JPH0728251A - Photopolymerizable photosensitive material - Google Patents

Abstract

PURPOSE:To prevent the deterioration of a photopolymerizable photosensitive material even when preserved under high-temp. and high-humidity conditions for a long time by incorporating an org. high molecular polymer and an alkali metal silicate into the protective layer. CONSTITUTION:At least a photopolymerizable layer and a protective layer transparent to an active beam and substantially impermeable to oxygen are provided on a substrate. The protective layer contains an org. high molecular polymer (a) soluble in water or a mixture of water and a water-miscible org. solvent and an alkali metal silicate (b). The polymer (a) is substantially transparent to an active beam when provided in layers and impermeable to oxygen, and the polymer soluble in water or a mixture of water and water-miscible org. solvent is used. Sodium silicate, lithium silicate, potassium silicate and cesium silicate are used as the alkali metal silicate (b), and sodium silicate and potassium silicate are preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material having a photopolymerizable layer, and more particularly to a photosensitive material having an oxygen-blocking protective layer and excellent in storage stability.

[0002]

2. Description of the Related Art Photopolymerizable photosensitive materials are widely used as printing plates, resist materials, hologram sensitive materials and the like.
However, it is known that the storage stability is low. In particular, there was a problem with storage stability at high temperatures or under high temperature and high humidity. As a countermeasure, addition of a polymerization inhibitor or a metal chelating agent is known. Further, addition of a mineral acid or an organic acid to the protective layer, which is disclosed in JP-B-4-21184, JP-A-60-2
62153, the addition of acid to the photopolymerizable layer is known, as disclosed in JP-A-1-201652.

[0003]

However, the above-mentioned method is not sufficient and is excellent in storage stability, especially at high temperature.
There is also a demand for a photopolymerizable photosensitive material which does not deteriorate in performance even when stored under high temperature and high humidity for a long time.

[0004]

In order to solve the above problems, that is, to improve the storage stability of a photopolymerizable photosensitive material, the present invention has been earnestly studied, and as a result, the present invention has been completed. Arrived That is, the present invention provides a photopolymerizable light-sensitive material, which comprises at least a photopolymerizable layer and a protective layer which is transparent to actinic rays and substantially impermeable to oxygen on a support. Is a photopolymerizable photosensitive material containing (a) an organic high molecular polymer soluble in water or a mixed solvent of water and a water-miscible organic solvent, and (b) an alkali metal silicate. . The protective layer of the present invention contains at least (a) an organic polymer and (b) an alkali metal silicate. The above component (a)
The organic high molecular polymer is a substance which is substantially transparent to actinic rays when provided in a layered form and has a property of blocking oxygen, and is water-soluble or water-miscible organic compound. What is soluble in the mixed solvent with the solvent is used. As such an organic high molecular polymer, polyvinyl alcohol and a partial ester of polyvinyl alcohol containing an unsubstituted vinyl alcohol unit required for it to be solvent-soluble as described above, an ether and an acetal,
80-90% hydrolyzed polyvinyl acetate, carboxymethyloxycellulose, methylcellulose, partially saponified polyacrylic acid ester, hydroxypropylcellulose, gelatin, gum arabic, methyl vinyl ether /
A mixture of maleic anhydride copolymers is used. Of these, polyvinyl alcohol is preferable because it has a particularly excellent oxygen barrier property. As the alkali metal silicate of the component (b), sodium silicate, lithium silicate, potassium silicate, and cesium silicate are used. Of these, sodium silicate and potassium silicate are particularly preferable.

The above-mentioned alkali metal silicates are used alone or
The above combinations can be used. The amount used is in the range of 5 to 80% by weight, based on the total weight of the protective layer,
It is particularly preferably 8 to 50% by weight. Further, a surfactant may be added for uniform coating. The coating thickness of the protective layer is in the range of 0.1 to 10 g / m ² , more preferably 0.3.
~ ² g / m ² . The ethylenically unsaturated compound used in the present invention is a monomer suitable for chain growth addition reaction initiated by free radical, and examples thereof include pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, Examples thereof include polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate. The photoinitiator used in the present invention is not particularly limited, but α-carbonyl compound, acyloin ether, aromatic acyloin compound, polynuclear quinone, hexaarylbisimidazole, trihalomethyl-S-triazine, acridine. , Phenazine, onium salts such as triphenylsulfonium salts and diaryliodonium salts, titanocene, iron allene complexes and the like. The amount used is in the range of 0.2 to 20% by weight, preferably 1 to 10% by weight, based on the total composition of the photopolymerizable layer.

A thermoplastic high molecular weight organic polymer binder may preferably be present in the composition of the present invention. Polymer binder types include (i) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid, (ii) polyamides, (ii)
i) vinylidene chloride copolymer, (iv) ethylene / vinyl acetate copolymer, (v) cellulose ether,
(Vi) polyethylene, (vii) synthetic rubber, (viii) cellulose ester, (ix) polyvinyl ester including polyvinyl acetate / acrylate and polyvinyl acetate / methacrylate copolymer, (x) polyacrylate and poly α-alkyl acrylate ester, for example Polymethyl acrylate and polyethyl methacrylate, (xi) high molecular weight ethylene oxide polymer (polyethylene glycol) having a weight average molecular weight of 4,000 to 4,000,000, (xii) polyvinyl chloride and copolymers thereof,
(xiii) polyvinyl acetal, (xiv) polyformaldehyde, (xv) polyurethane, (xvi) polycarbonate and (xvii) polystyrene. In the compositions of the present invention, a particularly preferred polymeric binder is one in which the unexposed photopolymerizable coating is soluble in predominantly aqueous solutions, such as alkaline solutions, but relatively insoluble after exposure to actinic radiation. Such polymeric binders are preferred. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups.

There are methacrylic acid copolymers, acrylic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like. In addition, there are cellulose having a carboxyl group in the side chain, a polymer having a hydroxyl group in the side chain and a cyclic acid anhydride added thereto, and the like. The binder is 0 to 80% by weight, preferably 30 to 70% by weight. Further, a sensitizer may be present if necessary. In particular, it is necessary to increase sensitivity to visible light, and examples thereof include cyanine, carbocyanine, merocyanine, aromatic carbonyl, styryl, acridine, thiazine, oxazine, coumarin, polycyclic aromatic hydrocarbon, and polyaryl. Examples include dyes such as amine, pyrylium, thiapyrylium, and xanthene. In addition, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photopolymerizable composition. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, di-t-butylcatechol, benzoquinone, 2-
Examples include mercaptobenzimidazole and N-nitrophenylhydroxyamine primary cerium. The amount of the thermal polymerization inhibitor added is 0.01 to 5% by weight based on the total composition.
Is preferred. Further, if necessary, an inert additive such as a non-polymerizable plasticizer, a dye, a pigment and a filler may be blended to such an extent that the photopolymerizability is not significantly impaired.

In the present invention, the thickness of the photopolymerizable composition is
The thickness is 0.1 to 250 μm, preferably 0 to 50 μm.
The desired thickness is determined by the application. The supports used in the present invention include all natural or synthetic supports, preferably those which may be present in the form of flexible or rigid films or sheets. For example, the material is a metal sheet or foil,
Synthetic organic resin sheet or film, cellulose paper,
It may be fiberboard or the like or a composite of two or more of these materials. Specific materials include alumina-plasted aluminum, anodized aluminum, aluminum-plasted polyethylene terephthalate film, polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, cellulose acetate. Examples include films and the like. The particular material will generally be determined by the relevant application purpose. For example, if a printed circuit is manufactured, the material can be a copper coated plate on a fiberboard. In the manufacture of lithographic printing plates, the material can be anodized aluminum.

[0009]

EXAMPLES The present invention will be described in more detail with reference to the following examples, in which parts and% are based on weight. Example 1 A brush-polished aluminum plate having a thickness of 0.24 mm was immersed in 5% sodium hydroxide at 30 ° C. for 1 minute, washed with water, neutralized with nitric acid, and washed with water. Current density 3A / in 10% sulfuric acid
It was anodized to have a thickness of 3 g / m ^{2 in} dm ² .
After that, the aluminum substrate was obtained by immersing in 70 ° C. 2% No. 3 water glass for 1 minute, washing with water and drying. Next, apply the photosensitive layer coating liquid of the following composition and dry it at 100 ° C for 1 minute with a hot air drier.
A coating film of 2.0 g / m ² was obtained. (Composition of photosensitive layer coating liquid) Poly (methyl methacrylate / methacrylic acid) 52 parts 85/15 molar ratio Molecular weight 80,000 Tetraethylene glycol diacrylate 40 parts 2,2 '-(0-chlorophenyl) -4,4', 5,5'-Tetraphenylbisimidazole 5 parts Michler's ketone 3 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts

Next, a protective layer coating solution having the following composition was applied and dried at 100 ° C. for 1 minute with a hot air dryer to provide a protective layer having a thickness of 1 g / m ² to obtain a test piece. (Composition of coating liquid for protective layer) Polyvinyl alcohol 100 parts (Complete saponification, degree of polymerization 500) Nonionic surfactant 1 part (Neugen EA150 Daiichi Kogyo Seiyaku) Alkali metal silicate (shown in Table 1) 0- 50 parts Water 900 parts The test piece was left under the condition of 40 ° C and 80% RH for 10 days.
Imagewise exposed with an ultra-high pressure mercury lamp (Oak's bright room printer), and a negative PS plate developer (Fuji Photo Film, DN-3C).
) It was immersed in a 1: 1 diluted solution (30 ° C.) for 20 seconds, washed with water to remove the uncured portion, and air-dried to obtain a lithographic printing plate. The lithographic printing plate obtained in this way was applied to the Ryobi printing machine 3200MCD.
When printed on high-quality paper with commercially available black ink using
As shown in Fig. 4, the printing plate without the alkali metal silicate added to the protective layer (Sample 9) showed scumming, while the added printing plate (Samples 1 to 8) had no scumming and could be printed. It was The printing plate was evaluated in the following three stages. ○: Good △: Partial background stain ×: Background stain occurred

[0011]

[Table 1]

Example 2 On the aluminum substrate described in Example 1, a photosensitive layer coating solution having the following composition was applied and dried with hot air to obtain a coating film having a thickness of 1.8 g / m ² . (Photosensitive layer coating liquid composition) Poly (methyl methacrylate / methacrylic acid / n-hexyl methacrylate) 52 parts Molar ratio 65/15/20 Tetraethylene glycol dimethacrylate 40 parts (η ⁵ -Cyclopetadienyl) ( η ⁶ -Toluene) iron (II) hexafluorophosphate 5 parts 7-diethylamino-3- (2-benzothiazolyl) -coumarin 3 parts methyl ethyl ketone 150 parts dimethylformamide 150 parts Next, as in Example 1, a protective layer coating solution was applied. It was applied and dried in a hot air dryer at 100 ° C. for 1 minute, and a protective layer having a thickness of 1.2 g / m ² was provided to obtain a test piece. The obtained test piece was left under the condition of 40 ° C. and 80% RH for 10 days, and then imagewise scanned and exposed by an argon ion laser (50 mW, beam diameter 25 μ). Then, it was immersed in the developer used in Example 1 at 30 ° C. for 23 seconds, washed with water to remove the uncured portion, and air-dried to obtain a lithographic printing plate. Then, a printing test was conducted in the same manner as in Example 1 and Table 2 was obtained.

[0013]

[Table 2]

[0014]

The photopolymerizable light-sensitive material of the present invention has good developability even after long-term storage under high temperature and high humidity and, in the case of a lithographic printing plate, is free from stains on non-image areas. Printed matter can be obtained.

Claims (1)

[Claims] 1. A photopolymerizable light-sensitive material having at least a photopolymerizable layer and a protective layer, which is transparent to actinic rays and substantially impermeable to oxygen, on a support. (A) an organic high molecular polymer soluble in water or a mixed solvent of water and a water-miscible organic solvent, and (b) an alkali metal silicate salt.