JPS63249840A - Image forming material - Google Patents

Abstract

PURPOSE:To obtain the titled material having the less photodiffusion and the excellent resolving power, even in the case of gather-heating and capable of developing with a practical time by incorporating a specified ternary copolymer, a photoinitiator and an ethylenic unsatd. monomer in the titled material. CONSTITUTION:In the titled material comprising at least a photosensitive resin layer and a protective layer mounted on a supporting body, the photosensitive resin layer contains the ternary copolymer obtd. from a vinylmonomer contg. an acidic group, vinylmonomers which does not contain the acidic group and has <=9.3 SP value, and >=11.0 SP value respectively, the photoinitiator and the ethylenic unsatd. monomer. The former acidic group free vinylmonomer is exemplified by styrene and hexylmethacrylate, etc., the latter acidic group free vinylmonomer is exemplified by acrylonitrile and vinylacetate, etc. The vinylmonomer is exemplified by acrylic acid and methacrylic acid, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an image-forming material useful in the field of photography, particularly a non-silver salt lithium film used as a mask film;
This invention relates to photosensitive image-forming materials used in the manufacture of lithographic printing plates, printed circuits, etc.

(Prior art) Lith film, lithography, etc. require high resolution, and Lith film in particular is used as an image-forming material for character extraction, overprinting,
It is used in a variety of complex ways, such as reverse firing. The plate-making process of blank letters and overprinting is used to insert blank letters into a mesh, and 2 to 5 or more sheets of various films are layered between the negative and the photosensitive material and exposed. .

(Problem to be solved by the invention) In the conventional technology, when many layers of film are stacked, the light is diffused greatly while it reaches from the negative to the photosensitive material, making it difficult to achieve accurate resolution. There is no. In other words, a negative pattern has a problem in that the line width is thick, and a positive pattern is filled with a large amount of line width.

What can be easily analogized to solve this problem is
This is a method of reducing the amount of light to suppress the amount of light diffusion, but reducing the amount of light reduces curing inside the photosensitive layer, leading to loss of images during development, lowering film strength, and various other problems. So I don't like it.

Furthermore, currently, all commercially available non-silver salt photosensitive image-forming materials do not have satisfactory performance when used for this stamping and overprinting operation due to the reasons mentioned above. be.

(Means for Solving the Problems) The present invention solves the above-mentioned conventional drawbacks, and its purpose is to improve the character overprinting property, achieve high resolution, and provide clear images. The object of the present invention is to provide an image-forming material capable of reproducing. That is, the present invention provides an image-forming material having a photosensitive resin layer and a retention trlI layer on a support, in which the photosensitive resin layer contains a vinyl monomer containing an acid group, SPPO 23 or less, and does not contain an acid group. A terpolymer (A
), a photoinitiator (B), and an ethylenically unsaturated monomer (C).

In the ternary copolymer (A) used as a binder contained in the photosensitive resin layer of the present invention, the ternary copolymer constituting the copolymer is a vinyl monomer containing an acid group, S
Acid group-free vinyl monomer with a PPO of 23 or less and S
It consists of a vinyl monomer that does not contain acid groups and has a P value of 11.0 or more. In the present invention, the SP value is a value determined by the Fedors method, and indicates a solubility parameter. For example, the higher the value, the stronger the polarity. It means getting closer to water.

Specifically, examples of acid group-free vinyl monomers with an SPPO of 23 or less (hereinafter referred to as monomer a) include styrene, hexyl methacrylate, pentafluoropropyl methacrylate, trifluoroethyl methacrylate, butyl acrylate, etc. As an agent, it plays the role of imparting water resistance and high film strength.

On the other hand, an acid group-free vinyl monomer with an SP value of 11.0 or more
(hereinafter referred to as monomer b) is relatively hydrophilic and serves as a binder to provide alkaline developability, and specific examples thereof include acrylonitrile, vinyl acetate, and methyl acrylate.

Furthermore, examples of the acid group-containing vinyl monomer (hereinafter referred to as C monomer) constituting the terpolymer of the present invention include acrylic acid, methacrylic acid, and the like.

The amount of each monomer in the terpolymer is 2 to 93 parts by weight of monomer a, preferably '5
~85 parts by weight, 2 to 93 parts by weight of the B monomer, preferably 5 to 85 parts by weight, and 5 to 50 parts by weight, preferably 8 to 40 parts by weight of the C monomer.

Preferred combinations include, for example, styrene/vinyl acetate/methacrylic acid, styrene/acrylonitrile/methacrylic acid, hexyl methacrylate/vinyl acetate/methacrylic acid, and the like.

Next, as the photoinitiator (B) contained in the photosensitive resin layer, benzyl, benzophenone, Michler's ketone, 4.41-
Benzophenone derivatives such as bis(diethylamino)benzophenone and 4-methoxy-41-dimethylaminobenzophenone; aromatics such as anthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, and phenanthraquinone; Ketones, benzoin, benzoin alkyl ethers, benzoin derivatives such as α-methylbenzoin, benzyl, dimethylkecool and polynuclear quinone mixtures, mixtures of 2,4,5-triarylimidazole dimers and free radical generators. and so on.

Among these, a photoinitiator consisting of a 2,4,5-triarylimidazole dimer and a free radical generator is preferably used because of its high sensitivity.

As the 2,4,5-triarylimidazolite, %2-(0-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4
・5-=-diphenylimidazole dimer, 2-(p-
triphenylimidazole dimers such as methylmercaptophenyl)-4,5-diphenylimidazole dimer, 2-(1-naphthyl)-4,5-diphenylimidazole dimer, 2-(9-anthryl)-4・5-diphenylimidazole dimer, 2-(2-methoxy-1-
naphthyl)-4,5-diphenylimidazole dimer,
Examples include polycyclic aryl-4,5-diphenylimidazole dimers such as 2-(2-chloro-1-naphthyl)-4°5-diphenylimidazole dimer.

Examples of the free W1 radical generator include p-aminophenyl ketone compounds such as p,p'-bis(dimethylamino)benzophenone, leucotriphenylmethane dyes such as leucomalachite green and leuco crystal violet, and 2,4-diethyl- Ring diketone compounds such as 1,3-cyclobutanedione, thioketone compounds such as 4,41-bis(dimethylamino)thiobenzophenone, 2-
Examples include mercaptan compounds such as mercaptobenzothiazole, N-phenylglycine, dimedone, and 7-diethylamino-4-methylcoumarin.

Two or more kinds of the above photoinitiators may be mixed. Furthermore, it is also possible to add sensitizers to increase the sensitivity of these photoinitiators. As the sensitizer, xanthine-based, acridine-based, thiazine-based, cyanine-based dyes, and the like are suitably used.

The ethylenically unsaturated monomer (C) contained in the photosensitive resin layer of the present invention is a monomer and/or oligomer having one or more polymerizable double bonds in the molecule. Such compounds can undergo addition polymerization to form polymers through radical reactions initiated by photoinitiators. Specifically, hexyl (meth)acrylate [(meth)acrylate refers to acrylate and/or methacrylate]
, cyclohexyl (meth)acrylate, rariul (meth)acrylate, benzyl (meth)acrylate and other alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, N,N'-dialkylaminoalkyl (meth)acrylates, methoxy ethyl(
Alkyl ether (meth)acrylates such as meth)acrylate, ethoxyethyl (meth)acrylate,
Halogenated alkyl (meth)acrylates, alkyl (meth)acrylamides, diethylene glycol di(
Polyalkyl ether (meth)acrylates such as meth)acrylate and triethylene glycol di(meth)acrylate, (meth)acrylates of polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol, and (meth)acrylic acid. , reaction products of glycidyl (meth)acrylate and active hydrogen-containing compounds, reaction products of glycidyl compounds and (meth)acrylic acid, condensates with N-methylol compounds, polyisocyanate compounds and hydroxyalkyl (
These include reaction products with meth)acrylates. Two or more types of ethylenically unsaturated monomers (C) may be mixed. These seven polymers include the proportion of the monomer in the photosensitive resin layer, the type of binder, the type and amount of photoinitiator, and the type and amount of actinic ray absorbers such as carbon black, which will be described later. The type and amount of the compound are determined in consideration of the compatibility, film-forming properties, stability, desired photosensitivity, etc. of the compound.

If the monomer has a low boiling point, it tends to be effective during or after film formation, so monomers with a high boiling point are more preferred.

In the present invention, the photosensitive resin color may contain an actinic ray absorber if necessary. Actinic ray absorbers are used for the purpose of making images easier to see after development, or for purposes such as adjusting lith film.As actinic ray absorbers,
Compounds whose ultraviolet or visible absorption spectrum overlaps with that of the photoinitiator used, such as ultraviolet absorbers, ultraviolet absorbing dyes, other dyes, and pigments, are used. Examples include powders of carbon black, titanium oxide, iron oxide, various metals, metal oxides, sulfides, pigment black (C, r, 5044
0), Chrome Yellow Light (C, 1, 77803)
, 2,21-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, hydroxyphenylbenzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)benzotriazole, resorcinol monobenzoate, ethyl-2-cyano -3
・3-Diphenylacrylate, Toluidine Yellow GW (C,I, 71880), Molybdenum Orange (C,I, 77805), Sudan Yellow (C
, I, 30), oil orange (C, 1°1205
5) etc. Among the actinic light absorbers mentioned above, carbon black is particularly preferably used.

The actinic ray absorber is blended so that the total absorbance of the photosensitive resin layer, the protective layer described below, and the subbing layer provided if necessary is in the range of 1.5 to 4 within the active ray range used. Preferably.

An actinic ray absorbing layer is provided between the photosensitive resin and the support,
An actinic ray absorber may be included here. As the polymer constituting the actinic ray absorbing layer, for example, the same compound as that used for the above-mentioned binder is used. The amount of actinic ray absorber contained in the entire image forming plate including this notification (
(excluding the support) is adjusted so that the absorbance is within the above range.

The thickness of the photosensitive resin layer and the actinic ray absorption layer is not particularly limited, but in order to obtain high resolution, the thickness of each is 1 to 5.
It is desirable that the thickness is about μm + 2 to 4 μm.

In the present invention, for the purpose of protecting the surface or preventing inhibition of the photopolymerization reaction by oxygen in particular, the photosensitive resin layer is a protective film with good light transmittance and removable, or a protective film soluble in an aqueous solvent. It may be coated with Ir3. Therefore, resins such as polyvinyl alcohol, polyacrylic acid, and methyl cellulose that are soluble in aqueous solvents can be used.

In particular, polyvinyl alcohol is preferable because it has excellent oxygen barrier properties and can reduce the radical polymerization damage prevention effect caused by oxygen.

Examples of the support for the image-forming material of the present invention include glass plates, plastic films, metal plates, and papers. Examples of the plastic film include films made of polyester, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cellulose acetate, and the like. In particular, a biaxially stretched polyester film is preferred because it has excellent dimensional stability and transparency. The thickness of the support is not particularly limited, but is usually 7
It is 5 to 175 μm.

An adhesive layer, a metal thin film, or the like may be provided as an undercoat to improve the adhesion between the support and the photosensitive resin layer formed on the surface of the support. A thin layer of polymeric material is utilized for the subbing layer, particularly the adhesive layer. Such polymeric substances include, for example, polyacrylate, polyvinylidene chloride-acrylonitrile-itaconic acid copolymer,
Examples include reaction products of vinyl chloride-vinyl acetate-maleic anhydride copolymers, terephthalic acid-isophthalic acid-glycol copolymers, and incyanate compounds. The thickness of the layer is not particularly limited, but is usually 0.2 to 2 μm.

In producing the image-forming material of the present invention, a photosensitive resin layer is formed by melt molding or solution coating on a support that has a coloring order in advance, and is dried. The resulting photosensitive resin composition is optionally laminated with a protective film or coated with a protective film.

(Example) The present invention will be specifically explained below using Examples.

Example 11 Comparative Examples 1 to 4 A 100 μm thick polyester film (support) was coated with a composition containing an unsaturated polyester adhesive and a solvent as main components using a reverse coater and dried to give a thickness of 0.5 μm. A coating layer (contacting agent layer) was formed. Next, a photosensitive resin composition in which the following compounds were mixed and dispersed was prepared, and coated onto the adhesive elbow using a t<-X:1-tar to form a 3 μm thick photosensitive resin layer.

Table 1 (Photosensitive resin composition) Binder (see Table 2) 41 (parts by weight) Carbon black 12 2-(2-chloro-1-naphthyl)4,5-diphenyl 8 imidazoyl dimer hydroquinone monomethyl ether 0
．． 03 Jimedon
3 Michler Ketone
2. Methanol
140 chloroform
120 ethyl acetate
80 n-propyl acetate 40 isopropyl alcohol 40
Table 2 Binder Next, a 7% aqueous solution of polyvinyl alcohol (degree of polymerization 500) was coated on each of the obtained photosensitive resin layers using a reverse coater to form a protective layer with a thickness of 1.5 μm to obtain an image-forming material. Ta.

A portion of each of the resulting imaging materials was heated for a period of 30 minutes.
The sample was immersed in a 0.75% sodium carbonate aqueous solution at a temperature of 0.75%, and then rubbed with a sponge under running water.The time required for the photoresist to be completely removed was measured, and the development time for each was determined.

On the other hand, as shown in Fig. 1, each of the obtained image-forming materials was overlaid with a negative film and densely packed in a vacuum frame, and then exposed using an ORC ultra-high pressure mercury lamp (3KW) (polymer printer manufactured by Oak Co., Ltd.). It was exposed to light and developed using the developer for 1.3 times the respective development time. The results are shown in Table 3.

Margin Table 3 (Effects) As is clear from Table 3, the image-forming material of the present invention using a terpolymer as an integrating agent forms a strong film even at a low exposure dose, and therefore has little light diffusion. It can be seen that the resolution is excellent even when overprinted, and development can be done in a practical amount of time.

[Brief explanation of the drawing]

FIG. 1 is a simplified cross-sectional view of a state in which negative films are overlapped and exposed using the image forming material of the present invention. 1.2
．． 4 is a transparent negative film, 3 is a character negative film, 5 is a mesh negative film, 8 & 3 supports t 3 on the photosensitive resin layer 6
The image-forming material of the present invention has the following properties.

Claims (1)

[Claims] In an image-forming material having at least a photosensitive resin layer and a protective layer on a support, the photosensitive resin layer comprises a vinyl monomer containing an acid group, a vinyl monomer not containing an acid group having an SP value of 9.3 or less, and A terpolymer (A
), photoinitiator (B) and ethylenically unsaturated monomer (
An image-forming material characterized by containing C).