JPH0876369A - Photopolymerizable photosensitive material - Google Patents

Abstract

PURPOSE: To improve the preservation stability of a photopolymerizable compsn. CONSTITUTION: A layer of a polymer obtd. by polymerizing at least acrylic acid and/or methacrylic acid is formed on a substrate and a layer of a photopolymerizable compsn. contg. at least (a) an ethylenically unsatd. compd. which is not gas at ordinary temp., (b) a phenylglycine deriv. represented by the formula and (c) a photopolymn. initiator is further formed to obtain the objective photopolymerizable photosensitive material. In the formula, R<1> is 1-12C alkyl, 2-12C alkenyl, etc., R<1> may form a condensed polkycyclic compd. in combination with the benzene ring. (n) is 0 or 1 and each of R<2> and R<3> is H or 1-12C alkyl.

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 highly sensitive photopolymerizable material having excellent 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 a low molecular weight organic acid to the protective layer, which is disclosed in JP-B-4-21184, JP-A-Sho 6
No. 0-262153, the addition of an acid to the photopolymerizable layer disclosed in JP-A-1-201652 is known.

[0003]

However, the photopolymerizable composition containing the phenylglycine derivative is not sufficient in the above-mentioned method and is excellent in storage stability, especially at high temperature or even when stored for a long time under high temperature and high humidity. A photopolymerizable photosensitive material that does not deteriorate in performance is required.

[0004]

In order to solve the above problems, that is, to improve the storage stability of a photopolymerizable photosensitive material containing a phenylglycine derivative, the present invention has been earnestly studied, and as a result, The invention was completed. That is, the present invention provides a high-molecular polymer layer obtained by polymerizing a monomer containing at least acrylic acid and / or methacrylic acid on a support, and further at least (a) one type of non-gaseous substance at room temperature. An ethylenically unsaturated compound (b) is a photopolymerizable photosensitive material provided with a layer of a photopolymerizable composition containing a phenylglycine derivative (c) photoinitiator represented by the general formula (1). As the high molecular weight polymer obtained by polymerizing acrylic acid and / or methacrylic acid used in the present invention, a molecular weight of 1,000 to 100,000 is suitable. The above polymer obtained by polymerizing acrylic acid and / or methacrylic acid can be used alone or in combination of two or more.

As a method for treating a support for providing a polymer layer obtained by polymerizing a monomer containing at least acrylic acid and / or methacrylic acid, a treatment solution having a concentration of 0.01 to 30% by weight is used. It is suitable to carry out the immersion treatment within the range, the temperature range of 10 to 90 ° C. and the treatment time range of 5 to 300 seconds. On the support thus obtained, at least (a) one kind of non-gaseous ethylenically unsaturated compound at room temperature (b) phenylglycine derivative represented by the general formula 1 (c) photoinitiator is contained. There is provided a photopolymerizable composition containing a photopolymerizable photosensitive material provided with a layer composed of the photopolymerizable composition. The ethylenically unsaturated compound used in the present invention may be any monomer as long as it is a monomer suitable for the chain growth addition reaction initiated by free radicals.

Preferable examples include pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and the like.

Specific examples of the phenylglycine derivative used in the present invention include N-phenylglycine and N- (3
-Chlorophenyl) glycine, N- (2,4 dichlorophenyl) glycine, N- (2-nitrophenylyl) glycine, N- (4-acetylphenyl) glycine, N-
(4-Nitrophenylyl) glycine, N- (4-cyanophenylyl) glycine, N- (4-chlorophenyl) glycine, N- (2-methylphenyl) glycine, N-
(2-Methoxyphenyl) glycine, N- (2,4-dimethoxyphenyl) glycine, N-methyl-N-phenylglycine, N- (3cyanophenyl) glycine, N-
(4-carbamoylphenyl) glycine, N- (4-sulfamoylphenyl) glycine, and the like.

The photoinitiator to be used in the present invention is not particularly limited, but α-carbonyl compound, acyloin ether, aromatic acyloin compound, polynuclear quinone, hexaarylbisimidazole, trihalomethyl-S- Also included are triazine, acridine, phenazine, onium salts such as triphenylsulfonium salts and diaryliodonium salts, titanocene, iron allene complexes and the like.

A sensitizer may be added to the present invention.
Although not particularly limited, preferably cyanine, carbocyanine, merocyanine, aromatic carbonyl, styryl, acridine, thiazine, oxazine, coumarin, polycyclic aromatic hydrocarbon, polyarylamine, pyrylium,
It is at least one dye selected from the group consisting of thiapyrylium and xanthene.

A thermoplastic high molecular weight organic polymer binder may preferably be present in the composition of the present invention. Polymeric binder types include (1) terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid based copolyesters, (2) polyamides,
(3) vinylidene chloride copolymer, (4) ethylene /
Vinyl acetate copolymer, (5) cellulose ether, (6) polyethylene, (7) synthetic rubber, (8) cellulose ester, (9) polyvinyl ester including polyvinyl acetate / acrylate and polyvinyl acetate / methacrylate copolymer, ( 10) Polyacrylates and poly α-alkyl acrylate esters such as polymethyl acrylate and polyethyl methacrylate, (11) high molecular weight ethylene oxide polymers having a weight average molecular weight of 4,000 to 4,000,000 (polyethylene glycol), (12) polyvinyl chloride and its Copolymer,
(13) Polyvinyl acetal, (14) Polyformaldehyde, (15) Polyurethane, (16) Polycarbonate and
(17) Examples include 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 after exposure to actinic radiation. Polymeric binders that are insoluble in it 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 copolymer, acrylic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer 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.

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 and di-t.
-Butyl-p-cresol, pyrogallol, di-t-butylcatechol, benzoquinone, 2-mercaptobenzimidazole, N-nitrophenylhydroxyamine primary cerium and the like. The addition amount of the thermal polymerization inhibitor is preferably 0.01 to 5% by weight based on the total composition. 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.

The photopolymerizable composition of the present invention can be coated on a wide variety of substrates. By "substrate" herein is meant any natural or synthetic support, preferably one that may be present in the form of a flexible or rigid film or sheet. For example, the material can be a metal sheet or foil, a synthetic organic resin sheet or film, cellulosic paper, fiberboard or the like or a composite of two or more of these materials. Specific materials include alumina plast aluminum, anodized aluminum, aluminum plast polyethylene terephthalate film, polyethylene terephthalate film,
Examples include electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, cellulose acetate film and the like.

The particular material is generally determined by the relevant application purpose. For example, if a printed circuit is manufactured,
The material can be a plate coated with copper on a fiberboard. In the manufacture of lithographic printing plates,
The material can be anodized aluminum.

In the present invention, the thickness of the photopolymerizable composition is
The thickness is 0.1 to 250 μm, preferably 0.5 to 50 μm. The desired thickness is determined by the application. On the layer of the photopolymerizable composition provided on the substrate, a protective layer made of a polymer having an excellent oxygen barrier property, such as polyvinyl alcohol, is provided in order to prevent a polymerization inhibitory action by oxygen in the air. Alternatively, a cover film such as a polyethylene terephthalate film may be laminated.

The light source used for the exposure is a carbon arc lamp, high pressure, medium pressure, low pressure mercury lamp, xenon lamp, metal halide lamp, argon ion laser, laser such as helium cadmium laser, helium neon laser, fluorescent lamp, Tank stain light and sunlight can be used.

[0017]

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, it was immersed in a 0.1% polyacrylic acid aqueous solution at 35 ° C. for 1 minute, washed with water and dried to obtain an aluminum substrate. Next, a photosensitive layer coating solution having the following composition was applied and dried at 100 ° C. for 1 minute with a hot air dryer to obtain a coating film having a thickness of 2.0 g / m ² . (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 '-(O-chlorophenyl) -4,4', 5,5'-Tetraphenylbisimidazole 5 parts Michler's ketone 3 parts N-phenylglycine 6 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 drier 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) Water 900 parts After leaving 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.
The background stain was evaluated when 10,000 copies were printed on a high-quality paper using a commercially available black ink. The printing plate was evaluated in the following three stages. ○: Good △: Partial background stain occurred ×: Background stain occurred

Example 2 Polymethacrylic acid was used instead of polyacrylic acid in Example 1, and the same operation as in Example 1 was repeated to evaluate the background stain of the printing plate.

COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was repeated and the background smear of printing was evaluated by using 70 ° C. 2% water glass No. 3 in place of the 35 ° C. 0.1% polyvinyl aqueous solution in Example 1. Examples 1 and 2
The results of Comparative Example 1 are shown in Table 1.

[0021]

[Table 1]

Examples 5 to 9 A coating solution for the photosensitive layer having the following composition was applied on the aluminum substrate described in Example 1 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 -Cyclopentadienyl) (η ⁶ -Toluene) iron (II) hexafluorophosphate 5 parts 7-diethylamino-3- (2-benzimidazolyl-coumarin 3 parts phenylglycine derivative 6 parts methyl ethyl ketone 150 parts dimethylformamide 150 parts Next, the same protective layer coating solution as in Example 1 Was applied and dried in a hot air drier for 1 minute at 100 ° C., and a protective layer having a thickness of 1.2 g / m ² was provided to obtain a test piece. After leaving it for 10 days, it was imagewise scanned and exposed with an argon ion laser (50 mW, beam diameter 25 μ), and immersed in the developer used in Example 1 at 30 ° C. for 23 seconds and washed with water to obtain an uncured portion. Remove Dried to obtain a lithographic printing plate. And scumming was carried out printing tests as in Example 1 was able to satisfactorily print without.

Comparative Examples 2 to 4 70 instead of polyacrylic acid in Examples 3, 5 and 6
Using the No. 3 water glass at 2 ° C., the same operation was repeated, and the background stain of the printing was evaluated. The above results are shown in Table 2.

[0024]

[Table 2]

[0025]

The photopolymerizable light-sensitive material of the present invention has excellent storage stability and does not deteriorate in developability even after long-term storage. In the case of a lithographic printing plate, stains do not occur on non-image areas. Good printed matter can be obtained.

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Claims (1)

[Claims] 1. A high-molecular polymer layer obtained by polymerizing a monomer containing at least acrylic acid and / or methacrylic acid is provided on a support, and at least (a) one kind of non-gaseous at room temperature. A photopolymerizable photosensitive material comprising an ethylenically unsaturated compound (b), a phenylglycine derivative represented by the following general formula (1), and a layer comprising a photopolymerizable composition containing a photoinitiator (c). Embedded image In the formula, R ¹ is a C _{1 to} C ₁₂ alkyl group, a C _{2 to} C ₁₂ alkenyl group, a C _{2 to} C ₁₂ alkynyl group, a C _{1 to} C ₈ alkoxy group, a cyano group, an alkylthio group, a phenoxy group, monocarboxylic acids and esters and amides of C ₂ -C _6, phenyl group, an alkanoyl group of C ₂ -C _5, an ammonium salt, a pyridinium group, a nitro group, an alkylsulfinyl group, alkylsulfonyl group, selected from Surufamonoru group, benzene N, which may form a condensed polycyclic compound with a ring, is 0 or 1, R ² and R ³ are the same or different groups, and are selected from hydrogen or a C _{1 to} C ₁₂ alkyl group. .