JPH09258443A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable compsn. having high sensitivity and excellent in shelf stability by incorporating a specified compd., a sensitizing dye, an optical radical generating agent and an oxime ether compd. SOLUTION: This compsn. contg. an addition polymerizable compd. having at least one ethylenically unsatd. double bond, a sensitizing dye represented by formula I, an optical radical generating agent and an oxime ether compd. represented by formula II. In the formula I, R<1> is H, 1-4C optionally substd. alkyl, 6-14C optionally substd. aryl, etc., and each of R<2> -R<5> is H, 1-6C optionally substd. alkoxy, 1-6C optionally substd. alkenyloxy, 1-6C optionally substd. alkylthio, dialkylamino in which each alkyl group has 1-4C atoms, etc. In the formula II, each of R<12> -R<14> is a monovalent org. group and R<12> -R<14> may be different from one another.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition. In particular, it has extremely high sensitivity to light rays in the visible light region. For example, Ar ⁺ laser light, YAG-SH
The present invention relates to a photopolymerizable composition exhibiting good sensitivity to G laser light.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known, and are used in a wide range of fields such as printing plates, printed circuits, paints, inks, hologram recording, and three-dimensional modeling. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond and a photopolymerization initiator, an organic polymer binder used as desired, a thermal polymerization inhibitor, and the like is coated on a support. A method of forming a cured relief image by providing as a layer, polymerizing and exposing an exposed portion by image exposure of a desired image, and dissolving and removing an unexposed portion,
Providing a layer of the above-described photopolymerizable composition between two supports, at least one of which is transparent, exposing the support after image exposure from the transparent support side to induce a change in adhesive strength by light; A method of forming an image by the method, a photosensitive material provided with a microcapsule layer having a color material such as a photopolymerizable composition and a leuco dye in the content is prepared, and the photosensitive material is image-exposed to expose the exposed portion capsule to light. Curing, breaking the unexposed portions of the capsules by pressure treatment or heat treatment, developing the color by contacting with a color material developer, forming a colored image, etc., by the light of the photopolymerizable composition An image forming method using a change in toner adhesion, an image forming method using a change in refractive index of a photopolymerizable composition by light, and the like are known.

Many of the photopolymerizable compositions applied to these methods have benzyl. Benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone and the like have been used. However, these photopolymerization initiators, compared with the photopolymerization initiation ability for ultraviolet light of 400 nm or less, 400 nm
The photopolymerization initiation ability with respect to the visible light described above was remarkably low, and as a result, its application range was significantly limited.

In recent years, with the development of image forming technology, there has been a demand for a photopolymer having high sensitivity to light rays in the visible region. It is a photosensitive material suitable for non-contact type projection exposure plate making, visible light laser plate making, and the like. As such a visible light laser, Ar ⁺ laser 48
8 nm light, 532 nm light of YAG-SHG laser, etc. are considered promising.

[0005] Many proposals have been made for photopolymerization initiation systems capable of responding to light rays in the visible light region. For example, some sensitive dyes described in U.S. Pat. No. 2,850,445, complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189), hexaarylbiimidazole, radical generator and dye Combination system (Japanese Patent Publication No. 45-3
7377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Examined Patent Publication No. 47-
No. 2528, JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-8).
No. 4183), a system of substituted triazine and merocyanine dyes (JP-A No. 54-151024), and a system of 3-ketocoumarin and an activator (JP-A Nos. 52-112681 and 58-58).
-15503), biimidazole, styrene derivative,
System of thiol (JP-A-59-140203), system of organic peroxide and dye (JP-A-59-140203, JP-A-59-189340), system of dye of rhodanine skeleton and radical generator ( JP-A-2-244050) and the like.

The effectiveness of titanocene as a photopolymerization initiator is disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-10602, JP-A-63-41484, It is described in JP-A-3-12403. Examples of use as a combined system include titanocene and 3-ketocoumarin dyes (JP-A-63-221).
No. 110), a system in which a titanocene, a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group are combined (JP-A-4-22195).
No. 8, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061).
And the like.

However, although these prior arts are certainly effective for visible light, they have insufficient sensitivity or exhibit high sensitivity, but have problems such as poor storage stability and can be put to practical use. Did not.

[0008]

An object of the present invention is to provide a photopolymerizable composition having high sensitivity and excellent storage stability. Especially, 488n that corresponds to the output of visible light of 400nm or more, Ar ⁺ laser, YAG-SHG laser
It is to provide a photopolymerizable composition having high sensitivity to light such as m and 532 nm.

[0009]

Means for Solving the Problems The present inventor has found that a combination system of a sensitizing dye having a specific structure and a titanocene compound capable of generating an active radical upon irradiation with light in the coexistence of the sensitizing dye is 400 nm or more. The present invention has been found to have extremely high sensitivity to visible light, and has reached the present invention. That is,
The present invention is achieved by the following specific item (1). (1) A photopolymerizable composition containing at least the following components i) to iv): i) addition-polymerizable compound having at least one ethylenically unsaturated double bond ii) sensitizing dye represented by formula (I) iii) photoradical generator iv) oxime ether represented by formula (II) Compound

[0010]

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R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms,
A substituted or unsubstituted alkenyloxy group having 1 to 6 carbon atoms,
A substituted or unsubstituted alkylthio having 1 to 6 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms in each alkyl group, a hydroxyl group, an acyloxy group, a halogen, a nitro group, or 5
Or it represents a 6-membered heterocyclic group; provided that two or three and the R ² to each fused ring becomes a ring-constituting carbon atom to which substituent R ⁵ is bonded together in R ² to R ⁵ is Fused rings or fused ring systems that are 5 or 6 membered rings may be formed. R ¹ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or R ⁶ —CO—. (Here, R ⁷ represents an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryloxy group, an alkenyloxy group, an aralkyloxy group, an alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, or the following substituent (Formula 2). .

[0012]

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(R ^{7 to} R ¹⁰ are hydrogen atoms, alkyl groups,
Shows a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, a cycloalkyl group,
n and m each represent an integer of 1 to 5. )); Q is-
Represents CN, a heterocycle, or -Z-R < ¹¹ >. (Here R ¹¹
Is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkoxy group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or a ring. A substituted or unsubstituted heterocyclic group having 5 to 15 carbon atoms and hetero atoms, or a hydroxyl group, an acyl group; and Z is a carbonyl group, a sulfonyl group, a sulfinyl group or an arylenedicarbonyl group,-(CH = CH ) _N (n is 1 or 2))

[0014]

[Chemical 6]

R ¹² , R ¹³ and R ¹⁴ represent the same or different monovalent organic groups. As the photoradical generator of the component iii), at least one compound selected from the group consisting of the following (A) to (G) can be mentioned. (A) Compound having carbon-halogen bond (b) Organic peroxide (c) Thio compound represented by the following general formula (III)

[0016]

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In the formula, R ¹⁵ represents an alkyl group, an aryl group or a substituted aryl group, and R ¹⁶ represents a hydrogen atom or an alkyl group. R ¹⁵ and R ¹⁶ are bonded to each other to form oxygen,
The non-metal atomic group necessary for forming a 5- to 7-membered ring which may contain a hetero atom selected from sulfur and nitrogen atoms is shown. (D) Hexaarylbiimidazole (e) Aromatic onium salt (f) Ketoxime ester (to) titanocene compound Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail.

The compound having an 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. Examples of the monomer include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, the unsaturated carboxylic acid and a fat. Examples thereof include amides with group polyvalent amine 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.

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- (acryloxy ethoxy)
Phenyl] dimethyl methane and the like.

Examples of 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 tetramethacrylate and the like.

As the crotonic acid ester, ethylene glycol dicrotonate, tetrameterene 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. Further, specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenemethylenebis-acrylamide, 1,6-hexamene. Methylene bis-
Examples include methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

Other examples include Japanese Examined Patent Publication No. 48-417.
No. 08, the polyisocyanate compound having two or more isocyanate groups in one molecule is added with a vinyl monomer having a hydroxyl group represented by the following general formula (A) in one molecule. Examples thereof include vinyl urethane compounds containing a polymerizable vinyl group. CH ₂ ═C (R) COOCH ₂ CH (R ′) OH (A) (wherein R and R ′ represent H or CH ₃ ). Also, as described in JP-A-51-37193. Urethane acrylates, 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 cited. Furthermore, Japan Adhesive Association magazine vol. 20, No. 7, pages 300-308 (19
Those introduced as photo-curable monomers and oligomers in 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 abbreviated as%), preferably 10 to 40%, based on all components of the photopolymerizable composition. When it is more than 50%, the coating film formation becomes poor (sticky), and 5
%, It is not preferable because curing failure occurs. The sensitizing dye represented by the formula (I) of the component ii) used in the present invention will be described. Q is -CN, heterocycle, -Z-
R ¹¹ represents R ^11, including methyl, ethyl, propyl, isopropyl, t-butyl, isobutyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl and cycloalkyl such as cyclopentyl, cyclohexyl and the like. Alkyl having 1 to 10 carbon atoms; Substituted alkyl; Aryl such as phenyl; Substituted with substituted amino such as nitro, alkoxy, halogen, carboalkoxy, alkyl, aryl, carboxy, hydroxy, amino, dialkylamino or trialkylammonium. A substituted aryl; an alkoxy such as methoxy, ethoxy, butoxy; an aryloxy such as phenoxy; a heterocyclic group having about 5 to 15 ring carbon atoms and hetero atoms, for example, a formula

[0026]

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(In the formula, R ¹⁷ is methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl,
C1-C4 alkyl including s-butyl and the like, X
^- the FSO ₃ ^-, Br ₄ ^-, p-toluenesulfonate, halogen (e.g., Cl, Br, I) is an anion, and the like) of pyridinium; nicotinyl; Nikochiniumu; furyl; 2- benzofuranyl; 2-thiazolyl; 2-thienyl, etc .; or formula

[0028]

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(Wherein R ^{a to} R ^e are selected from the same groups as the above substituents) is an acyl group such as 3-substituted coumarinyl and acetyl, and Z is carbonyl, sulfonyl, sulfinyl or arylene. It is a bonding group selected from carbonyl. Examples of the aryl group of R ¹ include a phenyl group, a naphthyl group, an indenyl group and the like. Further, examples of the heterocycle include those having a structure represented by the following formula.

[0030]

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Here, A represents —CH or a nitrogen atom, B represents —CH ₂ —, NH, S, W is a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon residue or mononuclear, or It represents a binuclear aromatic heterocyclic group. In particular,

[0032]

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And the like. The following can be mentioned as examples of the sensitizing dye of the formula (I). 3-benzoyl-5,7-dimethoxycoumarin 3-benzoyl-7-methoxycoumarin 3-benzoyl-6-methoxycoumarin 3-benzoyl-8-ethoxycoumarin 7-methoxy-3- (p-nitrobenzoyl) coumarin 3-benzoyl Coumarin 3- (p-nitrobenzoyl) coumarin 3-benzoylbenzo [f] coumarin 3,3'-carbonylbis (7-methoxycoumarin) 3-acetyl-7-methoxycoumarin 3-benzoyl-6-bromocoumarin 3,3 '-Carbonylbiscoumarin 3-benzoyl-7-dimethylaminocoumarin 3,3'-Carbonylbis (7-diethylaminocoumarin) 3-carboxycoumarin 3-carboxy-7-methoxycoumarin 3-ethoxycarbonyl-6-methoxycoumarin 3- Ethoxycar Nyl-7-methoxycoumarin 3-acetylbenzo [f] coumarin 3-acetyl-7-methoxycoumarin 3- (1-adamantoyl) -7-methoxycoumarin 3-benzoyl-7-hydroxycoumarin 3-benzoyl-6-nitro Coumarin 3-benzoyl-7-acetocoumarin 3-benzoyl-7-diethylaminocoumarin 7-dimethylamino-3- (4-iodobenzoyl) coumarin 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin 7-methoxy-3- (4-Methoxybenzoyl) coumarin 3- (4-Nitrobenzoyl) benzo [f] coumarin 3- (4-Ethoxycinnamoyl) -7-methoxycoumarin 3- (4-Dimethylaminocinnamoyl) coumarin 3- (4- Diphenylaminocinnamoyl) coumarin 3-[(3-methylbenzothiazole-2-ylidene)
Acetyl] coumarin 3-[(1-methylnaphtho [1,2-d] thiazole-
2-ylidene) acetyl] coumarin 3,3′-carbonylbis (6-methoxycoumarin) 3,3′-carbonylbis (7-acetoxycoumarin) 3,3′-carbonylbis (7-dimethylaminocoumarin) 3,3 '-Carbonylbis- (5,7-diisopropoxy) coumarin 3,3'-carbonylbis- (5,7-di-n-propoxy) coumarin 3,3'-carbonylbis- (5,7-di- n-Butoxy) coumarin 3-cyano-6-methoxycoumarin 3-cyano-7-methoxycoumarin 7-methoxy-3-phenylsulfonylcoumarin 7-methoxy-3-phenylsulfinylcoumarin 1,4-bis (7-diethylamino-3) -Coumarylcarbonyl) benzene 7-diethylamino-5 ', 7'-dimethoxy-3,
3'-Carbonylbiscoumarin 7-Dimethylamino-3-thenoylcoumarin 7-Diethylamino-3-furoylcoumarin 7-Diethylamino-3-thenoylcoumarin 3-Benzoyl-7- (1-pyrrolidinyl) coumarin 5,7, 6'-trimethoxy-3,3'-carbonylbiscoumarin 5,5,7'-trimethoxy-3,3'-carbonylbiscoumarin 7-diethylamino-6'-methoxy-3,3'-carbonylbiscoumarin 3-nicotinoyl -7-Methoxycoumarin 3- (2-Benzofuranylcarbonyl) -7-methoxycoumarin 3- (7-Methoxy-3-coumarinoyl) -1-methylpyrimidinium fluorosulfate 3- (5,7-diethoxy-3) -Coumarinoyl-1-methylpyrimidinium fluoroborate N- (7-methoxy 3 Kumari hexanoyl methyl) pyridinium bromide 9- (7-diethylamino-3-Kumarinoiru) -1,
2,4,5-Tetrahydro-3H, 6H, 10H [1]
Benzopyrano [a, 9a.l-gh] quinolazine-10
-ON

[0034]

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[0035]

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[0036]

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These sensitizing dyes may be used alone or in combination of two or more kinds. The amount of these sensitizing dyes used is 0.05 to 30 parts by weight, preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of the compound having an ethylenically unsaturated double bond.
The amount is 0 parts by weight, more preferably 0.2 to 10 parts by weight.

Next, the photoradical generator as the component iii) will be described. As the compound (a) having a carbon-halogen bond, the compounds shown below are preferable.

[0039]

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(In the formula, X represents a halogen atom. Y ²
Is ^{_{-CX 3, -NH 2, -NHR 21}} , -NR 21, -OR 21
Represents Here, R ²¹ is an alkyl group, a substituted alkyl group,
Represents an aryl group or a substituted aryl group. R ²⁰ is -C
X _3, alkyl group, substituted alkyl group, an aryl group, a substituted aryl group, a substituted alkenyl group. ).

[0041]

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(However, R^{twenty two}Is an alkyl group, substituted alkyl
Kill group, alkenyl group, substituted alkenyl group, aryl
Group, substituted aryl group, halogen atom, alkoxy group, position
A substituted alkoxy group, a nitro group or a cyano group, and X is
It is a logen atom, and n is an integer of 1 to 3. )
Compound. General formula (VI) R^{twenty three}-Z^Three-CH_2-mX_m-R^{twenty three} (However, R^{twenty three}Is an aryl group or a substituted aryl group
R^{twenty four}Is -CO-NR ^{twenty five}R²⁶,

[0043]

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Or halogen, Z^ThreeIs -CO-,-
CS- or -SO_Two− And R^{twenty five}, R ²⁶Is alkyl
Group, substituted alkyl group, alkenyl group, substituted alkenyl
A group, an aryl group or a substituted aryl group, R²⁷Is general
R in formula [V]^{twenty two}And m is 1 or 2
You. ).

[0045]

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In the formula, R ²⁸ represents an optionally substituted aryl group or heterocyclic group, and R ²⁹ represents 1 to 1 carbon atoms.
It is a trihaloalkyl group or a trihaloalkenyl group having three, and p is 1, 2 or 3. General formula (VIII)

[0047]

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However, L is a hydrogen atom or the formula: CO- (R
³⁰ ) _n (CX ₃ ) _m substituent, M is a substituted or unsubstituted alkylene group, Q ² is sulfur, selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1 , 2-phenylene group or NR ³¹ group, and M
+ Q together form a 3- or 4-membered ring, R ³¹ is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ³⁰ is a carbocyclic or heterocyclic aromatic group, and X is
Is a chlorine, bromine or iodine atom, q = 0 and r = 1
Or q = 1 and r = 1 or 2. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group; General formula (IX)

[0049]

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(However, X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ³² is a hydrogen atom or a CH _{3 -t} X _t group, and R is ³³ is an s-valent unsaturated organic group which may be substituted)
-Halogeno-5- (halogenomethyl-phenyl) -oxazole derivatives. General formula (X)

[0051]

[Chemical 21]

(However, X is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ³⁴ is a hydrogen atom or a CH _3-v X _v group, and R is ³⁵ is a u-valent unsaturated organic group which may be substituted)
-(Halogenomethyl-phenyl) -4-halogeno-oxazole derivatives.

Examples of such a compound having a carbon-halogen bond include Wakabayashi et al., Bull. Chem. Soc.
Compounds described in 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-trichloroethyl)-
4,6-bis (trichloromethyl) -S-triazine and the like can be mentioned. 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, JP-A-53-133.
No. 428, for example, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxynaphtho-1).
-Yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphtho-
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-trichloromethyl-S-triazine, etc., German Patent 3337.
The compounds described in Japanese Patent No. 024, for example, the following compounds can be mentioned.

[0054]

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[0055]

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Also, J. Org Che by FC Schaefer et al.
m .; 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S.
-Triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-
Examples thereof include 6-tribromomethyl-S-triazine and 2-methoxy-4-methyl-6-trichloromethyl-S-triazine. Further, JP-A-62-5824
The compounds described in No. 1 such as the following compounds can be mentioned.

[0057]

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[0058]

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Further, compounds described in JP-A-5-28128, for example,

[0060]

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

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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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

[0072]

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[0073]

[Table 1]

[0074]

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Alternatively, the group of compounds described in German Patent No. 3021599, for example,

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The following may be mentioned. As the organic peroxide of the component (b) used in the present invention, oxygen in the molecule-
The compound which has an oxygen bond can be mentioned. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide, 1,1
-Bis (tert-butylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1, -bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide , Parameteran hydroperoxide, 2,5
-Dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary) Butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-
Dimethyl-2,5-di (tertiarybutylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Succinic acid peroxide, benzoyl peroxide,

2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxy. Carbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctano Ato,
Tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate,
Ditertiary butyl peroxyisophthalate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxymaleic acid, tert-butylperoxyisopropyl carbonate,
3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) 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-hexylperoxydihydrogen diphthalate) and the like.

Among these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) 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 (c) used in the present invention is represented by the above general formula (III). − General formula (II
The alkyl group for R ¹⁵ and R ¹⁶ in I) is preferably one having 1 to 4 carbon atoms. The aryl group of R ¹⁵ has 6 to 10 carbon atoms such as phenyl and naphthyl.
The substituted aryl group is preferably a substituted aryl group as described above, which is 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 or an ethoxy group. Is included.

Specific examples of the thio compound represented by the general formula (III) include the compounds shown in the table below.

[0081]

[Table 2]

[0082]

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[0083]

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The hexaarylbiimidazole of the component (d) used in the present invention 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-trifluoromethylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and the like.
Examples of the ketoxime ester include 3-benzoyloximinobtan-2-one and 3-acetoxyiminobutan-
2-one, 3-propionyloxy iminobutan-2-
On, 2-acetoxyiminopentan-3-one, 2-
Acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropane-1
-One, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-
1-phenylpropan-1-one and the like.

As the aromatic onium salt of the component (e) used in the present invention, there are listed V, VI and VII of the periodic table.
Group elements, specifically N, P, As, Sb, Bi, O,
Includes aromatic onium salts of S, Se, Te, or I. As such an aromatic onium salt, Japanese Patent Publication No.
-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 5
The compound shown in No. 2-14279 can be mentioned, and the following compounds can be specifically mentioned.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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Preferred among these are BF ₄ salts,
Alternatively, a compound of a PF ₆ salt is more preferable, and a BF ₄ salt or an BF ₆ salt of an aromatic iodonium salt is more preferable. Examples of the ketooxy ester of the component (f) used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-
3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2- Examples thereof include ethoxycarbonyloxyimino-1-phenylpropan-1-one. The titanocene compound (g) is a titanocene compound capable of generating an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye, and examples thereof include JP-A-59-152396 and JP-A-61. Known compounds described in JP-A-151197 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pendafluorophen-1-yl (hereinafter referred to as A-1), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetra Flurophen-1-yl, di-cyclopentadienyl-Ti-
Bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-T
i-bis-2,4-difluorophen-1-yl, di-
Methylcyclopentadienyl-Ti-bis-2,3
4,5,6-Pendafluorophen-1-yl (hereinafter A
-2), di-methylcyclopentadienyl-Ti
-Bis-2,3,5,6-tetraluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-
2,4-Difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium (hereinafter (A-
3) and the like. The amount of the photo radical generator used is 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of the compound having an ethylenically unsaturated double bond. It can be used in the range of. The oxime ether compound of the component (l) used in the present invention has the following general formula (II
It is a compound represented by a).

(R ⁴¹ ) (R ⁴² ) C═N—O—R ^{43 In the} formula, R ⁴¹ , R ⁴² and R ⁴³ represent the same or different monovalent organic residues. In the general formula (IIa), R ⁴¹ and R ⁴² are more preferably the same or different from each other, and a hydrogen atom,
Halogen atom, hydrocarbon group which may have a substituent and may contain unsaturated bond, heterocyclic group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted Represents an amino group, a substituted carbonyl group, a carboxylase group, a sulfo group, a sulfonato group, a substituted sulfinyl group, a substituted sulfonyl group, a phosphono group, a substituted phosphono group, a phosphonato group, a substituted phosphonate group, a cyano group, a nitro group, and R ⁴¹ And R ⁴² may combine with each other to form a ring.

R ⁴³ may have a substituent, and
It represents a hydrocarbon group or a heterocyclic group which may contain an unsaturated bond, and R ⁴³ and R ⁴² may be bonded to each other to form a ring. Next, in the general formula (IIa), R ⁴¹ ,
Examples of R ⁴² and R ⁴³ are shown below. The hydrocarbon group which may have the above-mentioned substituent and may contain an unsaturated bond includes an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group and an alkynyl group. Groups and substituted alkynyl groups.

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

The substituted alkyl group includes a substituent and an alkylene group.
And the substituent is one except hydrogen.
A non-valent non-metallic atomic group is used.
Halogen atom (-F, -Br, -Cl, -I), hydroxy
Sil group, alkoxy group, aryloxy group, mercapto
Group, alkylthio group, arylthio group, alkyldithio
Group, aryldithio group, amino group, N-alkylamino
Group, N, N-dialkylamino group, N-arylamino
Group, N, N-diarylamino group, N-alkyl-N-
Arylamino group, acyloxy group, carbamoyloxy
Si group, N-alkylcarbamoyloxy group, N-ary
Rucarbamoyloxy group, N, N-dialkylcarbamo
Yloxy group, N, N-diarylcarbamoyloxy
Group, N-alkyl-N-arylcarbamoyloxy
Group, alkylsulfoxy group, arylsulfoxy group,
Silthio group, acylamino group, N-alkyl acylamido
Group, N-arylacylamino group, ureido group, N '
-Alkylureido group, N ', N'-dialkylurei group
Group, N'-arylureido group, N ', N'-diali
Ureido group, N'-alkyl-N'-aryluree
Id group, N-alkyl ureido group, N-aryl ureide
Group, N'-alkyl-N-alkylureido group, N '
-Alkyl-N-arylureido group, N ', N'-di
Alkyl-N-alkylureido group, N ', N'-dia
Alkyl-N-arylureido group, N'-aryl-N
-Alkyl ureido group, N'-aryl-N-aryl
Ureido group, N ', N'-diaryl-N-alkyl
RAID group, N ', N'-diaryl-N-aryluree
Id group, N'-alkyl-N'-aryl-N-alkyl
Luureido group, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-NA
Reyloxycarbonylamino group, N-aryl-NA
Lucoxycarbonylamino group, N-aryl-N-ali
-Carbonyloxyamino group, formyl group, acyl group,
Carboxyl group and its conjugate base (hereinafter Carboxyl group
), An alkoxycarbonyl group, aryloxy
Carbonyl group, carbamoyl group, N-alkylcarbamo
Group, N, N-dialkylcarbamoyl group, N-ary
Carbamoyl group, N, N-arylcarbamoyl
Group, N-alkyl-N-arylcarbamoyl group,
Killsulfinyl group, arylsulfinyl group, alkyl
Group, arylsulfonyl group, sulfo group (-
SO_ThreeH) and its conjugate base group (hereinafter referred to as a sulfona group)
A), alkoxysulfonyl group, aryloxysulfo
Nyl group, sulfinamoyl group, N-alkylsulfina
Moyl group, N, N-dialkylsulfinamoyl group, N
-Arylsulfinamoyl group, N, N-diaryls
Rufinamoyl group, N-alkyl-N-arylsulf
Inamoyl group, sulfamoyl group, N-alkylsulfate
Amoyl group, N, N-dialkylsulfamoyl group, N
-Arylsulfamoyl group, N, N-diarylsul
Famoyl group, N-alkyl-N-arylsulfamo
Group, N-acylsulfamoyl group and conjugate bases thereof
Group, N-alkylsulfonylsulfamoyl group (-SO
_TwoNHSO_Two(alkyl)) and its conjugated base group, N-ary
Rusulfonylsulfamoyl group (-SO_TwoNHSO_Two(all
yl)) and its conjugated base groups, N-alkylsulfonylcapsules
Lubamoyl group (-CONHSO_Two(alkyl)) and its conjugates
Base group, N-arylsulfonylcarbamoyl group (-C
ONHSO_Two(allyl)) and its conjugated bases, alkoxy
Silyl group (-Si (Oalkyl)_Three), Aryloxysilyl group
(-Si (Oallyl)_Three), A hydroxysilyl group (-Si
(OH)_Three) And its conjugate base group, phosphono group (—PO_Three
H_Two) And its conjugated base group (hereinafter referred to as phosphonate group)
), A dialkylphosphono group (-PO _Three(alkyl)_Two), Zia
Reel phosphono group (-PO_Three(aryl)_Two), Alkyrie
Ruphosphono group (-PO_Three(alkyl) (aryl)), monoalkyl
Phosphono group (-PO_ThreeH (alkyl)) and its conjugate base group
(Hereinafter referred to as alkylphosphonato group), monoaryl
Phosphono group (-PO_ThreeH (aryl)) and its conjugated base groups
(Hereinafter referred to as arylphosphonate group), phosphonooki
Si group (-OPO_ThreeH_Two) And its conjugate base group (hereinafter
Honatooxy group), dialkylphosphonooxy group
(-OPO_Three(alkyl) _Two), Diarylphosphonooxy groups
(-OPO_Three(aryl)_Two), Alkylarylphosphonoki
Si group (-OPO_Three(alkyl) (aryl)), monoalkyl phospho
Nooxy group (-OPO_ThreeH (alkyl) and its conjugate base group
(Hereinafter referred to as an alkylphosphonatooxy group), monoa
Reel phosphonooxy group (-OPO_ThreeH (aryl)) and
Conjugate base group (hereinafter referred to as an arylphosphonatooxy group)
), Cyano group, nitro group, aryl group, alkenyl
Group and alkynyl group. In these substituents
As specific examples of the alkyl group, the aforementioned alkyl group is
As specific examples of the aryl group, a phenyl group,
Biphenyl group, naphthyl group, tolyl group, xylyl group,
Cytyl group, cumenyl group, fluorophenyl group, chlorophenyl group
Phenyl group, bromophenyl group, chloromethylphenyl
Group, hydroxyphenyl group, methoxyphenyl group, eth
Xyphenyl group, phenoxyphenyl group, acetoxyf
Phenyl group, benzoyloxyphenyl group, methylthiophe
Nyl group, phenylthiophenyl group, methylaminophenyl
Group, dimethylaminophenyl group, acetylaminophen
Nyl group, carboxyphenyl group, methoxycarbonyl group
Phenyl group, ethoxycarbonylphenyl group, phenoxy
Carbonylphenyl group, N-phenylcarbamoylphene
Nyl group, phenyl group, nitrophenyl group, cyanopheni
Group, sulfophenyl group, sulfonatophenyl group, phos
Examples include honophenyl and phosphonatophenyl groups.
Can be. Further, as an example of the alkenyl group, vinyl
Group, 1-propenyl group, 1-butenyl group, cinnamyl
Group, 2-chloro-1-ethenyl group, and the like.
Examples of the quinyl group include ethynyl group and 1-propynyl group.
Group, 1-butynyl group, trimethylsilylethynyl group, phenyl group
Examples thereof include a phenylethynyl group.

As the above-mentioned acyl group (R ⁴⁴ CO—),
Examples of R ⁴⁴ include a hydrogen atom and the above-mentioned alkyl group, aryl group, alkenyl group and alkynyl group. On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to form a divalent organic residue. Can be a straight chain having 1 to 12 carbon atoms, a straight chain having 3 to 12 carbon atoms, a branched chain, or a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of the preferred substituted alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, an allyloxymethyl group, a phenoxymethyl group, a methylthiomethyl group, and a trimethylmethyl group. Ruthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N- Methylbenzylaminopropyl group, 2-oxoethyl group,
2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, methoxycarbonylmethyl group,
Methoxycarbonylbutyl group, ethoxycarbonylmethyl group, butoxydicarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group,
Methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N
-Dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethyl Sulfamoylmethyl group,
N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group,

[0098]

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Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxy Propyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl 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 given.

Examples of the aryl group 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, and specific examples include phenyl. Examples thereof include a group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable.

The substituted aryl group is a group in which a substituent is bonded to an aryl group, and a group having a monovalent non-metal atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aryl group is used. To be 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 these substituted aryl groups include a biphenyl group, a tolyl group, a 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, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxy Phenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-
Methylcarbamoylphenyl group, N, N-cypropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfa Moylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, Phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1 -Propenylmethyl group, 2 Butenyl, 2-methyl-allyl phenyl group, 2-methyl propenyl phenyl group, 2-propynyl phenyl group, 2-butynyl phenyl group, 3-butynyl phenyl group, etc. may be mentioned.

Examples of the alkenyl group include those mentioned above. The substituted alkenyl group is a substituent in which a hydrogen atom of the alkenyl group is replaced and bonded, and the substituent in the above-mentioned substituted alkyl group is used as the substituent, and the -alkenyl group is the above-mentioned alkenyl group. be able to. Examples of preferred substituted alkenyl groups include

[0103]

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Examples of the alkynyl group include those mentioned above. A substituted alkynyl group is a substituent in which a hydrogen atom of an alkynyl group is replaced and bonded,
As the substituent, the substituent in the above-mentioned substituted alkyl group can be used, while the alkyl group can use the above-mentioned alkynyl group.

The heterocyclic group means a monovalent group obtained by removing one hydrogen atom on the heterocyclic ring, and one hydrogen atom is further removed from this monovalent group so that the substituent group in the above-mentioned substituted alkyl group is bonded. It is a monovalent group (substituted heterocyclic group) formed by Examples of preferred heterocycles are:

[0106]

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[0107]

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And the like.

The substituted oxy group (R ⁴⁵ O-) includes R ⁴⁵
Is a monovalent non-metallic atomic group other than 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. Examples thereof include a group, N-alkyl-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group and 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, the aryl group and the substituted aryl group. In addition, an acyl group (R ⁴⁶
Examples of CO-) include those in which R ⁴⁶ is the above-mentioned alkyl group, substituted alkyl group, aryl group or substituted aryl group. 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, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyl Examples thereof include an oxy group, a naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group and a phosphonatoxy group.

As the substituted thio group (R ⁴⁷ S-), those in which R ⁴⁷ is a monovalent non-metal atomic group excluding hydrogen can be used. Preferred examples of the substituted thio group 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, those can be mentioned as shown as the substituted aryl group, R ⁴⁶ of the acyl group in the acylthio group (R ⁴⁶ CO-) in 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, methoxycarbonylthio, and the like.

Substituted amino group (R⁴⁸NH-, (R⁴⁹)
(R⁵⁰) N-) is R⁴⁶, R⁴⁸, R ⁵⁰Removes 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-alkyl ureido group, N-aryl ureide
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
Reelureido group, alkoxycarbonylamino group,
Reeloxycarbonylamino group, N-alkyl-NA
Lucoxycarbonylamino group, N-alkyl-N-ali
-Roxycarbonylamino group, N-aryl-N-al
Coxycarbonylamino group, N-aryl-N-ary
Roxycarbonylamino group may be 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 (R⁴⁶R of CO-)⁴⁶Is mentioned above
It is as follows. Among these, more preferable ones
Is an N-alkylamino group, N, N-dialkylamino
Group, N-arylamino group, acylamino group, and the like.
It is. Specific examples of preferred substituted amino groups include methyl
Amino group, ethylamino group, diethylamino group, morpho
Rino group, piperidino group, pyrrolidino group, phenylamino
Group, benzoylamino group, acetylamino group, etc.
It is.

As the substituted carbonyl group (R ⁵¹ —CO—), those in which R ⁵¹ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, N, N-diarylcarbamoyl group and 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 substituents include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-
Examples include a phenylcarbamoyl group, an N, N-diethylcarbamoyl group, and a morpholinocarbonyl group.

As the substituted sulfinyl group (R ⁵² —SO—), those in which R ⁵² 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, an N-alkyl-N-arylsulfinamoyl group. 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 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 ⁵³ —SO ₂ —), one in which R ⁵³ is a monovalent nonmetallic atomic group can be used.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl 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. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

[0115] sulfonato group (-SO ₃ ^-) are as described above, means a conjugate base anion group of a sulfo group (-SO ₃ H), is usually used preferably in combination 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 ⁺ , C).
a ²⁺ , Zn ^2+, etc.).

[0116] carboxylate group (-CO ₂ ^-) as described above means a conjugate base anion group of a carboxyl group (CO ₂ H), it is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (N
a ⁺ , 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 preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

[0118] phosphonate group ^{_{(-PO 3 2+, -PO 3 H}} -)
As mentioned above, the phosphono group (—PO ₃ H ₂ ) means a conjugate base anion group derived from the acid first dissociation or the acid second dissociation. 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+ and the} like).

The substituted phosphono group means the above-mentioned substituted phosphono group.
Of the groups, the
The base is an anionic group, and specific examples thereof include the above-mentioned mono
Alkylphosphono group (-PO_ThreeH (alkyl), monoant
Phosphono group (-PO_ThreeThe conjugate base of H (aryl) is
I can do it. Usually used with counter cations
Is preferred. Such counter cations are generally
Known ones, namely various oniums (ammoni
Um, sulfonium, phosphonium, iodonium
Mums, aziniums, etc.), and metal ions (N
a⁺, K⁺, Ca ²⁺, Zn²⁺Etc.).

Next, R¹And R^Two, R^TwoAnd R^ThreeAre bound to each other
An example of forming a ring by R ¹And R^Two, R^TwoAnd R^ThreeBut
The aliphatic ring formed by bonding to each other is a 5-membered ring, 6
A membered ring, a 7-membered ring and an 8-membered aliphatic ring can be mentioned.
And more preferably a 5-membered or 6-membered aliphatic ring.
Can be These are the carbons that make them up
It may have a substituent on the atom (as an example of the substituent
May include the substituents on the above-mentioned substituted alkyl group.
And some of the ring-constituting carbons are heteroatoms (oxygen
Atom, sulfur atom, nitrogen atom, etc.)
Yes. Furthermore, part of this fat-release ring part of the aromatic ring
It may be formed.

The above oxime ether compound is more preferably an α-represented by (IIb) represented by the following general formula.
It is a substituted ketoxime ether compound.

[0122]

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In the formula, R ⁵² and R ⁵³ are the same or different from each other and represent a hydrocarbon group which may have a substituent and which may contain an unsaturated bond, or a heterocyclic group. R ⁵² and R ⁵³ may combine with each other to form a ring. R ⁶⁴ and R ⁶⁵ are the same or different from each other, and are a hydrogen atom, a hydrocarbon group which may have a substituent and which may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group. , A mercapto group, a substituted thio group, an amino group, and a substituted amino group. R ⁶⁴ and R ⁶⁵ are bonded to each other to form a ring,

[0124]

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Represents an alkylene group having 2 to 8 carbon atoms which may be contained in the linking main chain of the ring. R ⁶⁶ represents a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a substituted carbonyl group. X
Is a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond,
Hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, carboxylate group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, Phosphonato group, substituted phosphonato group, cyano group,
Alternatively, it represents a nitro group.

The oxime ether compound is more preferably an α-aminoketo oxime ether compound represented by the following general formula (IIc).

[0127]

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In the formula, R ⁵² , R ⁵³ , R ⁶⁴ and R ⁶⁵ have the same meanings as described above. R ⁶⁷ and R ⁶⁸ are the same or different from each other and represent a hydrogen atom, a hydrocarbon group which may have a substituent, and which may contain an unsaturated bond. Also,
R ⁶⁷ and R ⁶⁸ are bonded to each other to form a ring,

[0129]

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Represents an alkylene group having 2 to 8 carbon atoms which may contain in the linking main chain. R ⁶⁹ represents a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. Further, the above ketoxime ether is most preferably represented by the following general formula (II
It is an α-aminoketoxime ether compound represented by d).

[0131]

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In the formula, R ⁶² , R ⁶⁴ , R ⁶⁵ , R ⁶⁷ and R ⁶⁸ have the same meanings as described above. Y represents a hydrocarbon linking group which may have a substituent and may contain an unsaturated bond (a divalent group obtained by removing one of hydrogen in the hydrocarbon group). Z has a substituent having an acid group having a pKa in the acid first dissociation of 0 or more and 16 or less, a precursor of the acid group and a conjugated base group of the acid group, or a hydrogen atom which dissociates the acid group. Represents a group substituted with a good hydrocarbon group (referred to as a substituted acid group).

Among such acid groups, precursors, conjugated base groups and substituted acid groups, particularly preferable groups include, for example, the above-mentioned hydroxyl group, substituted oxy group, mercapto group, substituted carbonyl group, carboxylate group, Sulfo group, sulfonato group, sulfamoyl group and its conjugate base group, N-alkylsulfamoyl group and its conjugate base group, N-arylsulfamoyl group and its conjugate base group, N-acylsulfamoyl group and its conjugate Base group,
N-alkylsulfonylsulfamoyl group and its conjugate base group, N-arylsulfonylsulfamoyl group and its conjugate base group, N-alkylsulfonylcarbamoyl group and its conjugate base group, N-arylsulfonylcarbamoyl group and its conjugate base Examples thereof include groups, phosphono groups, substituted phosphono groups, phosphonato groups, substituted phosphonato groups, cyano groups, alkoxysilyl groups, aryloxysilyl groups, hydroxysilyl groups, and conjugate base groups thereof.

Examples of compounds will be shown below, but the invention is not limited thereto. Preferred specific examples of the ketoxime ether compound represented by the general formula (IIb) include

[0135]

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[0136]

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[0137]

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And a compound represented by the general formula (IIc)

Preferred specific examples of the α-aminoketoxime ether compound represented by the general formula (IIc) include:

[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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And a compound represented by the general formula (IId)

Preferred specific examples of the α-aminoketoxime ether compound represented by the general formula (IId) include:

[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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And the like. General formula (IIa) or general formula (II) used for the photopolymerizable composition of the present invention
The b), (IIc) or (IId) oxime ether compounds may be used alone or in combination of two or more. In addition, the compounds of the general formulas (IIa) to (IId) are usually 0.05 to 50%, preferably 0.5 to 35%, more preferably 1 to 25% with respect to the total components of the photopolymerizable composition. % Amounts are used. If the amount is more than 50%, poor coating film formation (crack) will occur, and if it is less than 0.05%, poor curing will occur, which is not preferable. The photopolymerizable composition of the present invention preferably contains a linear organic polymer as a binder. As such a "linear organic high molecular polymer", any linear organic high molecular polymer which is compatible 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 high molecular polymer is selected and used not only as a film-forming agent for the composition but also as a developer for water, weak alkaline water or an organic solvent. 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, JP-B-54-34327, JP-B-58-12577, and JP-B-5812577. No. 54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, a methacrylic acid copolymer,
Examples include acrylic acid copolymers, itaconic acid copolymers, croton brew copolymers, maleic acid copolymers, partially 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 monomer] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition polymerizable vinyl monomers] copolymers are suitable if necessary. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. Further, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film. These linear organic high molecular polymers can be mixed in an arbitrary amount in the whole 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. It is preferably 30 to 85% by weight. The weight ratio of the photopolymerizable ethylenically unsaturated compound to the linear organic 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 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 haloid quinone, 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 and the like. The amount of the thermal polymerization inhibitor added is about 0.01 based on the weight of the entire composition.
Weight percent to about 5 weight percent 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 applied to the surface of the photosensitive layer during the drying process after coating. It may be unevenly distributed. The amount of the higher fatty acid derivative added is about 0.5% by weight of the total composition.
About 10% by weight is preferred.

Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. Examples of colorants include phthalocyanine pigments, azo pigments, carbon black,
Pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes,
There are cyanine dyes. The amount of dye and pigment added is preferably about 0.5% to about 5% by weight of the total composition. in addition,
Inorganic fillers and other known additives such as plasticizers may be added to improve the physical properties of the cured film. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc. 10% by weight or less based on the total weight of the organic compound and the binder can be added.

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, methoxymethoxy Ethanol, 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, .gamma.-butyrolactone, methyl lactate and ethyl lactate. 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 about 0.1 g / dry weight.
range of m ² ~ about 10 g / m ² are suitable. It is more preferably 0.5 to 5 g / m ² . A dimensionally stable plate is used as the support. Examples of the dimensionally stable plate include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), zinc, copper, etc. Metal plates, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, plastic films such as polyvinyl acetal, Paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited may be used. 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.

Further, in the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. It is preferable that 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,
What is immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is, for example, 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 non-aqueous solution of a salt thereof, or an electrolytic solution obtained by combining two or more kinds. It is carried out by passing an electric 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
No. 2, JP-A No. 52-30503, a surface treatment in which a support subjected to electrolytic graining is combined with the anodizing treatment and sodium silicate treatment is also useful.

Further, it is also preferable that mechanical graining, chemical etching, electrolytic graining, anodic oxidation treatment and sodium silicate treatment are sequentially carried out as disclosed in JP-A-56-28893. Further, after these treatments, a water-soluble resin, for example, polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate), or Those undercoated with a yellow dye, an amine salt or the like are also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in Japanese Patent Application No. 5-304358 is preferably used.

These hydrophilization treatments are carried out in order to prevent the harmful reaction of the photopolymerizable composition provided thereon, in addition to the treatment for making the surface of the support hydrophilic, and the adhesion of the photosensitive layer. It is given to improve the sex. On the layer of the photopolymerizable composition provided on the support, in order to prevent the polymerization inhibiting action by oxygen in the air, for example, polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more, acidic celluloses, etc. You may provide the protective layer which consists of such a polymer excellent in oxygen barrier property. A method for applying such a protective layer is described in, for example, US Pat.
No. 8,311 and JP-A No. 55-49729.

The photopolymerizable composition of the present invention can be used in ordinary photopolymerization reactions. 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 visible light laser such as Ar ⁺ laser and YAG-SHG-laser, good effects can be obtained.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to imagewise exposure, and then the unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developers for using these photopolymerizable compositions for preparing a lithographic printing plate include those described in JP-B-57-7427, such as sodium silicate and potassium silicate. Like sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of a suitable inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. It is added so that the concentration of the nuclear alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by 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. 5,171 and 3,615,480. Further, Japanese Patent Application Laid-Open
No. 26601, No. 58-54341, Japanese Patent Publication No. 56-
The developers described in 39464 and 56-42860 are also excellent.

[0173]

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 an alternating current with a sinusoidal wave, this is 3
The electrolytic surface-roughening treatment was performed at an anode charge of 00 coulomb / dm ² . Subsequently, 40% in 1% aqueous sodium hydroxide solution
Immersion in 30% sulfuric acid aqueous solution,
After desmutting at 40 ° C. for 40 seconds, it was anodized for 2 minutes in a 20% sulfuric acid aqueous solution at a current density of 2 A / dm ^{2 so} that the thickness of the anodized film would be 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μ (Ra display). The back surface of the substrate thus treated was coated with the following sol-gel reaction solution using a bar coater and dried at 100 ° C. for 1 minute, and a support provided with a back coat layer having a coating amount after drying of 70 mg / m ² A was created.

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, heat generation 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 (MW2000) 4 parts by weight dimethyl phthalate 5 parts by weight Fluorosurfactant (N-butylperfluorooctane sulfonamide ethyl acrylate / polyoxyethylene acrylate copolymer / molecular weight 20,000) 0.7 parts by weight methanol silica sol ( Nissan Chemical Industries, Ltd., methanol 30%) 50 parts by weight Methanol 800 parts by weight

On the aluminum plate thus treated, a photosensitive composition having the following composition was applied in a dry coating weight of 1.4 g.
/ M ² and coated at 80 ° C. for 2 minutes to form a photosensitive layer. Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Sensitizing dye 3.0 × 10 ^-4 mol Photo radical initiator 3.0 × 10 ^-4 mol Oxime ether compound 0.50 g Fluorine type nonionic surfactant (F-177P) 0.03 g Thermal polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt 0.01 g Pigment dispersion 2.0 g Pigment dispersion composition Composition: Pigment Blue 15: 6 30 parts Allyl methacrylate / methacrylic acid copolymer 20 parts (Copolymerization molar ratio 83/17) Cyclohexanone 35 parts Methoxypropyl acetate 35 parts Propylene glycol monomethyl ether 80 parts Methyl ethyl ketone 20 g Propylene glycol monomethyl ether 20 g

On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (a saponification degree of 98 mol% and a polymerization degree of 550) was applied so that the dry coating weight was 2 g / m ² ,
C./minute was dried for 2 minutes. A Fuji PS step guide manufactured by Fuji Photo Film Co., Ltd. (gray scale in which the transmission density changes discontinuously at ΔD = 0.15) was brought into close contact with the light-sensitive material thus obtained, and exposure was performed from above. did. Xenon lamp is used as the light source, and Kenko optical filter B is used.
It was illuminated with light through P-49. 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 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. still,
The development was carried out by immersing in the following developer at 25 ° C. for 10 seconds. DP-4 (manufactured by Fuji Photo Film Co., Ltd.) 66.5 g Water 881.4 g Lipomin LA (20% aqueous solution) 52.1 g The results are shown in Tables 1 and 2.

[0177]

[Table 3]

[0178]

[Table 4]

[0179]

[Table 5]

[0180]

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[0181]

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From the results shown in Tables 1 and 2, in the photopolymerizable composition of the present invention, the photopolymerization initiation system in which the oxime ether compound was added to the sensitizing dye of the present invention and the photoradical generator was The sensitivity is clear.

[0183]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet light to visible light.
Therefore, as the light source, 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, sunlight, etc. Can be used. Further, in the present invention, since two or more kinds of sensitizing dyes are used in combination, it is difficult for the dyes to be deposited during storage, so that it is possible to add them at a high concentration, and it is possible to obtain a sensitive material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03F 7/027 511 G03F 7/027 511 7/029 7/029

Claims (1)

[Claims] 1. A photopolymerizable composition comprising at least the following components i) to iv): i) addition-polymerizable compound having at least one ethylenically unsaturated double bond ii) sensitizing dye represented by formula (I) iii) photoradical generator iv) oxime ether represented by formula (II) Compound embedded image R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
A substituted or unsubstituted alkenyloxy group having 1 to 6 carbon atoms
Represents a substituted or unsubstituted alkylthio, a dialkylamino group in which each alkyl group has 1 to 4 carbon atoms, a hydroxyl group, an acyloxy group, a halogen, a nitro group, or a 5- or 6-membered heterocyclic group. Provided that two or three of R ² to R ⁵
And the ring-constituting carbon atoms to which the substituents of R ² to R ⁵ are bonded may together form a fused ring or fused ring system in which each fused ring is a 5- or 6-membered ring. ; R ¹
Represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or R ⁶ —CO—. (Here, R ⁶ is an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryloxy group,
An alkenyloxy group, an aralkyloxy group, an alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, or the following substituent (Formula 2) is shown. Embedded image (R ^{7 to} R ^{10 each} represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group or a cycloalkyl group, and n and m each represent an integer of 1 to 5)); Q is -CN, heterocyclic, or represents -Z-R ^11. (Where R ¹¹ is 1 carbon atom
-10 substituted or unsubstituted alkyl group, alkenyl group or alkoxy group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or carbon atoms constituting a ring And a substituted or unsubstituted heterocyclic group having 5 to 15 different atoms, a hydroxyl group, an acyl group; and Z is a carbonyl group, a sulfonyl group, a sulfinyl group or an arylenedicarbonyl group,-(CH = CH) _n (n Is 1 or 2)) R ¹² , R ¹³ and R ¹⁴ represent the same or different monovalent organic groups.