JPH11237739A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain photopolymerizable composition high in sensitivity by incorporating a compound having an additionally polymerizable ethylenically unsaturated bond and a pyridiniomethyl ester of an organic acid selected from carboxylic acid, carbonic acid, and carbamic acid. SOLUTION: This photopolymerizable composition contains the compound having an additionally polymerizable ethylenically unsaturated bond and a pyridiniomethyl ester of an organic acid selected from carbonylic acid, carbonic acid, and carbamic acid. The reason why the optionally substituted pyridiniomethyl ester compound, specified as a photopolymerization initiator, of the organic acid selected from the carboxylic acid, the carbonic acid, and the carbamic acid is suprior in that this pyridiniomethyl ester bond is easily cut off after this compound is irradiated with light at the characteristic site of the chemical structure, and further, acid radicals produced after the decomposition cause decarbonation reaction, and deactivation of the radicals due to recombination after decomposition is hindered.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition. More specifically, the present invention relates to a photopolymerizable composition containing a polymerizable compound having at least an addition-polymerizable ethylenically unsaturated bond and a photopolymerization initiator having a novel composition.

[0002]

2. Description of the Related Art A photopolymerizable composition is a material which causes a change in physical properties of a composition as a result of a polymerization reaction caused by light irradiation.
It is used in a wide range of fields, such as paints, inks, hologram recording, and three-dimensional modeling, and its applications are expanding more and more. Such a composition basically comprises an addition-polymerizable ethylenically unsaturated compound and a photopolymerization initiator. This type of composition undergoes a polymerization reaction upon irradiation with light, and cures and insolubilizes. Therefore, a photosensitive composition obtained by further adding a binder resin having a film forming ability, a thermal polymerization inhibitor, and the like to such a composition as necessary. A desired cured image can be formed by forming an object into an appropriate film, irradiating light through a desired negative image, and removing only a non-irradiated portion with an appropriate solvent (hereinafter simply referred to as development). It is well known that such an image forming method is extremely useful as a method used when preparing a printing plate or the like.

[0003] In addition, compounds having an ethylenically unsaturated bond capable of addition polymerization alone have not been sufficiently photosensitized, and it has been proposed to add a photopolymerization initiator to enhance photosensitivity. Benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like have been used as suitable photopolymerization initiators. However, when these photopolymerization initiators are used, it takes a long time for image exposure in image formation because the photopolymerizable composition has low sensitivity to curing. Therefore, in the case of a fine image, if there is a slight vibration in the operation, an image with good image quality cannot be reproduced, and further, since the amount of energy radiation of the light source for exposure must be increased, a large amount of heat generated thereby is generated. Radiation had to be considered. In addition, there has been a problem that the film of the composition is easily deformed and deteriorated by heat.

In recent years, the sensitivity to ultraviolet rays has been increased,
A method of forming an image using a laser has been studied, and UV projection exposure method, laser plate making, laser facsimile, holography, etc. in printing plate preparation are already in the practical stage, and a high-sensitivity photosensitive material corresponding to these is desired. It is rarely under development. However, it cannot be said that a photosensitive material having sufficient sensitivity has been found yet.

[0005]

It is an object of the present invention to provide a highly sensitive photopolymerizable composition. That is,
An object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator which generally increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an addition-polymerizable unsaturated bond. is there.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a pyridiniomethyl ester compound-based photopolymerization initiator is polymerizable having an addition-polymerizable unsaturated bond. The present inventors have found that the photopolymerization rate of various compounds is significantly increased, and have reached the present invention. A good effect of using a pyridiniomethyl ester compound is that the storage stability of the photosensitive material is good.

That is, the present invention is as follows. (1) A photopolymerizable composition comprising at least the following components A) and B). A) A compound having an addition-polymerizable ethylenically unsaturated bond. B) Pyridiniomethyl ester compounds of organic acids selected from carboxylic acids, carbonic acids and carbamic acids.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The photopolymerizable composition of the present invention comprises: A) a compound having an ethylenically unsaturated bond capable of addition polymerization, and B) an optionally substituted pyridiniomethyl of an organic acid selected from carboxylic acid, carbonic acid and carbamic acid. Contains an ester compound.

As the photopolymerization initiator, the specific ester compound B) a pyridiniomethyl ester compound which may be substituted with an organic acid selected from carboxylic acid, carbonic acid and carbamic acid is excellent because of its structural characteristics. The pyridiniomethyl-ester bond is easily cleaved after the compound is photoactivated by irradiation with light, and the acid radical generated after the decomposition causes a decarboxylation reaction. Is due to being inhibited.

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail. The polymerizable compound having an addition-polymerizable unsaturated bond of the component A) used in the present invention is selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds. As the monomer, for example, unsaturated carboxylic acid (for example, acrylic acid,
Examples include esters of methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid) with aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with aliphatic polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate , 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

The itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis −
Examples include methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

Another example is disclosed in JP-B-48-417.
JP-A-08-208, in which a hydroxyl group-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule, two or more in one molecule: And a vinyl urethane compound containing a polymerizable vinyl group. CH ₂ CC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. In addition, Journal of the Adhesion Society of Japan vol. 20, No. 7, 300-30
Those introduced as photocurable monomers and oligomers on page 8 (1984) can also be used. In the present invention, these monomers may be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

The amount of these used is 5 to 50% by weight (hereinafter sometimes abbreviated as%), preferably 10 to 40%, based on all components of the photopolymerizable composition. If the amount used is large, it is easy to cause poor coating formation (stickiness), and if the amount used is small, curing failure tends to occur, which is not preferable.

The optionally substituted pyridiniomethyl ester compound of an organic acid selected from carboxylic acid, carbonic acid and carbamic acid as component B) used in the present invention is represented by the following general formula (1). Compound.

[0020]

Embedded image

[0021] Equation (1), R ¹ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group,, R ^2, R ^{3, R 4, R 5,} R
⁶ may be the same or different and represents a hydrogen atom, a halogen atom or a monovalent organic residue, and at least one has a group having a structure represented by the general formula (2) . R ¹ and R ² , R ¹ and R ⁶ , R ² and R ³ , R ³ and R ⁴ ,
R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine with each other to form a ring.

[0022]

Embedded image

R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group; R
⁷ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group, an amino group or Represents a substituted amino group. R ⁸ and R ⁹ , R ⁷ and R ⁸ , and R ⁷ and R ⁹ may be bonded to each other to form a ring.

Z represents a counter anion. n represents an integer of 1 to 4.

In the general formula (1), R ² , R ³ , R ⁴ ,
R ⁵ and R ⁶ are more preferably each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, a hydroxyl group. Group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonate group, cyano group , A nitro group or a silyl group can be used. R ¹ and R ² , R ¹ and R ⁶ , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ may be bonded to each other to form a ring.

Next, preferred examples of R ¹ in the general formula (1) will be described in detail. Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, Examples include a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent for the substituted alkyl group, a monovalent nonmetallic atomic group other than hydrogen is used. Preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, Alkoxy, aryloxy, mercapto, alkylthio, arylthio, alkyldithio, aryldithio, amino, N-alkylamino, N, N-dialkylamino, N-arylamino, N, N- Diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N An arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group,
N'-alkyl ureido group, N ', N'-dialkyl ureide group, N'-aryl ureide group, N', N'-diaryl ureide group, N'-alkyl-N'-aryl ureide group, N-alkyl ureide Group, N-arylureido group, N′-alkyl-N-alkylureido group,
N′-alkyl-N-arylureido group, N ′, N ′
-Dialkyl-N-alkylureido group, N ', N'-
Dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'- Diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-
N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-
N-alkoxycarbonylamino group, N-alkyl-N
-Aryloxycarbonylamino group, N-aryl-N
-Alkoxycarbonylamino group, N-aryl-N-
Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N
- arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugate Base group (referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N , N-Diarylsulfamoyl group N- alkyl -N- arylsulfamoyl group, (referred to as phosphonato group) phosphono group (-PO ₃ H ₂₎ and its conjugated base group, a dialkyl phosphono group _{(-PO 3 (alkyl) 2:} alkyl = alkyl group The same applies hereinafter), diarylphosphono group (—PO ₃ (aryl) ₂ :
aryl = an aryl group, hereinafter the same), an alkyl aryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ (alkyl)) and its conjugated base group (alkylphosphonato group referred), referred to as monoarylphosphono group (-PO ₃ H (aryl)) and its conjugated base group (aryl phosphite Hona preparative group), phosphonooxy group (-O
PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃
H (alkyl) ₂ ), a diarylphosphonooxy group (—O
PO ₃ (aryl) ₂ ), alkyl aryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (alkyl phosphonate) referred to as group), referred to as monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (aryl phosphite Hona preparative group), a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group And a silyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl and the like. , Cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl, phenylthiophenyl A methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group,
Examples include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group. Examples of the alkenyl group include a vinyl group, a 1-propenyl group,
Examples thereof include a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group. Acyl group (R ¹²
Examples of R ¹² in CO—) include a hydrogen atom and the above-described alkyl and aryl groups. Of these substituents, still more preferred are a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N
-Alkyl-N-arylcarbamoyl group, sulfo group,
Sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N
-Arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono Group, an arylphosphonato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, and an alkenyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining such a substituent with an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and a methoxyethoxyethyl group. , Allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl, trimethylsilylmethyl, methylphenylaminomethyl, ethylaminoethyl, diethylaminopropyl, morpholinopropyl, acetyloxymethyl, benzoyloxymethyl Group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, Ruboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoyl Ethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group,
N-tolylsulfamoylpropyl group, N-methyl-N
-(Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Tolyl phosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group,
Benzyl group, phenethyl group, α-methylbenzyl group, 1
-Methyl-1-phenylethyl group, p-methylbenzyl group, p-butylbenzyl group, cinnamyl group, allyl group,
Examples thereof include a 1-propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group. These may be further substituted.

Next, as the aryl group as R ¹ in the general formula (1), one in which one to three benzene rings form a condensed ring, and a benzene ring and a five-membered unsaturated ring form a condensed ring Can be mentioned, and as a specific example,
Examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

As the substituted aryl group, those having, as a substituent, a group consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom on the ring-forming carbon atom of the aforementioned aryl group are used. Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of such a substituted aryl group include biphenyl, tolyl, xylyl, mesityl, cumenyl, butylphenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, and triphenyl. Fluoromethylphenyl, hydroxyphenyl, nitrophenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholino Phenyl, acetyloxyphenyl, benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methyl Benzoylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, carbamoylphenyl, N-methylcarbamoylphenyl, N, N-dipropylcarbamoylphenyl, N- (Methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N- Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonoff Nyl, diphenylphosphonophenyl, methylphosphonophenyl, methylphosphonatophenyl, tolylphosphonophenyl, tolylphosphonatophenyl, allylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl , 2
-Methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like.

Alkenyl, substituted alkenyl, alkynyl, and substituted alkynyl groups (—C (R ¹³ ) ＝ C
As (R ¹⁴ ) (R ¹⁵ ) and —C≡C (R ¹⁶ )), those in which R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a group consisting of a monovalent nonmetallic atomic group can be used. Preferred R ¹³ , R ¹⁴ ,
Examples of R ¹⁵ and R ¹⁶ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those described above.
More preferred groups of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ include a hydrogen atom, a halogen atom and a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Such alkenyl groups, substituted alkenyl groups,
Preferred specific examples of the alkynyl group and the substituted alkynyl group include a vinyl group, a 1-butenyl group, a 1-propenyl group, a 1-pentenyl group, a 1-hexenyl group, a 1-octenyl group, and a 1-methyl-1-propenyl group. A 2-methyl-1-propenyl group, a 2-methyl-1-butenyl group,
Examples thereof include a 2-phenyl-1-ethenyl group, a 2-chloro-1-ethenyl group, an ethynyl group, a 1-propynyl group, and a phenylethynyl group.

More preferred specific examples of R ¹ in the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s
-Butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, allyl group, 1-propenylmethyl group,
2-butenyl group, 2-methylallyl group, 2-methylpropenyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenethyl Group, p-methylbenzyl group, cinnamyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, allyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, morpholinoethyl group, morpholinopropyl group, sulfopropyl group, Sulfonatopropyl group, sulfobutyl group, sulfonatobutyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, methoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, phenoxycarbonylmethyl group, methoxycarbonylpropyl group, - methylcarbamoyl ethyl group,
N, N-ethylaminocarbamoylmethyl group, N-phenylcarbamoylpropyl group, N-tolylsulfamoylbutyl group, p-trienesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group,
Phosphonoethyl group, phosphonopropyl group, p-phosphonobenzylaminocarbonylethyl group, phosphonatomethyl group, phosphonatopropyl group, phosphonatobutyl group, p-
Examples include a phosphonatobenzylaminocarbonylethyl group, a vinyl group, and an ethynyl group.

Next, R ² , R ³ , R in the general formula (1)
Preferred examples of ⁴ , R ⁵ and R ⁶ other than the structure represented by the general formula (2) will be described in detail. As the halogen atom, a fluorine, chlorine, bromine or iodine atom is preferable. Alkyl group,
Preferred examples of the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, and the substituted alkenyl group include those described above as examples of R ¹ .

As the substituted oxy group (R ¹⁷ O ⁻ ), R ¹⁷
Is a monovalent non-metallic atomic group other than hydrogen. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy group. Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Examples thereof include a phosphonooxy group and a phosphonatoxy group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Examples of the acyl group (R ¹⁸ CO—) in the acyloxy group include those in which R ¹⁸ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group described above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferred. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumethyloxy group, methoxyphenyloxy group,
Ethoxyphenyloxy group, chlorophenyloxy group,
Examples thereof include a bromophenyloxy group, an acetyloxy group, a benzoyloxy group, a naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, and a phosphonatoxy group.

As the substituted thio group (R ¹⁹ S-), those wherein R ¹⁹ is a monovalent non-metallic atomic group other than a hydrogen atom can be used.
Examples of preferred substituted thio groups include alkylthio, arylthio, alkyldithio, aryldithio,
An acylthio group can be mentioned. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group, those can be cited shown as substituted aryl group, R ¹⁸ of the acyl group (R ¹⁸ CO-) in the acylthio group is As described above. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include methylthio, ethylthio, phenylthio, ethoxyethylthio, carboxyethylthio,
And a methoxycarbonylthio group.

The substituted amino group (R ²⁰ NH—, (R ²¹ ) (R
²²⁾ The ^{N-), R 20, R 21} , R 22 can be used a monovalent nonmetallic radical other than hydrogen. Preferred examples of the substituted amino group include an N-alkylamino group, N,
N-dialkylamino group, N-arylamino group, N,
N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-
Alkyl ureide group, N ′, N′-dialkyl ureide group, N′-aryl ureide group, N ′, N′-diaryl ureide group, N′-alkyl-N′-aryl ureide group, N-alkyl ureide group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-
Alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-
Alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N ′ -Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl —N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group and N-aryl-N-aryloxycarbonylamino group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Substituted alkyl group, and aryl group include those shown as the substituted aryl group, an acylamino group, N- alkyl acyl amino group, R ¹⁸ of the acyl group (R ¹⁸ CO-) in the N- arylacylamino group As described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino, ethylamino, diethylamino, morpholino, piperidino, piperidino, pyrrolidino,
Examples include a phenylamino group, a benzoylamino group, and an acetylamino group.

As the substituted carbonyl group (R ²³ —CO—), those in which R ²³ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N-N-dialkylcarbamoyl group, N-arylcarbamoyl group, An N, N-diarylcarbamoyl group and an N-alkyl-N-arylcarbamoyl group are exemplified. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred substituents include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N′N-
Examples thereof include a dialkylcarbamoyl group and an N-arylcarbamoyl group, and still more preferable examples include a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group And a morpholinocarbonyl group.

As the substituted sulfinyl group (R ²⁴ —SO—), those wherein R ²⁴ is a monovalent nonmetallic atomic group can be used. Preferred examples include an alkylsulfinyl group, an arylsulfinyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N, N-dialkylsulfinamoyl group, an N-arylsulfinamoyl group, and an N, N-diarylsulfinamoyl. And N-alkyl-N-arylsulfinamoyl groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Among these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R ²⁵ —SO ₂ —), those in which R ²⁵ is a monovalent nonmetallic atomic group can be used.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples include the substituted alkyl group, the aryl group, and the substituted aryl group. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

The sulfonato group (SO ₃ ^-) are as described above,
It means a conjugate base anion group of a sulfo group (—SO ₃ H), and it is usually preferably used together with a counter cation.
As such counter cations, those generally known,
That is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , C
a ²⁺ , Zn ^2+, etc.).

The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted by another organic oxo group. Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group, Examples thereof include an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, and a diphenylphosphono group.

[0043] phosphonate group ^{_{(-PO 3 2-, -PO 3 H}} -)
As I mentioned above the means phosphono group (-PO ₃ H _2), first dissociation or acid, a conjugated base anion group derived from the second dissociation acid. Usually it is preferred to use it with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na
^{_{+, K +, Ca 2 +}} , Zn 2+ etc.).

The substituted phosphonate group is a conjugate base anion group obtained by substituting one hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups, and specific examples thereof include the above-mentioned monoalkylphosphono group (-PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl). Usually, it is preferably used together with a counter cation. Generally known, namely, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na
⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

A silyl group ((R ²⁶ ) (R ²⁷ ) (R ²⁸ ) Si
As-), those in which R ²⁶ , R ²⁷ , and R ²⁸ are monovalent nonmetallic atomic groups can be used. Preferred examples include those in which the above-described alkyl group, substituted alkyl group, aryl group, and substituted aryl group are used. Can be mentioned. Examples of preferred silyl groups include trimethylsilyl, tributylsilyl, t
-Butyldimethylsilyl group, dimethylphenylsilyl group and the like.

The above R ² , R ³ , R ⁴ , R ⁵ , R ⁶
Among the examples, more preferred are a hydrogen atom, a halogen atom (-F, -Cl, -Br, -I), an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted oxy group, and a substituted thio group. Group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, cyano group,
Still more preferably, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted carbonyl group can be mentioned.

Next, R ¹ and R ² , R ¹ and R ⁶ , R ² and R ³ , R
^{An example in which 3} and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are bonded to each other to form a ring is shown. Examples of such are: R ¹ and R ² , R ¹ and R ⁶ , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ are mutually bonded and saturated, or Examples thereof include those which form an unsaturated aliphatic ring, and are preferably a 5-membered ring, a 6-membered ring,
Those which form a 7-membered ring and an 8-membered aliphatic ring can be mentioned. More preferably, a 5- or 6-membered aliphatic ring can be mentioned. Further, they may further have a substituent on the carbon atom constituting them (for examples of the substituent, the substituents on the substituted alkyl group mentioned above as examples of R ⁴ and R ⁷ ) And a part of the ring-constituting carbon atoms may be substituted with a hetero atom (an oxygen atom, a sulfur atom, a nitrogen atom, or the like). Further, a part of the aliphatic ring may form a part of an aromatic ring. Preferred examples of these include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclo-1,3-dioxapentane ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, and a cyclo-octene ring.
Examples thereof include a 1,3-dioxapentene ring, a cyclo-1,3-dioxahexene ring, a cyclohexadiene ring, a benzocyclohexene ring, a benzocyclohexacene ring, and a tetrahydropyranone ring.

Next, R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵
And R ⁶ are bonded to each other to form an aromatic ring, such as a quinoline ring, isoquinoline ring, acridine ring, phenanthridine ring, benzquinoline ring in cooperation with a pyridine ring containing a carbon atom to which they are bonded. And those forming a benzisoquinoline ring, and more preferably those forming a quinoline ring. Further, these may have a substituent on the constituting carbon atom (an example of the substituent is the above-mentioned substituent on the substituted alkyl group).

Next, preferred examples of R ⁸ and R ⁹ in the general formula (2) will be described in detail. As the halogen atom, a fluorine, chlorine, bromine or iodine atom is preferable. Alkyl group,
Preferred examples of the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group include those described above as examples of R ¹ . More preferred R ⁸ and R ⁹ are a hydrogen atom and an alkyl group.

Next, preferred examples of R ⁷ in the general formula (2) will be described in detail. Alkyl group, substituted alkyl group,
Preferred examples of aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, and substituted amino group
Examples of the aforementioned R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ can be given. R ⁷ is more preferably an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an alkenyl group.

Further, R ⁸ and R ⁹ , R ⁷ and R ⁸ , and R ⁷ and R ⁹ may be bonded to each other to form a saturated or unsaturated aliphatic ring. And a carbon atom which forms a 5-, 6-, 7- or 8-membered aliphatic ring in combination with a carbon atom. More preferably, a 5- or 6-membered aliphatic ring can be mentioned. Further, they may further have a substituent on the carbon atom constituting them (examples of the substituent include the above-mentioned examples of the substituent in the substituted alkyl group). Further, a part of the ring-constituting carbon atoms may be substituted with a hetero atom (an oxygen atom, a sulfur atom, a nitrogen atom, or the like). Further, a part of the aliphatic ring may form a part of an aromatic ring. Preferred examples of these include a cyclopentane ring, a cyclohexane ring,
Cycloheptane ring, cyclooctane ring, cyclo-1,3
-Dioxapentane ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclo-1,3-dioxapentene ring, cyclo-1,3-dioxahexene ring, cyclohexadiene ring, benzocyclohexene ring, benzocyclohexadiene And a perhydropyranone ring.

[0052] Next pairs in the general formula (1) anion Z ^-
A preferred example will be described in detail. Z ^- As a preferred example, a halide ion ^{(F -, Cl -, Br} -,
I ⁻ ), a sulfonate ion, an organic boron anion, a perchlorate ion (ClO ₄ ⁻ ) and an anion represented by the general formula (3) or (4): MXr (3) MXr-1 (OH) (4) ( In the formula, M represents a boron atom, a phosphorus atom, an arsenic atom, or an antimony atom, X represents a halogen atom,
r represents an integer of 4 to 6. ).

Preferred examples of the sulfonate ion include:
Methanesulfonic acid ion, benzenesulfonic acid ion,
p-toluenesulfonic acid ion (TsO ⁻ ), p-styrenesulfonic acid ion, β-naphthoquinone-4-sulfonic acid ion, anthraquinone-1,5-disulfonic acid ion, anthraquinone-1,8-disulfonic acid ion,
Anthraquinone-1-sulfonic acid ion, anthraquinone-2-sulfonic acid ion, quinoline-8-sulfonic acid ion, hydroquinonesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 1-naphthalenesulfonic acid ion, 2-naphthalenesulfonic acid Ion, 2-amino-1-naphthalenesulfonic acid ion, 2-naphthol-
6-sulfonic acid ion, dibutylnaphthalenesulfonic acid ion, naphthalene-1,3,6-trisulfonic acid ion, m-benzenedisulfonic acid ion, p-phenolsulfonic acid ion, dodecylbenzenesulfonic acid ion, 2-hydroxy-4 -Methoxybenzophenone-5
-Sulfonic acid ion, 4-acetylbenzenesulfonic acid ion, 4-nitrotoluene-2-sulfonic acid ion,
o-benzaldehyde sulfonic acid ion, diphenylamine-4-sulfonic acid ion, benzaldehyde-2,
4-disulfonic acid ion, mesitylenesulfonic acid ion, trifluoromethanesulfonic acid ion, chlorosulfonic acid ion, fluorosulfonic acid ion, 9,10-
And dimethoxyanthracene-2-sulfonate ion.

Examples of the organic boron anion include compounds represented by the following general formula (5).

[0055]

Embedded image

(Wherein R ³¹ , R ³² , R ³³ and R ³⁴ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted An alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, wherein R ³¹ , R ³² , R ³³ and R ³⁴ form a cyclic structure by bonding of two or more of the groups; May be).

The alkyl groups represented by R ^{31 to} R ³⁴ include linear, branched and cyclic alkyl groups, and preferably have 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examples of the substituted alkyl group include a halogen atom (for example, -Cl, Br, etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, and the following groups.

[0058]

Embedded image

(Where R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms or an aryl group), —COOR ³⁷ (where R ³⁷ represents a hydrogen atom, a carbon number 1-14 alkyl group shown, or aryl group,), -. OCOR ³⁸ or -OR ³⁸ (wherein R ³⁸ represents what has as a substituent a) an alkyl group or an aryl group, 1 to 14 carbon atoms. Is included.

The aryl group of R ^{31 to} R ³⁴ includes a 1 to 3 ring aryl group such as a phenyl group and a naphthyl group, and the substituted aryl group includes the above-mentioned substituted alkyl group Group substituent or 1 to 1 carbon atoms
Those having 14 alkyl groups are included.

As the alkenyl group of R ^{31 to} R ³⁴ ,
It includes straight-chain, branched and cyclic ones having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include those described above as the substituent of the substituted alkyl group.

The alkynyl groups of R ^{31 to} R ³⁴ include:
It includes straight or branched ones having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those described above as the substituent of the substituted alkyl group.

Examples of the heterocyclic group of R ^{31 to} R ³⁴ include a 5- or more-membered, preferably 5- to 7-membered heterocyclic group containing at least one of N, S and O. The heterocyclic group may contain a condensed ring. Further, it may have the substituents described above as the substituents of the substituted aryl group.

Examples of the compound represented by the general formula (5) include the following.

[0065]

Embedded image

Specific examples of the anions represented by the general formulas (3) and (4) include SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and BF
^{_{4 -, SbF 5 (OH)}} - , and the like.

Hereinafter, examples of the compounds will be shown, but the present invention is not limited thereto. Preferred specific examples of the optionally substituted pyridiniomethyl ester compound of an organic acid selected from carboxylic acid, carbonic acid, and carbamic acid include the following.

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

The above-mentioned pyridiniomethyl ester compounds used in the photopolymerizable composition of the present invention may be used alone or in combination of two or more.

Further, the photosensitive composition of the present invention may further comprise component C)
It is preferable to coexist with a spectral sensitizing dye or dye which is already known. Examples of preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B), rose bengalocyanines (eg, thia Carbocyanine,
Oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionin, methylene blue, toluidine blue),
Acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, metal porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, central metal) Substituted chlorophyll),
Metal complexes, such as

[0078]

Embedded image

Anthraquinones (eg, anthraquinone), squariums (eg, squarium) and the like can be mentioned.

More preferred examples of component C) spectral sensitizing dyes or dyes are listed below. First, styryl dyes described in JP-B-37-13034, for example, are as follows.

[0081]

Embedded image

The cationic dyes described in JP-A-62-143044 are, for example, the following.

[0083]

Embedded image

The quinoxalinium salts described in JP-A-59-24147 are, for example, the following.

[0085]

Embedded image

New methylene blue compounds described in JP-A-64-33104, for example,

[0087]

Embedded image

Anthraquinones described in JP-A-64-56767, for example, the following:

[0089]

Embedded image

Benzoxanthene dyes described in JP-A-2-174.

JP-A-2-226148 and JP-A-2-226148
Acridines described in U.S. Pat. No. 226149, for example,

[0092]

Embedded image

The pyrylium salts described in JP-B-40-28499 are, for example, the following.

[0094]

Embedded image

Cyanines described in JP-B-46-42363, such as the following:

[0096]

Embedded image

Benzofuran dyes described in JP-A-2-63053, for example, the following:

[0098]

Embedded image

JP-A-2-85858, JP-A-2-21
Conjugated ketone dyes described in No. 6154, for example, the following.

[0100]

Embedded image

Dyes described in JP-A-57-10605. Azocinnamylidene derivatives described in JP-B-2-30321, for example, are as follows.

[0102]

Embedded image

The cyanine dyes described in JP-A-1-287105 are, for example, the following.

[0104]

Embedded image

JP-A-62-31844, JP-A-62-31844
Xanthene dyes described in JP-A-31848 and JP-A-62-143043, for example, the following.

[0106]

Embedded image

The aminostyryl ketones described in JP-B-59-28325, for example, the following:

[0108]

Embedded image

Merocyanine dyes represented by the following formulas [1] to [8] described in JP-B-61-9621, for example, the following:

[0110]

Embedded image

In the general formulas [3] to [8], X ⁸
Is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an aryl group, a substituted aryl group, an aryloxy group,
Represents an aralkyl group or a halogen atom. General formula [2]
In the above, Ph represents a phenyl group. General formula [1]-
In [8], R ⁴⁸ , R ⁴⁹ and R ⁵⁰ each represent an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group,
Represents a substituted aryl group or an aralkyl group, which may be equal to or different from each other;

There are dyes represented by the following formulas [9] to [11] described in JP-A-2-179463.

[0113]

Embedded image

A: oxygen atom, sulfur atom, selenium atom,
Represents a tellurium atom, an alkyl or aryl substituted nitrogen atom, or a dialkyl substituted carbon atom. Y ^{3 represents a} hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group. R ⁵¹ and R ⁵² : a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
Alternatively, as a substituent, R ⁵³ O—, the following groups,

[0115]

Embedded image

-(CH ₂ CH ₂ O) _x -R ⁵³ , a substituted alkyl group having 1 to 18 carbon atoms and having a halogen atom (F, Cl, Br, I). R ⁵³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and B represents a dialkylamino group, a hydroxyl group, an acyloxy group, a halogen atom, or a nitro group.
w represents an integer of 0 to 4, and x represents an integer of 1 to 20.

Further, there is a merocyanine dye represented by the following general formula [12] described in JP-A-2-244050.

[0118]

Embedded image

(Wherein R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom , Selenium atom,
Represents a tellurium atom, an alkyl or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom. X
⁹ represents a nonmetallic atomic group necessary for forming a nitrogen-containing 5-membered heterocyclic ring.

Y ⁴ represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z ³ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group,
Represents a substituted amino group, an acyl group, or an alkoxycarbonyl group, which may be bonded to Y ⁴ to form a ring;

Preferred specific examples include the following. Also, there is (d) of the embodiment.

[0122]

Embedded image

There is a merocyanine dye represented by the following formula [13] described in JP-B-59-28326.

[0124]

Embedded image

In the above formula, R ⁵⁶ and R ⁵⁷ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl or aralkyl group, which may be equal or different from each other. X ¹⁰ is Hammett (Hammet
t) represents a substituent having a sigma (σ) value in the range of -0.9 to +0.5. There is a merocyanine dye represented by the following general formula [14] described in JP-A-59-89303.

[0126]

Embedded image

(Wherein R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ is Hammett)
(Hammett) represents a substituent having a sigma (σ) value in the range of -0.9 to +0.5. Y ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group. Preferred specific examples include the following.

[0128]

Embedded image

There is a merocyanine dye represented by the following general formula [15] described in Japanese Patent Application No. 6-269047.

[0130]

Embedded image

(Wherein R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁸ ,
R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Substituted aryl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonato group, a substituted phosphonate group, a cyano group, or a nitro group, or R ⁶⁰ and R ^61, R ⁶¹ and R ^62, R ⁶²
And R ⁶³ , R ⁶⁸ and R ⁶⁹ , R ⁶⁹ and R ⁷⁰ , and R ⁷⁰ and R ⁷¹ may combine with each other to form an aliphatic or aromatic ring.
R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group,, R ⁶⁵ represents a substituted or unsubstituted alkenyl group or a substituted or unsubstituted alkynyl group,, R ⁶⁶ , R ⁶⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted carbonyl group. Preferred specific examples include the following.

[0132]

Embedded image

More preferred examples of the component C) in the present invention include the merocyanine dyes described in JP-B-61-9621, the merocyanine dyes described in JP-A-2-179643, and the merocyanine dyes described in JP-A-2-244050. Dyes, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, and merocyanine dyes described in Japanese Patent Application No. 6-269047 can be exemplified.

The component C) according to the present invention may be used alone or
It is preferably used in combination of two or more kinds. Further, a known compound having an action of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added to the photopolymerizable composition of the present invention as a cosensitizer.

Examples of such co-sensitizers include amines such as those described in MRSander et al., Journal of Polymer Socie.
ty ", Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-2
0189, JP-A-51-82102, JP-A-52-102
No. 134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 3382
No. 5, and the like, and specific examples thereof include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806 and JP-A-5-142772, No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is mentioned.

Another example is an amino acid compound (eg, N-phenylglycine, etc.), Japanese Patent Publication No. 48-429.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, sulfur compounds described in JP-A-5-91089 (eg,
Trithiane, etc.), phosphorus compounds described in Japanese Patent Application No. 5-32147 (diethyl phosphite, etc.), and Japanese Patent Application No. 6-1916.
Si-H and Ge-H compounds described in No. 05 are exemplified.

As yet another example, see US Pat.
No. 8791, EP 0284561 A1, aminoketone compounds, such as the following. In addition, there is also an example using (e).

[0139]

Embedded image

Still another example is described in JP-A-8-202.
The oxime ethers described in No. 035 are also suitable. Specific examples include the following. Also,
There is also an embodiment using (f).

[0141]

Embedded image

The amount of each of the components B) and C) in the composition of the present invention is determined based on the amount of the ethylenically unsaturated compound capable of being polymerized and the amount of the linear organic high molecular polymer as a binder added as required. 0.01 to 60% by weight based on the total
, More preferably in the range of 1 to 30% by weight.

The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. Such a “linear organic high molecular polymer” includes
Any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Preferably, a water-soluble or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic polymer is appropriately selected and used depending on whether water, weakly alkaline water or an organic solvent is used as a developer as well as a film-forming agent of the photopolymerizable composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No., JP-B-58-12577, JP-B-54-2595
7, JP-A-54-92723, JP-A-59-538.
36, JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, There are esterified maleic acid copolymers and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamides and polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular polymers can be incorporated in any amount into the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85% by weight. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization inhibitor is used to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. Suitable thermal polymerization inhibitors include hydroquinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl −
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% To about 5% is preferred. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

In the present invention, a dye or pigment can be added for the purpose of coloring the photosensitive layer. The amount of the dye or pigment added is from 0.01% to 20% of the total composition, more preferably from 0.5 to 10%. Pigments are more preferable than dyes.

As the pigment, commercially available pigments and known pigments described in various documents and the like can be used. For literature, refer to the Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by the Japan Pigment Technical Association (1977), “Latest Pigment Application Technology” CMC Publishing (1986), “Printing Ink Technology” CMC Publishing ( 1984).

Examples of the types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound pigments. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments,
Examples thereof include azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, and inorganic pigments. Among them, more preferred are insoluble azo pigments, azo lake pigments, phthalocyanine pigments, anthraquinone pigments and the like.

These pigments may be dispersed in the presence of a polymer. Examples of such a polymer include those represented by formulas (a) to (c) described in Japanese Patent Application No. 6-193357. ), A polymer having an aliphatic double bond in a main chain or a side chain.

[0149]

Embedded image

Wherein R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R
⁴⁴ and R ⁴⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group. X, Y and Z are each independently a divalent linking group. Q is an atomic group forming an aliphatic ring.

As the alkyl group, an alkyl group having preferably 20 or less, more preferably 10 or less, and still more preferably 6 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, hexyl, isopropyl) And the like).

Examples of the aryl group include an aryl group having 6 to 22 carbon atoms (for example, a phenyl group, a naphthyl group, an anthryl group, etc.).

The alkyl group and the aryl group may be substituted with an alkoxy group, an amide group, an alkoxycarbonyl group and the like.

Each of R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a methyl group.

Examples of the divalent linking group represented by X and Y include an alkylene group, an arylene group, a carbonyl group,
Mention may be made of imino groups, oxygen atoms, sulfur atoms and combinations thereof. The divalent linking group may be substituted with an aryl group, a halogen atom, a hydroxyl group, a cyano group, or the like.

As the alkylene group, an alkylene group having preferably 10 or less, more preferably 6 or less, still more preferably 3 or less carbon atoms (for example, --CH ₂ CH ₂ CH _{2)
2 -, - CH 2 CH 2} -, - CH 2 CH (CH 3) - , etc.)
Is mentioned.

Examples of the arylene group include an arylene group having 6 to 22 carbon atoms, for example, the following groups.

[0158]

Embedded image

X is preferably an alkylene group. Y is preferably an alkylene group, a carbonyl group, an oxygen atom, or a combination thereof.

The aliphatic ring formed by Q is preferably a 5- or 6-membered combined aliphatic ring having 5 to 30 carbon atoms (eg, a cyclohexane ring, a norbornenyl ring, a dicyclopentadiene ring). Aliphatic rings include bicyclic or tricyclic hydrocarbons having a bridgehead carbon atom. It is preferable that there be one double bond between carbon atoms in the aliphatic ring.

The photopolymerizable composition of the present invention may contain an inorganic filler or other known additives in order to improve the physical properties of the cured film.

It is preferable to add a surfactant in order to improve the surface state in coating. As the surfactant, a fluorine-based surfactant is preferable.

The photopolymerizable composition of the present invention is usually used after being coated on a support.

When used after being coated on a support, it is used after being dissolved in various organic solvents. As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone,
Diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate,
N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably, it is 0.5 to 5 g / m ² .

A dimensionally stable plate is used as the support. Dimensionally stable plate-like objects include paper,
Plastics (eg polyethylene, polypropylene,
Paper laminated with polystyrene, etc., for example, aluminum (including aluminum alloy), zinc,
Plates of metal such as copper, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,
Examples include plastic films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic films on which the above-described metals are laminated or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation. Is preferably performed. Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. After anodizing the aluminum plate as described in JP-B-47-5125,
Those immersed in an aqueous solution of an alkali metal silicate are preferably used. The anodizing treatment may be, for example, an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or an electrolytic solution obtained by combining two or more types. It is carried out by passing a current through an aluminum plate as an anode.

Also, silicate electrodeposition as described in US Pat. No. 3,658,662 is effective. Furthermore, JP-B-46-27481 and JP-A-52-5860.
No. 2, JP-A-52-30503, and a surface treatment in which the above-described anodic oxidation treatment and sodium silicate treatment are combined are also useful.

It is also preferable to sequentially perform mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-55-28893. Furthermore, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to adhere the photosensitive layer to the support. This is performed for the purpose of improving the performance. On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 95% or more, acidic celluloses may be used in order to prevent polymerization inhibition by oxygen in the air. For example, a protective layer made of a polymer having excellent oxygen barrier properties such as the above may be provided. Regarding the method of applying such a protective layer, for example, U.S. Pat.
No. 458,311 and JP-A-55-49729.

Further, the photopolymerizable composition of the present invention can be used for a usual photopolymerization reaction. Further, the present invention can be applied to various fields such as a photoresist for producing a printing plate, a printed board, and the like. Particularly, due to the high sensitivity and the wide spectral sensitivity characteristic up to the visible light region, which are characteristics of the photopolymerizable composition of the present invention,
When applied to a photosensitive material for a visible light laser such as an Ar ⁺ laser and a YAG-SHG laser, a good effect can be obtained.

The photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, so that it can be particularly advantageously used for an image forming system using microcapsules. For use in an image forming system using microcapsules, see, for example, JP-A-57-197538.
No. 61-130945, No. 58-88739,
No. 58-88740, EP 223,587 A1
References can be referred to. In this image forming method, for example, a photopolymerization initiator composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a microcapsule containing a dye precursor are coated on a support, and the photosensitive sheet is exposed by imagewise exposure. After curing some of the microcapsules,
By overlapping the developer sheet and pressing the entire surface, the microcapsules in the unexposed areas are destroyed, and the color image forming substance (for example, a dye precursor) is transferred to an image receiving element (for example, a developer layer) to form a color. is there.

The photosensitive material using the photopolymerizable composition of the present invention may be heated after image exposure. Heating temperature is 6
0 ° C to 160 ° C, more preferably 80 ° C to 1 ° C
30 ° C. The heating time is preferably from 1 second to 5 minutes.

Further, an unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image.

A preferred developer for use of these photopolymerizable compositions for preparing a lithographic printing plate is described in
And sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tertiary phosphate, and the like. Aqueous solutions of inorganic alkali agents such as ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as monoethanolamine or diethanolamine are suitable. Such an alkali agent is added so as to have a concentration of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Further, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
No. 0-26601, No. 58-54341, Tokubo Sho56
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

However, when an organic solvent or the like is contained, problems such as toxicity at work, hygiene problems such as odor, safety problems such as fires, workability problems such as generation of bubbles, pollution problems due to waste liquid, and the like. Therefore, those containing substantially no organic solvent are preferred. As such an aqueous alkaline developer substantially containing no organic solvent, for example, a developer composition described in JP-A-59-84241 and JP-A-57-192952 can be used.

A commercially available developer preferably used is DP-
4 (Fuji Photo Film Co., Ltd.) with water 1/6 to 1/3
This is a solution diluted to zero.

The photosensitive lithographic printing plate using the photopolymerizable composition of the present invention is described in JP-A-54-8002 and JP-A-55-115.
No. 045, the methods described in JP-A-59-58431, that is, after development processing, washed with water and then desensitized, or directly desensitized, or treated with an aqueous solution containing an acid, Alternatively, a desensitization treatment may be performed after treatment with an aqueous solution containing an acid. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing machine. The processing capacity is reduced.
Nos. 62004, 55-22759 and 55-115
No. 039, No. 56-12645, No. 58-95349
No. 64-21451, JP-A-1-180548
, The replenishing solution and the replenishing method described in JP-A-2-3065 can recover the processing capacity.

Further, the above-described plate making process is disclosed in
It is preferably carried out using an automatic developing machine as described in JP-A-7054 and JP-A-2-32357. In addition, as the desensitized gum which is applied as required in the final step of the plate making process, JP-B-62-16834 and JP-B-62-25118.
No. 63-52600, JP-A-62-11693
And those described in JP-A-62-83194 are preferred.

Further, after the development treatment, a burning heat treatment or a post-exposure can be performed to improve the printing durability during printing.

[0181]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. A synthesis example is also shown.

[Synthesis Example 1] Synthesis of Compound 1 4-pyridinemethanol (9.5 g) in benzene (10 g)
Benzoyl chloride (14.7 g) was added dropwise to the solution (0 g) and stirred at room temperature for 4 hours. The reaction solution was poured into ice water and stirred for a while. The mixture was extracted three times with ethyl acetate (300 g), and the organic layer was extracted with a saturated aqueous sodium hydrogen carbonate solution (500 g).
) And saturated brine (500 g), dried over magnesium sulfate, filtered and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in acetonitrile (50 g), and benzyl bromide (7 g) was added dropwise. After reacting at room temperature for 24 hours, the precipitated crystals were taken out by filtration. The resulting crystals were dissolved in a small amount of methanol, it poured into KPF ₆ saturated aqueous. The precipitated crystals are taken out by filtration,
14 g of Compound 1 was obtained (40% yield). Compound 1 is ¹ H
The structure was confirmed by NMR and MASS spectra. The melting point was 110-112 ° C.

Synthesis Example 2 Synthesis of Compound 22 In a solution of 2-chloromethylpyridine hydrochloride (12 g) in dimethylacetamide (150 g) was added thiophenoxyacetic acid (19 g), potassium carbonate (25 g), and tetrabutylammonium iodide (1 g). ) Was added, followed by heating to 90 ° C. and reacting for 3 hours. After cooling to room temperature, the reaction solution was poured into water and stirred for a while. The mixture was extracted four times with ethyl acetate (300 g). The organic layer was extracted with water (500 g) and saturated saline (5 g).
After drying with magnesium sulfate and filtration, the solvent was distilled off under reduced pressure. 6 g of the obtained residue (13 g) was dissolved in acetonitrile (50 g), and pt-butylbenzylbromide (5 g) was added dropwise. 24 hours,
After reacting at room temperature, the precipitated crystals were taken out by filtration. The resulting crystals were dissolved in a small amount of methanol, it poured into KPF ₆ saturated aqueous. The precipitated crystals were taken out by filtration to obtain 8 g of Compound 22 (yield: 45%).
The structure of Compound 22 was confirmed by ¹ H NMR and MASS spectra. The melting point was 105-107 ° C.

Synthesis Example 3 Synthesis of Compound 40 In a solution of 4-chloromethylpyridine hydrochloride (10 g) in dimethylacetamide (150 g), sodium pt-butyl benzoate (19 g), potassium carbonate (10 g), tetrabutylammonium After adding iodide (1g),
The mixture was heated to 90 ° C. and reacted for 3 hours. After cooling to room temperature,
The reaction solution was poured into water and stirred for a while. Ethyl acetate (3
The organic layer was washed with water (500 g) and saturated saline (500 g), dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue (1
7 g of 5 g) was dissolved in acetonitrile (50 g).
Benzyl bromide (5 g) was added dropwise. After reacting at room temperature for 24 hours, the precipitated crystals were taken out by filtration. After dissolving the obtained crystals in a small amount of methanol,
aBF ₄ was poured into a saturated aqueous solution. The precipitated crystals were collected by filtration to obtain 10 g of Compound 40 (yield 70%). The structure of Compound 40 was confirmed by ¹ H NMR and MASS spectra. The melting point was 100-102 ° C.

Synthesis Example 4 Synthesis of Compound 30 Acetonitrile (5 g) of 4-pyridinemethanol (5 g) was used.
0 g) to the solution was added triethylamine (6 g),
Cooled down. Di-t-butyl dicarbonate (13 g
) Was added dropwise, followed by reaction at room temperature for 24 hours. The reaction solution was poured into ice water and stirred for a while. Ethyl acetate (3
The organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate (500 g) and a saturated aqueous solution of sodium chloride (500 g), dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. N-Heptyl tosylate (6.5 g) was added to the obtained residue, heated to 100 ° C., and reacted for 1 hour. After cooling to room temperature, recrystallize with ethyl acetate,
5 g of compound 30 was obtained (40% yield). Compound 30 is ¹
The structure was confirmed by 1 H NMR and MASS spectra. Melting point was 98-100 ° C.

The compounds 1, 22, 4 according to the present invention
Pyridiniomethyl ester compounds other than 0,30 could be easily synthesized by the same method.

Example 1 An aluminum plate having a thickness of 0.30 mm was etched by immersing it in 10% sodium hydroxide at 60 ° C. for 25 seconds, washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. did. This was subjected to electrolytic surface-roughening treatment in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode charge of 300 coulomb / dm ² . Followed by 1%
After immersion in aqueous sodium hydroxide solution at 40 ° C for 5 seconds, 30
% Of immersed in an aqueous solution of sulfuric acid, was 40 seconds desmutting at 60 ° C., aqueous 20% sulfuric acid, a current density of 2A / dm ²
In the above, anodizing treatment was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μm (Ra indication).

The following sol-gel reaction solution was coated on the back surface of the substrate treated in this manner with a bar coater, dried at 80 ° C. for 1 minute, and provided with a back coat layer having a coating amount of 70 mg / m ² after drying. Support A was prepared.

(Preparation of sol-gel reaction liquid) Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

When the above components were mixed and stirred, exotherm started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a backcoat coating solution.

Pyrogallol formaldehyde condensation resin (MW 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant (N-butyl perfluorooctane 0.7 parts by weight) Sulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer・ Molecular weight 20,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd .: methanol 30%) 50 parts by weight Methanol 800 parts by weight

On the surface of the aluminum plate thus treated, a photosensitive composition having the following composition was applied in a dry coating weight of 1.5%.
g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Component B) Xg (Table 1) Fluorinated nonionic surfactant (F-177 large) Nippon Ink Co., Ltd.) 0.03 g Thermal polymerization inhibitor N-nitrosophenylhydroxylammonium salt 0.01 g Pigment dispersion 2.0 g Composition P. B. 15: 6 (copper phthalocyanine) 30 parts by weight Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17) 20 parts by weight Cyclohexanone 35 parts by weight Methoxypropyl acetate 35 parts by weight Propylene glycol monomethyl ether 80 parts by weight Methyl ethyl ketone 20 g propylene Glycol monomethyl ether 20g

An aqueous 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 1000) was applied on the photosensitive layer so that the dry coating weight was 2 g / m ² ,
C./2 minutes drying to form a protective layer.

The photosensitive materials thus obtained are designated as Sample Nos. 1, 2, 11, and 12. A Fuji PS step guide manufactured by Fuji Photo Film Co., Ltd. (a gray scale whose transmission density changes discontinuously at ΔD = 0.15) was brought into close contact with each of these photosensitive materials, and exposed from above.

As a light source, a xenon lamp was used, and light was passed through a Kenko optical filter BP-49. P
The energy on the S step guide surface was 0.25 mJ / cm ² .

The exposed photosensitive material was heated at 120 ° C. for 20 seconds and then developed. The sensitivity was indicated by the number of clear steps of the PS step guide after development. The higher the value of the number of stages, the higher the sensitivity. The development was carried out in the following developer:
C. for 10 seconds.

DP-4 (Fuji Photo Film Co., Ltd.) 65.0 g Water 880.0 g Lipomin LA (20% aqueous solution) 50.0 g The results are shown in Table 1. In the table, component B) of the present invention is shown.
The comparative compounds (a) and (b) used in place of the above were also component B)
As shown.

[0199]

[Table 1]

Example 2 Sample No. 3 was prepared in the same manner as in the sample of the photosensitive material of Example 1, except that the photosensitive composition was changed to the following composition.
-8, 13-16.

Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymer molar ratio 80/20) 2.0 g Component B) Xg (Table 2) Component C) Yg (Table 2) Co-sensitization Agent (S) Zg (Table 2) Fluorinated nonionic surfactant (F-177, manufactured by Dainippon Ink Co., Ltd.) 0.03 g Thermal polymerization inhibitor N-nitrosophenylhydroxylammonium salt 0.01 g Pigment dispersion 2.0 g Composition P. B. 15: 6 (copper phthalocyanine) 30 parts by weight Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17) 20 parts by weight Cyclohexanone 35 parts by weight Methoxypropyl acetate 35 parts by weight Propylene glycol monomethyl ether 80 parts by weight Methyl ethyl ketone 20 g propylene Glycol monomethyl ether 20g

The sensitivity of these photosensitive materials was evaluated in the same manner as in Example 1. In addition, a storage stability test was performed at the same time. In the test for storage stability, the photosensitive material prepared above was subjected to forced aging at 60 ° C. for 3 days in an oven, and the presence or absence of precipitates was observed with an optical microscope.

Table 2 shows the results. In the table, the comparative compound (a) used in place of the component B) of the present invention,
(B) is also indicated as component B).

[0204]

[Table 2]

From the above table, it is clear that the use of the component B) in the present invention increases the sensitivity and provides good storage stability. In Tables 1 and 2, (a), (b),
The compounds (d), (e) and (f) are as follows.

[0206]

Embedded image

[0207]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet to visible light, and has good storage stability of a photosensitive material obtained by using the same. .

Claims (1)

[Claims] 1. A photopolymerizable composition comprising at least the following components A) and B). A) A compound having an addition-polymerizable ethylenically unsaturated bond. B) Pyridiniomethyl ester compounds of organic acids selected from carboxylic acids, carbonic acids and carbamic acids.