JPH01298348A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To improve the sensitivity of the title composition for active rays having a broad wavelength region from a UV ray to a visible ray by incorporating at least 3 kinds of compds. selected from each 3 kinds of specified groups, in a photopolymerization initiator. CONSTITUTION:The photopolymerization initiator contains at least 3 kinds of the compds. selected from each 3 kinds of the group A composed of an org. boron compd. anionic salt of an org. cationic dye or a combination of at least one kind of the org. cationic dye and the org. boron compd. anionic salt, the group B composed of at least one kind selected from a compd. having carbon-halogen binding, an aromatic onium salt or an aromatic halonium salt and an org. peroxide and the group C shown by formula I. In formula I, Ar is an aromatic group shown by for example, formula II, R<1> and R<2> are each hydrogen atom or alkyl group. In formula II, R<3>-R<7> are each hydrogen atom, etc., R<9> is alkyl group, etc., R<8> is hydrogen atom, etc. Thus, the sensitivity of the composition for the active rays having the broad wavelength region from the UV ray to the visible ray is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to photopolymerizable compositions. More specifically, it relates to a photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator having a novel composition, and optionally a linear organic polymer, for example, The present invention relates to a photopolymerizable composition useful for a photosensitive layer of a photosensitive printing plate, etc., which is also sensitive to an argon laser light source.

[Conventional technology]

A photosensitive composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having an appropriate film-forming ability and a thermal polymerization inhibitor, is used to produce a photographic effect. Techniques for duplicating images are currently known. i.e. U.S. Patent 2,927
, No. 022, No. 2,902.356 or No. 3,8
As described in No. 70,524, this type of photosensitive composition undergoes photopolymerization, hardens, and becomes insolubilized by irradiation with light. Light is irradiated through the negative image, and only the unexposed areas are removed using an appropriate solvent (hereinafter simply referred to as development).
By this, a cured image of the desired photopolymerizable composition can be formed. It goes without saying that this type of photosensitive composition is extremely useful for making printing plates and the like.

In addition, conventionally, polymerizable compounds having ethylenically unsaturated bonds alone do not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to increase photosensitivity. Benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, etc. have been used. However, when these photopolymerization initiators are used, the curing sensitivity of the photopolymerizable composition is low, so that image exposure during image formation requires a long time. For this reason, in the case of detailed images, if there is slight vibration during operation, the image will not be reproduced with good quality.
Furthermore, since the amount of energy emitted by the light source for exposure must be increased, it is necessary to consider the dissipation of a large amount of heat accompanying this increase. In addition, there are problems such as the composition film being easily deformed and deteriorated by heat.

Further, these photopolymerization initiators have a significantly lower photopolymerization ability with respect to a light source in the visible light region of 400 nm or more than that with a light source in the ultraviolet region of 400 nm or less. Therefore, the range of application of conventional photopolymerizable compositions containing photopolymerization initiators is extremely limited.

Several proposals have been made regarding photopolymerization systems sensitive to visible light. As such a proposal, U.S. Pat.
According to No. 50445, certain photoreducible dyes, e.g.
It has been reported that rose bengal, eosin, erythrosin, etc. have effective visible light sensitivity. In addition, as an improved technology, a composite initiation system of dye and amine (Special Publication No. 44-
20189), a system of hexaarylbiimidazole, 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, JP-A-54) -155292), a system of 3-ke14-substituted marine compounds and active halogen compounds (JP-A-58-15
503), substituted triazine and merocyanine dye system (
Proposals such as Japanese Patent Application Laid-open No. 15102/1983 have been made. These techniques are certainly effective for visible light.

However, the photosensitive speed is still not fully satisfactory, and further improved technology has been desired.

In addition, in recent years, increased sensitivity to ultraviolet rays and methods of forming images using lasers have been studied, and methods such as UV projection exposure for printing plate creation, laser direct plate making, laser facsimile, and holography are already in practical use. , high-sensitivity photosensitive materials corresponding to these are currently being developed. However, it cannot be said that it has sufficient sensitivity yet.

[Problem to be solved by the invention]

An object of the present invention is to provide a highly sensitive photopolymerizable composition.

That is, an object of the present invention is to generally provide a photopolymerizable composition containing a photopolymerization initiator that increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond. It's a stop.

Another object of the present invention is to provide visible light of 400 nm or more,
In particular, it is an object of the present invention to provide a photopolymerizable composition containing a photopolymerization initiator that is highly sensitive to light around 488 nm, which corresponds to the output of an Ar'' laser.

[Means to solve the problem]

As a result of intensive research aimed at achieving the above object, the present inventors have found that a certain photoinitiator system significantly increases the photopolymerization rate of a polymerizable compound having an ethylenically unsaturated bond, and also shows that a specific photopolymerization initiator system significantly increases the photopolymerization rate of a polymerizable compound having an ethylenically unsaturated bond. The present invention was achieved based on the discovery that it exhibits high sensitivity even to visible light above I.

That is, the present invention includes a polymerizable compound having at least one ethylenically unsaturated bond that can be photopolymerized by actinic rays, a photopolymerization initiator, and, if necessary, a linear organic polymer. The photopolymerizable composition is characterized in that the photopolymerization initiator contains at least three compounds selected from the following groups A, B, and 0, respectively.

(A) (i) an organic boron compound anion salt of at least one organic cationic dye; or (ii) a combination of at least one organic cationic dye and an organic boron compound anion salt; (B) (i) having a carbon-halogen bond; Compound (ii) aromatic onium salt or aromatic halonium salt i) At least one organic peroxide (C) - formula (wherein Ar is an aromatic selected from one of the following general formulas) R1 and R2 represent a hydrogen atom or an alkyl group, and R1 and R2 may combine with each other to represent an alkylene group. (However, in the formula, R3 and R7 independently represent a hydrogen atom or an alkyl group.) Atom, halogen atom, alkyl group, alkenyl group, aryl group, substituted aryl group, hydroxyl group, alkoxy group, substituted alkoxy group, ~5-R9 group, -3O-
R9 group or -SO□R9 group, provided that a small number of groups 3 to R7 (each one represents a -3-R' group, -3o-R' group or -302R9 group, R9 is an alkyl group, The alkenyl group R11 represents a hydrogen atom, an alkyl group, or an acyl group.

The polymerizable compound having an ethylenically unsaturated bond used in the present invention is defined as having at least one compound in its chemical structure.
More preferably, it is a compound having at least two ethylenically unsaturated bonds. For example, it has chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of hetamine and copolymers thereof include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like.

Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol as acrylic esters. 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,
Examples include dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acryloyloxyethyl)isocyanurate, and polyester acrylate oligomers.

Examples of meccrylic 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
-hydroxypropoxy)phenyl]dimethylmethane,
Examples include bis-[p-(acryloxyethoxy)phenyl]dimethylmethane.

As the itaconic acid ester, ethylene glycol shitaconate, propylene glycol shitaconate, 1
．． 3-butanediol shiitaconate, 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate,
Examples include sorbitol tetrataconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetramaleate.

Isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate.

Furthermore, mixtures of the aforementioned ester monomers may also be mentioned.

In addition, specific examples of amide combinations of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,
Examples include 6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

As another example, the following general formula (
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl hexamer containing a hydroxyl group is added as shown in A).

CH2= C(R) COOCHt CH(R')
OH(A) (where R and R' are H or CH
, is shown. ) Also, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-A-52-30490
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid as described in each publication can be mentioned. Furthermore, Japan Adhesive Association Journal Vo1.20, r1kl? , pages 300 to 308 as photocurable monomers and oligomers can also be used. The amount of these used is 5 to 50% by weight (hereinafter abbreviated as %), preferably 10 to 40%, based on the total components.

Next, the photopolymerization initiator, which is a significant feature in the photopolymerizable composition of the present invention, will be explained.

Organic boron compound anion salt of organic cationic dye that can be effectively used in the present invention, that is, component (A)-(
i) is, for example, the following - formula (1) % formula % where D- is an organic cationic dye; Rlo, R
1. RIZ and RI'I may be the same or different, and are an alkyl group, substituted alkyl group, aryl group, substituted aryl group, aralkyl group, alkaryl group, alkenyl group, alkynyl group, alicyclic group, heterocycle group, allyl group, and derivatives thereof; R10
, R"% R" and RI3 may be a cyclic structure in which two or more of the groups are bonded.

In the present invention, organic cationic dyes include, for example, cationic methine dyes, preferably polymethine dyes, cyanine dyes, azomethine dyes, more preferably cyanine, carbocyanine, hemicyanine; carbonium dyes, preferably triarylmethane dyes, xanthine dyes. , acridine dyes, more preferably rhodamine; quinoneimine dyes, preferably azine dyes, oxazine dyes, thiazine dyes; quinoline dyes; thiazole dyes, (thia)pyrylium dyes, etc. One or a combination of dyes can be used. .

In the present invention, the above-mentioned organic cationic dyes that are commercially available or known in the industry can be used. Examples of these dyes include the section on basic paints in the Dye Handbook edited by the Organic Chemistry Society, and the book by T.H.
``The Theory of Photographic Process'' by
the Photographic Process)
Maca+1llan Pub
lishing Co., Inc.) 19 of 1977
Pages 4-290 and "Chemistry of Functional Dyes" published by CMC Publishing Co., Ltd., pages 1-32, pages 189-206, and 4.
Reference may be made to pages 01 to 413, Japanese Patent Application Laid-open No. 189340/1983, and the like.

Among the above dyes, particularly useful in the present invention are cyanine dyes and xanthine dyes. Specific examples of cyanine dyes useful in the present invention include dyes represented by the following general formula (I[).

- Ritual (II) In the formula, Zl, 2g is a heterocyclic nucleus commonly used in cyanine dyes, especially a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, an oxazoline nucleus, a paidioxazole nucleus, a naphthoxazole nucleus, Necessary to complete the tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidacilline nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, or indolenine nucleus, etc. Represents a group of atoms. These nuclei include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups, hydroxyl groups, and carbon atoms of 1 to 4.
may be substituted with an alkoxy group, carboxyl group, alkoxycarbonyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group, nitro group, etc.

Ll, L2 or L3 represents a methine group or a substituted methine group. Examples of the substituted methine group include methine groups substituted with lower alkyl groups such as methyl group and ethyl group, phenyl group, substituted phenyl group, aralkyl group such as methoxy group, ethoxy group, and phenethyl group.

When Ll and RI4, L3 and Rls and ω=3, L2 and L
2 may be alkylene bridged to form a 5- or 6-membered ring.

RI4 and RIB are a lower alkyl group (more preferably an alkyl group having 1 to 8 carbon atoms), a carboxy group, a sulfo group,
An alkyl group having a substituent such as a hydroxy group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a substituted phenyl group (preferably, the alkylene portion is a C5 to C5
), for example, β-sulfoethyl, γ-sulfopropyl, T-sulfobutyl, δ-sulfobutyl, 2- (
2-(3-sulfopropoxy)ethoxy]ethyl, 2-
Hydroxysulfopropyl, 2-chlorosulfopropyl, 2-methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2.2°3.3-
Tetrafluoropropyl, 3.3-1-lifluoroethyl; represents an allyl group and other substituted alkyl groups commonly used as N-substituents of cyanine dyes. ω represents 122 or 3. X- represents the boron compound anion of the above structural formula (I).

Specific examples of xanthine dyes useful in the present invention include dyes represented by the following general formula (1).

R16, R1? , R11 and R19 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a C 6 to 14
represents an aryl group, X represents a boron compound anion of the above structural formula (1), and Y represents an alkyl group, an aryl group, a hydrogen atom, or an alkali metal.

Examples of preferred organic boron compound anion salts of organic cationic dye compounds that can be used in the present invention are listed below. However, the present invention is not limited to the following compounds.

-to <<<<<<<<<<<< l 1
1<<< In addition, as the component (A) used in the present invention, anion salts other than organic boron compound anions of organic cationic dyes, such as halogen anion salts such as C1-, Br-, and I-, and BF4 -, anion salts such as PF6-1, and cation salts other than organic dye cations of organic boron compound anions, such as N"(CH3)4, N"(C
It may also be a mixture with a quaternary ammonium cation salt such as tH5)4, N''(nC4H9)4, or an alkali metal cation salt such as Na'' or K''.

The above-mentioned compound (2) may be of the general formula (n) or (II
[) in which X is a halogen ion (e.g. C1-, Br
-% I-, etc.). In addition, the above compound■
Other examples of organic boron compound anion salts include U.S. Pat. Nos. 3,567.453 and 4,343.8.
91, European Patent No. 109.772, European Patent No. 109.772.
Examples include the compounds described in No. 773 and those shown below.

A -20 (nc4H1+B -N (nc4ttJ4
Examples of the compound having a carbon-halogen bond used in the present invention include Wakabayashi et al., Bull.

Chem, Soc, Japan, ■Cluster, 2924
(1969), for example, 2-phenyl 4
．． 6-bis(trichloromethyl)-3-triazine, 2
- <p-chlorophenyl)-4,6-bis(trichloromethyl)-3-triazine, 2-(p-tolyl)-4
, 6-bis(trichloromethyl)-3-triazine, 2
-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-3-triazine, 2-(2',4'-dichlorophenyl)-4,6-bis(trichloromethyl)-
3-) riazine, 2,4.6-)lis(trichloromethyl)-8-triazine, 2-methyl-4,6-bis(trichloromethyl)-3-triazine, 2-n-nonyl-
4,6-bis(trichloromethyl)-s-triazine,
Examples include 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-3-)riazine. Other compounds described in British Patent No. 1388492, such as 2-styryl-4,6-bis(trichloromethyl)-3-1 riazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl) )-3-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-3-1-riazine, 2-(p-
Compounds described in JP-A-53-133428, such as 2-(4-methoxystyryl)-4-amino-6-trichloromethyl-S-triazine;
1-yl) = 4.6-bis-trichloromethyl-S-+
-Riazine, 2-(4-ethoxy-naphth-1-yl)
-4,6-bis-trichloromethyl-S-+-lyazine, 2-(4-(2-ethoxyethyl)-naphth-1-yl)-4,6-bis-trichloromethyl-S-)lyazine, 2 - (4,7-dimethoxy-naphthol-1-yl)
-4,6-bis-trichloromethyl-S-triazine,
2-(acenaphth-5-yl)-4,6-bis-trichloromethyl-S-toIJ azine, etc., German Patent No. 3337
Compounds described in No. 024, such as CCI! .

C.B. C13 etc. and others CCI! 3 C.C.Z.

C.C.Z.

etc. can be mentioned.

Also, J, OrB by P, C, 5chaefer et al.
Chem. , 2,4.6-tris(dibromomethyl)-3-triazine, 2-amino-4
-Methyl-6-dolipromemethyl-S-triazine, 2
-Methoxy-4-methyl-6-trichloromethyl-S-
Triazines and the like can be mentioned.

Furthermore, compounds described in JP-A No. 62-58241, such as C(13 CC13 tlff CC!!2 C13) can be mentioned.

or even M, P,) Iutt, E, F, El
Jour by Slager and Ori, M. Werbel
al of Heterocyclic Chemist
ry volume 7 (iih3), pages 511 et seq. (1970), the following compound group CH3 C1130 or the following compound group can be easily synthesized by those skilled in the art. Group B-68 B-69 or compounds as described in German Patent No. 2641100, for example 4-(4-methoxostyryl)-6-(3,3,3-trichloropropenyl) −
2-pyrone and 4-(3,4,5-trimethoxosetyryl)-6-dolychloromethyl-2-pyrone, or the compounds described in German Patent No. 3333450, for example, or German Patent No. 3021590 For example, the group of compounds described in , or the group of compounds described in German Patent No. 3021599 can be mentioned.

Examples of the aromatic onium salts used in the present invention include compounds shown in Japanese Patent Publication No. 14278/1982 and Japanese Patent Publication No. 14279/1982.

in particular, etc. can be given.

Furthermore, as an aromatic halonium salt,
Examples include the compounds shown in No. 277. Specifically, I can give you the following. Among these, the preferred one is
Compounds of BF, salts, or PF, salts More preferably, BF, salts, or PF, salts of aromatic iodonium salts.

The "organic peroxide" used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule, examples of which include methyl ethyl ketone peroxide, cyclohexanone peroxide,
3,3.5-1-limethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1.1-bis(tert-butylperoxy)-3,3,5-1-limethylcyclohexane, 1.1 -Bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisoprobylhensen hydroperoxide, paramenthane hydroperoxide oxide, 2,5-dimethylhexane-2,5-cybidrobar oxide, 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(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane- 3. Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3゜5.5-)limethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2. 4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di(3- Methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxy acetate, tert-butyl peroxy pivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxy octanoate,
tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxy acetate, di-tert-butyl civa-oxyisophthalate, 2.
5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxide maleic acid, tert-butyl peroxyisopropyl carbonate, 3
．． 3'.

4.4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3.3',4.4'-tetra-(t
-amylperoxycarbonyl)benzophenone, 3.
3',4.4'-tetra(hexyloxycarbonyl)benzophenone, 3.3',4.4'-tetra(t-octylperoxycarbonyl)hensiphenone, 3.3'.

4.4'-tetra(cumylperoxycarbonyl)benzophenone, 3.3',4.4'-tetra(p-isopropylcumylperoxycarbonyl)hensiphenone,
Examples include carbonyl di(t-butyl baroxydihydrogen diphthalate) and carbonyl di(t-hexyl baroxy dihydrogen diphthalate).

Among these, 3.3', 4.4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3.3'
, 4.4'-tetra-(t-amylperoxycarbonyl)benzophenone, 3°3', 4.4'-tetra(t
-hexyloxycarbonyl)benzophenone, 3
．． 3',4゜4'-tetra(t-octylperoxycarbonyl)benzophenone, 3.3',4.4'-tetra(cumylperoxycarbonyl)benzophenone, 3
．． Peroxide esters such as 3',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone and di-t-butylciba-oxyisophthalate are preferred.

-ceremony (However, Ar is one of the following general formulas.

In the compound represented by the above, examples of the alkyl group represented by R1 and R2 include those having 1 to 20 carbon atoms such as methyl, ethyl, and propyl. Examples of the alkylene group formed by combining R1 and R2 include tetramethylene and pentamethylene. R3- in 8r
Examples of the alexyl group for R7 include those having 1 to 4 carbon atoms. In addition, the alkenyl group has 3 to 12 carbon atoms.
I can give you something. Further, as the aryl group for R3-R7, a phenyl group can be mentioned. Furthermore, examples of the alkoxy group include those having 1 to 4 carbon atoms.

In addition, the substituents for the substituted aryl group and substituted alkoxy group of R3-R7 include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. , a halogen atom, a nitro group, etc. Examples of the acyl group for R8 include acetyl, propionyl, and acryloyl. Furthermore, examples of the alkyl group for R9 include those having 1 to 8 carbon atoms, and examples of the alkenyl group for R9 include those having 2 to 8 carbon atoms.

Specific examples of such compounds include: caLt etc.

Among these, preferred are C-1, C-2, C-8 and C-9.

The concentration of these photopolymerization initiator systems in the composition of the invention is usually small. In addition, if the amount is inappropriately high, undesirable results such as blocking of effective light rays will occur. The amount of the photopolymerization initiator system in the present invention is from 0.01% to 60% based on the total of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer added as necessary. It is preferable to use within the range. More preferably from 1% to 3
Good results are obtained with 0%. Furthermore, the weight ratio of component (A):component (B):component (C) used in the present invention is 1:0.0.
01-10:0.001-10 is suitable, preferably 1:0.005-5:0.005-5, most preferably 1:0.01-3:0.01-3. . In addition, when component (B) is used in the embodiment (ii), the weight ratio of the pigment of component (■) to the boron compound of component (2) is 1:0.05 to 1.
00 is suitable, preferably 1:0.1-10, most preferably 1:0.2-5.

Furthermore, in the photopolymerizable composition of the present invention, the ability to initiate photopolymerization can be further increased by using various organic amine compounds in combination, if necessary.

Examples of these organic amine compounds include triethanolamine, dimethylamine, jetanolaniline, p-dimethylaminobenzoic acid ethyl ester, and Michler's ketone.

The amount of organic amine compound added is 50% of the total amount of photopolymerization initiator.
% to about 200% is preferable.

Furthermore, N-phenylglycine, 2-mercaptobenzothiazole, N
The ability to initiate photopolymerization can be further enhanced by adding a hydrogen-donating compound such as N-dialkylbenzoic acid alkyl ester.

Such a hydrogen donating compound is preferably added in an amount of 1 to 30% based on the total weight of the photopolymerizable composition of the present invention.

As the "linear organic polymer" that can be used in the present invention, any linear organic polymer can be used as long as it is naturally compatible with photopolymerizable ethylenically unsaturated compounds. You may use . Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water should be selected so that it can be developed in water or weakly alkaline water. The linear organic high molecular weight polymer is used not only as a film forming agent of the composition, but also water, a weak alkaline aqueous solution, and an organic solvent developer depending on the purpose.

For example, water development becomes possible when a water-soluble organic high molecular weight polymer is used. As such linear organic polymers,
Addition polymers having carboxylic acid in the side chain, such as JP-A-5
9-44615, JP 54-34327, JP 58-12577, JP 54-25957, JP 54-92723, JP 59-53836, JP 59-71048 Those listed include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like.

Similarly, there are acidic cellulose derivatives having carboxylic acid in their side chains. In addition to these, addition polymers having hydroxyl groups to which a cyclic acid anhydride is added are useful. In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as required] copolymer and [allyl (meth)acrylate/(
A copolymer of meth)acrylic acid/other addition-polymerizable vinyl monomer if necessary is suitable. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide.

In addition, to increase the strength of the cured film, alcohol-soluble nylon and 2,2-bis-(4-hydroxyphenyl)-
Also useful are polyethers of propane and shrimp chlorohydrin. Any amount of these linear organic high molecular weight polymers can be mixed into the entire composition. However, if it exceeds 90% by weight, favorable results will not be obtained in terms of the strength of the formed image. Preferably it is 30-85%. Further, the weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer is preferably in the range of 1/9 to 7/3. A more preferable range is 3/7 to 515.

In addition to the above-mentioned basic ingredients, in the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds during the production or storage of the photosensitive composition. It is desirable to do so. Suitable thermal polymerization inhibitors include noihydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, 1-butylcatechol, benzoquinone, 4.4'-
Thiobis(3-methyl-6-t-butylphenol),
2.2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N
- Nitrosophenylhydroxyamine cerous salt, etc. The amount of the thermal polymerization inhibitor added is preferably about 0.01% to 1% to about 5% by weight of the total composition. Further, if necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added and floated on the surface of the photosensitive layer in order to prevent polymerization inhibition by oxygen. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.Furthermore, dyes or pigments may be added for the purpose of coloring the photosensitive layer. The amount of dyes and pigments 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 applying the photopolymerizable composition of the present invention onto a support, it can be used after being dissolved in various organic solvents.

The solvents used here include 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 motsubutyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol motsubutyl ether acetate, 3-methoxypropanol , methoxymethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide , γ-butyrolactone, methyl lactate, ethyl lactate, etc. These solvents can be used alone or in combination. The appropriate solid content in the coating solution is 2 to 50% by weight.

The coating amount is about 0.1 g/r+ (~about 1
A range of 0 g/m is suitable. More preferably 0.5~
5 g/m.

As the support, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.) laminated materials, aluminum (including aluminum alloys), zinc, steel, etc. Further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose i'flElf acid, cellulose nitrate,
Examples include plastic films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and plastic films laminated or vapor-deposited with the above metals. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. In addition, the special public
8-18327 on a polyethylene terephthalate film, as described in No. 8-18327. Also preferred are composite sheets in which the sheets are bonded together.

In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably.

Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Patent Publication No. 47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The above anodizing treatment can be carried out using an electrolytic solution, for example, of an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. This is carried out by passing an electric current through the aluminum plate as an anode.

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-586
Also useful is a surface treatment that combines a support coated with electrolytic grains with the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in No. 02 and JP-A-52-30503.

Also suitable are those which have been subjected to mechanical roughening, chemical etching, electrolytic graining, anodic oxidation, and sodium silicate treatment in this order as disclosed in JP-A No. 56-28893.

Furthermore, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in their side chains, polyacrylic acid, water-soluble metal salts (e.g. zinc borate), or Undercoating with yellow dye, amine salt, etc. is also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. It is done for the ring.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, particularly polyvinyl alcohol with a degree of saponification of 99% or more, acidic cellulose, etc., is added to prevent the polymerization inhibiting effect caused by oxygen in the air. A protective layer made of a polymer with excellent oxygen barrier properties such as .

A method for applying such a protective layer is described in detail in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.

Furthermore, the photopolymerizable composition of the present invention can be used in ordinary photopolymerization reactions. Furthermore, it can be applied in many ways, such as as a photoresist in the production of printing plates, printed circuit boards, and the like. In particular, the photopolymerizable composition of the present invention has high sensitivity and a wide range of spectral sensitivity characteristics up to the visible light region, so that good effects can be obtained when applied to photosensitive materials for visible light lasers such as Ar'' lasers.

A photosensitive material using the photopolymerizable composition of the present invention is imagewise exposed, and unexposed areas of the photosensitive layer are removed with a developer to obtain an image. Preferred developing solutions when using these photopolymerizable compositions as lithographic printing plates include those described in Japanese Patent Publication No. 57-7427, which contain sodium silicate, potassium silicate, Inorganic alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, sodium diphosphate, ammonium triphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. Aqueous solutions of organic alkaline agents such as monoethanolamine or jetanolamine are suitable. The concentration of the alkaline solution is 0.1-10% by weight, preferably 0.5-. It is added in an amount of 5% by weight.

In addition, the alkaline aqueous solution may contain a surfactant, benzyl alcohol, 2-phenoxyethanol, 2
- Small amounts of organic solvents such as butoxetanol may be included. For example, those described in US Pat. No. 3,375,171 and US Pat. No. 3,615,480 can be mentioned.

Furthermore, JP-A-50-26601 and JP-A-58-54341
The developing solutions described in Japanese Patent Publication No. 56-39464 and Japanese Patent Publication No. 56-42860 are also excellent.

〔Effect of the invention〕

The photopolymerizable composition of the present invention has high sensitivity to active light in a wide range from ultraviolet light to visible light.

Therefore, light sources include ultra-high pressure, high pressure, medium pressure, and 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.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 9, Comparative Examples 1 to 5 An aluminum plate with a thickness of 0.30 m was used with a nylon brush.
The surface was gritted using a water suspension of 00 mesh pumice stone, and then thoroughly washed with water. After etching by immersing in 10% sodium hydroxide at 70° C. for 60 seconds, washing with running water, neutralizing with 20% nitric acid, and then washing with water. This was subjected to electrolytic surface roughening treatment using an alternating sinusoidal waveform current under the condition of ■^ = 12.7 V in a 1-% nitric acid aqueous solution with an anode special electricity amount of 160 coron/dm''. .

When the surface roughness was measured, it was 0.6μ (Ra display)
It was then immersed in a 30% aqueous sulfuric acid solution.
After desmutting at 5°C for 2 minutes, in a 20% sulfuric acid aqueous solution,
At a current density of 2 A/dm, the thickness of the anodized film is 2
．． It was anodized for 2 minutes to give a weight of 7 g/rd.

On the thus treated aluminum plate, a photosensitive composition having the following composition was coated so that the dry coating weight was 1.4 g/d, and dried at 80° C. for 2 minutes to form a photosensitive layer.

Trimethylolpropane tri(acryloyloxypropyl)ethyl 2.0g Allyl methacrylate/methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0g Photopolymerization initiator Xg Fluorine tea-based nonionic surfactant 0.03 g methyl ethyl ketone
20 g Propylene glycol monomethyl ether acetate 20 g A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification 86.5-89 mol%, degree of polymerization 1000) was applied onto this photosensitive layer so that the dry coating weight was 2 g/rd. 100℃
/ Dry for 2 minutes.

The photosensitivity test used monochromatic light of visible light and Ar'' laser light (wavelength = 488011).For visible light, a tungsten lamp was used as the light source, and a Kenko optical filter (Keiko) was used as the light source.
nko optical filter) B P
-49. Photosensitivity measurements were carried out using a Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet with a transmission optical density of 0.05 at the first stage and increasing successively by 0.15 up to 15 stages).

It is indicated by the number of clear steps of the PS step guide when exposed for 120 seconds at an illuminance of 25 LUX on the surface of the photosensitive material film.

The laser beam is Ar” laser (Refcell model 95
-3) single line with a wavelength of 488 nm and a beam diameter of 2
Scanning was performed by changing the intensity of the Ar'' laser used at 5μ (ND filter was used).

The line width obtained after development was measured, and the intensity of the Ar'' laser when a line width of 25 μm was reproduced was defined as the sensitivity.

Development was performed by immersing the film in the following developer at 25° C. for 1 minute.

Table 1 shows the sensitivity results when the photopolymerization initiator was changed.

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---Ken Challenge Examples 10 to 15 On the photosensitive layer, instead of the above protective layer, saponification degree of 99.3
~99.9%, using polyvinyl alcohol with a degree of polymerization of 1000, and further adding 1.4 parts by weight of fluorosurfactant W1104 to 100 parts by weight of this polyvinyl alcohol.
Photosensitive lithographic printing plates obtained in the same manner as in Example 1, 8, and 9 were subjected to photosensitivity measurements in the same manner as in Example 1, except that 1.8.9 (manufactured by Asahi Glass ■) was used. The results are shown in Table 2.

Table 2 Example 10 Same as Example 4 12.6 0.3
0 Example 11 Same as Example 5 13.2 0.
25 Example 12 Same as Example 6 13.0 0
．． 27 Example 13 Same as Example 7 10.2
0.72 Example 14 Same as Example 8 10.4
0.65 Example 15 Same as Example 9 10.4
0.65 Procedural Supplementary Amendment Commissioner Yoshi 1) Mr. Moon Tsuyoshi■, Indication of the case Patent Application No. 129647 of 1988
No. 2, Title of the invention Photopolymerizable composition 3, Relationship with the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Initiator 6, Subject of amendment Details Detailed description of the invention in the book (1) Replace “D-wa” in the first line of page 17 of the specification with rD
-ha” and correct it.

(2) Structural formula-13 on page 27 of the same book is corrected as follows.

Claims (1)

[Scope of Claims] A polymerizable compound having at least one ethylenically unsaturated bond that can be photopolymerized by actinic rays, a photopolymerization initiator, and optionally a linear organic polymer. A photopolymerizable composition comprising: the photopolymerization initiator containing at least three compounds selected from Group A, Group B, and Group C below. (A) (i) an organic boron compound anion salt of at least one organic cationic dye; or (ii) a combination of at least one organic cationic dye and an organic boron compound anion salt; (B) (i) having a carbon-halogen bond; Compound (ii) At least one type of aromatic onium salt or aromatic halonium salt (iii) Organic peroxide (C) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, Ar is the following It represents an aromatic group selected from one of the general formulas, R^1 and R^2 represent a hydrogen atom or an alkyl group, and R^1 and R^2 combine with each other to represent an alkylene group. ) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^3 to R^7 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, Hydroxyl group, alkoxy group, substituted alkoxy group, -S-R^9 group, -SO-R^9 group, or -
SO_2R^9 group, provided that at least one of R^3 to R^7 groups represents -S-R^9 group, -SO-R^9 group, or -SO_2R^9 group, and R^9 is The alkyl group, alkenyl group, and R^8 represent a hydrogen atom, an alkyl group, or an acyl group. Y^1 represents a hydrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.