JPH0354961B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photopolymerizable resin composition. For more details, use formula (1) (In formulas (1a) and (1b), R ₁ is a hydrogen atom, a chlorine atom, or a methyl group, R ₂ is a hydrogen atom, a chlorine atom,
a methyl group or a methoxy group; R ₃ is a C _1-4 alkyl group; an alkoxyalkyl group having 3 to 4 carbon atoms;
Hydroxyethyl group; Acetyl group; Propionyl group; Represents a benzoyl group which may be substituted with a methyl group, propyl group, or carboethoxy group. Z represents an oxygen atom or a sulfur atom. However, formula (1) is a mixture of isomers of formula (1a) and formula (1b)) or formula (2) (In formula (2), R ₄ is a C _1-8 alkyl group; a C _4-7 alkyl group which may be interrupted by 1 to 2 oxygen atoms; an ethyl group or a propyl group substituted with a hydroxyl group; N,N-dimethylaminopropyl group; chlorine atom, phenyl group which may be substituted with butyl group, R ₅ is hydrogen atom, methyl group, methoxy group,
Each represents an ethoxy group, a dimethylamino group, or a diethylamino group. Further, X represents a hydrogen atom or a chlorine atom, and Y represents an oxygen atom or a sulfur atom. ) and optionally as a photopolymerization accelerator, aliphatic tertiary amines; aromatic tertiary amines; N-phenylglycines; phenoxyacetic acids; thiophenoxyacetic acids; aromatic tertiary amines; The present invention relates to a photopolymerizable resin composition containing a compound selected from class amines and thioxanthone and a compound having at least one ethylenically unsaturated double bond. Recently, in the field of information recording, the use of visible light including laser light has been actively studied in place of the conventionally widely used ultraviolet light. For example, an image is formed on a photosensitive resin film using visible light of around 500 nm such as an argon laser. The purpose of this is because it is expected to simplify the process of image formation (for example, direct plate making) by utilizing the features of laser beams, such as high-density energy and the ability to perform scanning exposure in conjunction with a computer. It is. Furthermore, in fields where it is necessary to cut out the ultraviolet part of the continuous spectrum and use only visible light, there is a desire to develop photopolymerization initiators that are sensitive to visible light. An object of the present invention is to provide a visible light region polymerizable resin composition containing a novel photopolymerization initiator that is sufficiently sensitive not only to ultraviolet light but also to visible light. Conventional radical type photoinitiators such as benzoin alkyl ether and benzyl dimethyl ketal are 230~
Although it is relatively efficiently sensitive to ultraviolet light of 400 nm, it has almost no photopolymerization initiator ability to visible light, especially light around 500 nm. The present inventors have conducted intensive studies on compounds that have an initiator effect even with visible light, and have arrived at the present invention. That is, the organic dye of formula (1) or (2) of the present invention is 330-
It has a photosensitive wavelength range of 650 nm, and its excellent initiator effect is observed not only in ultraviolet rays but also in visible light, especially light around 500 nm. Furthermore, the organic dye of formula (1) or (2) is an aliphatic or aromatic tertiary amine; N-phenylglycine;
It is also clear that a photopolymerizable resin composition with even higher sensitivity can be obtained by containing a compound selected from phenoxyacetic acids; thiophenoxyacetic acids, aromatic tertiary amines, and thioxanthone as a polymerization initiation scavenger. Summer. The compound of formula (1) is generally synthesized according to the following reaction formula. (In the above formula, R ₁ , R ₂ , R ₃ and Z have the same meanings as above. W is a halogen, p-toluenesulfonic acid ester residue, sulfuric acid ester residue, benzenesulfonic acid ester residue, etc.) Formulas (1a) and (1b) (representing an alkylation reactive group) are isomers and are used as a mixture without separation. The compound of formula (2) is generally synthesized according to the following reaction formula. (In the above formula, R ₄ , R ₅ , X and Y have the same meanings as above) Specific examples of R ₃ in formula (1) include C _1-4 alkyl such as methyl group, ethyl group, and butyl group. Base;
Examples include alkoxyalkyl groups having 3 to 4 carbon atoms such as methoxyethyl group and ethoxyethyl group; hydroxyethyl group; acetyl group; propionyl group; benzoyl group optionally substituted with methyl group, propyl group, and carboethoxy group. It will be done. Specific examples of R ₄ in formula (2) include methyl group, ethyl group, butyl group, and octyl group.
C _1-8 alkyl group, C _4-7 alkyl group such as methoxypropyl group, butoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group where the alkyl chain may be interrupted with 1 or 2 oxygen atoms. hydroxypropyl groups such as alkyl groups, hydroxyethyl groups, β-hydroxypropyl groups,
Examples include phenyl groups which may be substituted with a chlorine atom or a butyl group, such as an N,N-dimethylaminopropyl group, a phenyl group, a p-chlorophenyl group, and a p-butylphenyl group. The photopolymerization initiator of formula (1) or (2) above may be used in combination with a photopolymerization accelerator. Preferred photopolymerization accelerators include aliphatic or aromatic tertiary amines,
N'-phenylglycines, phenoxyacetic acids,
Examples include thiophenoxyacetic acids, and further examples include systems consisting of aromatic tertiary amines and thioxanthones. Aliphatic or aromatic tertiary amines include tributylamine, N,N-dimethylaniline, tribenzylamine, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid butoxyethyl ester, p-dimethylaminobenzoic acid butoxyethyl ester,
-dimethylaminobenzoic acid amyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid, p-dimethylaminobenzaldehyde, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, etc. Can be mentioned. Examples of N-phenylglycine include N-phenylglycine, p-chloro-N-phenylglucine, m-methyl-N-phenylglycine, and p-methoxyphenylglycine. Examples of phenoxyacetic acids or thiophenoxyacetic acids include phenoxyacetic acid, thiophenoxyacetic acid, p-chlorophenoxyacetic acid, p-chlorothiophenoxyacetic acid, p-methylphenoxyacetic acid, p-methylthiophenoxyacetic acid, p-methoxyphenoxyacetic acid, Examples include p-methoxythiophenoxyacetic acid, m-chlorophenoxyacetic acid, m-chlorothiophenoxyacetic acid, and the like. In addition, thioxanthone includes 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
Examples include 2,4-diisopropylthioxanthone and 2-chlorothioxanthone. The photopolymerizable resin composition of the present invention includes the above-mentioned polymerization initiator, a photopolymerization accelerator used if necessary, a binder usually made of an organic polymer, and further a thermal polymerization inhibitor, a plasticizer, etc. if necessary. It is prepared by mixing the usual additives. Photopolymerizable resins are monomers, oligomers, prepolymers, or mixtures thereof that have ethylenically unsaturated double bonds and can be crosslinked and polymerized under irradiation with ultraviolet rays and visible light, and specific examples include ethyl acrylate. , butyl acrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol ketacrylate, pentaerythritol methacrylate, dipentaerythritol tetramethacrylate, acrylic or methacrylic esters of monohydric or polyhydric alcohols; polyhydric alcohols Polyester acrylate obtained by reacting methacrylic acid with a polyester prepolymer obtained by condensing monobasic or polybasic acid; The resulting polyurethane acrylate includes epoxy methacrylate, which is a reaction product of methacrylic acid and a low molecular weight epoxidized resin such as bisphenol dicrycidyl ether or epoxidized polybutadiene. As a binder, polymethacrylic acid ester or its partial hydrolyzate polystyrene, polyvinyl acetate or its partial hydrolyzate, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylpyrrolidone, polyethylene oxide. An organic polymer substance such as polymethacrylic acid or a methacrylic acid copolymer having a carboxyl group in a side chain is used. These binders are used in approximately the same amount as the photopolymerizable resin. The amount of the photopolymerization initiator of formula (1) or (2) above is preferably 0.1 to 30 parts per 100 parts of the photopolymerizable resin.
It is used in a range of 0.5 to 15 parts. Furthermore, a photopolymerization accelerator selected from aliphatic or aromatic tertiary amines, N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, etc., which is used depending on the case, is added to one part of the photopolymerization initiator. 0.1~
It is used in a proportion of 10 parts, preferably 0.2 to 5 parts. Furthermore, in the case of a photopolymerization accelerator consisting of an aromatic tertiary amine and a thioxanthone, it is used in the same ratio as above to the photopolymerization initiator, and the ratio of the thioxanthone to 1 part of the aromatic amine is
The ratio is from 0.2 to 5 parts. As a light source for curing the photopolymerizable resin composition of the present invention, ordinary curing light sources such as a mercury lamp, a xenon lamp, a halogen lamp, and a laser beam can be used, but it is most convenient to use a halogen lamp, a gas laser, and especially an argon laser. Therefore, it is also possible to use only ultraviolet rays or visible rays by using a filter if necessary. The present invention will be explained in more detail with reference to Examples below. Reference Example 1 Synthesis example of photopolymerization initiator of formula (1): Obtained by reacting benzothioxanthone-3,4-dicarboxylic anhydride with phenynylacetic acid and potassium acetate. 45.2g of compound (a) of the following formula Dissolve in 200 g of dimethylformamide, add 8.4 g of anhydrous potassium carbonate, and heat under reflux for 30 minutes. Distill the produced water, cool to 60℃, and add 25.2g of dimethyl sulfate.
was added over a period of 2 hours, and the mixture was further stirred at the same temperature for 2 hours.
After cooling, methanol was added to the reaction solution to precipitate crystals, which were filtered and dried to obtain the following dark red dye (mixture). The o-acylated product is also synthesized from the above compound (a) and acid chloride or acid anhydride by a conventional method. Table 1 shows photopolymerization initiators of formula (1) synthesized by a method similar to the above.

【table】

[Table] Reference example 2 Synthesis example of formula (2): 4.0g of the following compound, A mixture of 0.9 g of γ-methoxypropylamine and 200 ml of chlorobenzene is stirred at 70 to 100° C. for about 3 hours to form a red transparent solution. This was cooled, poured into a large amount of methanol, and the precipitated crystals were separated to obtain red crystals of the following formula. λmax 498 nm (in methylcellosolve) A compound represented by formula (2) was obtained by almost the same operation. Structural formula and λmax of the compounds obtained in Table 2
(in methylcellosolve).

【table】

[Curing test]

The photopolymerizable resin compositions obtained in Examples 1 to 37 were uniformly dissolved in 1000 parts of methyl cellosolve. Next, this solution was applied onto an anodized aluminum plate using a spinner so that the dry film thickness was 1 μm. Photosensitivity tests were then conducted for visible light and Reger light. The laser beam used was a 488 nm single line of a 5W argon laser with a beam diameter of 1.25 mm. Visible light was used by using a fluorescent chemical lamp with a sharp cut filter Y-43 (manufactured by Toshiba) to cut out ultraviolet light. After exposing the dried film to light using each light source, the uncured portion was eluted with ethanol, and the presence or absence of curing was determined by staining with a methyl blue/ethanol solution. Sensitivity was measured by the minimum irradiation energy required to photocure the coating. In the case of laser exposure, the sensitivity was defined as the irradiation energy required to obtain the same cured diameter as the beam diameter. The smaller the numerical value, the higher the sensitivity of the photosensitive resin composition to light, which indicates that the effect of the photopolymerization initiator or photopolymerization accelerator is excellent.

【table】

【table】

[Table] Examples 38 to 45 Photopolymerized resin compositions were prepared in the same manner as Examples 1 to 37 using aromatic tertiary amines and thioxanthone as photopolymerization accelerators, and their sensitivities were measured. . The results are shown in Table 4.

【table】

[Table] Examples 46 to 73 100 parts of pentaerythritol triacrylate,
A photopolymerizable resin composition was obtained by mixing 100 parts of poly-N-vinylpyrrolidone with the photopolymerization initiator and photopolymerization accelerator shown in Table 5.

【table】

【table】

[Table] Examples 74-76 6 parts of compound of dye number 42 in Table 2, 2,4
- A photopolymerizable resin composition was obtained from 8 parts of diisopropylthioxanthone, 8 parts of p-dimethylaminobenzoic acid, 100 parts of polyethylene oxide (binder), and 100 parts of the photopolymerizable resin shown in Table 6 below, and this was used in Examples Sensitivity (by visible light) was measured in the same manner as in Nos. 1 to 37. The results are shown in Table 6.

【table】

Claims (1)

[Claims] 1 Formula (1) (In formulas (1a) and (1b), R ₁ is a hydrogen atom, a chlorine atom, or a methyl group, R ₂ is a hydrogen atom, a chlorine atom,
a methyl group or a methoxy group; R ₃ is a C _1-4 alkyl group; an alkoxyalkyl group having 3 to 4 carbon atoms;
Hydroxyethyl group; Acetyl group; Propionyl group; Represents a benzoyl group which may be substituted with a methyl group, propyl group, or carboethoxy group. Z represents an oxygen atom or a sulfur atom. However, formula (1) is a mixture consisting of isomers of formula (1a) and formula (1b)) or formula (2) (In formula (2), R ₄ is a C _1-8 alkyl group; a C _4-7 alkyl group which may be interrupted by 1 to 2 oxygen atoms; an ethyl group or a propyl group substituted with a hydroxyl group; N,N-dimethylaminopropyl group; chlorine atom, phenyl group which may be substituted with butyl group, R ₅ is hydrogen atom, methyl group, methoxy group,
Each represents an ethoxy group, a dimethylamino group, or a diethylamino group. Further, X represents a hydrogen atom or a chlorine atom, and Y represents an oxygen atom or a sulfur atom. ) and a compound having at least one ethylenically unsaturated double bond. 2. A patent characterized by containing a compound selected from aliphatic or aromatic tertiary amines; N-phenylglycines; phenoxyacetic acids; thiophenoxyacetic acids; aromatic tertiary amines and thioxanthones A composition according to claim 1.