JPH052228B2 - - Google Patents

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photopolymerizable composition comprising an unsaturated monomer, a photoinitiator and, if necessary, a linear organic polymer. The present invention relates to a photopolymerizable composition that can provide a photocured image useful for the production of printing original plates, photoresists, and the like. [Prior art] A polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and if necessary, a linear organic polymer having an appropriate film-forming ability, a thermal polymerization inhibitor, etc. are mixed and exposed to light. The method of reproducing images using photographic techniques using a photosensitive composition is now widely known. Namely, Special Publication No. 35-5093, Special Publication No.
As described in Publication No. 35-8495, etc., the photosensitive composition undergoes photopolymerization and becomes insolubilized by irradiation with actinic rays. Therefore, the photosensitive composition can be formed into a suitable film to form a negative image of a desired image. A desired photopolymerized image can be formed by irradiating actinic rays through the film and removing only the unexposed areas using a suitable solvent (hereinafter simply referred to as development). It goes without saying that this type of photosensitive composition is extremely useful as a photosensitive agent for printing plates, photoresists, and the like. Conventionally, benzyl, benzoin,
Representative examples include benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, and 2-ethyl anthraquinone. However, these initiators do not necessarily exhibit sufficient photopolymerization initiation ability for practical use, and it takes a long time to form an image by light irradiation. In order to improve this drawback, a combination of a radical generator and a light absorber is usually used, for example, the trihalomethyl compound of the S-triazine compound represented by the general formula () of the present invention.
Aromatic thiazole compound shown in Publication No. 28328,
Merocyanine dyes shown in JP-A-54-151024, aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-58-40302, and other 9-phenylacridine, By combining light absorbers such as, and further combining these combinations with hydrogen donors such as N-phenylglycine, 2-mercaptobenzothiazole, and ethyl N,N'-dimethylaminobenzoate, It is known to exhibit sufficient photopolymerization initiation ability. However, when these radical generators and light absorbers are combined with compounds capable of forming salts, such as basic dyes, in some cases the photopolymerization initiating ability is not sufficient, or the basic dyes This has the disadvantage that the printout properties (image forming properties due to discoloration of the dye due to acid generated after exposure) are impaired. [Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and therefore contains a combination of photopolymerization initiators with extremely high photopolymerization initiation ability and is suitable for printing. The object of the present invention is to provide a photopolymerizable composition capable of producing a photocured image useful for the production of original plates, photoresists, and the like. [Means for Solving the Problems] In view of the current state of the technology as described above, the present inventors have conducted intensive research and found that in a photopolymerizable composition,
The present invention was accomplished based on the finding that a useful photopolymerizable composition can be obtained when a specific triazine compound and a thioxanthone compound are used in combination as a photopolymerization initiator. That is, the present invention provides a photopolymer containing a monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic light, a photopolymerization initiator, and, if necessary, a linear organic polymer. In the polymerizable composition, at least one type of the following general formula () as a photopolymerization initiator: (X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and Y
represents -COOH or -COOR', and R' represents an alkyl group or an aryl group. ) and at least one of the following general formulas (): (X represents a halogen atom. Y represents -CX ₃ , -
_NH2 , -NHR', _-NR'2 , -OR'. here
R' is an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group. Further, R represents -CX ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ) It relates to a photopolymerizable composition characterized in that it uses a combination of the compounds represented by: The photopolymerizable ethylenically unsaturated addition-polymerizable compound used in the present invention has at least one, more preferably two or more addition-polymerizable ethylenic compounds in each molecule, with a boiling point of 100°C or higher at normal pressure. A monomer or oligomer with an unsaturated group and a molecular weight of 10,000 or less. Such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene di( meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate
After adding ethylene oxide or propylene oxide to polyhydric alcohol such as acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, glycerin or trimethylolethane. (Meta)acrylate, Special Publication No. 48-41708
Urethane acrylates such as those described in Japanese Patent Publication No. 50-6034 and Japanese Patent Application Publication No. 51-37193; Polyester acrylates, epoxy resins and (meth) listed in each publication
Examples include polyfunctional acrylates and methacrylates such as epoxy acrylates that are reacted with acrylic acid. Furthermore, Japan Adhesive Association Journal
Those introduced as photocurable monomers and oligomers in Vol. 20, No. 7, pages 300 to 308 can also be used. The compound represented by the general formula () used in the present invention is described in German Patent No. 3018891. General formula () used in the present invention The compound represented by Wakabayashi et al., Bull.
Chem.Soc.Japan, 42 , 2924 (1969), for example, 2-phenyl-4,6-bis(trichloromethyl)-S-triazine, 2-(p-chlorophenyl)-4,6-bis( trichloromethyl)-S-triazine, 2-(p-tolyl)-4,
6-bis(trichloromethyl)-S-triazine,
2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine, 2-(2',
4'-dichlorophenyl)-4,6-bis(trichloromethyl)-S-triazine, 2,4,6-tris(trichloromethyl)-S-triazine, 2
-Methyl-4,6-bis(trichloromethyl)-
S-triazine, 2-n-nonyl-4,6-bis(trichloromethyl)-S-triazine, 2-(α,
Examples include α,β-trichloroethyl)-4,6-bis(trichloromethyl)-S-triazine. Other compounds described in British Patent No. 1388492, such as 2-styryl-4,6-bis(trichloromethyl)-S-triazine, 2-(p
-methylstyryl)-4,6-bis(trichloromethyl)-S-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-S
-triazine, 2-(p-methoxystyryl)-4
-amino-6-trichloromethyl-S-triazine, etc., compounds described in JP-A-53-133428,
For example, 2-(4-methoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichlor Methyl-S-triazine, 2-[4-(2-ethoxyethyl)-naphth-1-yl]-4,6-bis-trichloromethyl-S-triazine, 2-(4,7-dimethoxy-naphtho-1 -yl)-4,6-bis-trichloromethyl-S-triazine, 2-(acenaphth-5-yl)-4,6-bis-trichloromethyl-S-triazine, etc., as described in German Patent No. 3337024 Compounds, e.g. etc. can be mentioned. Also, J.Org Chem. by F.C. Schaefer et al.;
29, 1527 (1964), such as 2-methyl-4,6-bis(tribromomethyl)-S-
Triazine, 2,4,6-tris(tribromomethyl)-S-triazine, 2,4,6-tris(dibromomethyl)-S-triazine, 2-amino-4-methyl-6-tribromomethyl-S- Examples include triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, and the like. It is particularly preferable to use a compound in which Y in the general formula () is _-CX3 . The concentration of the photopolymerization initiator used is usually a small amount, and if it is unsuitably high, undesirable results such as effective light shading will occur. The amount of the photopolymerization initiator in the present invention is such that the total of the compounds represented by the general formula () and the general formula () is the photopolymerizable ethylenically unsaturated compound and, if necessary, the linear organic polymer. From 0.01% by weight of the total
A range of 20% by weight is sufficient, more preferably 1
Good results are obtained with % to 10% by weight. In addition, the proportions of general formula () and general formula () to the total amount of photopolymerization initiator are 80 to 20% by weight and 20 to 80% by weight, respectively.
Preferably, it is % by weight. Furthermore, by adding a hydrogen-donating compound such as N-phenylglycine, 2-mercaptobenzothiazole, or N,N-dialkylbenzoic acid alkyl ester to the photopolymerization initiator used in the present invention, the photopolymerization can be further carried out. You can improve your starting ability. Naturally, the linear organic polymer used in the present invention must be selected to be compatible with the photopolymerizable ethylenically unsaturated compound.
Any linear organic polymer may be used as long as it is compatible with the photopolymerizable ethylenically unsaturated compound, but it is preferable to use a linear organic polymer that can be developed with water or weakly alkaline water. A linear organic high molecular weight polymer should be selected. The linear organic polymer is used not only as a film-forming agent in the composition, but also as a water, weak alkaline water, or organic solvent developer depending on the application. For example, water development becomes possible when a water-soluble organic polymer is used. Examples of such linear organic polymers include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, and maleic acid copolymers. There are acid copolymers, partially esterified maleic acid copolymers, etc., and similarly there are acidic cellulose derivatives having carboxylic acid in the side chain. Other useful materials include addition polymers having hydroxyl groups to which a cyclic acid anhydride is added. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin are also useful. These linear organic polymers can be mixed in any amount in the total composition, but 90%
Exceeding % by weight will not give favorable results in terms of the strength of the image formed. Furthermore, in the present invention, in addition to the above-mentioned basic ingredients, a small amount of a thermal polymerization inhibitor is added in order to prevent unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds during the production or storage of the photosensitive composition. This is desirable. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t
-butyl-p-cresol, pyrogallol, t-
Butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol),
Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, and N-nitrosophenylhydroxyamine cerous salt. In some cases, dyes or pigments may be added for the purpose of coloring the photosensitive layer, and inorganic fillers may be added for the purpose of improving the physical properties of the cured film. The photopolymerizable composition of the present invention includes, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether,
It can be provided on a support by dissolving it in a suitable solvent such as 3-methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone, ethylene dichloride, etc. alone or in a mixed solvent of an appropriate combination thereof. The appropriate amount of the coating is in the range of about 0.1 g/m ² to about 10 g/m ² based on the weight after drying.
More preferably, it is 0.5 to 5 g/m ² . Furthermore, it goes without saying that the photopolymerizable composition of the present invention may contain other known additives (for example, print-out agents, etc.) to achieve the intended purpose. As the support, a dimensionally stable plate-like material is used. Such dimensionally stable plate-like materials include those conventionally used as supports for printing plates, and these can be suitably used. Such supports include paper, paper laminated with plastic (e.g. polyethylene, polypropylene, polystyrene, etc.), plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., e.g. cellulose diacetate, Plastic films such as cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper laminated or vapor-deposited with metals such as those mentioned above. Or plastic film is included. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore,
A composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred. In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably. In addition, as described in U.S. Patent No. 2,714,066, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution, and as described in Japanese Patent Publication No. 47-5125, an aluminum plate can be used as an anode. Those obtained by oxidation treatment and then immersion treatment in an aqueous solution of an alkali metal silicate are also suitably used. The above anodic oxidation treatment can be performed using, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution consisting of an aqueous solution or a non-aqueous solution of an inorganic acid such as boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more of them. Ru. Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662. Furthermore, Japanese Patent Publication No. 1974-27481, Japanese Patent Application Publication No. 1973-
Also useful is a surface treatment that combines a support coated with electrolytic grains with the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in JP-A-58602 and JP-A-52-30503. Furthermore, it is also preferable to use brush grain, electrolytic grain, anodic oxidation treatment, and sodium silicate treatment as disclosed in JP-A-56-28893. Furthermore, after these treatments, it is also suitable to apply an undercoat with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, or the like. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. This is done for the purpose of improvement. On the layer of the photopolymerizable composition provided on the support, in order to completely prevent the polymerization inhibiting effect caused by oxygen in the air, a material with excellent oxygen barrier properties such as polyvinyl alcohol or acidic cellulose is used. A protective layer made of a polymer may also be provided. A method for applying such a protective layer is described in detail in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. A photosensitive plate provided with the photopolymerizable composition of the present invention on a support is imagewise exposed using a light source rich in ultraviolet rays such as a metal halide lamp or a high-pressure mercury lamp, and then treated with a developer to remove the photosensitive layer. A printing plate is prepared by removing the exposed area and finally applying a gum solution. The above-mentioned developing solution is preferably benzyl alcohol, 2-phenoxyethanol, 2-phenoxyethanol, or
- an alkaline aqueous solution containing a small amount of an organic solvent such as butoxyethanol, e.g.
Examples include those described in No. 3475171 and No. 3615480. Furthermore, Japanese Patent Application Publication No. 50-26601, Publication No. 56-39464
The developers described in the publications No. 56-42860 are also excellent as developers for the photosensitive printing plates mentioned above. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Example 1 A substrate was obtained by the method disclosed in JP-A-56-28893. Specifically, the surface of an aluminum plate with a thickness of 0.30 mm was grained using a nylon brush and a 400 mesh water suspension of pumice stone, and then thoroughly washed with water. 10% sodium hydroxide 70
After etching by immersion at ℃ for 60 seconds, washing with running water, neutralization washing with 20% _HNO3 , and then washing with water.
This was carried out at 160 clones/d in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of V _A = 12.7V.
Electrolytic surface roughening treatment was performed with an anode electricity amount of m ² . When the surface roughness was measured, it was 0.6μ (Ra display). Subsequently, after immersion in a 30% aqueous H ₂ SO ₄ solution and desmatting at 55°C for 2 minutes, the 20%
Anodizing was performed in an aqueous H ₂ SO ₄ solution at a current density of 2 A/dm ² for 2 minutes to a thickness of 2.7 g/m ² . A photosensitive solution having the composition shown below was coated on the aluminum plate thus treated so that the dry coating weight was 1.5 g/m ² and dried at 100° C. for 2 minutes to obtain a photosensitive plate. Allyl methacrylate/methacrylic acid copolymer (copolymerization molar ratio 80/20) 3.2g Pentaerythritol tetraacrylate
1.7g Photopolymerization initiator A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification 86.5-89 mol%, degree of polymerization 1000) was applied to give a dry coating weight of 2 g/m ² and dried at 100° C. for 2 minutes. Exposure was performed from a distance of 1 m using a vacuum baking device with a PS Light S type (metal halide lamp, 2KW) manufactured by Fuji Photo Film Co., Ltd. For sensitivity measurement, a continuous step wedge with an LTF concentration step of 0.15 was used. For development, use 30g of 1K potassium silicate.
Potassium hydroxide 15g, 25℃ with a developer consisting of 3g and 1000g of water.
I soaked it for 1 minute. Table 1 shows the sensitivity and printout results after exposure when the combination of photoinitiators was changed. [Table] [Table] Table 1 shows that the combination of compounds of formula () and () of the present invention When used, sensitivity increases dramatically. Furthermore, compared to the basic light absorbers listed in Comparative Examples 5 and 6, the printout after exposure was not impaired. Example 2 Next, a photosensitive plate was produced in the same manner as in Example 1 according to the prescription. Benzyl methacrylate/methacrylic acid copolymer (copolymerization molar ratio 67/33) 3.2g Dipentaerythritol hexaacrylate
1.7g Steel phthalocyanine pigment 0.2g Fluorinated nonionic surfactant (manufactured by 3M Company, Fluorado FC-430) 0.03g Methyl ethyl ketone 20g Ethylene glycol monomethyl ether acetate 20g The dry coating weight of this photosensitive plate was 1.5g/ ^m2 . As in Example 1, an oxygen barrier layer made of PVA was provided on this photosensitive plate, and when it was exposed and developed using the same exposure device as in Example 1, it cleared 7 steps using a step wedge with an appropriate exposure time of 1 second. images were obtained. Example 3 In the production of the aluminum substrate of Example 1, 20
% _H2SO4 instead _of anodizing in aqueous solution
% phosphoric acid aqueous solution at a current density of 2 A/dm ² for 2 minutes to a thickness of 0.8 g/m ² , and then anodized with a 3% sodium silicate aqueous solution at a current density of 2 A/dm 2 for 2 minutes.
The photosensitive solution of Example 2 was applied onto the substrate treated at 10° C. for 10 seconds. The dry coating weight of this photosensitive plate was 1.5 g/m ² . Then, in the same manner as in Example 1, an oxygen barrier layer made of PVA was provided on this photosensitive plate, and it was exposed and developed in the same manner as in Example 1. The appropriate exposure time for this plate was 0.2 seconds. When this photosensitive plate was exposed using a commercially available projection exposure machine, a proper image was obtained in 1 to 2 seconds. [Effects of the Invention] By using the photopolymerizable composition of the present invention, a photosensitive plate with good sensitivity and good printout after exposure can be obtained. Therefore, the photopolymerizable composition of the present invention can be widely used for various printing plates and image formation, and among these, it can be particularly suitably used for producing photosensitive printing original plates, photoresists, and the like.

Claims (1)

[Scope of Claims] 1. At least one compound that can be photopolymerized by actinic rays.
In a photopolymerizable composition comprising a monomer having ethylenically unsaturated groups, a photopolymerization initiator, and, if necessary, a linear organic polymer, at least one 2 General formula () below: (X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and Y
represents -COOH or -COOR', and R' represents an alkyl group or an aryl group. ) and at least one of the following general formulas (): (X represents a halogen atom. Y represents -CX ₃ , -
Represents NH ₂ , -NHR', -NR ₂ , -OR'. here
R' is an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group. Further, R represents -CX ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ) A photopolymerizable composition characterized by using a combination of compounds represented by the following.