Properties (Condition 1 and Condition 2) and active storage. The results are shown in Table 1. Further, the anthracene derivative A-4 is 2-benzyl-2-ydimethylamine-1-(4-morpholinylphenyl)-butanone-1. [Example 9] A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the ion-adsorbing agent was changed to B-4, and the polymerizable compound was changed to C-3, and the same procedure as in Example 1 was carried out. Evaluation of sensitivity, insulation reliability (Condition 1 and Condition 2), and activity preservability. The results are shown in Table 1. Further, the ionic adsorbent B-4 is an ammonium pentoxide hydrate. The polymerizable compound c-3 was the same as that of the user of Example 5. [Example 10] A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the ion-adsorbing agent was changed to B-5, and the polymerizable compound was changed to C-3, and the same procedure as in Example 1 was carried out. To evaluate sensitivity, insulation reliability (Condition 1 and Condition 2), and activity preservability. The results are shown in Table 1. Further, the ionic adsorbent B-5 is a trioxide record. The polymerizable compound C-3 was the same as that of the user of Example 5. [Comparative Example 1] -90-200941138 A laminate and a permanent pattern were produced in the same manner as in Example 1 except that the ionizable adsorbent was not used and the polymerizable compound was changed to C-3, and the same procedure as in Example 1 was carried out. Evaluation of sensitivity, insulation reliability (Condition 1 and Condition 2), and activity preservability. The results are shown in Table 1. The polymerizable compound C-3 was the same as that of the user of Example 5. ❹ ❹ [Table 1] Antimony Derivative (Initiator) Ion Adsorbent Polymerization Hybrid Sensitivity Insulation Reliability (Condition 1) Insulation Reliability (Condition 2) Activity Preservation Example 1 A-1 B-1 C- 1 30 ◎ ◎ 〇 Example 2 A-1 B-2 C-1 30 ◎ ◎ 〇 Example 3 'A-1 B-3 C-1 30 〇Δ 〇 Example 4 A-1 B-1 C-2 30 ◎ ◎ 〇 Example 5 A-1 B-1 C-3 30 〇〇〇 Example 6 A-2 B-1 C-1 50 ◎ ◎ 〇 Example 7 A-3 B-1 C-1 100 Δ X 〇 Example 8 A-4 B-1 C-1 200 ◎ 〇 X Example 9 A-1 B-4 C-3 30 Δ X 〇 Example 10 A-1 B-5 C-3 30 △ X 〇 Comparative Example 1 A-1 dice. That C-3 30 XX ◦ [Industrial Applicability] The photosensitive film of the present invention can improve the reliability of the insulation while maintaining the development performance, and can form high-definition efficiently. The permanent pattern can be suitably used for various pattern formations such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar, a rib, and a spacer. Manufacturing of liquid crystal structural members such as walls, holograms, micro For forming a pattern such as a machine or a sample, it is particularly suitable for forming a permanent pattern for use in a printed substrate. In the pattern forming method of the present invention, the photosensitive composition can be suitably used for various pattern formations such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, and a color filter 'column. The production of liquid crystal structural members such as ribs, spacers, and partition walls, formation of holograms, micro-machines, and patterns such as proofs can be suitably formed using a permanent pattern from a printed circuit board. [Circular simple description] Λητ. No 0 [Main component symbol description] &gt;frrr No 0

Claims (1)

200941138 VII. Patent application scope: 1. A photosensitive composition characterized by comprising a binder, a polymerizable compound, an anthracene derivative and an ion adsorbent. 2. The photosensitive composition of claim 1, wherein the ion adsorbent comprises a phosphoric acid pin. 3. The photosensitive composition according to claim 1 of the patent application, further comprising a binder. 4. For example, the photosensitive composition of claim 1 of the patent scope further contains heat © crosslinker. 5. The photosensitive composition according to claim 1, wherein the anthracene derivative is represented by the following formula (1): N 〇-R1 (R2)m || C^: Formula (1) wherein In the above formula (1), R1 represents a hydrogen atom, a thiol group which may have a substituent, an alkoxycarbonyl group and an aryloxycarbonyl group, and R2 each independently represents a halogen atom or an alkyl group. Any one of an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group and an amine group, m represents an integer of 〇~4, and two or more may be bonded to each other to form a ring, and A represents Any of the 4, 5, 6 and 7 member rings. 6. The photosensitive composition of claim 5, wherein the anthracene derivative is as shown in the following formula (2), -93- 200941138 In the above formula (2), R1 represents any one of a hydrazine group, an alkoxycarbonyl group and an aryloxycarbonyl group which may have a substituent of a hydrogen atom, and R2 each independently represents Any one of a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a thiol group, an arylthio group and an amine group 'm series means an integer of 0 to 4 ©, and X means ch2, o and S Any one of '1' represents an integer of 1 to 3. 7. The photosensitive composition of claim 5, wherein the anthracene derivative is represented by any one of the following general formulae (3) and (4). N^〇—R1 Formula (3) Formula (4) wherein, in the above formulas (3) and (4), 'Rl represents a hydrogen atom' may also have a substituent, alkoxycarbonyl and aryl Any of the oxycarbonyl groups, R2 each independently represents a halogen atom, a aryl group, an aryl group, an aristocratic group, an aryloxy group, a sulfur-sulfur group, an arylthio group, and an amine group. -94- 200941138, * An integer of ～4, χ indicates any of Ch2, 0, and S, and 1 indicates an integer of 1 to 3. 8. The photosensitive composition of claim 6, wherein in the formula (2), the X system represents any one of 〇 and S, and any of the 1 series 1 and 2, the R1 series may have Any one of a substituent thiol group and an alkoxycarbonyl group. 9. The photosensitive composition of claim 7, wherein in the general formulae (3) and (4), the X system represents any one of 〇 and S, and any of the 1 series 1 and 2, the R1 system The watch may also have any one of a substituent thiol group and an alkoxycarbonyl group. The photosensitive composition of claim 1, wherein the weight of the I/O値 of the polymerizable compound is 0.5 or less on average. A photosensitive film comprising a photosensitive layer composed of a photosensitive composition according to item 1 of the patent application of the patent application. A photosensitive laminate comprising a photosensitive layer comprising a photosensitive composition according to the first item of the patent application of the patent application. A permanent pattern forming method characterized by comprising at least a photosensitive layer formed by using a photosensitive composition of the first aspect of the application. 14. The permanent pattern forming method according to claim 13, wherein the exposure is performed by a microlens array formed by arranging microlenses, the microlens having the ability to correct the light modulation by means of optical modulation The aspherical surface of the deviation caused by the deformation of the exit surface of the drawing portion of the light modulation means. 15. The method of forming a permanent pattern according to claim 13 of the patent application, wherein the exposure of the photosensitive layer is performed after exposure to -95-200941138. 16. The permanent pattern forming method according to claim 13, wherein after the development, the photosensitive layer is subjected to a hardening treatment. A printed circuit board characterized in that a permanent pattern is formed in accordance with the permanent pattern forming method of claim 13 of the patent application. -96- .200941138 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 a, 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: