JPS624045B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photopolymerizable composition,
More specifically, the present invention relates to a photopolymerizable composition characterized by a photopolymerization initiator. 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. Patent No. 3,551,235.
No. 3551246, No. 3551311 and No. 3551246, No. 3551311 and No.
No. 3558387, Belgian Patent No. 808179, JP-A-Sho
49-110781, the products obtained by this technology have excellent flexibility,
It has characteristics such as chemical resistance, abrasion resistance, gloss, adhesion, and hue, but 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 it is difficult to produce detailed images. In the case of imaging, if there is slight vibration during operation, images of good quality cannot be reproduced, and the amount of energy emitted by the exposure light source or particle beam source must be increased, resulting in a large amount of heat generated. It is necessary to take into account radiation, and there are also problems such as deformation and deterioration of the film of the composition due to heat. 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 polymerizable compounds having saturated double bonds can be significantly increased. An object of the present invention is to provide a highly sensitive photopolymerization initiator and a photopolymerization initiator system for use in photopolymerization compositions (a type of so-called photoresists). Yet another object of the present invention is to provide a photoinitiator that generally increases the photopolymerization rate (sensitivity) of photopolymerizable compositions containing addition polymerizable compounds having ethylenically unsaturated double bonds. be. The present invention provides: (1) at least one ethylenically unsaturated double bond;
In a photopolymerizable composition comprising an addition polymerizable compound and a photopolymerization initiator as essential components, the photopolymerization initiator has (a) a P-dialkylaminophenyl aromatic compound represented by the general formula [1]; group compound or P- represented by general formula [2]
dialkylaminobenzylidene amino compound and
(b) A combination with a compound having at least one oxo oxygen atom bonded to an aromatic ring or a compound having at least one oxo oxygen atom bonded to a carbon atom bonded to a carbon atom of an aromatic ring. Photopolymerizable composition. In general formulas [1] and [2], R ¹ and R ² each represent an alkyl group, a substituted alkyl group, or an aralkyl group, and may be the same or different from each other. In general formula [1]
R ³ is 5 or 6 members containing N, S or O atoms
Represents a monovalent group derived from a membered monocyclic or fused polycyclic heterocyclic compound. In general formula [2], R ⁴ represents R ³ or an acylamino group. (2) The photopolymerizable composition according to (1), further comprising an organic polymeric substance having a film-forming ability as a binder and having compatibility with the components. It is. In this specification, the compounds of component (b) are collectively referred to as aromatic carbonyl compounds. The addition-polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter referred to as an ethylenic compound) used in the present invention refers to an addition-polymerizable compound having at least one ethylenically unsaturated double bond in its molecule. A general term that includes not only monofunctional, difunctional, and trifunctional monomers, which are compounds with 1, 2, and 3 monofunctional monomers, but also oligomers that are polyfunctional and have a molecular weight of about 10,000 or less. It is. It refers to mixtures of these as well as polymers in which the ethylenic bonds of these mixtures are partially copolymerized. In the present invention, a preferable ethylenic compound is a compound having two or more ethylenic double bonds in the molecule, and at least one, more preferably almost all of the ethylenic double bonds are carbon or These are compounds in which a carbon is conjugated and adjacent to a double bond with a heteroatom such as oxygen, nitrogen, or sulfur. Ethylenic compounds that exhibit particularly remarkable effects are compounds in which an addition-polymerizable ethylenic double bond is conjugated with a carbonyl group of an ester or amide bond. Examples of these ethylenic compounds include the following esters of unsaturated carboxylic acids and aliphatic polyols, oligoesters (or polyesters) of polyhydric carboxylic acids and aliphatic polyols, and unsaturated carboxylic acids that are ester bonded. There are oligoester (or polyester) unsaturated carboxylates. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid. Specific examples of aliphatic polyol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol,
Tetramethylene glycol, neopentyl glycol, 1,10-decanediol, trimethylolethane, trimethylolpropane, 1,2-butanediol, 1,3-butanediol, propylene glycol, glycerin, diglycerin, pentaerythritol, dipenta These include erythritol, tripentaerythriere, other multimeric pentaerythritols, sorbitol, d-manitol, and dihydroxymaleic acid. Specific examples of esters of aliphatic polyol compounds and unsaturated carboxylic acids include acrylic esters and methacrylic esters, and specific examples thereof include:
Ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, glycerin triacrylate These include methacrylate, diglycerine dimethacrylate, 1,3-propanediol diacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate. Examples of oligoester unsaturated carboxylates include oligoester (meth)acrylates, compounds which can often be used as preferred ethylenic compounds in the materials of the invention. Oligoester (meth)acrylate is a reaction product obtained by the esterification reaction of acrylic acid or methacrylic acid, a polybasic acid, and a polyhydric alcohol, and its estimated structural formula is the general formula [3] It is a compound represented by, where R represents a hydrogen atom or a methyl group, Q represents an ester residue containing at least one ester bond consisting of a polyhydric alcohol and a polybasic acid, and n is 1 to 6. , preferably an integer from 2 to 6. Examples of the polyhydric alcohol constituting the ester residue Q include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol,
Polyhydric alcohols represented by 1,6-hexanediol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, glycerin, pentaerythritol, and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol There are polyether-type polyhydric alcohols represented by , dipropylene glycol, tripropylene glycol, and polypropylene glycol. On the other hand, examples of polybasic acids constituting the ester residue Q include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid, and benzophenone dicarboxylic acid. Aromatic polybasic acids, maleic acid, fumaric acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, unsaturated aliphatic polyhydrochloric acids such as Δ ² -tetrahydrophthalic acid, Δ ⁴ -tetrahydrophthalic acid, malonic acid , succinic acid,
Examples include saturated aliphatic polybasic acids such as glutaric acid, adipic acid, pimelic acid, sebacic acid, dodecanoic acid, and 2,3-norbornanedicarboxylic acid. The ester residue Q includes those composed of one type each of polyhydric alcohol and polybasic acid as described above, and those composed of one or both of them composed of two or more types. . Also included are those in which one molecule each of polyhydric alcohol and polybasic acid is contained in the ester residue Q, and those in which two or more molecules of one or both of them are contained. That is, anything can be used as long as Q contains at least one ester bond. Also included are those in which a hydroxyl group remains in Q, or those in which the hydroxyl group forms an ester with a monovalent carboxylic acid, or is substituted with an alkoxy group such as a methoxy group or an ethoxy group. Further, the carboxylic acid may remain in Q. The number of n in general formula [3] and the number of ester bonds contained in Q are determined by the type or preparation of acrylic acid or methacrylic acid, polyhydric alcohol, or polybasic acid when synthesizing oligoester (meth)acrylate. It can be adjusted by molar ratio. In order to prevent gelation during the synthesis process, the value of n is usually selected in the range of 1 to 6. When the value of n is 2 or more, one oligoester (meth)acrylate molecule containing only either an acryloyl group or a methacryloyl group may be used; and methacryloyl groups in any proportion, and the type of oligoester (meth)acrylate to be used depends on the sensitivity and sensitivity required for the photopolymerizable composition of the present invention.
Alternatively, it can be selected depending on the properties of the cured product obtained by photopolymerization. Estimated structural formulas of specific examples of oligoester (meth)polyols are listed in Table 1. In addition to this, JP-A-47
-9676 (corresponding to US Pat. No. 3,732,107), unsaturated esters and the like described in the specification can also be cited as examples of oligoesters. 1st
In the table, Y in the structural formula is an acryloyl group

[Formula] or methacryloyl group

Represents [formula].

【table】

[Table] Ethylenic compounds can be used alone or in combination of two or more. Next, the photopolymerization initiator, which is a significant feature in the photopolymerizable composition of the present invention, will be explained. The photopolymerization initiator is a component that generates radicals upon irradiation with actinic light, and the radicals react with the ethylenic compound in the photopolymerizable composition to initiate addition polymerization of the ethylenic compound. In the present invention, component (a) and component (b) are used in combination as a photopolymerization initiator. The substituents R ¹ and R ² of the P-dialkylaminophenyl heterocyclic compound represented by the general formula [1] of component (a) represent an alkyl group, a substituted alkyl group, or an aralkyl group, and they may be the same or different. You can leave it on. Examples of the alkyl group include linear and branched alkyl groups having 1 to 18 carbon atoms, and cyclic alkyl groups having 5 to 18 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, butyl group, 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, 2-
Examples include an adamantyl group, an α-decalyl group, and a β-decalyl group. Among these, linear and branched alkyl groups having 1 to 10 carbon atoms and cyclic alkyl groups having 6 to 10 carbon atoms are preferred. Substituents for substituted alkyl groups include halogen atoms (fluorine, chlorine, bromine, iodine) and hydroxyl groups, while alkyl groups have the aforementioned carbon atoms of 1 to 18, preferably 1 to 10. Examples include linear, 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, 16- Methylheptadecyl group, chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 2
-hydroxybutyl group, 5-hydroxypentyl group, 10-hydroxydecyl group, 2-hydroxyoctadecyl group, 2-(hydroxymethyl)ethyl group, hydroxycyclohexyl group, and 3-hydroxy-2-norbornyl group. 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 6 carbon atoms, is substituted with a phenyl group or a naphthyl group. Specific examples include benzyl group, phenethyl group, 3-phenylpropyl group, 3-phenylhexyl group, 10-phenyldecyl group, 4-phenylcyclohexyl group, 1-naphthylmethyl group, 2-
Examples include (1-naphthyl)ethyl group and 2-naphthylmethyl group. The substituent R ³ is a monovalent group derived from a monocyclic or condensed ring heterocyclic compound containing a 5- or 6-membered ring structure containing N, S or O; ), or a monovalent group derived from a heterocycle containing N, S, or O having a substituent whose σ value ranges from -0.9 to +0.7 . Monovalent groups derived from heterocycles containing N, S or O include furyl group, benzofuranyl group, isobenzofuranyl group, pyranyl group, pyrrolyl group,
Dioxolanyl group, indolyl group, isoindolyl group, indolenyl group (3H-indolyl group), thienyl group, benzothienyl group, imidazolyl group,
imidazolidinyl group, benzimidazolyl group, oxazolyl group, benzoxazolyl group, dibenzoxazolyl group, naphthoxazolyl group, phenanthraoxazolyl group, thiazolyl group, benzothiazolyl group, naphthothiazolyl group, pyridyl group,
Examples include quinolyl group and isoquinolyl group. Monovalent groups derived from N, S or O-containing heterocycles having a substituent with a Hammett's σ value in the range of -0.9 to +0.7 include the aforementioned N, S or O-containing heterocycles. A monovalent group derived from the above may be substituted with one or more substituents having a Hammett's σ value within the above-mentioned range. In this specification, the definition of Hammett's σ value is in accordance with "Organic Reaction Kinetics" by JELeffler, translated by Yuho Tsuno (Tokyo, Hirokawa Shoten, published in 1968). Specific examples include hydrogen atom, methyl group, ethyl group, isopropyl group, tert-butyl group, phenyl group, trifluoromethyl group, cyano group, acetyl group, ethoxycarbonyl group, carboxyl group, carboxylate 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, Aminosulfonyl group, dimethylsulfonyl group (-S
( _CH3 ) ₂ ), sulfonate group ( _-SO3 ), fluorine atom, chlorine atom, bromine atom, iodine atom, iodyl group, trimethylsilyl group (-Si( _CH3 ) ₃ ), triethylsilyl group, trimethylstannyl group (−Sn
(CH ₃ ) ₃ ) can be given. Among these substituents, preferred are a hydrogen atom, a methyl group,
They are ethyl group, methoxy group, ethoxy group, dimethylamino group, diethylamino group, chlorine atom, bromine atom, and cyano group. Specific examples of monovalent groups derived from N, S, or O-containing heterocyclic compounds having substituents with a Hammett's σ value in the range of -0.9 to +0.7 include methylpyridyl group, chloropyridyl group, , methylquinolyl group, chloroquinolyl group, phenylthiazolyl group, 4,5-diphenylthiazolyl group, chloropenzothiazolyl group, phenyloxazolyl group,
4,5-diphenyloxazolyl group, chlorobenzoxazolyl group, phenylbenzoxazolyl group, dibenzoxazolyl group, methylbenzoxazolyl group, methylbenzofuranyl group, chlorobenzofuranyl group , methylimidazolyl group, phenylimidazolyl group, 1,3-dimethylimidazolidinyl group, and 1,3-diphenylimidazolidinyl group. The substituent R ¹ and the P-dialkylaminobenzylideneamino compound represented by the general formula [2]
R ² is a substituent R ¹ and a P-dialkyl phenyl aromatic compound represented by the above general formula [1].
It has the same meaning as R ² , and R ⁴ represents the above-mentioned substituent R ³ or an acylamino group. The acylamino group represents an alkylcarbonylamino group, an aralkylcarbonylamino group, an arylcarbonylamino group, or an arylcarbonylamino group having a substituent having a Hammett σ value ranging from -0.9 to +0.7. The aforementioned alkyl group and aralkyl group in the acylamino group have the same meanings as the alkyl group and aralkyl group in the aforementioned substituent R ³ , respectively. The aryl group of the arylcarbonylamino group is
phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group,
Represents a fluorenyl group or a biphenylyl group. Specific examples of arylcarbonylamino groups having substituents with a Hammet σ value ranging from -0.9 to +0.7 include: , tolyl group, ethyl phenyl group, tert-butylphenyl group, trifluoromethyl phenyl group, cyanophenyl group, acetylphenyl group, ethoxycarbonylphenyl group, carboxyphenyl group, amino phenyl group, (methylamino) phenyl group, (dimethyl Amino)phenyl group, methoxyphenyl group, hydroxyphenyl group, (methylthio)phenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, fluorophenyl group, phenoxyphenyl group, acetoxyphenyl group, methoxysulfonylphenyl group group, aminonaphthyl group, (dimethylamino)naphthyl group, chloronaphthyl group, methylnaphthyl group, chloroanthryl group, methylanthryl group, bromophenanthryl group, ethylphenanthryl group, methylindenyl group, or chloro Represents an indenyl group. Specific examples of the acylamino group include acetylamino group, propionylamino group, butyrylamino group, valerylamino group, pivaloylamino group, benzoylamino group, 1-naphthoylamino group, 2
Examples include -naphthoylamino group, p-toluoylamino group, o-toluoylamino group, and p-chlorobenzoylamino group. Specific examples of p-dialkylaminophenyl aromatic compounds include 2-[p-(dimethylamino)phenyl]benzothiazole, 2-[p-(dimethylaminophenyl]naphthothiazole, 2-p-
(dimethylaminophenyl-4,5-diphenylthiazole, 2-[p-(dimethylamino)phenyl]benzoxazole, 2-[p-(dimethylamino)phenyl]naphthoxazole, 2-[p
-(dimethylamino)phenyl]dibenzoxazole, 2-p-(dimethylamino)phenyl-
4,5-diphenyloxazole, 2-p-(dimethylamino)phenyl-1,3-dioxolane, 2-p-(dimethylamino)phenyl-1,
Examples include 3-diphenylimidazolidine, 2-p-(dimethylamino)phenyl-1,3-dimethylimidazolidine, and 2-[p-(dimethylamino)phenyl]phenanthraoxazole. Specific examples of p-dialkylaminobenzylideneamino compounds include 2-p-(dimethylamino)benzylideneamino-1,3-benzothiazole, 2-p-(dimethylamino)benzylideneamino-1,3-benzoxazole, N ′-[p
-(dimethylamino)benzylidene]benzhydrazide. Next, the aromatic carbonyl compound of component (b) will be explained. Compounds having at least one oxo oxygen atom bonded to an aromatic ring include polycyclic fused aromatic ketones and polycyclic fused quinones containing a cyclopentadienone type structure or a cyclohexadienone type structure. At least one oxo oxygen atom bonded to a carbon atom bonded to an aromatic carbon atom
The compounds include aromatic acyloins, aromatic acyloin ethers, and aromatic ketones. Specific examples of aromatic acyloins include benzoin, o-toluoin, p-toluoin, and furoin. Specific examples of aromatic acyloin ethers include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin sec-butyl ether, o-toluoin methyl ether, p-
One example is toluoine methyl ether. Aromatic ketones include benzophenone,
Phenyltolyl ketone, 2-chlorobenzophenone, 2-chloroacetophenone, acetophenone, propiophenone, benzyl, 2,2'-dimethylbenzyl, phenyl β-naphthyl ketone, Michler ketone, bis(p-aminophenyl) ketone can be given. Specific examples of polycyclic condensed aromatic ketones containing a cyclopentadienone type structure or a cyclohexadienone type structure include fluorenone, anthrone, benzanthrone,
We can give 10,10'-bianthrone.
Polycyclic fused quinones include anthraquinone,
1-Hydroxyanthraquinone, 1-methylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 1-bromoanthraquinone, 2-chloroanthraquinone, phenanthraquinone, 1-methyl phenanthraquinone, 4-ethylphenanthraquinone, 2-chlorophenanthraquinone, 3-bromophenanthraquinone, 2,7-dimethylphenanthraquinone,
2,7-di-tert-butylphenanthraquinone,
Mention may be made of 1,2-benz-9,10-anthraquinone. Among these aromatic carbonyl compounds, benzanthrone ,1,2
-benz-9,10-anthraquinone and fluorenone are preferred. The amount of photoinitiator contained in the photopolymerizable compositions of the present invention can range broadly from about 0.01% to about 20% by weight relative to the ethylenic compound, preferably also Approximately 0.1
% to about 10%. The photoinitiator component weight ratio (a):(b) ranges from about 30:1 to about 1:30, preferably from about 10:1 to 1:10. The photopolymerizable composition of the present invention containing the above-mentioned ethylenic compound and photopolymerization initiator further contains a known polymer substance (binder) having film-forming ability,
Additives such as thermal polymerization inhibitors, plasticizers, colorants, and surface smoothing agents can be included as necessary. In particular, for the purpose of creating a resist (thick) image on a photosensitive material, such as a photosensitive material for peeling development as described below, or a photosensitive material for liquid development, a polymer material with film-forming ability is used. (binder) can be used together. Any organic polymer can be used as the binder as long as it is compatible with the ethylenic compound and the photopolymerization initiator, but it is preferable that it be capable of peel development, water development, or weak alkaline water development. High molecular weight polymers should be selected. 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 a cyclic acid anhydride is added. Other useful water-soluble organic polymers include polyvinylpyrrolidone and polyethylene oxide.
In addition, alcohol-soluble nylon and 2,2-bis(4
Polyethers of -hydroxyphenyl)propane and epichlorohydrin are also useful. These organic high molecular weight polymers can be mixed in any amount in the total 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 in the photopolymerizable composition used as the photosensitive layer of the peel-developable photosensitive material is chlorinated polyolefin (with a chlorine content of approx.
60 to about 75% by weight), polymethyl methacrylate,
Polyacrylic acid, polymethacrylic acid, polyacrylic acid alkyl ester (alkyl groups include methyl, ethyl, butyl, etc.), acrylic acid alkyl ester (alkyl groups are the same as above), acrylonitrile, vinyl chloride, vinylidene chloride, styrene , copolymers with at least one monomer such as butadiene, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, polyvinylidene chloride,
Copolymer of vinylidene chloride and acrylonitrile,
Polyvinyl acetate, copolymer of vinyl acetate and vinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile with butadiene and styrene, polyvinyl alkyl ether (as an alkyl group) , methyl group, ethyl group, isopropyl group, butyl group, etc.),
Polymethyl vinyl ketone, polyethyl vinyl ketone, polyethylene, polypropylene, polybutyne, polystyrene, poly-α-methylstyrene,
Polyamide (6-nylon, 6,6-nylon, etc.), poly-1,3-butadiene, polyisoprene, polyurethane, polyethylene terephthalate, polyethylene isophthalate, chlorinated rubber, polychloroprene, chlorinated rubber, ethyl cellulose,
Examples include homopolymers or copolymers such as acetylcellulose, polyvinyl butyral, polyvinyl formal, styrene-butadiene rubber, and chlorosulfonated polyethylene. 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 are present in a molar ratio.
A range of 10% or more and 50% 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 preferably used in the photopolymerizable composition of the present invention include chlorinated polyethylene (chlorine content of about 60 to about 75% by weight), chlorinated polypropylene (chlorine content of about 60 to about 75% by weight), 75% by weight), polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer (molar content of vinyl chloride 20-80%), vinylidene chloride-acrylonitrile copolymer (molar content of acrylonitrile 10-30%) %), vinyl chloride-acrylonitrile copolymer (molar content of acrylonitrile 10-30%), polystyrene, polyvinyl butyral, polyvinyl acetate, polyvinyl formal, ethyl cellulose, acetyl cellulose,
Examples include vinyl chloride-vinyl acetate copolymer, polychloroprene, polyisoprene, chlorinated rubber, and chlorosulfonated polyethylene. These polymers may be used alone, but
Two or more types of polymers can be mixed in an appropriate ratio so as not to cause demixing during the manufacturing process from preparing the solution (coating solution) of the photopolymerizable composition to coating and drying. . Specific examples of thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-tophthol, 2,6-di Examples include -t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, and organic acid copper (such as copper acetate). These thermal polymerization inhibitors are preferably contained in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the above-mentioned ethylenic compound. 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 coloring agents include pigments such as titanium oxide, carbon black, iron oxide, phthalocyanine pigments, and azo pigments, and dyes such as methylene blue, crystal violet, rhodamine B, fuchsin, auramine, azo dyes, and anthraquinone dyes. However, it is preferable that the colorant used does not absorb light at the absorption wavelength of the photopolymerization initiator.
Such coloring agents may be used in an amount of 0.1 to 30 parts by weight in the case of pigments and 0.01 to 10 parts by weight in the case of dyes, based on 100 parts by weight of the total amount of binder and ethylenic compound.
The content is preferably in the range of 0.1 parts by weight to 3 parts by weight. When containing the above-mentioned coloring agent, it is preferable to use dichloromethyl stearate and other chlorinated fatty acids as auxiliary substances for the coloring agent, and the amount thereof ranges from 0.005 parts by weight to 1 part by weight of the coloring agent. It can be used in a range up to 0.5 parts by weight. However, if a plasticizer is included in the photopolymerizable composition, no colorant auxiliary substance is required. Examples of plasticizers include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate, and dimethyl glycol phthalate. , ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate,
Glycol esters such as butylphthalyl butyl glycolate, triethylene glycol dicaprylate, phosphate esters such as tricresyl phosphate, triphenyl phosphate,
Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate,
Examples include aliphatic diacid acid esters such as diothyl azelate and dibutyl maleate, triethyl citrate, 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 photopolymerizable composition of the present invention as required, may be present 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 be used. The photopolymerizable composition of the present invention is dissolved in a solvent to form a coating solution (a solution of the photopolymerizable composition), which is applied onto a support by a known method, the solvent is removed, and the photopolymerizable composition is The most common way to use the photopolymerizable composition of the present invention is to use it as an optical material. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc.
Esters such as ethyl acetate, butyl acetate, amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate, ethyl benzoate, etc., aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene, etc., e.g. carbon tetrachloride. , trichlorethylene, chloroform, 1,
Halogenated hydrocarbons such as 1,1-trichloroethane, monochlorobenzene, chlornaphthalene, etc., such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether,
Examples include ethers such as ethylene glycol monoethyl ether acetate, dimethylformamide, and dimethyl sulfoxide. Supports for applying the photopolymerizable composition of the present invention in a suitable form (e.g. the aforementioned solutions) include:
There are planar materials and 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,
Alloys mainly composed of iron, chromium, nickel, silver, gold, platinum, palladium, aluminum, alloys mainly composed of zinc, alloys mainly composed of magnesium, copper-zinc alloys, iron-nickel-chromium alloys,
Copper-based alloys, metal compounds such as aluminum oxide, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), polymers such as regenerated cellulose,
Cellulose nitrate, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polystyrene, polyethylene terephthalate, polyethylene isophthalate, polycarbonate of bisphenol A, polyethylene, polypropylene, nylon ( 6-nylon, 6,6
-Nylon, 6,10-nylon, etc.), polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-
Examples include vinylidene chloride copolymer, polyacrylonitrile, polymethyl acrylate, and polymethyl methacrylate. In addition, two or more thin plates of the above-mentioned materials are laminated firmly, for example,
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 on the surface, known A chromium plate with a chromium oxide layer formed on its surface by the method described above, a glass plate with a tin oxide layer on its surface, and a silicon oxide plate with an indium oxide layer on its 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 transparent, it is not only colorless and transparent, but also J.
As described in SMPTE, Vol. 67, p. 296 (1958), dyes or pigments can be added to make it 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 those that are transparent materials with pigments such as dyes and titanium oxide added, and those that are surface-treated using the method described in Japanese Patent Publication No. 19068/1983. It is also possible to use paper, plastic film, etc., which have been made completely light-shielding by adding plastic film, carbon black, etc. 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, and metal whiskers 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 a decrease in sensitivity due to oxygen, the composition of the present invention can be exposed to light using a vacuum printing frame as described in U.S. Pat. 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 composition of the present invention photopolymerizes, cures, and dries include the nature of the support, especially its surface, specific components in the composition, and the total photopolymerizable composition of the photopolymerization initiator. These include the content in the substance, the thickness of the layer of the photopolymerizable composition, the properties of the light source (characteristics of the irradiation spectrum), the intensity, the presence or absence of oxygen, and the 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 composition of the present invention generally has a wavelength of about 180 nm to about 180 nm.
This is because it exhibits maximum sensitivity in the ultraviolet and visible light regions up to 450 nm. However, the composition of the present invention is also sensitive to short-wavelength electromagnetic waves in the range of vacuum ultraviolet rays, can be used. Examples of suitable light sources in the ultraviolet and visible range include sunlight,
Carbon arc lamps, mercury vapor lamps, xenon lamps, fluorescent lamps, argon glow discharge tubes,
These include photographic flat lamps and Van de Graaf accelerators. 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 of about 10°C to about 40°C. The photocured compositions of the present invention are dry and resilient, exhibiting abrasion and chemical resistance, as well as excellent ink receptivity, hydrophilic-hydrophobic balance, stain release properties, and initial printability. It has printing properties and is particularly suitable for use in pre-photosensitized printing plate materials for lithographic printing and photoresists. This composition is also suitable for printing inks; adhesives for metal foils, films, papers, textiles, etc.; metals, plastics, paper, wood, metal foils, textiles, etc.
It goes without saying that it can be used as a photocurable paint for 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 with various known organic pigments such as molybdate orange, titanium white, chrome yellow, phthalocyanine blue and carbo black. It can be colored with. Usable amounts of vehicle can range from about 20% to 99.9% of the weight of the gold composition and colorants can 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 photopolymerizable 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, e.g. polypropylene coated cellophane, polyethylene terephthalate film on metal such as aluminum or copper. There are aluminum coated with polypropylene, aluminum coated with polypropylene, etc. The photocurable composition of the present invention can be used as a coating for coating or printing on metal, glass and plastic surfaces by roller and spray methods. Pigmented coating systems may also be used on glass, polyester and vinyl polymer films, polymer-coated cellophane, treated and untreated polyethylene, treated and untreated polypropylene, etc. used in disposable cups and bottles, etc. Examples of metals that may be painted also include tinplate with or without sizing. A photosensitive image forming material prepared from the photocurable photopolymerizable composition of the present invention is a material having 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. 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 while the transparent plastic film is present, or when the support is transparent. Image exposure is carried out through the support, and then the transparent plastic film is peeled off, so that the exposed and hardened portions of the layer remain on the support, and the unexposed and uncured portions of the layer are removed from the transparent plastic film. (Alternatively, the exposed and cured portions of the layer remain on the transparent plastic film, and the unexposed and uncured portions of the layer remain on the support.), so-called peel-off development. It can be particularly advantageously used as a type of photosensitive material. A photosensitive imaging material using the composition of the present invention is prepared by exposing a specific portion of the layer of the photopolymerizable composition to light until the addition polymerization reaction in the irradiated portion reaches a desired thickness and is completed. Image exposure is completed by exposure to . 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 prepolymer) without dissolving the polymer, or by so-called peel development. . The thickness of the layer of photopolymerizable composition after solvent removal (drying) ranges from 0.5 μm to 150 μm, preferably from 1 μm to 100 μm. Flexibility decreases with increasing thickness, and abrasion resistance decreases with decreasing layer thickness. 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 paints. The photopolymerizable composition of the present invention has a feature of exhibiting high sensitivity to broad rays (ultraviolet light, near ultraviolet light, and visible light) from a wavelength of about 180 nm to about 450 nm, and therefore sunlight, high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon-mercury lamps, high-pressure xenon lamps,
A halogen lamp, a fluorescent lamp, etc. can be used as a light source for photopolymerization. The field of application of the photopolymerizable composition of the present invention is extremely wide, and it can be used as a photosensitive layer of photosensitive materials in various fields such as the production of printed wiring boards in the electronic industry, the production of lithographic or letterpress printing plates, and the reproduction of optical images. Therefore, the present invention is extremely useful. The present invention will be described in detail and specifically based on Examples 1 to 16 and Comparative Examples 1 to 10 below. The photosensitive materials in each example were prepared by the following methods and operations. (1) Preparation of photosensitive material Components of photopolymerizable composition Ethylene compound (Pen 50 parts by weight Taerythriere trimethacrylate) Photopolymerization initiator (Note 1) Component (a) 0.5 parts by weight Component (b) 0.5 parts by weight parts Binder (chlorinated poly 49.5 parts by weight ethylene) 1,2-dichloroethane 500 parts by weight (Note 1) In the case of a mixture of component (a) and component (b), the photopolymerization initiator is 0.5 parts by weight of both components. (1 part by weight in total), and in the case of only one component, 1 part by weight of component (a) or (b) was used alone. In the table below, "-" indicates that it was not used. (Note 2) Chlorinated polyethylene is 40% by weight.
Viscosity of toluene solution at 25℃ is approximately 90cps
It is a polymer compound with a chlorine content of approximately 69% by weight. The ingredients listed in the table above were placed in a container and stirred for 3 hours to dissolve.The resulting solution was coated on a 0.24 mm thick aluminum plate using a spinner (rotary coater) and coated at a temperature of 80℃ 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) Measurement of sensitivity of photosensitive material An optical wedge with an optical density ratio of √2 (optical density step 0.15) is placed on the photosensitive layer of the photosensitive material (optical density step number is 0 to 15 steps, minimum optical density is 0.10, maximum optical density is 2.30) were placed in close contact under reduced pressure and exposed for 15 seconds at a distance of 50 cm from a light source (mercury lamp, output 2KW), and then the photosensitive layer was treated with 1,1,1-trichloroethane for 30 seconds. I developed it. The highest number of optical wedges corresponding to the image that appears is expressed as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity. In the table below, E represents an example and C represents a comparative example. Examples 1 to 6 and Comparative Examples 1 to 8 Table 2 shows the results of experiments using benzaanthrone as the component (b) of the photopolymerization initiator and changing the component (a) to be combined.

[Table] Both the compound of component (a) and the benzaanthrone of component (b) have very low sensitivity or virtually no sensitivity when used alone, but by combining both components, the sensitivity becomes significantly high and the sensitivity is sufficiently high. It has become clear that the sensitivity is such that it can be put to practical use. Examples 7 to 16 and Comparative Examples 9 to 10 1 as the aromatic carbonyl compound (component (b)),
Table 3 shows the results of experiments using 2-benzo-9,10-anthraquinone or fluorenone and changing the component (a) used.

[Table] Both the compound of component (a) and the 1,2-benzo-9,10-anthraquinone and fluorenone of component (b) have extremely low sensitivity or virtually no sensitivity when used alone, but when both components are combined, It has become clear that the combination results in significantly higher sensitivity, which is sufficient for practical use.

Claims (1)

[Claims] 1 At least one ethylenically unsaturated double bond
In a photopolymerizable composition comprising an addition-polymerizable compound and a photopolymerization initiator as essential components, the photopolymerization initiator is (a) a P-dialkylaminophenyl complex represented by the general formula [1]. A ring compound or a P-dialkylaminobenzylidene amino compound represented by the general formula [2] and (b) a compound having at least one oxo oxygen atom bonded to an aromatic ring or a compound bonded to a carbon atom bonded to a carbon atom of an aromatic ring. A photopolymerizable composition characterized in that it is a combination with a compound having at least one oxo oxygen atom. In general formulas [1] and [2], R ¹ and R ² each represent an alkyl group, a substituted alkyl group, or an aralkyl group, and may be the same or different from each other. In the general formula [1], R ³ represents a monovalent group derived from a 5- or 6-membered monocyclic or condensed polycyclic heterocyclic compound containing N, S or O atoms. In general formula [2], R ⁴ represents R ³ or an acylamino group. 2. The photopolymerizable composition according to claim 1, further comprising an organic polymer substance having film-forming ability as a binder and having compatibility with the components.