JPH0522229B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a photopolymerizable composition that exhibits high sensitivity to light in a wide wavelength range including ultraviolet rays and visible light. In particular, the present invention relates to a photopolymerizable composition that exhibits excellent photosensitivity to visible laser light such as argon ion laser light. [Prior Art] When reproducing images using photographic techniques, compositions containing photosensitive compounds such as diazonium salts, azides, and quinone diazides, or photopolymerization initiators that act with ultraviolet light are used. A photopolymerizable composition containing the following is used. All of the above-mentioned compounds or compositions have a problem in that they exhibit photosensitivity to ultraviolet light but almost no photosensitivity to visible light. Visible light (wavelength 400~) instead of ultraviolet rays
Examples of photopolymerizable compositions having photosensitivity to 700 nm) include JP-A-57-114139 and JP-A-Sho 57-114139;
Compositions containing a dye and a photosensitizer are known, such as those disclosed in Japanese Patent No. 59-142205. In recent years, with advances in scanning exposure technology using laser light sources, and in particular the practical application of scanning exposure equipment that uses visible laser light, there has been a desire to develop photosensitive materials that are highly sensitive to visible laser light such as argon ion laser light. . However, with conventional photosensitive materials, not only those that are sensitive to ultraviolet rays but also those that are sensitive to visible light do not necessarily have sensitivity to visible laser light. This is not sufficient, and even if recording by laser beam scanning exposure is possible, it requires considerably high output power.
It wasn't economical. [Object of the Invention] An object of the present invention is to provide a photopolymerizable composition that exhibits high sensitivity to light in a wide wavelength range including ultraviolet rays and visible light. In particular, it is an object of the present invention to provide a photopolymerizable composition that exhibits excellent photosensitivity to visible laser light such as argon ion laser light. [Structure of the Invention] According to research conducted by the present inventors, in a system of a photopolymerizable composition containing an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, , certain xanthene or thioxanthene dyes, diaryliodonium salts,
We have discovered that the desired objective can be achieved by using a combination of compounds having a methylene group at the alpha position of the nitrogen atom, such as N-phenylglycine and N-phenylglycine. That is, according to the present invention, in a photopolymerizable composition containing an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, the photopolymerization initiator (a) has the following general formula [ ] [In the formula, A is an oxygen atom or a sulfur atom, ) is a double bond, and if Y is a nitrogen atom, the bond with the adjacent carbon atom is a single bond.)
Z is an oxygen atom (in this case, there is a double bond between adjacent carbon atoms), a lower alkoxy group or a lower alkanoyloxy group, R ¹ is a lower alkyl group,
In the hydroxy lower alkyl group, lower alkoxy lower alkyl group, di-lower alkylamino lower alkyl group or aryl group, R ² is a hydrogen atom, a lower alkoxy group or a di-lower alkylamino group.
In addition, Z and R ¹ are both combined as -Z-R ¹ -, It may also represent ] There is provided a photopolymerizable composition comprising a combination of a compound represented by (b) a diaryliodonium salt, and (c) a compound having a methylene group at the α-position of a nitrogen atom. In the compound represented by the above general formula [] (hereinafter sometimes referred to as component (a)), specific examples of the halogen atom represented by X include chlorine and bromine. Further, examples of the lower alkoxy group represented by Z include methoxy, ethoxy, propoxy, etc., and examples of the lower alkanoyloxy group include acetyloxy, propionyloxy, butyryloxy, etc. Further, specific examples of the lower alkyl group represented by R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., and specific examples of the hydroxy lower alkyl group include hydroxymethyl. , hydroxyethyl, hydroxypropyl,
Specific examples of lower alkoxy lower alkyl groups include methoxymethyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxyethyl, propoxypropyl, etc. Specific examples of di-lower alkylamino lower alkyl groups Examples include dimethylaminomethyl, dimethylaminoethyl,
Dimethylaminopropyl, diethylaminoethyl, diethylaminopropyl, diethylaminobutyl, etc., and specific examples of aryl groups include phenyl, xylyl, tolyl, naphthyl, etc.
Specific examples of the lower alkoxy group represented by R ² include methoxy, ethoxy, propoxy, etc., and specific examples of the di-lower alkylamino group include dimethylamino, diethylamino, etc. In addition,
The compound represented by the general formula [] is a substance generally known in the literature as a xanthene or thioxanthene dye. The above diaryliodonium salt (hereinafter referred to as component (b))
It is also sometimes called. ) is a compound represented by the following general formula []. [In the formula, R ³ to R ⁶ are the same or different and represent a hydrogen atom, a halogen atom (e.g. chlorine, bromine), a lower alkyl group (e.g. methyl, ethyl, propyl,
t-butyl), a lower alkoxy group (e.g. methoxy, ethoxy, propoxy) or a nitro group, and X ^- represents a halogen ion (e.g. Cl ^- , Br ^- ,
I ^- ), BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- or SbF ₆ ^- . ] The compound represented by the general formula [] is described in, for example, "Journal of Polymer Science Polymer Symposia" (J.Polym.Sci.Polym.Symp.)
56, pp. 383-395 (1976), for example, diphenyliodonium, bis(p-chlorophenyl)iodonium, ditolyliodinium, bis(p-t-butylphenyl). Examples include iodonium chlorides, bromides, borofluoride salts, hexafluorophosphate salts, hexafluoroarsenate salts, and hexafluoroantimonate salts of iodonium such as iodonium and bis(m-nitrophenyl)iodonium. Examples of the compound having a methylene group at the alpha position of the nitrogen atom (hereinafter sometimes referred to as component (c)) include triethylamine, N-methyldiethanolamine, triethanolamine, N-ethyl-N-benzylaniline, N,N-diethyl-
Examples include p-phenylenediamine and N-phenylglycine, with N-phenylglycine being particularly preferred. The addition-polymerizable compound having an ethylenically unsaturated double bond (hereinafter sometimes referred to as a double-bond-containing compound) is addition-polymerized and cured by the action of a photopolymerization initiator, becoming substantially insolubilized. Any monomer or polymer having an ethylenically unsaturated double bond that provides the following may be used. Specific examples include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds, and addition reaction products of unsaturated carboxylic acids and epoxides. , esters obtained by esterification reactions of unsaturated carboxylic acids and polyhydric carboxylic acids with polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic acid. Aliphatic polyhydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, propylene glycol, dihydric alcohols such as 1,2-butanediol, trimethylolethane, trimethylolpropane, glycerol, etc. Examples include trihydric alcohols, tetrahydric or higher polyhydric alcohols such as pentaerythritol and tripentaerythritol, and polyhydric hydroxycarboxylic acids. Examples of aromatic polyhydroxy compounds include hydroquinone, resorcinol, catechol, and pyrogallol. Epoxides include trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, diglycidyl ester of phthalic acid, and a reaction product of epichlorohydrin and 2,2-bis(4-hydroxyphenyl)-propane. There is. Examples of polyvalent carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, maleic acid, fumaric acid, malonic acid, glutaric acid, adipic acid, sebacic acid, Examples include tetrahydrophthalic acid. Typical examples of esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds or esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds include acrylics of the above aliphatic polyhydroxy compounds or aromatic polyhydroxy compounds. Acids or esters of methacrylic acid may be mentioned. Typical examples of esters obtained by the esterification reaction of unsaturated carboxylic acids and polyhydric carboxylic acids with polyhydric hydroxy compounds include those shown below. (However, Z' is an acryloyl group or a methacryloyl group.): Z′−(OC ₂ H ₄ )− ₂ OOC−(CH ₂ )− ₄ COO−(C ₂ H ₄ O)− ₂
Z′ Z′−(OC ₂ H ₄ )− ₃ OOC−CH=CH−COO−(C ₂ H ₄ O
) − ₃ Z′ Other examples of double bond-containing compounds that can be used in the present invention include acrylamide, acrylamides such as ethylenebisacrylamide and hexamethylenebismethacrylamide, methacrylamides such as ethylenebismethacrylamide and hexamethylenebismethacrylamide, and phthalamides. Examples include double bond-containing compounds such as allyl esters such as diallyl acid, diallyl malonate, diallyl fumarate, and triallyl isocyanurate. Regarding double bond-containing compounds as polymers,
Examples of substances having a double bond in the main chain include polyesters obtained by the polycondensation reaction of unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid) and dihydroxy compounds (e.g., the above-mentioned dihydric alcohols); Examples include polyamides obtained by a polycondensation reaction between a saturated dihydric carboxylic acid and a diamine (eg, ethylenediamine, hexamethylenediamine). Examples of compounds with a double bond in the side chain include dicarboxylic acids with a double bond in the side chain (e.g. itaconic acid, α-methylitaconic acid, γ-methylitaconic acid, propylidenesuccinic acid, α-ethylidene Examples include polyesters obtained by a polycondensation reaction between glutaric acid, ethylidenemalonic acid, propylidenemalonic acid) and the above-mentioned dividroxy compounds, and polyamides obtained by a polycondensation reaction between the above-mentioned diamines. Also usable are polymers obtained by a polymer reaction between a polymer having a functional group such as a hydroxyl group or a halogenated methyl group in a side chain and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or crotonic acid. Polymers with functional groups in side chains include polyvinyl alcohol, partially saponified polyvinyl acetate, copolymers of acrylonitrile with styrene, vinyl chloride, vinylidene chloride, etc., and copolymers of acrylonitrile with vinyl acetate. completely saponified products of 2-hydroxyethyl methacrylate and acrylonitrile, methyl methacrylate, butyl methacrylate, styrene, vinylidene chloride, vinyl acetate, etc., poly(4-hydroxystyrene),
Examples include poly(N-methylolacrylamide). Among the above double bond-containing compounds, it is particularly preferable to use monomers of acrylic esters or methacrylic esters. In the composition of the present invention, component (a) is added in an amount of 0.01 to 0.2 parts by weight per 1 part by weight of the double bond-containing compound.
Preferably 0.02 to 0.1 parts by weight, each of components (b) and (c) 0.005 to 0.2 parts by weight, preferably 0.01 to 0.08 parts by weight.
Use parts by weight. If the usage ratio of any of these three components is less than the respective lower limit,
The photosensitivity decreases and it takes a long time to insolubilize the composition. Moreover, if the amount exceeds the upper limit, the strength and solvent solubility resistance of the film formed from the composition will decrease, making it unsuitable for practical use. The composition of the present invention has a photopolymerization initiator consisting of a combination of the above-mentioned double bond-containing compound and components (a), (b), and (c) as an essential component. Polymerization inhibitors, plasticizers, colorants, etc. may be used in combination. The polymeric binder has various purposes for improving compatibility, film-forming properties, developability, adhesion, etc., and an appropriate type may be selected depending on the purpose. For example, to improve developability with an aqueous solvent, copolymers of acrylic acid (or methacrylic acid) and acrylic acid (or methacrylic acid) alkyl esters (such as methyl ester, ethyl ester, butyl ester), itaconic acid copolymers, Partially esterified maleic acid copolymer, acidic cellulose modified product having a carboxyl group in the side chain,
Polyethylene oxide, polyvinylpyrrolidone, etc. are useful for improving film strength and adhesion.
Polyethers and polyamides of epichlorohydrin and 2,2-bis(4-hydroxyphenyl)propane are useful. Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, and 2,6-di-
Useful examples include t-butyl-p-cresol and β-naphthol. Examples of useful plasticizers include phthalic acid diesters such as dioctyl phthalate, didodecyl phthalate, and dibutyl phthalate, and aliphatic dibasic acid esters such as dioctyl adipate, dibutyl adipate, and dibutyl sebacate. Useful colorants include, for example, phthalocyanine pigments, azo pigments, carbon black, titanium oxide pigments, triphenylmethane dyes, azo dyes, anthraquinone dyes, and the like. The composition of the invention may be prepared in a conventional manner.
For example, the above-mentioned essential components and optional components may be used as they are or as needed in a solvent (for example, a ketone solvent such as methyl ethyl ketone, acetone, or cyclohexanone, an ester solvent such as ethyl acetate or butyl acetate, an aromatic solvent such as toluene or xylene, Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, alcohol solvents such as methanol, ethanol, and propanol, and ether solvents such as tetrahydrofuran and dioxane) are mixed in a cool, dark place using, for example, a kneader or mixer. It can be prepared by [Effects of the Invention] A photosensitive layer based on the composition of the present invention can be formed by applying the composition onto a support according to a conventional method, for example, using a bar coater or a spinner, and drying it. Note that known techniques may be applied to the formed photosensitive layer to protect its surface and prevent adverse effects such as a decrease in sensitivity due to oxygen. For example, a removable transparent cover sheet may be provided on the photosensitive layer, or a coating layer made of a waxy material with low oxygen permeability, a water-soluble or alkali-soluble polymer, etc. may be provided. The photosensitive layer uses general-purpose light sources that generate ultraviolet or visible light such as lasers such as argon ion lasers, helium cadmium lasers, and krypton lasers, as well as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, and tungsten lamps. It can be made insolubilized by Incidentally, development after light irradiation may be carried out using an appropriate developer capable of dissolving the unexposed photosensitive layer depending on the composition of the photosensitive layer. As described above, the composition of the present invention exhibits high sensitivity to light in a wide range of wavelengths, including ultraviolet rays to visible light, and more specifically, from ultraviolet rays to around 600 nm, so that the applicability of the composition can be further expanded. I can do it. Moreover, it exhibits excellent photosensitivity to visible laser light in the above wavelength range, such as argon ion laser light, so it can directly capture image signals using a scanning exposure device without using conventional negative film. It is possible to write on objects coated with the composition of the present invention, such as lithographic printing plates, resists for producing printed wiring boards, original plates for producing hologram matrices, etc., and the practical effects thereof are very large. . [Examples] Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited to these Examples. Examples 1 to 8 and Comparative Examples 1 to 8 Preparation of photopolymerizable composition Methyl methacrylate/methacrylic acid copolymer (“BR-77” manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight approximately 70,000) 100 parts (parts by weight, hereinafter) (Similar) was dissolved in 1000 parts of methyl ethyl ketone, and then 100 parts of pentaerythritol triacrylate was dissolved therein to obtain a first liquid. Next, a photopolymerization initiator (component
Dissolve (a) to (c)) in 300 parts of methyl cellosolve to prepare a second liquid, add the entire amount of each to the first liquid, and stir well to obtain a solution of the photopolymerizable composition (photosensitive liquid). Ta. Preparation of photosensitive layer (test plate) The above photosensitive solution was coated on an aluminum support using a bar coater so that the coating amount was 2 g/m ² when dry, and dried for 3 minutes in a dryer at 60°C.
A photosensitive layer with a thickness of 2.0 μm was obtained. On this photosensitive layer, a 5% aqueous solution of polyvinyl alcohol (saponification degree 88%, polymerization degree 500) was applied to a thickness of 2.0 μm using a bar coater to form an overcoat layer. Sensitivity measurement Lay the above test plate on Kodatsu step tablet No. 2 (21 steps) and use the Toshiba KL light from a xenon lamp (manufactured by Ushio Inc., 150W)
Light with a wavelength of around 490 nm (light intensity 4.0 mW/cm ² ) extracted through a −49 filter is
Irradiated for seconds. Developed with a developer (10 parts by weight of anhydrous sodium carbonate, 50 parts of butyl cellosolve, and 3 parts of anionic activator dissolved in 1000 parts of water), and calculated the exposure energy required for curing based on the number of photocured stages. , and that value was defined as "sensitivity." The results are shown in Table 1. Image formation using argon ion laser light Laser light (488 nm) is focused from an argon ion laser light source with an output of 0.2 W through an optical system to a beam diameter of 20 μm, and is cylindrical scanned (1000 rpm, 600 lines/ inch). Next, this was developed with the developer described above to obtain an "image created by argon ion laser light." The results are shown in Table 1.

[Table] As is clear from the results in Table 1, when the three components (a) to (c) are used in combination as a photopolymerization initiator, the comparison is made when a combination of two of them is used. It is recognized that the sensitivity is about 3 to 5 times higher, indicating its high practicality, and that it exhibits high photosensitivity to visible laser light. Example 9 A test plate was prepared in the same manner as in Example 1 except that 100 parts of a compound obtained by adding 2 moles of acrylic acid to 1 mole of propylene glycol diglycidyl ether was used instead of 100 parts of pentaerythritol triacrylate in Example 1. We created it, measured its sensitivity, and formed an image using argon ion laser light. As a result, the sensitivity was 0.6 mJ/cm ² , and the image obtained by the argon ion laser was as clear as that obtained in Example 1.

Claims (1)

[Scope of Claims] 1. A photopolymerizable composition comprising an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, wherein the photopolymerization initiator (a) has the following general formula [] [In the formula, A is an oxygen atom or a sulfur atom, ) is a double bond, and if Y is a nitrogen atom, the bond with the adjacent carbon atom is a single bond.)
Z is an oxygen atom (in this case, there is a double bond between adjacent carbon atoms), a lower alkoxy group or a lower alkanoyloxy group, R ¹ is a lower alkyl group,
In the hydroxy lower alkyl group, lower alkoxy lower alkyl group, di-lower alkylamino lower alkyl group or aryl group, R ² is a hydrogen atom, a lower alkoxy group or a di-lower alkylamino group.
In addition, Z and R ¹ are both combined as -Z-R ¹ -, It may also represent ] A photopolymerizable composition comprising a combination of a compound represented by (b) a diaryliodonium salt, and (c) a compound having a methylene group at the α-position of a nitrogen atom. 2. The composition of item 1 above, wherein component (c) is selected from the group consisting of N-phenylglycine, triethylamine and triethanolamine.