JPS5928325B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable composition, and more particularly to a photopolymerizable composition characterized by a photopolymerization initiator.

This invention relates to a polymerizable composition. Conventionally, unsaturated compounds that can be cured by radiation irradiation have been used as components of compositions such as paints, printing inks, and adhesives, and such compositions have been exposed to electromagnetic waves such as visible light, ultraviolet rays, and X-rays, electron beams, neutron beams, and
It is widely known that when a particle beam such as a beam is applied, the above-mentioned compound in the composition polymerizes and hardens, and when such an action is performed in the presence of a polymerization initiator composition, the polymerization rate increases significantly. It is being

These techniques are described in, for example, U.S. Pat. No. 35,512.
No. 35, No. 3551246, No. 3551311 and No. 3558387, Perky National Patent No. 808
No. 179 and JP-A-49-110781, these techniques provide excellent flexibility, chemical resistance, abrasion resistance, gloss, adhesion, color, etc. However, on the other hand, the curing sensitivity of the composition is low, so it takes a long time to expose the image during image formation, so in the case of detailed images, slight vibration during operation may affect the quality of the image. images cannot be reproduced, and the amount of energy radiated by the exposure light source or particle beam source must be increased, resulting in the dissipation of a large amount of heat. There were problems such as deformation and deterioration of the material. On the other hand, many of these sensitizers absorb ultraviolet light, so they do not change color even when photoreacted, and they have drawbacks such as the exposure pattern cannot be recognized until development.

The present inventors have conducted extensive research to solve the above-mentioned problems by increasing the sensitivity of photopolymerizable compositions. The present invention was achieved by discovering that the photopolymerization rate of a polymerizable compound having a saturated double bond can be significantly increased, and a photodecoloring reaction or a photofading reaction of a photopolymerization initiator can occur.

゜The object of the present invention is to prepare a photopolymerizable composition (
The object of the present invention is to provide a highly sensitive photopolymerization initiator and a photopolymerization initiator system for use in so-called photosensitive resins or photoresists (a type of photoresist).

Another object of the present invention is to provide a photoinitiator and a photoinitiator system that impart color fading or photofading properties to photopolymerizable compositions.

Still another object of the present invention is to provide a photoinitiator and a photoinitiator system that form a discernible visible latent image in a photosensitive material using a photopolymerizable composition.

Yet another object of the present invention is to provide photoinitiators and photoinitiator systems that generally increase the rate of photopolymerization of photopolymerizable compositions containing polymerizable compounds having ethylenically unsaturated double bonds. That's true.

Further objects of the invention will become apparent from the description below.

The present invention relates to a polymerizable compound having one or more ethylenically unsaturated double bonds in one molecule (hereinafter simply referred to as an ethylenic compound).

The ethylenic compound is a general term that generally includes monomers, dimers, trimers, etc., and up to oligomers. ) and at least one photopolymerization initiator as an essential component, (1) the photopolymerization initiator is p-dimethylaminostyryl styryl ketone represented by the following structural formula (1). and (2) a photopolymerization initiator which is at least one of the following.
At least one p1-dimethylaminostyryl styryl ketone represented by the following structural formula (1), and 5 secondary and tertiary amine compounds represented by the following general formula (2) (hereinafter simply referred to as amine compounds); The photopolymerizable composition is a combination of at least one polyamine compound. In the above formula, X represents a substituent having a Hammett's σ value in the range of -0.9 to +0.7.

In the above formula, Rl, R2 and R3 are an alkyl group, an aryl group, an aralkyl group, a substituted alkyl group, an alkoxy group or an aryloxy group Rl, R2 and R3, respectively.
may be the same or different.

In addition, in this specification, the definition of Hammett's σ value is in accordance with "Organic Reaction Kinetics" by J.E. Leffler, translated by Yuho Tsuno (Tokyo, Hirokawa Shoten, published in 1968). . The present invention will be explained in detail below.

The polymerizable compound having an ethylenically unsaturated double bond (ethylenic compound) in the photopolymerizable composition of the present invention is a compound having at least one ethylenically unsaturated double bond in its chemical structure. monomers, prepolymers, i.e. dimers, trimers and other oligomers;
They have chemical forms such as mixtures thereof and copolymers thereof.

Examples thereof include unsaturated carboxylic acids and their salts, esters with aliphatic polyhydric polyol compounds, and the like. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, tarotonic acid, isocrotonic acid,
There is maleic acid.

Salts of unsaturated carboxylic acids include the sodium and potassium salts of the aforementioned acids. Examples of the aliphatic polyol compounds mentioned above include ethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, neopentyl glycol, 1,10-decanediol, trimethylolethane, trimethylolpropane, and 1,2-butanediol. , 1,3-butanediol, propylene glycol, pentaerythritol,
dipentaerythritol, tripentaerythritol,
Other multimeric pentaerythritol, sorbitol, d-
These include mannitol and dihydroxymaleic acid.

Specific examples of esters of aliphatic polyhydric polyol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol triacrylate, diacrylic acid 1,
3-butanediol ester, tetramethylene glycol diacrylate ester, propylene glycol diacrylate ester, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate ester ,
Tetraethylene glycol diacrylate ester, pentaerythritol diacrylate ester, pentaerythritol triacrylate ester, pentaerythritol tetraacrylate ester, dipentaerythritol diacrylate ester, dipentaerythritol triatalylate ester, dipentaerythritol tetraacrylate ester, pentaerythritol diacrylate ester dipentaerythritol nyster acrylate, dipentaerythritol hexaacrylate ester, tripentaerythritol octaacrylate ester, dipentaerythritol tetraacrylate ester, dipentaerythritol pentaacrylate ester, dipentaerythritol hexaacrylate ester, octaacrylic acid Examples include tripentaerythritol ester, triacrylic acid sorbitol ester, tetraacrylic acid sorbitol ester, pentaacrylic acid sorbitol ester, hexaacrylic acid sorbitol ester, and polyester acrylate oligomer.
As the methacrylic acid ester, dimethacrylic acid tetramethylene glycol ester, dimethacrylic acid triethylene glycol ester, dimethacrylic acid pentaerythritol ester, trimethacrylic acid pentaerythritol ester, dimethacrylic acid dipentaerythritol ester, dimethacrylic acid pentaerythritol ester, Pentaerythritol trimethacrylate ester, dipentaerythritol dimethacrylate ester, dipentaerythritol tetramethacrylate ester, tripentaerythritol octamethacrylate ester, ethylene glycol dimethacrylate ester, dimethacrylic acid 1,3-butanediol ester, Examples include tetramethylene glycol methacrylate ester and sorbitol tetramethacrylate ester. Itaconic acid esters include diitaconic acid ethylene glycol ester, diitaconic acid propylene glycol ester, diitaconic acid 1,3-butanediol ester, diitaconic acid 1,4
-butanediol ester, diitaconate tetramethylene glycol ester, diitaconate pentaerythritol ester, triitaconate dipentaerythritol ester, pentitaconate dipentaerythritol ester, hexitaconate dipentaerythritol ester, tetraitaconate sorbitol ester, and the like. Examples of crotonate esters include cyclotonate ethylene glycol ester, cyclotonate propylene glycol ester, cyclotonate tetramethylene glycol ester, cyclotonate pentaerythritol ester, and tetracrotonate sorbitol ester. Isocrotonic acid esters include diisocrotonic acid ethylene glycol ester, diisocrotonic acid pentaerythritol ester, tetraisocrotonic acid sorbitol ester, and the like. Examples of maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate ester, and sorbitol tetramaleate. Other examples include modified diacrylic acid tetramethylene glycol ester, modified triacrylic acid trimethylolpropane ester, modified triacrylic acid pentanyritritol ester, and methacrylated epoxy resin. Furthermore, mixtures of the aforementioned esters may also be mentioned. Next, the photopolymerization initiator and photopolymerization initiator system, which are significant features in the photopolymerizable composition of the present invention, will be explained.

p-dimethylaminostyryl styryl ketones (hereinafter referred to as component 5) represented by the above-mentioned structural formula (1) are p-dimethylaminostyryl styryl ketones (hereinafter referred to as component 5), which are obtained by a Perkin reaction from p-dimethylaminobenzaldehyde and acetone.
- Compounds obtained by a condensation reaction (Perkin reaction) between dimethylaminobenzalacetone and substituted benzaldehyde, etc., and are specifically described in "Ann J Vol. 441, pp. 228-265 (1925). P.Pf of
eifferlO. The method of Angen et al.
in. khim. ZhurJ Vol. 21, No. 619-62
B. as described on page 4 (1955). N. Dashkevi
ch and 1. V. SmOlanka's method, and '
Nauch. Zapiski. IJzhgrOd. I.J.
nivJ Vol. 18, pp. 15-19 (1957). V. It can be synthesized by Smedanka's method or the like. p- represented by structural formula (1)
Dimethylaminostyryl Styryl Examples of substituents , phenyl group, trifluoromethyl group, cyano group, acetyl group, ethoxycarbonyl group, carboxyl group, carbo
e xylate group (-COO), amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, acetylamino group, -PO3H group, methoxy group, ethoxy group, propoxy group, isopropoxy group,
Butoxy group, pentyloxy group, phenoxy group, hydroxyl group, acetoxy group, methylthio group, ethylthio group, isopropylthio group, mercapto group, acetylthio group, thiocyano group (-SCN), methylsulfinyl group,
Ethylsulfinyl group, methylsulfonyl group, ethylsulfonyl group, agnosulfonyl group, dimethylsulfonio group ▲(CH3)2), ? Rufuonato group (-S
O3), fluorine atom, chlorine atom, bromine atom, iodine atom, iodyl group, trimethylsilyl group (-Si(CH3)3)
, triethylsilyl group, trimethylstannyl group (-Sn
(CH3)3) can be mentioned.

Among these substituents, preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a dimethylamino group, a diethylamino group, a chlorine atom, a bromine atom, a nitro group, and a cyano group. Specific examples of the compound represented by structural formula (1) include p-dimethylaminostyryl, p-cyanostyryl ketone, and p-dimethylaminostyryl.
p-chlorostyryl ketone, p-dimethylamino m
-chlorostyryl ketone, p-dimethylaminostyryl p-bromostyryl ketone, p-dimethylaminostyryl styryl ketone, p-dimethylaminostyryl p-methylstyryl ketone, p-dimethylaminostyryl m-ethylstyryl ketone, p-dimethylamino styryl p-methoxystyryl ketone, p-
Examples include dimethylaminostyryl m-ethoxystyryl ketone and bis(p-dimethylaminostyryl) ketone.

Examples of Rl, R2 and R3 in the above general formula () are shown below.

First, examples of alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms, and specific examples include methyl, ethyl, propyl, butyl, and pentyl. group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group,
Octadecyl group, isopropyl group, isobutyl group, isopentyl group, isohexyl group, Sec-butyl group, neopentyl group, tert-butyl group, tert-pentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-norbornyl group. I can do it. Among these, straight lines with 1 to 10 carbon atoms,
Branched and cyclic alkyl groups are preferred. Aryl groups include residues of one benzene ring, residues of two and three fused benzene rings, residues of two benzene ring aggregates, and fused systems of a benzene ring and a five-membered unsaturated ring. and halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group,
Amino group, substituted amino group (monoalkyl substituted amino group (
Examples of alkyl groups. Methyl group, ethyl group, propyl group,
pentyl group, isopropyl group, Sec-butyl group, isopentyl group), dialkylamino group (examples of alkyl groups are the same as the examples of monoalkyl-substituted amines), monoacylamino groups (examples of acyl groups, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group), cyano group, alkyl group (linear, branched and cyclic alkyl group having from 1 to 18 carbon atoms, preferably 1 carbon atom) straight, branched and cyclic alkyl groups from trifluoromethyl group), alkoxyl group (examples of alkyl group, methyl group, ethyl group, butyl group, pentyl group, isopropyl group, isopentyl group, 2-methylbutyl group, Sec-butyl group), aryloxy group (aryl group) Example 6 phenyl group, 1-naphthyl group, 2-naphthyl group), alkoxycarbonyl group (examples of alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group), acyloxy group (examples of acyl group are mono (same as the example of acylamino group), alkoxysulfonyl group (example of alkyl group is the same as the example of alkyl group of alkoxyl group), etc. Substituted with the same substituent or two or more substituents or mutually different substituents I can list the residues. Specific examples of these aryl groups include phenyl group, chlorophenyl group, nitrophenyl group, aminophenyl group (
Methylamino) phenyl group, (ethylamino) phenyl group, (dimethylamino) phenyl group, acetylaminophenyl group, tolyl group, ethyl phenyl group, (chloromethyl) phenyl group, acetylphenyl group, phenoxy phenyl group, Methoxycarbonylphenyl group, ethoxycarbonylphenyl group, acetoxyphenyl group, methoxysulfonylphenyl group, naphthyl group, 2-amino-1-naphthyl group, 1-dimethylamino-2-naphthyl group, chloronaphthyl group, methylnaphthyl group Examples include anthryl group, phenanthryl group, indenyl group, biphenylyl group, chlorobiphenylyl group, aminobiphenylyl group, methylbiphenylyl group, and acenaphthenyl group. Among these, a residue of one benzene ring and a residue substituted with one or more of the above-mentioned substituents, which are the same or different from each other, are preferred. Examples of the aralkyl group include residues in which a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, is substituted with a phenyl group or a naphthyl group. Examples include benzyl group, phenethyl group, 3-phenylpropyl group, 3-phenylhexyl group, 10-phenyldecyl group, and 4-phenylcyclohexyl group.

Substituted alkyl groups include halogen atoms (fluorine,
chlorine, bromine, iodine) and hydroxyl groups, while alkyl groups have 1 to 18 carbon atoms.
and preferably likewise 1 to 10 straight, branched and cyclic alkyl groups.

Specific examples include chloromethyl group, bromomethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, 2-chloropentyl group, 1-(chloromethyl)propyl group, 10-bromodecyl group, 18- Methyl octadecyl group, chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxybutyl group, 5
-hydroxypentyl group, 10-hydroxydecyl group,
Examples include 2-hydroxyoctadecyl group, 2-(hydroxymethyl)ethyl group, hydroxycyclohexyl group, and 3-hydroxy-2-norbornyl group. Examples of the alkoxyl group include alkoxyl groups having linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, decyloxy group, isofukomaboxy group, Sec-butoxy group, tert-butoxy group, isopentyloxy group, cyclohexyloxy group, 2
-Norbornyloxy group can be mentioned. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and a biphenylyloxy group. General formula ()
Specific examples of amines represented by are trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, tris(decyl)amine, methyldiethylamine, ethyldibutylamine,
Dimethyldecylamine, dimethylcyclohexylamine, diethylcyclohexylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, N
-benzyl-N-methylaniline, N-benzyl-N-
Ethylaniline, N-benzyl-N-propylaniline, N-phenethyl-N-methylaniline, N-phenethyl-N-ethylaniline, N,N-diphenylaniline, N,N-dibenzylaniline, triphenylamine,
tribenzylamine, nitrilotrimethanol, 2,2
',2〃-nitrilotriethanol (or triethanolamine), 1,1',l''-nitrilotripropanol, 2,2',2''-nitrilotripropal, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentyl Amine, didecylamine, methylethylamine, ethylbutylamine, methylcyclohexylamine, ethylcyclohexylamine, N-methylaniline, N-ethylaniline, N-butylaniline,
Examples include N-benzylaniline, N-phenethylaniline, diphenylamine, dibenzylamine, diphenethylamine, bis(hydroxymethyl)amine, diethanolamine, and bis(3-hydroxypropyl)amine.

Specific examples of polyamine compounds include methylene diamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, propylene diamine, butylene diamine, 1,4-cyclohexanediamene, and funilene diamine. Examples include amine, (2-aminomethylbutyl)amine, triethylenetetramine, and hexamethylenetetramine.

Among the amine compounds mentioned above, triethanolamine, N-methyl-N-benzylaniline, N-ethyl-
N-benzylaniline and N-propyl-N-benzylaniline are preferred.

Only one type of the above-mentioned amine compounds may be used, but two or more types can also be used in combination.

The amount of the photopolymerization initiator contained in the photopolymerizable composition of the present invention is such that even when the photopolymerization initiator consists only of component 8, component 3 and the above-mentioned amine compounds (hereinafter referred to as component 5). ), the weight ratio of the tyrenic compound (monomer) to the photopolymerization initiator is from about 5:1 to about 100.
A wide range is possible, up to 0:1, preferably from about 10:1 to about 100:1. When the photopolymerization initiator consists of component 3 and component O, the
The four component weight ratio of 3:5 ranges from about 30:1 to about 1:30, preferably from about 10:l to 1:10. The photopolymerizable composition of the present invention containing the above-mentioned ethylenic compound (monomer) and photopolymerization initiator further contains a known binder, thermal polymerization inhibitor, plasticizer,
Additives such as colorants and surface smoothing agents may be included as necessary.

In particular, a photosensitive material for performing peeling development as described below,
Alternatively, for the purpose of forming a resist (thick) image on a photosensitive material, such as a photosensitive material for liquid development, a film-forming polymeric substance (binder) can be used in combination.

Any organic polymer can be used as long as it is compatible with the compound having a polymerizable ethylenically unsaturated double bond, but it is preferable to use peel development, water development, or weak alkaline water development. A high molecular weight polymer should be selected that enables the following. The organic polymer is used not only as a film-forming agent in the composition, but also in accordance with the type of water, weak alkaline water, or organic solvent used as a developer, and one selected to have affinity therewith. For example, water development becomes possible when a water-soluble organic polymer is used. Examples of such organic polymers include addition polymers having carboxyl groups in side chains, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, partially esterified maleic acid copolymers, and maleic acid copolymers. These include acid copolymers, crotonic acid copolymers, and the like, as well as acidic cellulose derivatives having carboxyl groups in their side chains. Other useful addition polymers having hydroxyl groups include those to which cyclic acid anhydrides have been added. Other useful water-soluble organic polymers include polyvinylpyrrolidone and polyethylene oxide. Alcohol-soluble nylon and polyether of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin are also useful in order to increase the strength of the film in the cured portion after exposure. These organic high molecular weight polymers can be mixed in any amount in the entire composition, but if it exceeds 90% by weight, it will not give favorable results in terms of the strength of the image formed. In addition, the linear organic polymer used for peel development is chlorinated polyethylene,
Chlorinated polyolefins such as chlorinated polypropylene, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, polyacrylic acid alkyl esters (alkyl groups include methyl, ethyl, butyl groups, etc.), acrylic acid alkyl esters (alkyl groups) ) and at least one monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, copolymer of vinyl chloride and acrylonitrile, polyvinylidene chloride, vinylidene chloride and acrylonitrile copolymers of, polyvinyl acetate, copolymers of vinyl acetate and vinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene, polyvinyl alkyl ethers (Alkyl groups include methyl group, ethyl group, isopropyl group, butyl group, etc.), polymethyl vinyl ketone, polyethyl vinyl ketone, polyethylene, polypropylene, polybutyne, polystyrene, poly-alpha-methylstyrene, polyamide (6-nylon , 6,6-nylon, etc.), poly-1,3-butadiene, polyisobrene, polyurethane, polyethylene terephthalate, polyethylene isophthalate, chlorinated rubber, polychloroprene, cyclized rubber, ethyl cellulose, acetyl cellulose, polyvinyl butyral, polyvinyl formal, styrene - Homopolymers or copolymers such as butadiene rubber and poly(chlorosulfonated ethylene). In the case of copolymers,
The content ratio of the component monomers can take a wide range of values, but in general, a small amount of monomer components is 10% or more in molar ratio.
% or less is preferable. Further, thermoplastic polymeric substances other than these can also be used in the present invention as long as they satisfy the above conditions. Among the above polymers, those suitable for use with the photopolymerizable composition of the present invention include chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride monovinylidene chloride copolymer (vinyl chloride molar content of 20-80%), vinylidene chloride-acrylonitrile copolymer (molar content of acrylonitrile 1
0-30%), vinyl chloride-acrylonitrile copolymer (molar content of acrylonitrile 10-30%), polystyrene, polyvinyl butyral, polyvinyl acetate, polyvinyl formal, ethyl cellulose, acetyl cellulose, vinyl chloride monovinyl acetate copolymer These include polychloroprene, polyisoprene, chlorinated rubber, and poly(chlorosulfonated ethylene).

These polymers may be used alone, but two or more types of polymers may be mixed in an appropriate ratio to avoid demixing during the manufacturing process from preparing the coating solution to coating and drying. Can be used.

Specific examples of thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di -t-butyl-
Examples include p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, and organic acid copper (such as copper acetate). These thermal polymerization inhibitors include the aforementioned compound 1 having an ethylenically unsaturated double bond.
The content is preferably from 0.001 parts by weight to 5 parts by weight per 00 parts by weight. A thermal polymerization inhibitor can be included for the purpose of improving the stability of the composition of the present invention over time before exposure. Examples of colorants include pigments such as titanium oxide, carbon black, iron oxide, phthalocyanine pigments, and azo pigments, and dyes such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, and anthraquinone dyes. However, it is preferable that the coloring agent used does not absorb light at the absorption wavelength of the photopolymerization initiator.

Such a coloring agent is used in an amount of 0.1 to 30 parts by weight in the case of a pigment, and 0.1 to 30 parts by weight in the case of a dye, based on 100 parts by weight of the total amount of the binder and the compound having an ethylenically unsaturated double bond.
The content is preferably in the range of 0.1 to 10 parts by weight, preferably 0.1 to 3 parts by weight. When the above-mentioned colorant is contained, it is preferable to use dichloromethyl stearate and other chlorinated fatty acids as auxiliary substances for the colorant, and the amount thereof is 0.005 parts by weight per 1 part by weight of the colorant. % to 0.5 part by weight. However, if a plasticizer is included in the photopolymerizable composition, no colorant auxiliary substance is necessary. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, synchhexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate, and dimethyl glycol. Glycol esters such as phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, triethylene glycol dicaprylate,
Phosphate esters such as tricresyl phosphate and triphenyl phosphate, aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, diotyl azelate, and dibutyl maleate, citric acid Examples include triethyl, glycerin triacetyl ester, and butyl laurate. Surface smoothing agents include lanolin, paraffin wax and natural wax.

The above-mentioned various modifiers, which can be contained in the composition of the present invention if necessary, can be used in an amount of up to 3% by weight, preferably up to 1% by weight, based on the total weight of the photopolymerizable composition. can.

The photopolymerizable composition of the present invention is dissolved in a solvent to form a coating photopolymerizable composition solution, which is coated onto a support by a known method, the solvent is removed, and used as a photopolymerizable photosensitive material. This is the most common way to use the photopolymerizable composition of the present invention.

Examples of solvents include acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc., esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate, ethyl benzoate, etc., such as toluene, xylene, benzene,
Aromatic hydrocarbons such as ethylbenzene, carbon tetrachloride, trichlorethylene, chloroform, 1,1,
Examples include halogenated hydrocarbons such as 1-trichloroethane, monochlorobenzene, chlornaphthalene, etc., ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, dimethylformamide, dimethyl sulfoxide, and the like.

Supports for applying the photopolymerizable compositions of the invention in suitable form (eg, solutions as described above) include planar materials or other shaped materials that do not undergo significant dimensional changes.

Examples of planar materials include glass, silicon oxide, ceramics, paper, metals such as aluminum, zinc, magnesium, copper, iron, chromium, nickel, silver, gold, platinum,
Alloys mainly composed of palladium, aluminum, alloys mainly composed of zinc, alloys mainly composed of magnesium,
copper-zinc gold, iron-nickel-chromium alloy, copper-based alloy, metal compounds such as aluminum oxide, tin oxide (SnO2), indium oxide (In2O3), polymers such as regenerated cellulose, cellulose nitrate, Cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polystyrene, polyethylene terephthalate, polyethylene isoptalade, polycarbonate of bisphenol A, polyethylene, polypropylene, nylon (6- Nylon, 6,6-nylon, 6
, 10-nylon, etc.), polyvinyl chloride, vinyl chloride monovinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride monovinylidene chloride copolymer, polyacrylonitrile, polymethyl acrylate, polymethyl methacrylate can be given. In addition, two or more thin plates of the above-mentioned materials are laminated firmly, such as cermet, iron-aluminum laminate, iron-copper aluminum laminate, iron-chromium-copper laminate, paper coated with polyethylene on the surface, Paper coated with cellulose triacetate on the surface, aluminum plate whose surface is anodized to form an aluminum oxide layer, chromium plate whose surface is coated with a chromium oxide layer using a known method, and a layer of tin oxide. A glass plate provided on the surface or a silicon oxide plate provided with an indium oxide layer on the surface can also be used as the support. These supports are selected from transparent or opaque depending on the purpose of the photosensitive image forming material.

When it is transparent, it is not only colorless and transparent, but also J. SMP
As described in TEL Vol. 67, p. 296 (1958), dyes or pigments may be added to make the material colored and transparent. In the case of opaque supports, in addition to those that are inherently opaque such as paper and metal, there are also transparent materials with pigments such as dyes and titanium oxide added to them;
It is also possible to use plastic film treated with the method described in Japanese Patent No. 9068, paper, plastic film, etc. that has been made completely light-shielding by adding carbon black or the like. It is also possible to use a support whose surface has been provided with fine depressions by graining, electrolytic etching, anodic oxidation, chemical etching, etc., and a support whose surface has been pretreated by corona discharge, ultraviolet irradiation, flame treatment, etc. .
Furthermore, it is also possible to use a plastic support in which reinforcing agents such as glass fibers, carbon fibers, boron fibers, various metal fibers, metal whiskers, etc. are mixed to increase the strength.
The support may be provided with other coating layers, an antihalation layer, an ultraviolet absorbing layer, or a visible light absorbing layer on its surface, if necessary, to facilitate bonding.

Furthermore, in order to prevent the composition of the present invention from decreasing sensitivity due to oxygen, exposure is carried out using a vacuum printing frame as described in U.S. Pat. No. 3,060,026. A cover may be provided, or a coating layer with low oxygen permeability may be provided on the photosensitive layer as described in Japanese Patent Publication No. 40-17828.

Factors that determine the rate at which the photopolymerizable silk composition of the present invention photopolymerizes, hardens, and dries include the properties of the support, especially its surface;
The specific components in the composition, the content of the photopolymerization initiator in the total photopolymerizable composition, the thickness of the layer of the photopolymerizable composition, the nature of the light source (
characteristics of the irradiation spectrum), intensity, presence or absence of oxygen, and ambient temperature. The light irradiation may be performed using any one of various methods or a combination thereof.
For example, the composition may be exposed to actinic radiation from any source and type of light so long as it provides an effective exposure dose. This is because the photopolymerizable compositions of the present invention generally exhibit maximum sensitivity in the ultraviolet and visible light range, with wavelengths ranging from about 180 nm to about 600 nm. However, the composition of the present invention is also sensitive to short-wavelength electromagnetic waves in the range of vacuum ultraviolet rays, Examples of suitable light sources in the ultraviolet and visible range that may be utilized include power-bond arc lamps, mercury vapor lamps, xenon lamps, fluorescent lamps, argon glow discharge tubes, photographic flat lamps, and van de lamps. Such as the Graf accelerator. The light exposure time must be sufficient to provide an effective amount of light.

Light irradiation may be carried out at any convenient temperature, but for practical reasons it is optimally carried out at room temperature, ie in the range from 10°C to 40°C. The photocured compositions of the present invention are dry and resilient, exhibiting abrasion and chemical resistance, and exhibit excellent ink receptivity, hydrophilic-hydrophobic balance, stain release properties, and initial roll-up. It is particularly suitable for use as plate materials for lithographic printing and photoresists that have been given photosensitivity in advance. This composition can also be used for printing inks; adhesives for metal foils, films, papers, textiles, etc.; metals, plastics, paper, wood, metal boxes, etc.
It goes without saying that it can be applied to photocurable paints used for textiles, glass, cardboard, box-making cardboard, etc., as well as signs for roads, parking lots, airports, etc. When the compositions of the present invention are used, for example, as vehicles for printing inks, they can be colored with known amounts of dyes and simultaneously coated with various known organic pigments, such as molybdate orange, titanium white, chrome yellow, phthalocyanine blue, and carbon black. Can be colored. The usable amount of vehicle may range from about 20% to 99.9% of the total weight of the composition, and the amount of colorant may range from about 0.1% to 80% by weight. Printing materials also include paper, clay-coated paper and boxboard. The compositions of the invention are further suitable for the treatment of natural and synthetic textiles, for example as vehicles for textile printing inks, or to provide waterproof, oil, stain, crease, etc. It can be used in vehicles for special treatments.

When using the composition of the invention as an adhesive, at least one of the substrates to be adhered must be translucent to ultraviolet or visible light.

Typical examples of laminates obtained by adhering substrates using the composition of the present invention include polymer-coated cellophane,
Examples include cellophane coated with polypropylene, metals such as aluminum or copper coated with polyethylene terephthalate film, and aluminum coated with polypropylene. The photocurable composition of the present invention can be used as a coating material for coating or printing on metal, glass, and plastic surfaces by a roller method or a spray method.

Also glass, polyester films and vinyl polymer films, polymer-coated cellophane, treated or untreated polyethylene used in disposable cups and bottles, etc.
Colored coating systems may be used for treated and untreated polypropylene, etc. Examples of metals that may be painted include:
Includes tinplate with or without sizing.
A photopolymerizable photosensitive imaging material prepared from the photocurable composition of the present invention has a layer comprising the composition of the present invention as a photosensitive element on the surface of a sheet-like or plate-like support. It is the material.

One form of a photosensitive image forming material using the composition of the present invention is one in which a layer of the composition of the present invention is provided on the surface of a support, and a transparent plastic film is further provided on the layer. . Materials with this structure can be used by peeling off the transparent plastic film just before the image exposure described below, or by passing the film through the transparent plastic film with the transparent plastic film still present, or when the support is transparent. is through the support,
Imagewise exposure is carried out, and then the transparent plastic film is peeled off, so that the exposed and hardened portion of the layer remains on the support, and the unexposed and uncured portion of the layer is placed on the transparent plastic film. (or, the exposed and hardened layer remains on the transparent plastic film, and the unexposed and uncured layer remains on the support), a so-called peel-and-developable type of material. It can be used particularly advantageously as A photosensitive imaging material using the composition of the present invention is prepared by using a specific portion of the layer of the photopolymerizable composition until the addition polymerization reaction in the irradiated portion reaches a desired thickness and is completed. Exposure to light completes the image exposure.

The unexposed parts of the layer of the composition are then removed, for example by using a solvent that dissolves only the ethylenic compound (monomer) or the bleed polymer without dissolving the polymer, or by so-called peel development. do.

When used in photosensitive image reproduction materials, the optimum solvent removal thickness of the photocurable composition is from 20 μm to 50 μm.
The range is up to μm. The flexibility decreases as the layer thickness increases, and the abrasion resistance decreases as the layer thickness decreases. When used as printing inks, coating compositions and adhesives, the compositions of the invention can be used without volatile solvents.

They have several advantages over known oleoresin-based and solvent-based inks or coatings. The present invention will be described in detail and specifically based on Examples 1 to 28 and Comparative Examples 1 to 9 below.

The photosensitive materials in each example were prepared by the following methods and operations. (1) Preparation of photosensitive material Ethylene compound, photopolymerization initiator, and binder (each in parts by weight as shown in Table 1, where [-] indicates that they are not used.

) was placed in a container with 500 parts by weight of dichloroethane (solvent) and stirred for 3 hours to dissolve.The obtained solution was applied onto an aluminum plate using a spinner (rotary coating machine), and this was applied at a temperature of 80°C for 10 minutes. The mixture was dried for a minute to form a photosensitive layer (layer of photopolymerizable composition). The thickness of the photosensitive layer after drying was about 10 μm. (2) Measuring the sensitivity of the photosensitive material An optical wedge (the number of optical density steps is O-15) is placed on the photosensitive layer of the photosensitive material.
It is a step.

) and exposed it for 30 seconds at a distance of 50 cm from the light source (mercury lamp, output 2 kW), and then exposed the photosensitive layer to 1, 1,
It was developed by processing with 1-trichloroethane for 30 seconds. The highest number of optical wedges corresponding to the image that appears is taken as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity. Examples 1 to 28 and Comparative Examples 1 to 9 were carried out according to the above methods and operations, and the compositions of the photosensitive layers were as shown in the table below.

The sensitivity of the sample was also as indicated. From the results shown in the table above, the photopolymerization initiators of Examples 1 to 20 have higher sensitivity than Comparative Examples 1 to 9, and when coexisting with an amine compound as in Examples 21 to 25, the sensitivity is even higher. show.

Further, during exposure, no color change occurred in Comparative Examples 1 to 9, but in Examples 1 to 25, decolorization of the color of the photopolymerization initiator (mainly red and orange) was observed.

From the results of Comparative Examples 8 and 9, the σ value of the fit is +0.7.
Larger nitro-substituted p-dimethylaminostyryl
It has been found that styryl ketone derivatives do not act as sensitive photoinitiators in the photopolymerizable compositions of the present invention.

Examples 26 to 28 The procedures were the same as in Examples 1 to 25, except that the ingredients in the table below were used, a 1 kW xenon discharge lamp was used as the light source, and exposure was performed for 1 minute at a distance of 60 mm from the light source.

1 Otsu 1 In this example, the wavelength range is from about 300 nm to about 70 nm.
It is estimated that the photosensitive layer was irradiated with near-ultraviolet light and visible light in the range of 0 nm, but comparison with Examples 1, 2, and 8 revealed that the photopolymerization initiator used in the photopolymerizable composition of the present invention was It has been revealed that photopolymerization can be initiated effectively and with high sensitivity not only by near-ultraviolet light but also by visible light.

Claims (1)

[Scope of Claims] 1. A photopolymerizable composition containing (1) a polymerizable compound having an ethylenically unsaturated double bond and (2) a photopolymerization initiator as essential components, the photopolymerization initiator A photopolymerizable composition characterized in that (a) is at least one type of p-dimethylaminostyrylstyryl ketones represented by the following structural formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the above formula, X has a Hammett σ value of -0.9
represents a substituent in the range from +0.7 to +0.7. 2 Claims in which the polymerization initiator is further a combination of at least one selected from the group consisting of (b) secondary and tertiary amine compounds and polyamine compounds represented by the following general formula (II) 1. The photopolymerizable composition according to 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the above formula, R^1, R^2 and R^3 are alkyl groups,
It represents an aryl group, an aralkyl group, a substituted alkyl group, an alkoxy group or an aryloxy group, and R^1, R^2 and R^3 may be the same or different from each other.