JPH08220756A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE: To obtain a photopolymerizable compsn. contg. a photopolymn. initiator having high sensitivity to visible radiation of >=400nm wavelength, especially 488nm wavelength corresponding to the output of Ar<+> laser and even to light of >500nm wavelength corresponding to the output of YAG-SHG laser or He-Ne laser. CONSTITUTION: This photopolymerizable compsn. contains a compd. (A) having at least one addition-polymerizable ethylenically unsatd. bond, a compd. (B) represented by the formula and a compd. (C) which generates active radicals when irradiated with light under coexistence of the compd. B. In the formula, A = is optionally substd. 2(1H)-pyridylidene or 4(1H)-pyridylidene, -X- is -O-, -S-, -NR<2> - or CONR<3> -, each of R<1> -R<3> is H, alkyl, etc., and = E is optionally substd. 1,3-dihydro-1-oxo-2H-inden-2-ylidene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photopolymerizable compositions. More specifically, it relates to a photopolymerizable composition comprising a photopolymerization initiation system having a novel composition having excellent photosensitivity to visible light.

[0002]

2. Description of the Related Art A photopolymerizable composition is a material that causes a change in the physical properties of the 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. The composition basically comprises an addition-polymerizable ethylenically unsaturated compound and a photopolymerization initiator. Since a composition of this kind undergoes a polymerization reaction upon irradiation with light and is cured and insolubilized, a photosensitive composition obtained by further adding a binder resin having a film-forming ability, a thermal polymerization inhibitor, etc. to the composition, if necessary. Form an appropriate film, irradiate light through the desired negative image,
A desired cured image can be formed by removing only the 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 printing plate or the like.

The photopolymerization initiator in the photopolymerizable composition has conventionally been benzyl, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine,
Alternatively, benzophenone or the like has been used. However, the composition comprising these photopolymerization initiators has a low photosensitivity, and further, the photopolymerization ability for visible light of 400 nm or more is significantly lower than the photopolymerization ability for light in the ultraviolet wavelength range of 400 nm or less. . Therefore, the application range of the conventional photopolymerizable composition comprising a photopolymerization initiator has been extremely limited.

There has been a long-felt need for a photosensitive composition that is capable of achieving high cure with a small amount of light irradiation. It is useful, for example, as a photosensitive material compatible with non-contact projection exposure. Further, in recent years, an image forming technique using a visible laser is in a practical stage, and a photosensitive composition having a high photopolymerization ability with respect to visible light is strongly desired. As the visible laser light, a method using Ar ⁺ laser having a wavelength of 488 nm is regarded as promising, and recently, YA
Vigorous studies have also been made on light sources with longer wavelengths such as 532 nm wavelength light of G-SHG laser and 543 nm wavelength light of He-Ne laser.

Several proposals have hitherto been made for a photopolymerization composition comprising a photopolymerization initiation system sensitive to visible light. For example, according to U.S. Pat. No. 2,850,445, certain photosensitive dyes such as rose bengal, eosin and erythrosine are reported to have effective visible light sensitivity. As an improved technology,
Complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189), hexaarylbiimidazole and radical generator and dye system (Japanese Patent Publication No. 45-37377), hexaarylbiimidazole and p-dialkylaminobenzylidene ketone System (Japanese Patent Publication No. 47-2528,
JP-A-54-155292), a system of a 3-ketocoumarin compound and an active halogen compound (JP-A-58-155).
No. 03), a system of substituted triazine and merocyanine dye (Japanese Patent Laid-Open No. 54-15102), and the like have been proposed. Although these techniques are effective for visible light, they are not very sensitive and are not sufficiently satisfactory from a practical point of view. Further, JP-A-2-244050 proposes a system of a dye having a 4-thiazolidinone skeleton and a radical generator as a highly sensitive initiation system. This system was certainly highly sensitive, but its photosensitivity had its maximum value in the wavelength region of 500 nm or less, and had a problem that sufficient photosensitivity was not obtained for a light source of 500 nm or more. .

[0006]

An object of the present invention is to provide a photopolymerizable composition having high sensitivity. That is, an object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator which increases the photopolymerization rate of a photopolymerizable composition containing an addition-polymerizable ethylenically unsaturated compound in general. Another object of the present invention is to deal with visible light of 400 nm or more, especially 488n corresponding to the output of Ar ⁺ laser.
m, and further, to provide a photopolymerizable composition containing a photopolymerization initiator that is highly sensitive to light having a wavelength longer than 500 nm, which corresponds to the output of a YAG-SHG laser or a He-Ne laser. .

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above object, a photopolymerizable composition containing a specific photopolymerization initiation system has an extremely high photopolymerization rate. In addition, the inventors have found that they also exhibit high photosensitivity to visible light having a wavelength of 400 nm or more, and further exhibit high photosensitivity to visible light having a wavelength longer than 500 nm, and have reached the present invention.

That is, the present invention provides the following components (i) to (iii)
It is a photopolymerizable composition characterized by containing. i) Compound having at least one ethylenically unsaturated bond capable of addition polymerization ii) General formula [I]

[0009]

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(In the formula, A = is a substituted or unsubstituted 2 (1
H) - pyridylidene group or 4 (1H) - represents a pyridylidene group, -X- is -O -, - S -, - NR 2 - or -CONR ³ - ^{represents, R 1, R 2, R} 3 are each Independently, it 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, and = E is a substituted or unsubstituted 1,3- Dihydro-1-
An oxo-2H-indene-2-ylidene group), and iii) a compound capable of generating an active radical upon irradiation with light in the coexistence with the component (ii).

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail. The compound having at least one addition-polymerizable ethylenically unsaturated bond of the component (i) used in the present invention is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Eg monomers, prepolymers, ie 2
It has a chemical form such as a trimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) with aliphatic polyhydric alcohol compounds, and unsaturated Examples thereof include amides of carboxylic acids and aliphatic polyvalent amine compounds.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters 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.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 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,
1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Examples include sorbitol tetradicrotonate. 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 polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis. −
Methacrylamide, diethylenetriamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide and the like.

Another example is Japanese Patent Publication No. 48-417.
In the polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-A-08,
Examples thereof include vinyl urethane compounds having two or more polymerizable vinyl groups in one molecule to which a vinyl monomer having a hydroxyl group represented by the following general formula (D) is added.

CH ₂ ═C (R) COOCH ₂ CH (R ′) OH (D) (wherein R and R ′ represent H or CH ₃ ), and are described in JP-A-51-37193. Urethane acrylates such as those described in JP-A-48-64183
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
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 No. 0 can be mentioned. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine Vol. 1, 20, No. 7, pages 300 to 308 (1984) can be used. The amount of these used is 5 to 70% by weight based on all components.
(Hereinafter abbreviated as%), preferably 10 to 55%.

The component (ii) used in the present invention is a compound represented by the above general formula [I]. In the general formula [I], A = 2 (1H) -pyridylidene group or 4 (1
The (H) -pyridylidene group is represented by the following partial structural formulas (A-1) and (A-2), respectively.

[0020]

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R ^{4 to} R ¹³ in the formulas (A-1) and (A-2)
Can independently be a monovalent non-metallic atomic group, but more preferably, R ⁴ and R ⁹ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. , An alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² and R
¹³ are 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, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted thio group, an amino group. , A substituted amino group, a substituted carbonyl group, a sulfo group, a sulfonato group, a substituted sulfinyl group, a substituted sulfonyl group, a phosphono group, a substituted phosphono group, a phosphonate group, a substituted phosphonate group, a cyano group, a nitro group, or a silyl group. R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ , R ¹² and R ¹³ are bonded to each other to form a ring. Those are also suitable.

Preferred examples of R ⁴ and R ^{9 in} the partial structural formulas (A-1) and (A-2) will be described in detail.

The alkyl group has 1 to 2 carbon atoms.
Examples thereof include linear, branched, and cyclic alkyl groups up to 0. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group,
Isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group be able to. Among these, straight-chain having 1 to 12 carbon atoms and 3 to 12 carbon atoms
And branched alkyl groups having 5 to 10 carbon atoms are more preferable.

Hydrogen is used as the substituent of the substituted alkyl group.
Except for monovalent non-metallic atomic groups, preferred examples are
Is a halogen atom (-F, -Br, -Cl, -I),
Droxyl group, alkoxy group, aryloxy group, merca
Group, alkylthio group, arylthio group, alkyldi group
Thio group, aryldithio group, amino group, N-alkyl group
Mino group, N, N-dialkylamino group, N-aryl group
Mino group, N, N-diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyl
Oxy group, N-alkylcarbamoyloxy group, N-a
Lille carbamoyloxy group, N, N-dialkylcarbyl
Vamoyloxy group, N, N-diarylcarbamoylo
Xy group, N-alkyl-N-arylcarbamoyloxy
Si group, alkylsulfoxy group, arylsulfoxy group,
Acylthio group, acylamino group, N-alkyl acyl group
Mino group, N-arylacylamino group, ureido group,
N'-alkylureido group, N ', N'-dialkyl group
RAID group, N'-arylureido group, N ', N'-di
Aryl ureido group, N'-alkyl-N'-aryl
Ureido group, N-alkylureido group, N-aryl group
RAID 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-ari
Group, N ', N'-diaryl-N-alkyl
Ruureido group, N ', N'-diaryl-N-aryl
Ureido group, N'-alkyl-N'-aryl-N-a
Rukiruureido 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, aryl
Roxycarbonyl group, carbamoyl group, N-alkyl group
Lubamoyl group, N, N-dialkylcarbamoyl group, N
-Arylcarbamoyl group, N, N-diarylcarba
Moyl group, N-alkyl-N-arylcarbamoyl
Group, alkylsulfinyl group, arylsulfinyl
Group, alkylsulfonyl group, arylsulfonyl group, sulfur
Ruho group (-SO₃H) and its conjugated base group (hereinafter
Honato group), alkoxysulfonyl group, arylo
Xysulfonyl group, sulfinamoyl group, N-alkyl
Sulfinamoyl group, N, N-dialkylsulfinamo
Group, N-arylsulfinamoyl group, N, N-di
Arylsulfinamoyl group, N-alkyl-N-ari
Sulfinamoyl group, sulfamoyl group, N-al
Kirsulfamoyl group, N, N-dialkylsulfamo
Group, N-arylsulfamoyl group, N, N-dia
Reel sulfamoyl group, N-alkyl-N-aryl
Sulfamoyl group, phosphono group (-PO₃H₂) And so
Conjugate base group (hereinafter, referred to as phosphonate group), dial
Killphosphono group (-PO₃(alkyl)₂), Diarylho
Phono group (-PO₃(aryl)₂), Alkylarylphos
Phono group (-PO₃(alkyl) (aryl)), monoalkylphos
Phono group (-PO₃H (alkyl)) and its conjugate base group (hereinafter
Later referred to as alkylphosphonate groups), monoarylphos
Phono group (-PO ₃H (aryl)) and its conjugated base groups
(Hereinafter referred to as arylphosphonate group), phosphono
Oxy group (-OPO₃H₂) And its conjugate base group (hereinafter,
Phosphonatooxy group), dialkylphosphono
Oxy group (-OPO₃(alkyl)₂), Diarylphosphonates
Nooxy group (-OPO₃(aryl)₂), Alkylarylphos
Sphonooxy group (-OPO₃(alkyl) (aryl)), monoa
Rukylphosphonooxy group (-OPO₃H (alkyl)) and
The conjugated base group (hereinafter, alkylphosphonatooxy group
A monoaryl phosphonooxy group (-OPO).
₃H (aryl)) and its conjugated base group (hereinafter aryl
(Suphonatooxy group), cyano group, nitro group, ant
Group, alkenyl group and alkynyl group. This
Specific examples of the alkyl group in these substituents include:
Specific examples of the aryl group include the above-mentioned alkyl groups.
Phenyl group, biphenyl group, naphthyl group, tolyl
Group, xylyl group, mesityl group, cumenyl group, chlorophene
Nyl group, bromophenyl group, chloromethylphenyl group,
Hydroxyphenyl group, methoxyphenyl group, ethoxy
Phenyl group, phenoxyphenyl group, acetoxypheni
Group, benzoyloxyphenyl group, methylthiophenyl
Group, phenylthiophenyl group, methylaminophenyl
Group, dimethylaminophenyl group, acetylaminophenyl
Group, carboxyphenyl group, methoxycarbonyl group
Nyl group, ethoxyphenylcarbonyl group, phenoxyca
Rubonylphenyl group, N-phenylcarbamoylphenyi
Group, phenyl group, cyanophenyl group, sulfophenyl
Group, sulfonatophenyl group, phosphonophenyl group,
Examples thereof include a phonatophenyl group. Also,
Examples of the alkenyl group include vinyl group and 1-propenyl group.
Group, 1-butenyl group, cinnamyl group, 2-chloro-1-
Ethenyl group, etc., and examples of the alkynyl group
Is an ethynyl group, a 1-propynyl group, a 1-butynyl group,
Examples thereof include a trimethylsilylethynyl group. Acyl group
(R¹⁴R in CO-)¹⁴As hydrogen, and
The above-mentioned alkyl group and aryl group can be mentioned.
Among these substituents, even more preferable is halo.
Gen atom (-F, -Br, -Cl, -I), alkoxy
Group, aryloxy group, alkylthio group, arylthio group
Group, N-alkylamino group, N, N-dialkylamino
Group, acyloxy group, N-alkylcarbamoyloxy
Group, N-arylcarbamoyloxy group, acylamino
Group, formyl group, acyl group, carboxyl group, alkoxy group
Cycarbonyl group, aryloxycarbonyl group, carbamo
Group, N-alkylcarbamoyl group, N, N-dial
Kircarbamoyl group, N-arylcarbamoyl group, N
-Alkyl-N-arylcarbamoyl group, sulfo group,
Sulfonato group, sulfamoyl group, N-alkylsulfate
Amoyl group, N, N-dialkylsulfamoyl group, N
-Arylsulfamoyl group, N-alkyl-N-ari
Sulfamoyl group, phosphono group, phosphonate
Group, dialkylphosphono group, diarylphosphono
Group, monoalkylphosphono group, alkylphosphonate
Group, monoarylphosphono group, arylphosphonate
Group, phosphonooxy group, phosphonatooxy group, ant
Group and alkenyl group. On the other hand, the replacement alk
As the alkylene group in the ru group, from the above-mentioned carbon number 1
Remove any one of the hydrogen atoms on the alkyl groups up to 20
However, a divalent organic residue may be mentioned, which is preferable.
More preferably, straight-chain carbon atoms having 1 to 12 carbon atoms
Branched from 3 to 12 and 5 to 1 carbon atoms
Mention may be made of cyclic alkylene groups up to 0. The
Obtained by combining substituents and alkylene groups
A preferred specific example of the substituted alkyl group is chlorometh
Cyl group, bromomethyl group, 2-chloroethyl group, trif
Luoromethyl group, methoxymethyl group, methoxyethoxy
Ethyl group, allyloxymethyl group, phenoxymethyl
Group, methylthiomethyl group, tolylthiomethyl group, ethyl
Aminoethyl group, diethylaminopropyl group, morpholin
Nopropyl group, acetyloxymethyl group, benzoyl group
Xymethyl group, N-cyclohexylcarbamoyloxy
Ethyl group, N-phenylcarbamoyloxyethyl group,
Acetylaminoethyl group, N-methylbenzoylamino
Propyl group, 2-oxoethyl group, 2-oxopropyl
Group, carboxypropyl group, methoxycarbonylethyl
Group, allyloxycarbonylbutyl group, chlorophenoxy
Sicarbonylmethyl group, carbamoylmethyl group, N-me
Tylcarbamoylethyl group, N, N-dipropylcarba
Moylmethyl group, N- (methoxyphenyl) carbamoy
Ruethyl group, N-methyl-N- (sulfophenyl) carb
Vamoylmethyl group, sulfobutyl group, sulfonatobutyl
Group, sulfamoylbutyl group, N-ethylsulfamoy
Rumethyl group, N, N-dipropylsulfamoylpropyi
Group, N-tolylsulfamoylpropyl group, N-methyl
Le-N- (phosphonophenyl) sulfamoyloctyl
Group, phosphonobutyl group, phosphonatohexyl group,
Diethylphosphonobutyl group, diphenylphosphonop
Ropyl group, methylphosphonobutyl group, methylphosphoro group
Natobutyl group, tolylphosphonohexyl group, tolylpho
Sphonatohexyl group, phosphonooxypropyl group,
Phosphonatooxybutyl group, benzyl group, phenethyl group
Group, α-methylbenzyl group, 1-methyl-1-phenyl
Ethyl group, p-methylbenzyl group, cinnamyl group, ant
Group, 1-propenylmethyl group, 2-butenyl group, 2-
Methylallyl group, 2-methylpropenylmethyl group, 2-
Propynyl group, 2-butynyl group, 3-butynyl group, etc.
Can be mentioned.

Next, partial structural formulas (A-1) and (A-2)
Examples of the aryl group as R ⁴ and R ^{9 in the above} include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring, Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable.

As the substituted aryl group, those having a monovalent non-metal atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the above-mentioned aryl group are used. Examples of preferred substituents are the above-mentioned alkyl groups, substituted alkyl groups,
In addition, the above-mentioned substituents for the substituted alkyl group can be mentioned. Specific examples of preferred substituted aryl groups include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. ,
Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyl Oxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxy Carbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N (Methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N- Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenyl Phosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpro Nirufeniru group, 2-propynyl phenyl group, 2-butynyl phenyl group, 3-butynyl phenyl group, and the like.

Alkenyl group, substituted alkenyl group, alk
And a substituted alkynyl group (-C (R^Fifteen) = C
(R¹⁶) (R¹⁷), And -C≡C (R¹⁸)) As
Is R ^Fifteen, R¹⁶, R¹⁷, R¹⁸Is a monovalent non-metallic atomic group
Can be used. Preferred R^Fifteen, R¹⁶, R¹⁷, R¹⁸Example
As, a hydrogen atom, a halogen atom, an alkyl group, a substitution
Examples include alkyl groups, aryl groups and substituted aryl groups
You can Specific examples of these are the above-mentioned examples.
Can be mentioned. R^Fifteen, R¹⁶,
R¹⁷, R¹⁸As a more preferred substituent of, a hydrogen atom,
Halogen atom and straight chain having 1 to 10 carbon atoms
Examples thereof include branched, branched, and cyclic alkyl groups.
R like this^Four, R⁹A preferred specific example of vinyl is
Group, 1-butenyl group, 1-pentenyl group, 1-hexenyl
Group, 1-octenyl group, 1-methyl-1-propenyl group
Group, 2-methyl-1-propenyl group, 2-methyl-1-
Butenyl group, 2-phenyl-1-ethenyl group, 2-chloro
Ro-1-ethenyl group, ethynyl group, propynyl group, phenyl group
A niethynyl group may be mentioned.

More preferred specific examples of R ⁴ and R ^{9 in} the partial structural formulas (A-1) and (A-2) are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group,
Isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 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, N
-Methylcarbamoylethyl group, N, N-ethylaminocarbamoylmethyl group, N-phenylcarbamoylpropyl group, N-tolylsulfamoylbutyl group, p-trienesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group, A phosphonoethyl group,
Examples thereof include phosphonopropyl group, p-phosphonobenzylaminocarbonylethyl group, phosphonatomethyl group, phosphonatopropyl group, phosphonatobutyl group, p-phosphonatobenzylaminocarbonylethyl group, vinyl group and ethynyl group. .

Next, partial structural formulas (A-1) and (A-2)
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹² , R ^{13 in}
A preferred example of is described in detail. The halogen atom is more preferably a fluorine, chlorine, bromine or iodine atom. Preferable examples of the alkyl group, the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, and the substituted alkenyl group include those mentioned above as examples of R ⁴ and R ⁹ .

The substituted oxy group (R ¹⁹ O--) includes R ¹⁹
Can be a monovalent non-metallic atomic group excluding hydrogen. Preferable substituted oxy groups are alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. 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 groups include those described above as the alkyl group, the substituted alkyl group, the aryl group and the substituted aryl group. The acyl group in the acyloxy group (R ²⁰ CO-), R ²⁰ is listed first, the alkyl group described as examples of R ^4, R ^9, substituted alkyl group, aryl group or substituted aryl group be able to. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include:
Methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group ,
Ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group , Mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, phenylsulfonyloxy group,
Examples thereof include a phosphonooxy group and a phosphonatooxy group.

As the substituted thio group (R ²¹ S-), those in which R ²¹ is a monovalent non-metal atomic group excluding hydrogen can be used. Examples of preferred substituted thio groups include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group include those shown as the substituted aryl group, R ²⁰ of the acyl group in the acylthio group (R ²⁰ CO-) in As mentioned above. Of these, an alkylthio group and an arylthio group are more preferable. Specific examples of the preferred substituted thio group include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group and a methoxycarbonylthio group.

Substituted amino group (R^{twenty two}NH-, (R^{twenty three})
(R^{twenty four}) N-) is R^{twenty two}, R^{twenty three}, R ^{twenty four}Removes hydrogen
A monovalent non-metallic atomic group can be used. Substituted amino
Preferred examples of the group include N-alkylamino group, N,
N-dialkylamino group, N-arylamino group, N,
N-diarylamino group, N-alkyl-N-aryl
Amino group, acylamino group, N-alkylacylamino
Group, N-arylacylamino group, ureido group, N'-
Alkylureido group, N ', N'-dialkylureido
Group, N'-arylureido group, N ', N'-diaryl
Ruureido group, N'-alkyl-N'-arylurei
Group, N-alkylureido group, N-arylureido group
Group, N'-alkyl-N-alkylureido group, N'-
Alkyl-N-arylureido group, N ', N'-dia
Rualkyl-N-alkylureido group, N ', N'-dial
Kill-N-arylureido group, N'-aryl-N-
Alkyl ureido group, N'-aryl-N-aryl group
Raid group, N ', N'-diaryl-N-alkyluree
Id group, N ', N'-diaryl-N-arylurei
Group, N'-alkyl-N'-aryl-N-alkyl
Ureido group, N'-alkyl-N'-aryl-N-a
Reel ureido group, alkoxycarbonylamino group,
Ryloxycarbonylamino group, N-alkyl-N-a
Lucoxycarbonylamino group, N-alkyl-N-ary
-Roxycarbonylamino group, N-aryl-N-ar
Coxycarbonylamino group, N-aryl-N-aryl
Roxycarbonylamino group is mentioned. In these
As the alkyl group and aryl group,
Substituted alkyl group, aryl group, and substituted aryl group
Can be mentioned as an acylamino
Group, N-alkylacylamino group, N-arylacyl
Acyl group in amino group (R²⁰R of CO-)²⁰Is the above
It is Among these, more preferable ones
Is an N-alkylamino group, N, N-dialkylamino
Group, N-arylamino group, acylamino group, and the like.
Be done. Specific examples of preferred substituted amino groups include methyl
Amino group, ethylamino group, diethylamino group, morpho
Reno group, piperidino group, pyrrolidino group, phenylamino
Group, benzoylamino group, acetylamino group, etc.
Be done.

As the substituted carbonyl group (R ²⁵ —CO—), those in which R ²⁵ 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, Examples thereof include N, N-diarylcarbamoyl group and N-alkyl-N-arylcarbamoyl group. Examples of the alkyl group and aryl group in these groups include the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred substituents include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-
Examples thereof include a dialkylcarbamoyl group and an N-arylcarbamoyl group, and more preferable examples thereof include a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferable substituents include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, A morpholino carbonyl group etc. are mentioned.

As the substituted sulfinyl group (R ²⁶ —SO—), those in which R ²⁶ is a monovalent nonmetallic atomic group can be used. Preferred examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group. Group, and an N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these groups include the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Among these, more preferable examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples thereof include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R ²⁷ —SO ₂ —), one in which R ²⁷ is a monovalent non-metallic atomic group can be used.
More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and aryl group in these, the aforementioned alkyl group,
Examples thereof include a substituted alkyl group, an aryl group and a substituted aryl group. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group. The sulfonate group (—SO ₃ ⁻ ) is as described above, and the sulfo group (—S
O ₃ H) means a conjugated base anion group and is usually preferably used together 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 phosphono group means one in which one or two of the hydroxyl groups on the phosphono group are substituted by another organic oxo group, and preferable examples thereof 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 preferable. Specific examples thereof include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

Phosphonato group (--PO ₃ ^2- , --PO
₃ H ^-) above and the Toh, phosphono group (-PO ₃ H ₂₎
Of the conjugated base anion group derived from the acid first dissociation or the acid second dissociation. Usually, it is preferably used together with a counter cation. For such counter cations,
Commonly known ones, namely various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.) Is mentioned.
With the substituted phosphono group, among the above-mentioned substituted phosphono groups,
Despite substituted hydroxyl groups on one organic oxo group is the conjugate base anion group, as specific examples, the aforementioned monoalkyl phosphono group _{(-PO 3 H (alkyl))} , monoaryl phosphono group (-PO ₃ A conjugate base of H (aryl) may be mentioned. Usually, it is preferably used together 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+ and the} like). A preferable example of the silyl group is a trialkylsilyl group.

The above-mentioned R ⁵ , R ⁶ , R ⁷ , R ⁸ and
Among the examples of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ , more preferable are hydrogen atom, halogen atom (—F, —Cl, —B).
r, -I), an alkyl group, a substituted alkyl group, an aryl group, a hydroxyl group (-OH), a substituted thio group, a substituted amino group, a substituted carbonyl group, a sulfo group, a sulfonato group, a cyano group, and further more. Preferably, the substituent on the substituted alkyl group is a halogen atom, —OR ²⁸ (R
Examples of ²⁸ include those which are the alkyl groups, substituted alkyl groups, aryl groups and substituted aryl groups described above). Next, R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ¹⁰ and R
^{An example in which 11} , R ¹² and R ¹³ are bonded to each other to form a ring will be shown. R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ ,
Examples of R ¹² and R ¹³ bonded to each other to form an aliphatic ring include 5-membered ring, 6-membered ring, 7-membered ring and 8-membered aliphatic ring, and more preferably 5 Examples thereof include a membered ring and a 6-membered aliphatic ring. These may further have a substituent on the carbon atom which constitutes them (examples of the substituent include the substituents on the aforementioned substituted alkyl group), and the ring-constituting carbon May be partially substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.).

R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ¹⁰ and R
^11, as an example of R ¹² and R ¹³ form an aromatic ring bonded to each other, cooperate with the pyridine ring containing carbon atoms to which they are attached, a quinoline ring, an isoquinoline ring, an acridine ring, a phenanthridine ring , A benzquinoline ring and a benzisoquinoline ring can be mentioned, and more preferably a quinoline ring can be mentioned. Further, these may have a substituent on the constituent carbon atom (an example of the substituent may be the substituent on the above-mentioned substituted alkyl group).

Next, preferred examples of -X- and R ¹ in the general formula [I] will be described. -X- is-
O -, - S -, - NR 2 -, or -CONR ³ - represents a 5-membered, including a nitrogen atom, or form a 6-membered ring. A substituent R ¹ on the nitrogen atom in such a ring,
Preferred examples of the alkyl group, the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, the substituted alkenyl group, the alkynyl group, or the substituted alkynyl group as R ² and R ³ include the partial structural formula (A -1), (A
Examples of R ⁴ and R ⁹ in -2) can be given. -X- is -O-, -S-,-.
NR ² — is more preferable, and further preferable —X— is —
S -, - NR ² - a, and still more preferably -X-
Is -S-.

The substituted or unsubstituted 1,3-dihydro-1-oxo-2H-indene-2-ylidene group of ═E in the general formula [I] is represented by the following partial structural formula (B).

[0042]

[Chemical 4]

R in the formula (B)²⁹, R³⁰, R³¹, R³², R
³³, R³⁴Are each independently a monovalent non-metal atom
Although those of the group can be used, more preferably, a hydrogen atom,
Halogen atom, alkyl group, substituted alkyl group, aryl
Group, substituted aryl group, alkenyl group, substituted alkenyl
Group, hydroxyl group, substituted oxy group, mercapto group, position
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,
Sphonato group, substituted phosphonato group, cyano group, nitro
A silyl group or a silyl group
It Preferred examples of these substituents include the above-mentioned moieties.
R for Structural Formulas (A-1) and (A-2)^Five, R⁶,
R⁷, R⁸, R^Ten, R ¹¹, R¹², R¹³As an example of
Any of these can be preferably used.

R ²⁹ and R ³⁰ may be bonded to each other to form an aliphatic ring, which may form a spiro ring together with a ring containing a carbon atom to which they are bonded. Preferred aliphatic ring is 5
Examples thereof include a membered ring, a 6-membered ring, a 7-membered ring and an 8-membered aliphatic ring, and more preferable examples include a 5-membered ring and a 6-membered aliphatic ring. These may further have a substituent on the carbon atom constituting them (examples of the substituent include the substituents on the substituted alkyl group mentioned above as examples of R ⁴ and R ⁹ ). It is also possible that a part of the ring-constituting carbon is substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Preferred specific examples thereof include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclo-1,3-
Dioxapentane ring, cyclo-1,3-dioxapentane ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclo-1,3-dioxapentene ring, cyclo-1,3-dioxahexene ring,
And the like.

Further, R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R
Those in which ³⁴ is bonded to each other to form an aliphatic or aromatic ring can be preferably used. Examples of such an aliphatic ring include a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered ring, more preferably a 5-membered ring and a 6-membered ring. A ring can be mentioned. It further may have a substituent on the carbon atoms constituting these (examples of the substituent, the above can be exemplified by the substituents described above as examples of R ⁵ to R ¹³⁾ , In addition, part of the ring-constituting carbon is a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.)
May be replaced with. Preferred specific examples thereof include a benzocyclopentene ring, a benzocyclohexene ring, a benzocycloheptene ring, a benzocyclooctene ring, in cooperation with a benzene ring containing a carbon atom to which they are bonded in the formula (B). , 3-benzocyclohexadiene ring, 1,3-dihydro-1,3-dioxaindene ring,
Examples thereof include those forming a julolidine ring. Further, as an example of forming an aromatic ring, in cooperation with a benzene ring containing a carbon atom to which these are bonded, a naphthalene or anthracene ring can be mentioned, and more preferably a naphthalene ring is formed. Can be mentioned. May have a substituent on the carbon atoms constituting these good (examples of the substituent include substituents cited as examples of R ⁵ to R ¹³ above)

Of these, even more preferred are R ²⁹ and R.
³⁰ includes a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group and a substituted carbonyl group, and R ^{31 to} R ³⁴ include a hydrogen atom, a halogen atom, an alkyl group and a substituted alkyl group. , An aryl group, a substituted aryl group, a hydroxyl group, a substituted oxy group,
Mercapto group, substituted thio group, amino group, substituted amino group,
A substituted carbonyl group is more preferred.

Specific examples of the preferred partial structure (B) are shown below.

[0048]

Embedded image

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

Embedded image

The compound represented by the general formula [I] is represented by the partial structure A = represented by the partial structural formulas (A-1) and (A-2) and the partial structural formula (B). And partial structure = E can be constructed by sequentially combining them on the general formula [I]. Specific preferred examples of the compound represented by formula [I] are shown below.

[0053]

[Chemical 9]

[0054]

[Chemical 10]

[0055]

[Chemical 11]

[0056]

[Chemical 12]

[0057]

[Chemical 13]

The compound group represented by the general formula [I] is represented by "Bu
ll. Soc. Chimie. Belges ", Volume 57, 364-37
Page 2 (1948) Abstract: It can be synthesized by the method described in "Chemical Abstracts", Vol. 44, columns 60c to 61d (1950). That is, for example, the compound (I-1) is 4,5-dihydro-3-ethyl-5-
[1-heptyl-2 (1H) -pyridylidene] -2-
It is obtained by condensing (methylthio) -4-oxothiazolium 4-methylbenzenesulfonate and 1-indanone under basic conditions. At this time, as the base, generally used bases such as organic amines, pyridines (trialkylamine, dimethylaminopyridine, etc.), metal amides (lithium diisopropylamide, etc.), metal alkoxides (sodium methoxide, potassium-t) are used. -Butoxide) and metal hydrides (sodium hydride etc.) can be preferably used. The general formula [I]
The method for synthesizing the compound is not limited to the above. The compound of the general formula [I] used in the photopolymerizable composition of the present invention is preferably used alone or in combination of two or more kinds.

Next, the component (iii) used in the present invention will be described in detail. Any of the compounds of the component (iii) in the present invention can be preferably used as long as they generate an active radical by light irradiation in the coexistence of the component (ii).
That is, a compound group that produces an active radical through some interaction (energy transfer, electron transfer, exciplex formation, etc.) with the component (ii) excited by light irradiation can be preferably used. Examples of preferred activators include (a) compounds having a carbon-halogen bond, (b) aromatic onium salt compounds, (c) organic peroxide compounds, (d) thio compounds,
(E) hexaarylbiimidazole compound, (f) ketoxime ester compound, (g) borate compound,
(H) azinium compound, (i) metallocene compound,
(J) Active ester compounds and the like.

Preferred examples of the compound having a carbon-halogen bond which is an example of the component (iii) include those represented by the following general formulas [II] to [VIII].

[0061]

Embedded image

(In the formula, X represents a halogen atom. Y ¹
Is _{-CX '3, -NH 2, -NHR} ', - NR '2, -O
Represents R '. Here, R'represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R is-
CX ₃ , alkyl group, substituted alkyl group, aryl group, substituted aryl group, and substituted alkenyl group. ) The compound represented by.

[0063]

[Chemical 15]

(Wherein R ³⁵ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group, and X ′
Is a halogen atom, and n is an integer of 1 to 3. ) The compound represented by.

General formula [IV]: R ³⁶ -Z-CH _(2-m) X " _m -R ³⁷ [IV] (wherein R ³⁶ is an aryl group or a substituted aryl group, and R ^{37 is-} C (= O) -NR ³⁸ R ³⁹ , -C (= S)
NR ³⁸ R ³⁹ ,

[0066]

Embedded image

Or halogen, Z is --C (═O)
-, - C (= S) - or -SO ₂ - and and, R ^38, R ³⁹
Is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R
⁴⁰ is the same as R ′ in the general formula [II], X ″ is a halogen atom, and m is 1 or 2.).

[0068]

[Chemical 17]

In the formula, R ⁴¹ represents an optionally substituted aryl group or heterocyclic group, and R ⁴² represents 1 to 1 carbon atoms.
It is a trihaloalkyl group or a trihaloalkenyl group having three, and p is 1, 2 or 3.

[0070]

Embedded image

(However, L is a hydrogen atom or a formula: CO-
(R ⁴³ ) _q (CX ₃ ) _{r is} a substituent, and Q is sulfur, selenium or an oxygen atom, a dialkylmethylene group, an alkene-
1,2-ylene group, 1,2-phenylene group or NR group, M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group,
R ⁴⁴ is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ⁴³ is a carbocyclic or heterocyclic divalent aromatic group, X is a chlorine, bromine or iodine atom,
q = 0 and r = 1 or q = 1 and r = 1 or 2
Is. ) A carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by:

[0072]

[Chemical 19]

(However, X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴⁵ is a hydrogen atom or a CH _{3 -t} X _t group, and R is ⁴⁶ is an s-valent unsaturated organic group which may be substituted)
-Halogeno-5- (halogenomethyl-phenyl) -oxazole derivatives.

[0074]

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(However, X'is a halogen atom, and v
Is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁷
Is a hydrogen atom or a CH _3-v X _v group, and R ⁴⁸ is a u-valent optionally substituted unsaturated organic group. ), Which is a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.

Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Ch.
em. Soc. Japan, 42 , 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis. (Trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2,
4,6-Tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl)-
S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-
Examples thereof include trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine. In addition, compounds described in British Patent No. 1388492, for example, 2
-Styryl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl)
-4-Amino-6-trichloromethyl-S-triazine and the like compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6.
-Bis-trichloromethyl-S-triazine, 2- (4
-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis- Compounds described in German Patent No. 3337024, such as trichloromethyl-S-triazine,
For example,

[0077]

[Chemical 21]

[0078]

[Chemical formula 22]

And the like. Also, FCScha
J. Org. Chem .; 29, 1527 (196) by Efer et al.
4) Described compounds, for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-
Tris (tribromomethyl) -S-triazine, 2,
4,5-tris (dibromomethyl) -S-triazine,
2-Amino-4-methyl-6-tribromomethyl-S-
Examples thereof include triazine and 2-methoxy-4-methyl-6-triclomethyl-S-triazine.

Further, compounds described in JP-A-62-58241, for example,

[0081]

[Chemical formula 23]

[0082]

[Chemical formula 24]

And the like. Further, JP-A-5-
281728 described compounds, for example,

[0084]

[Chemical 25]

And the like. Or even more
Journal of of MPHutt, EF Eslager and LM Merbel
Heterocyclic chemistry Volume 7 (No.3), Volume 511
Following groups of compounds that can be easily synthesized by those skilled in the art according to the synthetic method described on page (1970) and thereafter.

[0086]

[Chemical formula 26]

[0087]

[Chemical 27]

[0088]

[Chemical 28]

[0089]

[Chemical 29]

[0090]

Embedded image

[0091]

[Chemical 31]

Alternatively, compounds such as those described in German Patent 2641100, such as 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-Trimethoxy-styryl) -6-trichloromethyl-2-pyrone, or the compounds described in German Patent No. 3333450, for example,

[0093]

Embedded image

[0094]

[Chemical 33]

[0095]

Embedded image

Further, as an aromatic onium salt which is another example of the component (iii), elements of groups V, VI and VII of the periodic table, specifically N, P, As, Sb, Bi, O,
Aromatic onium salts of S, Se, Te, or I are included. Examples of such aromatic onium salts include the compounds described in JP-B-52-1277, JP-B-52-1278, and JP-B-52-1279.

Specifically,

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

[Chemical 38]

As the organic peroxide which is another example of the component (iii) used in the present invention, almost all organic compounds having at least one oxygen-oxygen bond in the molecule are included. Is methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy)-
3,3,5-Trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-
Bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Parameteran hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
1,3,3-Tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, bis (te
rt-Butylperoxyisopropyl) benzene, 2,5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-oxanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide , Diisopropyl peroxydicarbonate, di-2
-Ethylhexyl peroxydicarbonate, di-2-
Ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, te
rt-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctanoate, tert-
Butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tersyl carbonate, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3 , 3 ',
4,4'-tetra- (t-aminoperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra-
(T-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3', 4,4 '
-Tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t -Hexyl peroxy dihydrogen diphthalate) and the like.

Among these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-aminoperoxycarbonyl) Benzophenone, 3,3 ', 4,4'
-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone,
Peroxide ester systems such as di-t-butyldiperoxyisophthalate are preferred.

The thio compound as the component (iii) used in the present invention is represented by the following general formula [IX].

[0105]

[Chemical Formula 39]

(Wherein R ⁴⁹ represents an alkyl group, an aryl group or a substituted aryl group, R ⁵⁰ represents a hydrogen atom or an alkyl group, and R ⁴⁹ and R ⁵⁰ are bonded to each other to oxygen, sulfur and The non-metal atom group necessary for forming a 5-membered to 7-membered ring which may contain a hetero atom selected from nitrogen atoms is shown.) The alkyl group represented by R ⁴⁹ in the above general formula [IX] has a carbon atom number. One to four is preferable. The aryl group of R ⁴⁹ has 6 carbon atoms such as phenyl and naphthyl.
10 to 10 are preferable, and as the substituted aryl group,
The above aryl group includes those substituted with a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, an alkoxy group such as a methoxy group and an ethoxy group. R ⁵⁰ is preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the thio compound represented by the general formula [IX] include the compounds shown below.

[0108]

[Chemical 40]

As another example of the component (iii) used in the present invention, hexaarylbiimidazole is 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2 '-Bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'- Tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-trifluorophenyl) -4,4 ',
5,5'-tetraphenylbiimidazole and the like can be mentioned.

As the ketoxime ester which is another example of the component (iii) used in the present invention, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxy are exemplified. Iminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-
Phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.

Examples of the borate salt which is another example of the component (iii) in the present invention include compounds represented by the following general formula [X].

[0112]

Embedded image

(Here, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ , which may be the same or different, are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. An alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, R ⁵¹ ,
Two or more groups of R ⁵² , R ⁵³ and R ⁵⁴ may combine to form a cyclic structure. However, at least one of R ⁵¹ , R ⁵² , R ^53, and R ⁵⁴ is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation).

The alkyl groups represented by R ^{51 to} R ⁵⁴ include linear, branched and cyclic ones, and those having 1 to 18 carbon atoms are preferable. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. As the substituted alkyl group, a halogen atom (for example, -Cl, Br, etc.), a cyanami group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group,

[0115]

Embedded image

(Where R⁵⁵, R⁵⁶Are independently hydrogen atoms,
Indicates an alkyl group having 1 to 14 carbon atoms or an aryl group
You ), -COOR⁵⁷(Where R⁵⁷Is hydrogen atom, carbon number
1 to 14 represents an alkyl group or an aryl group. ),-
OCOR⁵⁸Or-OR⁵⁸(Where R ⁵⁸Has 1 to 14 carbon atoms
Represents an alkyl group or an aryl group. ) As a substituent
Included.

The aryl group represented by R ^{51 to} R ⁵⁴ 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 aryl group and the above substituted alkyl group. Substituent of group or carbon number 1 to 1
The alkenyl group represented by R ^{51 to} R ⁵⁴ , which includes an alkyl group having 4 alkyl groups, has 2 to 1 carbon atoms.
8 include straight chain, branched chain, and cyclic groups, and examples of the substituent of the substituted alkenyl group include those mentioned above as the substituent of the substituted alkyl group.

The above alkynyl group for R ^{51 to} R ⁵⁴ is
A straight chain or branched chain having 2 to 28 carbon atoms is included, and examples of the substituent of the substituted alkynyl group include those mentioned as the substituent of the above substituted alkyl group. In addition, the above R ^{51 to} R
The heterocyclic group of ⁵⁴ is at least one of N, S and O.
Examples of the heterocyclic group include a 5-membered ring or more, and preferably a 5-membered to 7-membered ring, which may include a condensed ring. Further, the substituent may have the substituents mentioned above as the substituent of the substituted aryl group.

Specific examples of the compound represented by the general formula [X] include US Pat. Nos. 3,567,453 and 4,34.
3,891, European Patents 109,772, 1
No. 09,773 and the compounds shown below.

[0120]

[Chemical 43]

Examples of the azinium salt compound which is another example of the component (iii) of the present invention include USP 4,743,528.
JP-A-63-138345, JP-A-63-142
No. 345, JP-A-63-142346, JP-A-63-
Examples include compounds having an NO bond described in JP-B-143537 and JP-B-46-42363.
Specific examples of such an azinium salt compound include 1-methoxy-4-phenylpyridinium tetrafluoroborate. Examples of the metallocene compound which is another example of the component (iii) include JP-A-59-1523.
96, JP-A-61-151197, JP-A-63-4
1484, JP-A-2-249, JP-A-2-4705.
And various titanocene compounds described in JP-A-5-83588, for example, di-cyclopentadienyl-Ti-bis-
Phenyl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-
2,4,6-Trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-
Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4
6-trifluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis- 2,3,4,5,6-pentafluorophen-1-yl etc. can be mentioned. Also,
Iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109 are also suitable.

Examples of the active ester compound which is another example of the component (iii) include imide sulfonate compounds described in JP-B-62-6223, active sulfonates described in JP-B-63-14340 and JP-A-59-174831. Can be mentioned.

The component (iii) in the present invention is preferably used alone or in combination of two or more kinds. These photopolymerization initiation systems in the compositions of the present invention, namely component (ii)
And the content concentration of the component (iii) is usually small. On the other hand, if the amount is inappropriately large, undesired results such as the blocking of effective rays will occur.

The amount of the photopolymerization initiation system in the present invention is 0.01% based on the total amount of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer added as necessary.
To 60%, more preferably 1% to 30%. The ratio of the component (ii) which is a component of the photopolymerization initiation system used in the present invention and the component (iii) is 0.01 to 50 with respect to 1 part by weight of the organic dye of the component (ii). It is appropriate to use parts by weight, more preferably 0.02 to 2
0 parts by weight, most preferably 0.05 to 10 parts by weight.

The photopolymerizable composition of the present invention may further contain a known compound having a function of further improving sensitivity or suppressing polymerization inhibition by oxygen as a cosensitizer. Examples of such co-sensitizers include amines such as MR Sander et al. “Journal of Polymer Societ”.
y ”, Volume 10, 3173 (1972), Japanese Examined Patent Publication No. 44
-20189, JP-A-51-82102, JP-A-5
2-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537,
JP-A-64-33104, Research Disclosure 33
No. 825 and the like, and specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples of the co-sensitizer include thiols and sulfides such as thiol compounds described in JP-A-53-705, JP-B-55-500806 and JP-A-5-142772, and JP-A-5-142772. No. 56-75643 disulfide compounds and the like, and specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

As another example, amino acid compounds (eg, N-phenylglycine, etc.), JP-B-48-429
No. 65 organic metal compound (eg, tributyltin acetate, etc.), Japanese Patent Publication No. 55-34414 hydrogen donor, Japanese Patent Application No. 5-91089, sulfur compound (eg,
Trithian et al.), Phosphorus compounds (diethyl phosphite etc.) described in JP-A-6-250389, Japanese Patent Application No. 6-191.
Examples thereof include Si-H and Ge-H compounds described in No. 605.

As yet another example, US Pat.
8,791, aminoketone compounds described in European Patent No. 0284562A1, for example,

[0129]

[Chemical 44]

And the like. Yet another example is
Oxime ethers described in Japanese Patent Application No. 7-13108 are also suitable. Specific examples include the followings.

[0131]

Embedded image

When such a co-sensitizer is used, it is suitable to use it in an amount of 0.01 to 50 parts by weight, more preferably 0.005 parts by weight, relative to 1 part by weight of the compound of component (ii). 02
-20 parts by weight, most preferably 0.05-10 parts by weight. The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder.
As such a “linear organic polymer”, any linear organic polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Absent. A linear organic polymer which is soluble or swellable in water or weak alkaline water, which enables water development or weak alkaline water development, is preferably selected. The linear organic high molecular polymer is appropriately selected and used not only as a film forming agent for the composition but also as a developer, which is water, weak alkaline water, or an organic solvent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. As such a linear organic high molecular polymer, an addition polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615.
No. 54-34327, Sho 58-1257
7, JP-B-54-25957, JP-A-54-927.
23, JP-A-59-53836, JP-A-59-71.
No. 048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
In addition to these, addition polymers having a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / another addition-polymerizable vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamide or 2,2-bis- (4
Polyethers of -hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular weight polymers can be mixed in arbitrary amounts in the entire composition. However, when it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the formed image. Preferably 3
0 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound to the linear organic polymer is 1/9 to 7
It is preferably in the range of / 3. A more preferable range is 3
/ 7 to 5/5.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is prevented in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add agents. Suitable thermal polymerization inhibitors include hydroquinone and 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), N-nitrosophenylhydroxyamine primary cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like. The amount of the thermal polymerization inhibitor added is about 0.
01% to about 5% is preferred. Further, 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 during the drying process after coating. . The amount of the higher fatty acid derivative added is about 0.5% to about 10% of the total composition.
Is preferred.

In the present invention, a dye or pigment may be added for the purpose of coloring the photosensitive layer. The amount of the dye or pigment added is 0.01% to 20% of the total composition, and more preferably 0.5% to 10%. Also, pigments are more preferable than dyes. As the pigment, commercially available pigments and known pigments described in various documents can be used. Regarding the literature, the Color Index (C.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), "Latest pigment application technology" (CMC Publishing,
1986, "Printing Ink Technology" (CMC Publishing, 1
Published in 984).

Examples of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, violet pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments. , Quinophthalone pigment, dyed lake pigment,
Examples thereof include azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments and inorganic pigments. Among these, 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, and examples of such a polymer include those represented by the general formulas (A) to (C) described in Japanese Patent Application No. 6-193357. And a polymer having an aliphatic double bond in its main chain or side chain.

[0137]

Embedded image

In the formula, R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ and R
⁶⁴ and R ⁶⁵ 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. The alkyl group has preferably 20 or less carbon atoms, more preferably 10 or less carbon atoms, and further preferably 6 or less carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, isopropyl group, etc.). Is mentioned.

Examples of the aryl group include aryl groups having 6 to 22 carbon atoms (eg, phenyl group, naphthyl group, anthryl group, etc.). The alkyl group and the aryl group may be substituted with an alkoxy group, an amide group, an alkoxycarbonyl group or the like as a substituent. R ⁵⁹ ,
R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each preferably a hydrogen atom or an alkyl group,
A hydrogen atom or methyl is particularly preferred.

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. The alkylene group preferably has 10 or less carbon atoms, more preferably 6 or less carbon atoms,
More preferably 3 or less alkylene groups (eg, -CH
_{2 CH 2 CH 2 -, -} CH 2 CH 2 -, - CH 2 CH
(CH ₃₎ -, etc.) and the like.

The arylene group is an arylene group having 6 to 22 carbon atoms (for example,

[0142]

[Chemical 47]

And the like). X is preferably an alkylene group. Y is preferably an alkylene group, a carbonyl group, an oxygen atom and a combination thereof. The aliphatic ring formed by Q is preferably a 5- to 6-membered combined aliphatic ring having 5 to 30 carbon atoms (for example, cyclohexane ring, norbornenyl ring, dicyclopentadiene ring). Aliphatic rings include bicyclic or tricyclic hydrocarbons having bridgehead carbon atoms. The number of carbon-carbon double bonds in the aliphatic ring is preferably one.

Inorganic fillers and other known additives may be added to the photopolymerizable composition of the present invention in order to improve the physical properties of the cured film. Furthermore, in order to improve the surface condition in coating, it is preferable to add a surfactant. As the surfactant, a fluorinated surfactant is preferable. When the photopolymerizable composition of the present invention is coated on a support, it is dissolved in various organic solvents before use. 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 concentration of solid content in the coating solution is 2
-50% by weight is suitable. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying.
It is more preferably 0.5 to 5 g / m ² .

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

In the case of a support having a surface of metal, especially aluminum, surface treatment such as graining, dipping in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization. It is preferable that As the graining treatment, brush grain or electrolytic grain is preferable. As an electrolytic solution of electrolytic grains, an aqueous solution of nitric acid or hydrochloric acid is preferable, and nitric acid is particularly preferable.

Further, an aluminum plate which has been grained and then dipped in an aqueous sodium silicate solution can be preferably used. As described in JP-B-47-5125, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment may be carried out, for example, in 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 an aqueous solution or a non-aqueous solution of a salt thereof, or a combination of two or more of them. It is carried out by passing a current through the aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Further, JP-B-46-27481 and JP-A-52-5860
A surface treatment in which the electrolytic grain as disclosed in JP-A-52-30503 and JP-A-52-30503 are combined with the anodizing treatment and sodium silicate treatment is also useful. However, the sodium silicate treatment is not always necessary.

Further, it is also preferable to use mechanical graining, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment in that order, as disclosed in JP-A-56-28893. Furthermore, after performing these treatments, a water-soluble resin such as polyvinyl phosphonic acid,
Polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate), yellow dyes, amine salts, and the like, which are undercoated, are also suitable.

These hydrophilization treatments are carried out not only to make the surface of the support hydrophilic, but also to prevent harmful reaction of the photopolymerizable composition provided thereon, and to adhere the photosensitive layer. It is given to improve the sex. Further, it is also preferable to apply a back coat described in JP-A-5-2271 and JP-A-6-35174 to the back surface of the support in order to prevent elution of aluminum into the developer.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, particularly saponification degree of 95, is used in order to prevent the polymerization inhibiting action of oxygen in the air.
%, A protective layer made of a polymer having an excellent oxygen barrier property such as polyvinyl alcohol and acidic celluloses may be provided. Regarding the coating method of such a protective layer,
For example, U.S. Pat. No. 3,458,311 and JP-A-55-
49729 in detail. Coating amount is 0.1
˜5.0 g is preferable, and 0.5˜3 g is more preferable.

The photopolymerizable composition of the present invention can be used in ordinary photopolymerization reactions. Further, it can be applied to various fields such as a photoresist when producing a printing plate, a printed circuit board and the like. In particular, due to the high sensitivity which is a feature of the photopolymerizable composition of the present invention and a wide spectral sensitivity characteristic up to the visible light region,
When applied to a light-sensitive material for visible light laser such as Ar ⁺ laser and YAG-SHG laser, good effects can be obtained.

Further, 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 utilizing microcapsules. For use in an image forming system using microcapsules, for example, Japanese Patent Laid-Open No. 57-197538.
No. 61-130945, No. 58-88739,
58-88740, European Patent No. 223,587A1.
You can refer to the specification etc. This image forming method is, for example, coating a microcapsule containing a photopolymerization initiator composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a dye precursor on a support, and exposing the photosensitive sheet imagewise for exposure. Part of the microcapsules are cured, and then a developer sheet is overlaid and pressure is applied to the entire surface to destroy the unexposed parts of the microcapsules, and the color image forming substance (eg, dye precursor) is transferred to the image receiving element (eg, developer). It is a method of transferring to a layer) to develop a color.

The light-sensitive material using the photopolymerizable composition of the present invention may be heated after imagewise exposure. The heating temperature is 6
0 to 160 ° C. is preferable, and 80 ° C. to 13 is more preferable.
0 ° C. The heating time is preferably 1 second to 5 minutes. Further, an unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image.
Preferred developing solutions when these photopolymerizable compositions are used for preparing a lithographic printing plate include the developing solutions described in JP-B-57-7427, sodium silicate and potassium silicate. , Such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. Aqueous inorganic alkaline agents and aqueous solutions of organic alkaline agents such as monoethanolamine or diethanolamine are suitable. The alkaline agent has a concentration of 0.1 to 10% by weight, preferably 0.5 to 5%.
It is added so as to become the weight%.

If necessary, the alkaline aqueous solution may contain a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol. For example, US Pat. No. 3,37
Examples thereof include those described in No. 5,171 and No. 3,615,480. Furthermore, JP-A-50
No. 26601, No. 58-54341, Japanese Patent Publication No. 56-
The developing solutions described in Japanese Patent Nos. 39464 and 56-42860 are also excellent.

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

A commercially available developer which is preferably used is DP-
4 (manufactured by Fuji Photo Film Co., Ltd.) with water 1/6 to 1/3
It is a solution diluted to 0. Photosensitive lithographic printing plates using the photopolymerizable composition of the present invention are disclosed in JP-A-54-8002 and JP-A-5-8002.
No. 5-115045 and JP-A No. 59-58431, that is, after development, washing with water and desensitization, or desensitization as it is, or an aqueous solution containing an acid. Or a desensitizing treatment may be performed after the treatment with an aqueous solution containing an acid. Furthermore, in the developing step of this type of photosensitive lithographic printing plate, the alkaline solution is consumed depending on the amount of treatment to reduce the alkali concentration, or the long-term operation of the automatic developing solution reduces the alkali concentration due to air. The processing capacity decreases, but at that time,
JP-A-54-62004, JP-A-55-22759, JP-A-55-115039, JP-A-56-12645, and JP-A-58-12.
-95349, 64-21451, JP-A 1-1.
80548, a replenisher described in JP-A-2-3065,
Also, the replenishment method can restore the processing capacity.

The plate-making process as described above is described in Japanese Patent Laid-Open No.
It is preferably carried out by an automatic developing machine as described in Nos. -7054 and 2-32357. The desensitizing gum that is optionally applied in the final step of the plate making process is described in JP-B Nos. 62-16834 and 62-25118.
No. 63-52600, JP-A No. 62-7595,
Those described in JP-A Nos. 62-11693 and 62-83194 are preferable.

Further, after the developing treatment, a burning heating treatment or a post-exposure treatment may be performed to improve the printing durability at the time of printing.

[0160]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet rays to visible rays. Therefore, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, and sunlight are used as light sources. it can.

[0161]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. An aluminum plate having a thickness of 0.3 mm was immersed in 10% sodium hydroxide at 60 ° C. for 25 seconds for etching, washed with running water, neutralized with 20% nitric acid, and then washed with water. Using a sinusoidal alternating current, this is 30% in 1% nitric acid aqueous solution.
The electrolytic surface roughening treatment was carried out with the amount of electricity at the anode of 0 coulomb / dm ² . Then 40% in 1% aqueous sodium hydroxide solution.
Immerse in 30% sulfuric acid aqueous solution for 5 seconds at ℃, 60
After desmutting at 40 ° C. for 40 seconds, it was anodized for 2 minutes in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ^{2 so} that the thickness of the anodized film was 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μ (Ra display).

The back surface of the thus treated substrate was coated with the following sol-gel reaction solution using a bar coater and dried at 80 ° C. for 1 minute to provide a back coat layer having a coating amount of 70 mg / m ² after drying. Support A was prepared. (Preparation of Sol-Gel Reaction Solution) 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, an exotherm started in about 5 minutes. After reacting for 60 minutes, a back coat coating solution was prepared by adding the following solution.

Pyrogallol formaldehyde condensation resin (MW 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorosurfactant (N-butyl perfluorooctane 0.7 parts by weight Sulfonamide ethyl acrylate / polyoxyethylene acrylate copolymer -Molecular weight 20,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.) 50 parts by weight Methanol 30%) Methanol 800 parts by weight The photosensitive composition having the following composition is dried and coated on the surface of the aluminum plate treated in this way. It was coated so that the weight was 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 2.0 g (copolymerization molar ratio 80/20) Component (ii) Xg Component (iii) Yg Cosensitizer (S) Zg Fluorine-based nonionic surfactant (F-177 0.03 g, manufactured by Dainippon Ink and Chemicals, Inc.) Thermal polymerization inhibitor N-nitrosophenyl 0.01 g Hydroxylamine aluminum salt

[0165]

[Table 1]

Methyl ethyl ketone 20 g Propylene glycol monomethyl ether 20 g Incidentally, the component (ii) and the component (iii) and the co-sensitizer (S).
See Table A below for details. A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 1000) was applied onto the photosensitive layer so that the dry coating weight was 2 g / m ^2, and dried at 100 ° C. for 2 minutes to form a protective layer. And

Fuji PS step guide manufactured by Fuji Photo Film Co., Ltd. (ΔD =
A gray scale whose transmission density changes discontinuously at 0.15) was brought into close contact, and exposure was performed from above. A xenon lamp is used as a light source, and a Kenko optical filter BP-53 is used.
It was irradiated with light. The energy on the PS 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 is indicated by the number of clear steps of the PS step guide after development. The larger the number of steps, the higher the sensitivity. In addition, the development is performed at 25 ° C. for 1
It was immersed for 0 seconds. DP-4 (manufactured by Fuji Photo Film Co., Ltd.) 65.0 g Water 880.0 g Lipomin LA (20% aqueous solution) 50.0 g

[0169]

[Table 2]

Similarly, a light-sensitive material having a photosensitive layer having the following composition was prepared, and its sensitivity was examined using a BP-51 filter.

Pentaerythritol tetraacrylate 2.4 g Allyl methacrylate / methacrylic acid copolymer 2.0 g (copolymerization molar ratio 75/25) Component (ii) Xg Component (iii) Yg Cosensitizer (S) Zg Fluorine-based nonionic surfactant (F-177 0.03 g, manufactured by Dainippon Ink and Chemicals, Inc.) Thermal polymerization inhibitor N-nitrosophenyl 0.01 g Hydroxylamine aluminum salt

[0172]

[Table 3]

Methyl ethyl ketone 20 g Propylene glycol monomethyl ether 20 g The contents of the components (ii) and (iii) and the co-sensitizer (S) are shown in Table B below.

[0174]

[Table 4]

It is obvious that the component (ii) in the present invention is superior to the compounds of Comparative Examples in sensitivity to visible light having a wavelength longer than 500 nm.

Claims (1)

[Claims] 1. i) A compound having at least one ethylenically unsaturated bond capable of addition polymerization. Ii) General formula [I] (In the formula, A = represents a substituted or unsubstituted 2 (1H) -pyridylidene group or 4 (1H) -pyridylidene group,
-X- is -O -, - S -, - NR 2 - or -CON
Represents R ³ −, and R ¹ , R ² , and R ³ are each independently 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. Represents a group, and = E is a substituted or unsubstituted 1,3-dihydro-1-oxo-2H-
A compound represented by indene-2-ylidene group),
And iii) a photopolymerizable composition comprising a compound capable of generating an active radical upon irradiation with light in the coexistence with the component (ii).