JPH0774906B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention comprises an unsaturated monomer, a photopolymerization initiator, and an organic boron compound, and further contains a linear organic high-molecular polymer, if necessary, and is photopolymerizable. The present invention relates to a composition, and more particularly to a photopolymerizable composition capable of providing a photocurable image useful for producing a printing original plate, photoresist and the like.

[Conventional technology]

A photosensitive composition prepared by mixing a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, a linear organic high molecular polymer having a proper film-forming ability as necessary, a thermal polymerization inhibitor, etc. A method of reproducing an image by a photographic method as an object is widely known at present. That is,
As described in JP-A-35-5093, JP-B-35-8495 and the like, the photosensitive composition undergoes photopolymerization upon irradiation with an actinic ray to become insoluble. Therefore, the photosensitive composition is formed into an appropriate film, the active light is irradiated through the negative image of the desired image, and only the unexposed area is removed with an appropriate solvent (hereinafter simply referred to as development). A superimposed image can be formed. It goes without saying that this type of photosensitive composition is extremely useful as a photosensitizer for printing plates or photoresists.

Conventionally, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, etc. are known as typical ones as photopolymerization initiators for polymerizable ethylenically unsaturated compounds. Has been. However, these initiators do not necessarily show sufficient photopolymerization initiation ability in practical use, and it took a lot of time for image formation by light irradiation. In order to improve this drawback, it has been generally proposed to combine a radical generator with a light absorber. For example, in the trichloromethyl compound of the S-triazine compound represented by the general formula (I) of the present invention, Japanese Patent Publication No.
Aromatic thiazole compounds shown in JP-A-8, JP-A-54
No. 151024, the merocyanine dye disclosed in JP-A-58-58
Aromatic thiopyrylium salt and aromatic pyrylium salt, other 9-phenyl acridine, A light absorber such as
It is known that a sufficient photopolymerization initiation ability is exhibited by combining a hydrogen donor such as -phenylglycine, 2-mercaptobenzothiazole, ethyl N ', N'-dimethylaminobenzoate and the like. However, when these radical generators are used in combination with a light absorber in the photosensitive layer of a lithographic printing plate, they have a drawback that they are strongly blocked by oxygen during image exposure.

[Problems to be solved by the invention]

The present invention has been made in order to solve the above problems, and therefore the effect of oxygen during image exposure can be reduced and the production of a printing original plate, a light which can give a useful photocured image to a photoresist or the like. It is intended to provide a polymerizable composition.

[Means for solving problems]

The present inventors, in view of the current state of the art as described above, as a result of earnest research, in a photopolymerizable composition, by adding an organic boron compound to a triazine-based compound as a photopolymerization initiator, oxygen at the time of image exposure The present invention has been completed based on the finding that the influence of the above can be reduced.

That is, the present invention relates to a monomer having at least one ethylenically unsaturated group capable of undergoing photopolymerization by actinic rays, a photopolymerization initiator of the general formula (I): Wherein R is an aryl group or a CH = CH _n W (but W is an aryl group or a heterocyclic group, n represents an integer of 1 to 3) is. ] And the general formula (II): [In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each is an alkyl group, an aryl group or a substituted aryl group. However, at least one of R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group. X ⁺ is an alkali metal or Is ammonium represented by. Here, R ₅ , R ₆ , R ₇ and R ₈ may be the same or different, hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group and an alicyclic group. And an allyl group. ] The photopolymerizable composition characterized by containing the organic boron compound represented by these.

"A monomer having at least one ethylenically unsaturated group capable of being photopolymerized by actinic rays" used in the present invention
Is 1 in at least one molecule with a boiling point of 100 ° C or higher at atmospheric pressure.
It is a monomer or oligomer having a molecular weight of 10,000 or less and having at least one ethylenically unsaturated group capable of addition polymerization. Examples of 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 diester. (Meth) acrylate, trimethylolethane tri (meth)
Acrylate, neopentyl glycol di (meth) acrylate, pentoerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, tri (acryloyloxyethyl) ) Isocyanurate, glycerin, trimethylolethane, and other polyhydric alcohols added with ethylene oxide or propylene oxide and then (meth) acrylated, JP-B-48-41708
Urethane acrylates as described in JP-B No. 50-6034, JP-A-51-37193, JP-A-48,
-64183, JP-B-49-43191, JP-B-52-30490, and other polyfunctional acrylates such as polyester acrylates, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, Methacrylate can be given. Furthermore, the Japan Adhesive Association magazine Vol.
The materials introduced as photocurable monomers and oligomers on pages 20, No. 7, pages 300 to 308 can also be used.

The photopolymerization initiator used in the present invention is a compound represented by the above general formula [I]. In formula [I], the aryl group preferably has 6 to 14 carbon atoms, and the heterocyclic group preferably includes furan, benzofuran, thiophene, pyrrole, benzoxazole and the like. The aryl group and the heterocyclic group may have a substituent. As these triazine compounds,
Wakabayashi et al., Bull. Chem. Soc. Japan, 42 , 2924 (1969), compounds such as 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- Examples thereof include bis (trichloromethyl) -S-triazine and 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine. In addition, compounds described in British Patent No. 1388492,
For example, 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 and the like, compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl). ) -4,6-Bis-trichloromethyl-S-
Triazine, 2- (4-ethoxy-naphth-1-yl)
-4,6-bis-trichloromethyl-S-triazine, 2
-[4- (2-Ethoxyethyl) -naphth-1-yl]
-4,6-bis-trichloromethyl-S-triazine, 2
-(4,7-Dimethoxy-naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis-triclomethyl-S-triazine Etc., compounds described in Japanese Patent Publication No. 59-1281, for example, Compounds described in German Patent No. 3337024, for example, Compounds described in Japanese Patent Application No. 60-198868, such as Etc., compounds described in Japanese Patent Application No. 61-186238, such as Etc. can be mentioned.

The organic boron compound used in the present invention has the general formula (I
It is a compound represented by I). In the formula, R _{1 to} R ₄ are preferably those having 1 to 18 carbon atoms, and may be derivatives such as the above-mentioned alkyl groups and aryl groups. Of these, R _{1 to} R ₄
Are preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group and a substituted phenyl group. On the other hand, R _{5 to} R ₈ are preferably those having 1 to 18 carbon atoms, and the above-mentioned derivatives such as alkyl groups can also be used. Of these, an alkyl group having 1 to 6 carbon atoms is preferable.

Examples of the alkali metal represented by X in the formula include sodium and potassium.

As the compound represented by the general formula [II], specifically, Etc. can be mentioned.

The content concentration of the photopolymerization initiator in the composition of the present invention is usually small, and when it is unsuitably high, unfavorable results such as shielding of effective rays are produced. A linear organic polymer in which the total of the photopolymerization initiator represented by the general formula (I) and the organic boron compound represented by the general formula (II) in the present invention is a photopolymerizable ethylenically unsaturated compound and optionally added The range of 0.01 to 20% by weight is sufficient with respect to the total amount of the polymer, and more preferably 1 to 10% by weight.
With good results. The proportions of the organic boron compound represented by the general formula (II) and the photopolymerization initiator of the general formula (I) are preferably 80 to 20% by weight and 20 to 80% by weight, respectively.

Further, the photopolymerization disclosing agent used in the present invention may optionally contain N-phenylglycine, 2-mercaptobenzothiazole, N,
The photopolymerization initiation ability can be further enhanced by providing a hydrogen-donating compound such as an N-dialkylbenzoic acid alkyl ester.

In the present invention, as the "linear organic high molecular polymer" to be added as necessary, it is of course necessary to select one having compatibility with the photopolymerizable ethylenically unsaturated compound. Any linear organic polymer that is compatible with the photopolymerizable ethylenically unsaturated compound may be used, but it is preferable that it be capable of developing with water or weak alkaline water. A linear organic high molecular polymer should be selected. The linear organic high molecular polymer is used not only as a film forming agent for the composition but also as a developer for water, weak alkaline water or an organic solvent. For example, water development becomes possible by using a water-soluble organic high molecular polymer. Examples of such linear organic polymer include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, and maleic acid. There are acid copolymers, partially esterified maleic acid copolymers and the like, and similarly, there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition to these, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In addition, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. In addition, alcohol-soluble nylon or a polyether ether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin is also useful for increasing the strength of the cured film. These linear organic high molecular weight polymers may be mixed in an arbitrary amount in the entire composition, for example, 100 to 900 parts by weight based on 100 parts by weight of a monomer having a photopolymerizable ethylenically unsaturated group. However, if it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the formed image.

Further, in the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photopolymerizable composition. It is desirable to do. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiopis (3-methyl-6-t-butylphenol). , 2,
Examples thereof include 2'-methylenebis (4-methyl-6-t-butylphenol), 2-menicaptobenzimidazole, N-nitrosophenylhydroxyamine primary cerium salt and the like. In some cases, an inorganic filler may be added for the purpose of improving the physical properties of the cured film.

The photopolymerizable composition of the present invention comprises, for example, a single solvent such as 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone and ethylene dichloride. Alternatively, these may be dissolved in a mixed solvent appropriately combined and provided on the support. The coating amount in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying are suitable, more preferably from 0.5 to 5 g / m ^2.

In the present invention, a diazo resin may be further added. The photosensitive diazo resin is a diazo resin represented by a condensation product of an aromatic diazonium salt and an active carbonyl group-containing compound such as formaldehyde.

Examples of the diazo resin include organic solvent-soluble diazo resin inorganic salts, which are reaction products of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, and hexafluorophosphate or tetrafluoroborate, and JP-B-47- 1167 and the sulfonates such as p-toluenesulfonic acid or a salt thereof, propylnaphthalenesulfonic acid or a salt thereof, butylnaphthalenesulfonic acid or a salt thereof, dodecylbenzenesulfonic acid or a salt thereof. An organic solvent-soluble diazo resin organic salt which is a reaction product of a salt, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or a salt thereof can be mentioned.

Further, 3-methoxy-4-diazo-diphenylamine as disclosed in JP-A-58-27141 is used as 4,4'-bis-
Those obtained by condensing with methoxy-methyl-diphenyl ether to give mesitylene sulfonate are also suitable.

The amount of the above-mentioned diazo resin added is arbitrary, but 0.5 to 20% by weight is preferably added.

Further, it is also known that a dye capable of forming a salt as a dye can be contained in the photopolymerizable composition, and by this, formation of a print-out image upon exposure and coloring of the image after development are realized. (For example, JP-A-50-138905).
No. 56-121031, No. 59-222842, No. 61-2744
33). Such dyes include crystal violet (CI42555), methyl violet 2B (CI42535), malachite green (CI42000), fuchsin (CI42510),
Crystal Violet-Carbinol Base (CI4255
5: 1), parafuchsin (CI42500), rhodamine B (CI45
170), Victoria Blue B (CI44045), Victoria Pure Blue BOH (CI42595), Brilliant Green (CI)
42040), Night Blue BX (CI51185), Neutral Red (CI50040), Rogerin Pure Blue 3G (CI510)
04), Orient Oil Blue # 603, Victoria Pure Blue BOH paratoluenesulfonate, naphthalenesulfonate or t-butylnaphthalenesulfonate, and crystal violet paratoluenesulfonate. The content of the dye is arbitrary, but it is preferably 0.1 to 5% by weight.

Furthermore, it goes without saying that the photopolymerizable composition of the present invention may contain other known additives for achieving the intended purpose (for example, a baking-out agent and the like).

As the above support, a dimensionally stable plate-like material is used. Such dimensionally stable plate-like materials include those conventionally used as a support for printing plates, and they can be preferably used. As such a support,
Paper, paper laminated with plastic (eg polyethylene, polypropylene, polystyrene, etc.), metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., eg cellulose diacetate, cellulose triacetate, propionic acid Includes plastic films such as cellulose, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and paper or plastic films laminated or vapor-deposited with the above metals. Be done. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Further, in the case of a support having a surface of metal, especially aluminum, it is subjected to surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment. Is preferred. Further, as described in the Japanese Patent No. 2,714,066, an aluminum plate that has been grained and then subjected to an immersion treatment in an aqueous solution of sodium silicate, an aluminum plate as described in Japanese Patent Publication No. 47-5125. It is also suitable to use an anodizing treatment followed by immersion treatment in an aqueous solution of an alkali metal silicate. The above-mentioned anodizing treatment is carried out, for example, by electrolysis of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid or the like, an organic acid such as oxalic acid, sulfamic acid or the like, or an aqueous solution or a non-aqueous solution of these salts, or a combination of two or more kinds. It is carried out by passing an electric current in a liquid using an aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

Further, a support subjected to electrolytic graining as disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503, and the anodizing treatment and sodium silicate Surface treatments that combine treatments are also useful.

Further, as disclosed in JP-A-56-28893, a brush grain, an electrolytic grain, an anodic oxidation treatment, and a sodium silicate treatment which are sequentially performed are also preferable.

Furthermore, after these treatments, a water-soluble resin such as polyvinyl phosphonic acid, a polymer or copolymer having a sulfonic acid group in its side chain, or a polyacrylic acid undercoat is also suitable.

These hydrophilization treatments are performed to make the surface of the support hydrophilic, in order to prevent harmful reactions of the publicly polymerizable composition provided thereon, and further to improve the adhesion of the photosensitive layer. It is provided for improvement.

On the layer of the photopolymerizable composition provided on the support, in order to completely prevent the polymerization inhibiting action by oxygen in the air,
For example, a protective layer made of a polymer having excellent oxygen barrier properties, such as polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more and acidic celluloses may be provided. The coating method of such a protective layer is described in detail, for example, in U.S. Pat. No. 3,458,311 and JP-B-55-49729.

The 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, a high pressure mercury lamp, etc. The exposed portion is removed, and the gum solution is finally applied to obtain a printing plate. Preferred as the developing solution is an alkaline aqueous solution containing a small amount of an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol. For example, U.S. Pat. No. 3,475,171.
And those described in No. 3,615,480.

Furthermore, JP-A-50-26601, JP-B-56-39464 and JP-A-56-39464
The developers described in the respective publications of 42860 are also excellent as developers for the above-mentioned photosensitive printing plate.

The present invention is described 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. That is, an aluminum plate having a thickness of 0.30 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. Ten%
It was immersed in sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and then washed with water. This was subjected to electrolytic surface-blocking treatment in an aqueous 1% nitric acid solution under the condition of V _A = 12.7 V in an aqueous 1% nitric acid solution at an anode charge of 160 clones / dm ² . When the surface roughness was measured, it was 0.6 μ ( _Ra display). Next, after soaking in 30% H ₂ SO ₄ aqueous solution and desmutting at 50 ° C for 2 minutes, the thickness becomes 2.7 g / m ² in 20% H ₂ SO ₄ aqueous solution at current density 2 A / dm ² . Then, it was anodized for 2 minutes. Then, it was immersed in a 2.5% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

On the aluminum plate thus treated, a dry coating weight of 2 g / m ^{2 of a} photosensitive solution comprising a photopolymerizable composition having the following composition was applied.
To obtain a photosensitive plate. The photopolymerization initiator used and the amount used in the photosensitive solution are shown in Table 1.

[Composition of Photosensitive Solution]

-Trimethylolpropane triacrylate 1 g-Copolymer of allyl methacrylate / methacrylic acid (copolymerization molar ratio 85/15) 5 g-Photoinitiator (shown in Table 1) X g-Organic boron compound (first (Shown in the table) Y g ・ Dodecylbenzene sulfonate of condensate of p-diazodiphenylamine and formaldehyde 0.3 g ・ Victoria Pure-BOH naphthalene sulfonate 0.2 g ・ Behenic acid 0.1 g ・ Behenamide 0.1 g ・ F -177 (Dainippon Ink and Co., Ltd., fluorinated surfactant) 0.05 g-Ethylene glycol monomethyl ether 50 g-Methanol 15 g-Methyl ethyl ketone 30 g-Pure water 5 g Fuji was placed on the photosensitive layer of the photosensitive lithographic printing plate thus obtained. Fuji PS Step Guide (ΔD = 0.
A gray scale whose transmission density changes discontinuously at 15) was brought into close contact, and 100 counts were performed from a distance of 1 m using a printer FT26V2UPNS (light source: 2KW metal halide lamp) manufactured by Nuark, USA. At this time, in order to compare the effect of oxygen of the sample, the degree of vacuum of the printer frame was adjusted.

Next, a developer having the following composition: -sodium sulfite 3g-benzyl alcohol 30g-triethanolamine 20g-monoethanolamine 5g-Perex NBL (sodium t-butylnaphthalenesulfonate, manufactured by Kao Atlas Co., Ltd.) 30g-water 1000g It was processed to remove the unexposed part.

The sensitivity was measured at different vacuum levels of 0 Torr and 600 Torr of the exposure machine by changing the combination of the photopolymerization initiator and the organic boron compound, and the results are shown in Table 1.

As shown in the products of the present invention in Table 1, it was found that when a specific photopolymerization initiator and an organic boron compound were combined, the sensitivity was higher than that of a single compound and the influence of oxygen was less likely to occur.

 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-57-19737 (JP, A) JP-A-59-95534 (JP, A) JP-A-59-107350 (JP, A) JP-A 62- 143043 (JP, A) JP 60-60104 (JP, A) JP 58-29803 (JP, A) JP 54-151024 (JP, A)

Claims (2)

[Claims] 1. A monomer having at least one ethylenically unsaturated group photopolymerizable by actinic rays, a photopolymerization initiator of the general formula (I): Wherein R is an aryl group or a CH = CH _n W (but W is an aryl group or a heterocyclic group, n represents an integer of 1 to 3) is. ] And the general formula (II): [In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each is an alkyl group, an aryl group or a substituted aryl group. However, at least one of R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group. X ⁺ is an alkali metal or Is ammonium represented by. Here, R ₅ , R ₆ , R ₇ and R ₈ may be the same or different, hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group and an alicyclic group. And an allyl group. ] The photopolymerizable composition characterized by containing the organic boron compound represented by these. 2. The photopolymerizable composition according to claim 1, which contains a linear organic polymer.