JPS60191248A - Binary type diazo copying material - Google Patents

Abstract

PURPOSE:To enhance image density and to solve a problem of development stains by using a specified acrylic resin as a precoat binder in a binary type diazo copying material formed by coating a support with the precoat layer. CONSTITUTION:An intended binary type diazo copying material can be obtained by preparing a copolymer of (meth)acrylate having >2C of the ester part, and acrylonitrile or vinyl acetate, such as butyl acrylate-acrylonitrile copolymer and 2-ethylhexyl acrylate-vinyl acetate copolymer, using this copolymer as the binder of a precoat, forming the precoat layer on a support, and forming a photosensitive layer contg. a diazonium compd., such as p-dimethylaminobenzenediazonium chloride.1/2ZnCl, and a coupler, such as resorcinol on said precoat layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field This invention relates to a precoat layer of a two-component diazo copying material;
Particularly regarding precoat resins.

Conventional technology diameter * 7% x 11 coats on the back neo side l - For the purpose of improving image density, the use of porous fillers and water-soluble molecular substances such as starch, and synthetic materials such as polystyrene. It is known to use resin.

However, water-soluble polymer substances such as starch increase the viscosity of the coating solution and make it difficult to remove air bubbles, so there is a limit to the amount of water-soluble polymers that can be used. The drawback was that it did not improve.

Furthermore, it has already been proposed to use vinyl acetate or acrylic ester as precoat resins, but when copying materials using these resins as precoat resins are dry-developed, the development stains are large, and dry diazo copying materials cannot be used. was difficult to apply.

Here, development stains mean that when developing with a dry copying machine,
The piano wire or metal plate that the photosensitive paper comes into contact with in the developing box causes the photosensitive layer or precoat layer of the photosensitive paper to peel off, and subsequently the coating material adheres to the piano wire, etc., resulting in the damage of the copy. This is a phenomenon in which stains occur when scratches or deposits are transferred to the photosensitive surface.

Object The object of the present invention is to provide a two-component diazo copying material that improves image density and eliminates development stains during dry development by selecting Pre-2 resin.

Structure The structure of the present invention is that in a diazo copying material in which a prerecorded layer and a photosensitive layer are provided on a support, the precoat binder of the precoat layer is mainly composed of an acrylic ester or a methacrylic ester and acrylonitrile or vinyl acetate. It is characterized in that it contains at least one type of resin selected from copolymers as a main component, and that the ester moiety of the acrylic ester or methacrylic ester of this copolymer has 3 or more carbon atoms. It is a two-component type diazo reproduction and photographic material.

Specific examples of copolymers used with the precoat binder include butyl acrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, 2-ethylhexyl acrylate-acrylonitrile copolymer, and butyl methacrylate. -acrylonitrile, 2-ethylhexyl methacrylate-acrylonitrile, propyl methacrylate-acrylonitrile, butyl acrylate-vinyl acetate copolymer, 2-ethylhexyl acrylate-vinyl acetate copolymer, propyl acrylate-vinyl acetate copolymer, Examples include butyl methacrylate-vinyl acetate, 2-ethylhexyl methacrylate-vinyl acetate, and propyl methacrylate-vinyl acetate copolymers. Furthermore, acrylic acid ester-acrylonitrile-vinyl acetate copolymers and the like may also be used. However, in this case, carbon〈3
If this ester is used, development stains will be large.

In addition, it is possible to incorporate other components such as styrene into the copolymer resin as long as the purpose of the present invention is not adversely affected, and it is also possible to mix other resins as long as the same purpose is not adversely affected. good. Furthermore, after Ic% copolymerization, a modified product in which a part of the composition or the terminals are treated can also be used.

Further, it is preferable to use a porous filler in the precoat layer of the present invention. For example, common organic and inorganic fillers such as silica, starch, clay, alumina, calcium carbonate, urea-formalin resin fine particles, and styrene resin fine particles are used.

In addition to the above-mentioned materials, various additives commonly used in diazo copying materials can be used in the present invention. For example, development accelerators such as ethylene glycol and triethylene glycol; storage improvers such as sodium naphthalene monosulfonate, sodium naphthalene disulfonate, sodium naphthalene trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate,
Cadmium chloride, zinc chloride, etc.; thiourea, urea, etc. as antioxidants; caffeine, theophylline, etc. as solubilizers; citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. as acid stabilizers are appropriately blended. In addition, a small amount of saponin can be added. In addition, an appropriate amount of inorganic or organic fine particles such as silica, starch, clay resin, etc. may be added to the photosensitive layer as an image density improver.

As the diazo compound and coupler used in this invention, those conventionally used in the field of two-component diazo copying materials can be used as they are.

Therefore, as a diazo compound, for example, 4-diazo-1
-dimethylaminobenzene, -4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-dibenzylaminobenzene, 4 -Diazo-1-ethylhydroxyethylaminobenzene, 4-diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-benzoylamino-2,
5-Die-1hexybenzene, 4-diazo-1-molisobenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-morpholino-2,
5-dibr-l-xybenzene, 4-diazo-1-anilinobenzene, 4-diazo-1-dimethylamine-3-carboxybenzene, 4-diazo-1-tolylmercapto-2,5-jethoxybenzene, 4- Diazo-1,4-
Double salts of diazo compounds such as methoxybenzoylamino-2,5-jethoxybenzene and metal halides of chlorides (zinc chloride, cadmium chloride, tin chloride, etc.), and sulfuric acid, boron tetrafluoride, hexafluoride of the diazo compounds Examples include salts of strong acids such as single-portion phosphoric acid, but are not limited to these, of course.

Examples of couplers include resorcin, phloroglucin, 2,5-dimethyl-4-morpholinomethylphenol, 3-hydroxycyanoacetanilide, p-sulfoacetanilide, 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonamide, 2 .2-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene-3,6-disulfonic acid sodium, 2,3-dihydroxy-6-sulfonic acid sodium, 2,5-dihydroxynaphthalene-6-sulfonic acid sodium, 1-hydroxy Sodium naphthalene-4-sulfonate, 1-amino-3-hydroxynaphthalene-3,6-disulfonamide, naphthol AS, naph]hale AS=D, 2-hydroxynaphthalene-3-biguanide, morpholinopropyl 2-hydroxynaphthoate amide, 2-hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid-N-dimethylamitube [1-viramide hydrochloride, 2.2-. 4.
4--Tetrahydroxydiphenyl 2.2-. 4.4'
-tetrahydroxydiphenyl sulfoxide and the like, but are not limited thereto, of course.

To prepare the diazo copying material of this invention, first, a coating solution containing mainly the above-mentioned resin and, if necessary, a porous filler and other additives is applied onto a support such as paper or film using a conventional method. 0.1g/m2 to 5g/l after coating and drying by coating method
A precoat layer 112 is provided, and a coating liquid comprising a diazo compound, a coupling component, and if necessary a porous filler and other auxiliary agents is applied thereon and dried to form a photosensitive layer. This will be specifically explained below using examples.

Example 1 Butyl acrylate-acrylonitrile copolymer (50% emulsion) 5111 silica
A coating solution consisting of 3 g and 100 g of water was applied to the surface of a base paper for diazo copying paper and dried to form a precoat layer of 2.0 g and 7 m 2 . Furthermore, p-dimethylaminebenzenediazonium chloride 7-1'
A coating solution consisting of 1/2 Zn Cl 2 0,592.3-dihydroxynaphthalene-6-sulfonic acid sodium 2 g citric acid 2 g zinc chloride 5 g thiourea 5 g ethylene glycol 5 g water 1009 was applied and dried. A photosensitive layer of /m2 was formed to obtain a diazo copying material (sample A).

On the other hand, for comparison, a diazo copying material was obtained in the same manner except that the precoat layer was removed and silica of the same molar mass as the silica in the precoat layer of Sample A was added to the photosensitive solution of Sample A instead (Sample B).

In addition, a diazo copying material was obtained in the same manner as in Sample A except that the butylacrylate-acrylonitrile in the precoat solution was removed and the same amount of casein was added instead (Sample C).
).

Furthermore, a diazo copying material was obtained in the same manner as in Sample A except that the butyl acrylate-acrylonitrile in the precoat solution was removed and the same amount of polyvinyl acetate was added instead (
Sample D).

A diazo copying material was also obtained in the same manner as Sample A except that the same amount of methyl acrylate-acrylonitrile was added in place of butyl acrylate-acrylonitrile in the precoat solution (Sample E).

Each sample obtained as described above was developed using a dry diazo copying machine (SM-1500 manufactured by Ricoh), and then the image density was measured using a Photovolt mi meter. In addition, stains on the carrier image during dry development are determined by the presence or absence of scratches and stains on each sample after the 5000 sheets are developed at a speed of 15 m/sin using the above-mentioned copying machine.
Judgment was made based on the presence or absence of dirt in the developing area. The results are shown in the table.

As shown in the table, it can be seen that this invention has a high density and no development stains are observed during dry development.

Example 2 A coating solution consisting of 2-edylhexyl acrylate-vinyl acetate copolymer (50% emulsion) 6g urea-formalin resin fine particles 3g water 100Q was applied to the surface of a base paper for diazo copying paper and dried to give 1.0g/■ Two precoat layers were applied. Furthermore, 2.5-jethoxy-4-morpholinobenzenediazonium chloride 1/2znC 122g 2-hydroxy-3-naphthoic acid morpholinoprobylamide 2.5g Zinc chloride 1.5g Thiourea 1.5g Tartar @ 29 tri A coating solution consisting of 3.5 g of ethylene glycol and 100 g of water was applied to the surface of a base paper for diazo copying paper and dried to provide a photosensitive layer. The obtained diazo copying material (Sample F) was developed in the same manner as in Example 1, and a clear high-density blue image was obtained. Also, as in Example 1, no development stains occurred.

On the other hand, for comparison, a photographic material was prepared in which the 2-edylhexyl acrylate to vinyl acetate copolymer of Sample F was removed and a polyacrylic acid resin was precoated in its place (Sample G). The image density of sample G was 0.15 lower than that of sample F, and the development stain was also large.

Example 3 Butymethacrylate-acrylonitrile copolymer 5
A coating solution consisting of 5 g of styrene resin particles (2 g of 0% water emulsion) and 100 g of water was applied to the surface of a base paper for diazo copying paper and dried to form a precoat layer of 0.6 o/m 2 .

A photosensitive layer was further provided thereon in the same manner except that 2 g of styrene resin fine particles were added to the photosensitive solution of Sample E to obtain a copying material (Sample H).

When the obtained sample was developed in the same manner as in Example 1, a high density image was obtained. Also, no development stains occurred.

Furthermore, Sample H was transferred using a semi-dry diazo copying machine (Ricoh ASO
-yoo), there were high density marks similar to dry development.

Effects As explained above, when the two-component diazo copying material of the present invention is used, the image density is high and dry development can be performed without scratches or stains.

Patent applicant Rico Co., Ltd. Agent Patent Attorney Hidetake Komatsu Agent Patent Attorney Hiroshi Asahi

Claims (1)

[Claims] In a diazo copying material having a prerecorded layer and a photosensitive layer on a support, the precoat binder of the precoat layer is mainly selected from copolymers of acrylic esters or methacrylic esters and acronitrile or vinyl acetate. A two-component diazo copying material containing at least one selected resin as a main component and characterized in that the ester moiety of the acrylic ester or methacrylic ester of this copolymer has 3 or more carbon atoms. .