JPH0572732A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To enhance sensitivity to active rays in a wide region by incorporating a compound having an additionally polymerizable bond and a compound having a benzo- or naphtho-imidazole ring and at least one of specified compounds. CONSTITUTION:This photopolymerizable composition comprises the compound having the additionally polymerizable bond, the compound represented by formula I, and further, a compound having a halogen-carbon bond, an organic peroxide, a thiocompound of formulae II and III, and at least one compound selected from hexaarylbiimidazole and ketoxime ester. In the formulae I-III, each of Z<1> and Z<2> is a nonmetallic atomic group necessary to form a benzo- or naphtho- imidazole ring; each of R<1>-R<4> is X<-> is a counter ion: n is 0 or 1: R<5> is alkyl or aryl or the like; R<6> is H or alkyl, and R<5> and R<6> may combine with each to form a 5-, 6-, or 7-membered ring.

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 containing a polymerizable compound having an addition polymerizable unsaturated bond, a photopolymerization initiator having a novel composition, and, if necessary, a linear organic polymer, The present invention relates to a photopolymerizable composition useful for a photosensitive layer of a photosensitive printing plate which is sensitive to an argon laser light source.

[0002]

2. Description of the Related Art A photosensitive composition in which a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, a binder having an appropriate film-forming ability, and a thermal polymerization inhibitor are mixed if necessary. A method for reproducing an image by using a photograph is currently known. That is, U.S. Patent Nos. 2,927,022, 2,902,356 or 3,870,
As described in No. 524, since a photosensitive composition of this type undergoes photopolymerization upon irradiation with light, and is cured and insolubilized, the photosensitive composition is formed into a suitable film, and a desired negative image is formed through it. A desired cured image of the photopolymerizable composition can be formed by performing light irradiation and removing only the unexposed portion with a suitable solvent (hereinafter, simply referred to as development). It goes without saying that this type of photosensitive composition is extremely useful as a material used for producing printing plates and the like.

Further, conventionally, a polymerizable compound having an addition-polymerizable unsaturated bond alone does not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to enhance the photosensitivity. As a polymerization initiator, benzyl, benzoin, benzoin ethyl ether, Michler's ketone,
Anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like have been used.
However, when these photopolymerization initiators are used, the photosensitivity of curing of the photopolymerizable composition is low, and thus it took a long time for image exposure in image formation. Therefore, in the case of a fine image, if there is a slight vibration in the operation, an image with good image quality cannot be reproduced, and the amount of energy emitted from the exposure light source must be increased, which causes a large amount of energy. It was necessary to consider the dissipation of fever. In addition, there is a problem that the coating film of the composition is easily deformed or deteriorated by heat.

Further, these photopolymerization initiators have a photopolymerization ability of 40 nm or less when compared with a light source in the ultraviolet region.
The photopolymerization ability for a light source in the visible light region of 0 nm or more is remarkably low. Therefore, the application range of the conventional photopolymerizable composition containing the photopolymerization initiator is extremely limited. Several proposals have been made in the past regarding photopolymerization systems sensitive to visible light. As such a proposal, according to U.S. Pat. No. 2,850,445, certain photoreducing 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)
No.), a system of hexaaryldiimidazole and a radical generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-Open No. 5528/1985).
4-155292), a system of 3-keto-substituted coumarin compounds and active halogen compounds (JP-A-58-15503).
No.), a system of substituted triazine and merocyanine dye (Japanese Patent Laid-Open No. 54-15102), and the like have been proposed. These techniques are certainly effective for visible light. However, the photosensitivity rate is not yet satisfactory,
Further improved techniques have been desired.

Further, in recent years, high sensitivity to ultraviolet rays,
A method of forming an image using a laser has been studied, and UV projection exposure method, laser direct plate making, laser facsimile, holography, etc. are already in practical use in printing plate making, and a highly sensitive photosensitive material corresponding to these has been developed. It is being done. However, it cannot be said that it still has sufficient sensitivity.

[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 that increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an addition polymerizable unsaturated bond in general. is there.

Another object of the present invention is to correspond to the visible light of 400 nm or more, especially the output of Ar ⁺ laser 488.
Another object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator that is highly sensitive to light near nm.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a specific photopolymerization initiator system is a photopolymerizable compound having an addition-polymerizable unsaturated bond. The present invention has been completed by finding that the polymerization rate is remarkably increased and that high sensitivity is exhibited even for visible light of 400 nm or more.

That is, the present invention includes (i) a polymerizable compound having an addition-polymerizable unsaturated bond, (ii) a compound represented by the following general formula (I)

[0010]

[Chemical 3]

Where Z¹And Z²Is benzimidazo
Or the naphthoimidazole ring necessary to form the ring
Represents a group of metal atoms, which may be the same or different. R
¹, R², R³And R^FourEven if each is replaced
Represents a good alkyl group. X ^-Represents a counter anion,
n is 0 or 1. (iii) (a) a compound having a carbon-halogen bond, (b) an aroma
Group onium salt, (C) Organic peroxide, (D) General formula
The thio compound represented by (II):

[0012]

[Chemical 4]

(Wherein R ⁵ represents an alkyl group, an aryl group or a substituted aryl group, R ⁶ represents a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ 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.), (E) hexaarylbiimidazole, and (f) ketoxime ester It is a photopolymerizable composition containing at least one compound selected from the group consisting of:

Each component of the photopolymerizable composition of the present invention will be described in detail below. Component (i) used in the present invention
The polymerizable compound having an addition polymerizable unsaturated bond of
It is selected from compounds having at least one, and preferably two or more terminal ethylenically unsaturated bonds. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Isocrotonic acid, maleic acid and the like) and an ester of an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound.

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.

Examples of 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. Further, a mixture of the above-mentioned ester monomers can be used. Specific examples of the amide monomer of an aliphatic polyvalent amine compound and an 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 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 two molecules in one molecule. Examples include vinyl urethane compounds containing at least one polymerizable vinyl group.

CH ₂ ═C (R) COOCH ₂ CH (R ′) OH (A) (wherein R and R ′ represent H or CH ₃ ).
Further, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183,
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
Examples thereof include 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-0. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine vol. 20, No. 7, pages 300 to 308 (1984) can also be used. The amount of these used is 5 to 50% by weight based on all components.
(Hereinafter abbreviated as “%”), preferably 10 to 40%.

The component (ii) used in the present invention is at least one compound selected from the compounds represented by the above general formula (I). The general formula (I) will be further described.
The benzimidazole ring or naphthimidazole ring formed by Z ¹ and Z ² is, for example, 1
-Alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl -5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5
-Trifluoromethylbenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5 -Methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1
-Alkylnaphtho [1,2-d] imidazole and 1-arylnaphtho [1,2-d] imidazole are preferable,
The above-mentioned alkyl group has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl).
Is preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl.

R ¹ , R ² , R ³ and R ⁴ are alkyl groups having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, Isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group (for example, aralkyl group (for example, benzyl group, 2-phenylethyl group), hydroxyalkyl group (for example, 2-hydroxy group) Ethyl group, 3-hydroxypropyl group), carboxyalkyl group (for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (for example, 2-methoxyethyl group) , 2- (2-
Methoxyethoxy) ethyl group), sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 3
-Sulfobutyl group, 4-sulfobutyl group, 2- [3-sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (for example, 3-sulfato) Propyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group), 2-acetoxyethyl Group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group}
Is preferred.

X₁ ^-Include various anions
It For example, SO_Four ^2-, S₂O₃ ^2-, SO ₃ ^-, Halogenio
ClO_Four ^-, BF_Four ^-, PF₆ ^-, SbF₆ ^-, BiCl_Five ^-, AsF₆
^-, SbCl₆ ^-, SnCl₆ ^-, R-SO₃ ^-, R-COO^-Etc.
You can However, R is a hydrogen atom, an alkyl group, or an aryl.
Represents a group or a heterocyclic group. General formula used in the present invention
The sensitizing dye represented by (I) is a heterocyclic
Compounds-Cyanine Soybean & Relayed
・ Compounds ("Heterocyclic compounds-Cyanine
dyes and related compounds- ") chapter IV, V, VI,
pages 86-199, F. M. Hamer, John.
Wiley & Sons (New York, London), 1964,
Terror Cyclic Compounds-Special Topic
Cus in Heterocyclic Chemistry ("Het
erocyclic compounds-Special topics in heterocyli
c chemistry- ") chapter VIII, sec. IV page482-
515, D. M. Sturmer, John Wiley & Sons (NewYo
based on the method described in 1977, etc.
And can be easily synthesized.

Representative examples of the compounds of the general formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

As the compound having a carbon-halogen bond, which is an example of the component (iii) used in the preferred embodiment of the present invention, compounds represented by the following general formulas (V) to (XI) are preferable. General formula (V)

[0030]

[Chemical 5]

(In the formula, X represents a halogen atom. Y represents
−CX₃, -NH₂, -NHR¹², -NR¹² ₂, -OR¹²Represents
You Where R¹²Is an alkyl group, a substituted alkyl group, an aryl
And a substituted aryl group. Also R¹¹Is −CX₃, A
Alkyl group, substituted alkyl group, aryl group, substituted aryl
And a substituted alkenyl group. ) Compounds
object.

General formula (VI):

[0033]

[Chemical 6]

(Wherein R ¹³ 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 alkoxy group, a nitro group or a cyano group, and X Is a halogen atom, and n is an integer of 1 to 3.).

The general formula ^{(VII) R 14 -Z-CH} 2-m X m -R 15 ( provided that, R ¹⁴ is an aryl group or a substituted aryl group, R ¹⁵ is -CO-NR ¹⁶ R ^17,

[0036]

[Chemical 7]

Or halogen, Z is --CO--, --C
S- or -SO₂− And R¹⁶, R ¹⁷Is an alkyl group,
Substituted alkyl group, alkenyl group, substituted alkenyl group,
A reel group or a substituted aryl group, R¹⁸Is the general formula
R in (V)¹²And m is 1 or 2. )
The compound represented by. General formula (VIII):

[0038]

[Chemical 8]

However, in the formula, R ¹⁹ is an optionally substituted aryl group or heterocyclic group, and R ²⁰ is 1 to 1 carbon atom.
It is a trihaloalkyl group or a trihaloalkenyl group having three, and p is 1, 2 or 3.

General formula (IX):

[0041]

[Chemical 9]

(However, L is a hydrogen atom or a formula: CO- (R ²¹ ).
_q (CX ₃ ) _{r is} a substituent, M is a substituted or unsubstituted alkylene group, Q is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group,
1,2-phenylene group or NR ²² group, M + Q together form 3 or 4 heterocycle, R ²² is alkyl group, aralkyl group or alkoxyalkyl group, R ^22
21 is a carbocyclic or heterocyclic aromatic group, X is a chlorine, bromine or iodine atom, q = 0 and r = 1, or q = 1 and r = 1 or 2. ) A carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by the formula:

General formula (X):

[0044]

[Chemical 10]

(However, X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ²³ is a hydrogen atom or a CH _{3 -t} X _t group, and R is ²⁴ is an s-valent unsaturated organic group which may be substituted). Represented by 4-halogeno-5- (halogenomethyl-phenyl)
-Oxazole derivatives.

General formula (XI):

[0047]

[Chemical 11]

(Wherein X is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ²⁵ is a hydrogen atom or a CH _3-v X _v group, and R is ²⁶ is a u-valent unsaturated organic group which may be substituted). A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative represented by:

Examples of such a compound having a carbon-halogen bond include Wakabayashi et al., Bull. Chem. 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-trichloroethyl)- 4,6-bis (trichloromethyl) -S
-Triazine and the like. Other British patent 138849
No. 2, compounds such as 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, etc., JP-A-53.
-133428, for example, 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)-
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
Compounds described in 3337024, for example

[0050]

[Chemical formula 12]

[0051]

[Chemical 13]

And the like. Also, FC Sc
Haefer et al., J. Org Chem .; 29, 1527 (19
64), 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-6-tribromomethyl-S-
Examples thereof include triazine and 2-methoxy-4-methyl-6-trichloromethyl-S-triazine.

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

[0054]

[Chemical 14]

[0055]

[Chemical 15]

And the like. Or even more
By MP Hutt, EF Elslager and LM Werbel
Journal of Heterocyclic chemistry Volume 7 (No.
3), the following group of compounds that can be easily synthesized by those skilled in the art according to the synthetic method described on page 511 and after (1970).

[0057]

[Chemical 16]

[0058]

[Chemical 17]

[0059]

[Chemical 18]

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

Alternatively, compounds such as those described in German Patent No. 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, such as

[0067]

[Chemical 25]

──────────────────────────────────── R ²⁸ M Ra (CX ₃ ) _b ── ───────────────────────────────── 1 C ₂ H ₅ 1,2-phenylene H 1 4-CCl ₃ 2 CH ₂ C ₆ H ₅ 1,2-phenylene H 1 4-CCl ₃ 3 C ₂ H ₅ 1,2-phenylene H 1 3-CCl ₃ 4 C ₂ H ₅ 1,2-phenylene H 1 4-CF ₃ 5 C ₂ H ₅ 5-CH ₃ -1,2-phenylene H 0 CCl ₃ 6 CH ₂ C ₆ H ₅ 1,2-phenylene H 0 CCl ₃ 7 C ₂ H ₄ OCH ₃ 1,2-phenylene H 14- CCl ₃ ─────────────────────────────────── or the group of compounds described in German Patent No. 3021590,

[0069]

[Chemical formula 26]

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

[0071]

[Chemical 27]

The following may be mentioned. Also, the component (iii)
Another example of the aromatic onium salt is an element of Group V, VI and VII of the periodic table, specifically N, P, As, S.
Included are aromatic onium salts of b, Bi, O, S, Se, Te, or I. Such an aromatic onium salt is disclosed in Japanese Patent Publication No.
The compounds shown in JP-B No. 2-14277, JP-B No. 52-14278 and JP-B No. 52-14279 can be mentioned.

Specifically,

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

[0078]

[Chemical 32]

[0079]

[Chemical 33]

[0080]

[Chemical 34]

Can be mentioned. Preferred among these are compounds of BF ₄ salt or PF ₆ salt, more preferably BF ₄ salt of aromatic iodonium salt, or PF ₆ salt.
It is salt. The "organic peroxide" which is another example of the component (iii) used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. , Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-
Trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane, 1,
1, -bis (tertiary butyl peroxy) cyclohexane, 2,2-bis (tertiary butyl peroxy) butane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, parametric hydroperoxide 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, Bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) Xing -3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethyl hexanoyl peroxide, peroxy succinic acid, 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, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctanoate, tersha L-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate, di-tert-butylperoxy Isophthalate, 2,5-dimethyl-2,5-di (benzoyl peroxy) hexane, tertiary Ryi butyl peroxide maleic acid, tert Ryi butylperoxy isopropyl 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- Hexyl peroxy dihydrogen 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 component (iii) (d) used in the present invention is represented by the above general formula (II). The alkyl group represented by R ⁵ in the general formula (II) preferably has 1 to 4 carbon atoms. Further, the aryl group of R ⁵ is preferably one having 6 to 10 carbon atoms such as phenyl and naphthyl, and the substituted aryl group includes a halogen atom such as chlorine atom and a methyl group as the above aryl group. Such as an alkyl group, a methoxy group,
Those substituted with an alkoxy group such as an ethoxy group are included.

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

[0085]

[Chemical 35]

As the hexaarylbiimidazole,
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 can be mentioned. As ketoxime ester, 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 content concentration of these photoinitiator systems in the compositions according to the invention is usually low. On the other hand, when the amount is inappropriately large, unfavorable results such as blocking of effective rays are produced. The amount of the photopolymerization initiator system in the present invention is from 0.01% to 6 with respect to the total of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer optionally added.
It is preferably used in the range of 0%. More preferably,
Good results are obtained with 1% to 30%.

The ratio of the component (ii), which is a component as the photopolymerization initiator used in the present invention, to the component (iii) is as follows:
Is preferably 0.05 to 30 parts by weight, more preferably 0.05 parts by weight.
It is 1 to 10 parts by weight, most preferably 0.2 to 5 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 high molecular polymer", any linear organic high molecular 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 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 polymer is used, water development becomes possible. As such a linear organic polymer, an addition polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54-3.
No. 4327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-
25957, JP-A-54-92723, and JP-A-59.
-53836, JP-A-59-71048, that is, methacrylic acid copolymers, alkaline acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, Examples include partially esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition to these, addition polymers having a hydroxyl group and a cyclic acid anhydride 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 / as necessary And other addition-polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, alcohol-soluble nylon, 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 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. It is preferably 30 to 85%.
The weight ratio of the photopolymerizable ethylenically unsaturated compound to the linear organic polymer is preferably 1/9 to 7/3. 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 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.
~ 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 preferably about 0.5% to about 10% of the total composition. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of dye and pigment added is preferably about 0.5% to about 5% of the total composition. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

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. Then, the concentration of the solid content in the coating solution is appropriately 2 to 50% by weight.

The coating amount is about 0.1 g / m ² by dry weight.
A range of from about 10 g / m ² is suitable. More preferably 0.
It is 5 to 5 g / m ² . As the above support, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.),
Further, for example, metal plates such as aluminum (including aluminum alloy), zinc, copper, etc., and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate. Examples thereof include plastic films such as polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and papers or plastic films on which the above metals are laminated or vapor-deposited. Of these supports, the aluminum plate is particularly preferable because it is dimensionally extremely stable and inexpensive. Further, 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.

Further, in the case of a support having a surface of a metal, particularly aluminum, a graining treatment, a dipping treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or a surface treatment such as anodizing treatment. It is preferable that Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution 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 above 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. Furthermore,
JP-B-46-27481, JP-A-52-58602
A surface treatment in which a support subjected to electrolytic graining as disclosed in JP-A-52-30503 and the above-mentioned anodizing treatment and sodium silicate treatment are combined is also useful.

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. 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 It is also preferable to undercoat a yellow dye, amine salt or the like.

These hydrophilization treatments are performed 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 for 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. 3,458,
311 and JP-A-55-49729.

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, 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 developing solutions when these photopolymerizable compositions are used for preparing a lithographic printing plate include the developing solutions described in JP-B-57-7427, and sodium silicate and potassium silicate. Like, 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. It is added so that the concentration of the 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, U.S. Pat. No. 3,375,
No. 171 and No. 3,615,480. Further, JP-A-50-266
No. 01, No. 58-54341, Japanese Patent Publication No. 56-3946
The developing solutions described in Japanese Patent Nos. 4 and 56-42860 are also excellent.

[0099]

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 a 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.

[0100]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Examples 1-18, Comparative Examples 1-11 An aluminum plate having a thickness of 0.30 mm and a nylon brush and 40
The surface was grained with a 0 mesh aqueous suspension of pumice and then thoroughly washed with water. After dipping in 10% sodium hydroxide at 70 ° C for 60 seconds for etching,
It was washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. This was subjected to 160 coulomb / dm in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of V _A = 12.7V.
^The electrolytic surface roughening treatment was performed with the amount of electricity at the time of ^{2 as} the anode. When the surface roughness was measured, it was 0.6 μ (Ra indication).
Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55 ° C for 2 minutes, and then a current density of 2% was applied in a 20% sulfuric acid aqueous solution.
Anodizing treatment was performed for 2 minutes so that the thickness of the anodized film at A / dm ² was 2.7 g / m ² .

On the aluminum plate thus treated, the photosensitive composition having the following composition was applied in a dry coating weight of 1.4 g /
It was coated so as to be m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Trimethylolpropane tri (acryloyl oxypropyl) ether 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Photoinitiator X g Fluorine-based nonionic surfactant 03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g Polyvinyl alcohol (saponification degree 86.5
~ 89 mol%, 3% by weight aqueous solution of polymerization degree 1000) is applied so that the dry coating weight is 2 g / m ^2, and the temperature is 100 ° C.
/ Dried for 2 minutes.

The photosensitivity test was conducted with visible light. As the visible light, a xenon lamp was used as a light source, and monochromatic light obtained through a Kenko optical filter BP-49 was used. For the photosensitivity measurement, a Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet in which the transmission optical density of the first step is 0.05 and sequentially increases by 0.15 to 15 steps) is used. Illuminance on the photosensitive film surface is 0.0132 mW / cm ²
It is indicated by the number of clear steps of the PS step guide when exposed for 240 seconds.

The development was carried out by immersing in the following developing solution at 25 ° C. for 1 minute. 1K Potassium silicate 30 g Potassium hydroxide 15 g Compound of the following formula 3 g

[0104]

[Chemical 36]

Water 1000 g The following compounds are used as the photopolymerization initiator, and the results of the sensitivity when the combinations are changed are shown in Tables 1 and 2. Compounds of dye numbers I-6, I-11, I-19

[0106]

[Chemical 37]

In Table 1 (), g is ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example No ( Compound of I) Compound of (iii) BP-49 Filter light 240 steps exposure clear stage ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━ 1 I-6 (0.14) (iii) -1 (0.1) 13 2 〃 (iii) -2 (0.1) 10 3 〃 (iii) -3 (0.16) 10 4 〃 (iii) -4 (0.1) 13 (iii) -5 (0.7) 5 〃 (iii) -6 (0.05) 8 6 〃 (iii) -1 (0.1) 14 (iii)- 4 (0.1) 7 I-11 (0.14) (iii) -1 (0.1) 11 8 〃 (iii) -2 (0.1) 8 9 〃 (iii) -3 (0.16) 8 10 〃 (iii) -4 (0.1) 11 (iii) -5 (0.7) 11 〃 (iii) -6 (0.05) 7 12 〃 (iii) -1 (0.1) 12 (iii) -4 (0.1) 13 I-19 (0.12) (iii) -1 (0.1) 10 14 〃 (iii) -2 (0.1) 7 15 〃 (iii) -3 ( 0.16) 8 16 〃 (iii) -4 (0.1) 10 (iii) -5 (0.7) 17 〃 (iii) -6 (0.05) 5 18 〃 (iii) -1 (0.1) 11 (iii) -4 (0.1) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Comparative Example No (I) Compound (iii) Compound BP-49 Number of clear steps with 240 seconds exposure of filtered light ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 1 I-6 ( 0.14) ─── 0 2 I-11 (0.14) ─── 0 3 I-19 (0.12) ─── 0 4 ─── (iii) -1 (0.1) 0 5 ─── (iii) -2 (0.1) 0 6 ─── (iii) -3 (0.7) 0 7 ─── (iii) -4 (0.1) 0 8 ─── (iii) -5 (0. 7) 0 9 ─── (iii) -6 (0.05) 0 10 ─── (iii) -4 (0.1) 0 (iii) -5 (0.7 0 11 ─── (iii) -1 (0.1) 0 (iii) -4 (0.1) 0 ━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━ From the results shown in Tables 1 and 2, the photopolymerizable composition of the present invention containing the components (ii) and (iii) has high sensitivity.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 31, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

[0085]

[Chemical 35]

Claims (1)

[Claims] 1. (i) Polymerization having an addition-polymerizable unsaturated bond
Possible compounds (ii) compounds represented by the following general formula (I):In the formula, Z¹And Z²Is benzimidazole or naphth
The group of non-metal atoms required to form the toymidazole ring
It may be the same or different. R¹, R², R
³And R^FourEach is an optionally substituted alkyl
Represents a group. X ^-Represents a counter anion, n is 0 or 1
Is. (iii) (a) a compound having a carbon-halogen bond, (b) an aromatic onium salt, (c) an organic peroxide, (d) a thio compound represented by the following general formula (II):(Where R^FiveIs an alkyl group, an aryl group or a substituted group
Indicates a reel group, R⁶Represents a hydrogen atom or an alkyl group
You Also, R^FiveAnd R⁶Are bound to each other by oxygen and sulfur.
And optionally containing a heteroatom selected from nitrogen atoms 5
The non-metallic atomic groups necessary to form a 6-membered ring
You ), (E) hexaarylbiimidazole, and (f) at least one compound selected from the group consisting of ketoxime esters.
A photopolymerizable composition comprising: