JPS6084540A - Two-component diazo copying material - Google Patents

Abstract

PURPOSE:To enhance image density and to improve resistance to development stains due to a dry developing process by using a specified copolymer for a precoat resin layer. CONSTITUTION:A precoat resin layer and a photosensitive layer are formed on a support to form a 2-component type diazo copying material, and a copolymer of at least one kind of a monomer selected from acrylates and methacrylates, and at least one kind of monomer selected from acrylonitrile and vinyl acetate is used for said precoat resin layer. Said precoat resin layer may contain other org. and inorg. fine particles, other monomer units of said copolymer, other resins, etc., in an amt. of about 0.1-5g/m<2> by dry basis.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a two-component diazo copying material that utilizes a coupling reaction (color-forming reaction) between a diazo compound and a coupler.

[Prior art]

Conventionally, it has been known to provide a two-component diazo copying material with a precoat layer containing a resin in order to improve image density. In this case, a water-soluble resin such as starch or polystyrene is used as the pre-coat resin, but in the case of the former, since it is water-soluble, the viscosity of the coating solution increases;
It has the disadvantage that the amount of use is limited, and in the latter case,
It has the disadvantage that the contribution rate to image density improvement is small. It is also known to use polyvinyl acetate or polyacrylic acid ester as the precoat resin, but these cases have the disadvantage that when the resulting copying material is dry developed, there is a large amount of development stain.

〔the purpose〕

An object of the present invention is to provide a two-component diazo copying material having a precoated resin layer free from the above-mentioned drawbacks.

〔composition〕

According to the present invention, in a two-component diazo copying material in which a precoat resin layer and a photosensitive layer are provided on a support, the precoat resin layer includes (a) at least one selected from acrylic esters and methacrylic esters; Seeds and (
b) A two-component diazo copying material is provided, characterized in that it uses a resin layer whose main component is a copolymer resin with at least one selected from acrylonitrile and vinyl acetate.

The product according to the invention, through the use of its particular precoat resin layer, provides improved image density and, at the same time, significantly improved development smudge during dry development.

Incidentally, the term "development stain" as used herein means a stain on the surface of a copy that occurs inside the development box. It is thought that such development stains occur in the following manner. That is, in the developing box, the photosensitive layer and the precoat resin layer are peeled off from the photosensitive paper due to contact between the photosensitive paper and the piano wire or the metal plate, and at the same time, the peeled off material is attached to the piano wire or the metal plate. As a result, this deposit causes scratches on the surface of the copy, or transfers the deposit onto the surface of the copy, making the surface of the copy dirty.

The precoated resin layer used in the present invention is composed of a resin layer mainly composed of a copolymer resin as described above.
Specific examples of the copolymer resin in this case include acrylic ester-acrylonitrile copolymer, acrylic ester-vinyl acetate copolymer, methacrylic ester-acrylonitrile copolymer, and methacrylic ester-vinyl acetate copolymer. etc., and conventionally known ones can be used. In this case, the type of acrylic ester or methacrylic ester is not limited, and examples include chain or cyclic alkyl esters such as methyl ester, ethyl ester, and cyclohexyl ester.

The pre-coated resin layer of the present invention also contains porous fillers such as starch, clay, alumina, calcium carbonate,
Conventionally used organic and inorganic fine particles such as urea-formalin resin fine particles and styrene resin fine particles can be contained. Furthermore, other resin components may be copolymerized or other resins may be mixed into the copolymer resin within a range that does not impede the object of the present invention. In addition, 3- the copolymer resin described above can also be used as a modified product in which other functional groups are introduced at the ends or the like.

In order to produce the diazo copying material of the present invention, firstly, a resin of the above-mentioned copolymer and, if necessary, a porous filler' and other additives are coated onto a support such as paper or film. Apply the liquid using a normal coating method and dry it to give a coating density of 0.1g/rrf.
A precoat layer of ~5 g/- is provided, and a coating solution consisting of a diazo compound, a coupling component, and if necessary, a porous filler and other auxiliary agents is applied and dried to form a photosensitive layer. .

〔effect〕

By using the specific copolymer resin layer as a precoat resin layer, the diazo copying material of the present invention provides copies with improved image density, and also provides high-quality copies without development stains during dry development. give something.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples 4- Ru.

Example 1 A coating solution consisting of 5 g of polyacrylic acid ester-acrylo nitrile copolymer (50% emulsion), 3 g of calcium carbonate, 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 1 g/ITr. .

Furthermore, on top of that, a coating consisting of 0.5 g of P-dimethylaminobenzenediazo, 1/2 ZnCQ, 62 g of 3-dihydroxynaphthalene-6-sulfonic acid, 2 g of sodium citric acid, 5 g of zinc chloride, 5 g of thiourea, 5 g of ethylene glycol, and 100 g of water was applied. The solution was applied and dried to form an Ig/rrr photosensitive layer to obtain a diazo copying material (sample A).

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

A diazo copying material was also obtained in the same manner as Sample A except that the polyacrylic ester-acrylonitrile copolymer 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 Sample A except that the polyacrylic acid ester-acrylonitrile copolymer in the precoat solution was removed and the same amount of polyvinyl acetate was added instead (Sample D).

Each sample obtained as described above was developed using a dry diazo copying machine (5N-1500 manufactured by Ricoh), and then the image density was measured using a photovolt densitometer. In addition, development stains during dry development were confirmed after developing 1,000 sheets of each sample at a speed of 15 m/i+in using the above-mentioned copying machine.
Judgment was made based on the presence or absence of scratches and stains on each sample of the 000th sheet and the presence or absence of stains in the developing area.

The results are shown in Table-1.

Table 1 As shown in Table 1, it can be seen that the products of the present invention have a high density and no development stains are observed during dry development.

Example 2 Methyl methacrylate-vinyl acetate 6g copolymer (50
A coating solution consisting of 3 g of urea-formalin resin fine particles and 100 g of water was coated on the surface of a diazo copying base paper and dried to form a precoat layer of 0.8 g/rrr. Furthermore, 7-2,5-jethoxy-4-morpholino 2g benzenediazonium chloride-1/2Zn (12 2-hydroxy-3-naphthoic acid 2.5g morpholinopropylamide zinc chloride 1.5g thiourea 1.5g A coating solution consisting of 2 g of tartaric acid, 3.5 g of triethylene glycol, and 100 g of water was applied and dried to provide a photosensitive layer.

When the obtained diazo copying material (Sample E) was developed in the same manner as in Example 1, a clear high-density blue image was obtained. Further, as in Example 1, development stains were also good.

On the other hand, for comparison, a diazo copying material was prepared in the same manner as Sample E except that the methyl methacrylate-vinyl acetate copolymer was removed from the precoat layer and a polyacrylate resin was used instead. obtained (sample F
), the image source 8° of sample F was 0.11 lower than that of sample E, and the development stain was also large.

Example 3 A coating solution consisting of methyl methacrylate-acrylo 5g nitrile copolymer (50% water emulsion) styrene resin fine particles 2g water 100g was coated on the surface of a base paper for diazo copying paper and dried to give 0.6g/ A precoat layer of rrr was provided.

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 liquid of Sample E to obtain a copying material (Sample G). When the obtained sample G was developed in the same manner as in Example 1, a high density image was obtained and the development stain was also good.

Furthermore, sample G was transferred to a semi-dry diazo copying machine (Ricoh S
When developed with D-700), the density was as high as in dry development.

Procedural amendment 1. Description of the case Patent Application No. 1939'26 of 1982 2, Title of the invention Two-component diazo copying material 3, Person making the amendment Relationship to the case Patent applicant Address 1-3-6 Nakamagome, Ota-ku, Tokyo Name (
674) Rico Co., Ltd. - Representative Hama 1) Hiro 4, Agent 〒151 Address 1-58-10-5 Yoyogi, Shibuya-ku, Tokyo Date of amendment order Voluntary 6 Number of inventions increased by amendment 0 7. Detailed explanation of the invention in the specification subject to amendment 8. Contents of the amendment The following amendments will be made in the specification of the application.

(1) "Copolymer resin" in the first line of page 4 will be corrected to "copolymer resin."

(2) Delete "-6" on the 9th line from the bottom of the 6th page.

(3) On page 9, in the 5th line from the bottom, ``in the 1st layer'' will be corrected to ``in the layer''.

(4) Insert the following sentence between the 3rd and 4th lines of page 5.

``As the diazo compound and coupler used in the present 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-jethoxybenzene, 4-diazo-1- Morpholinobenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-anilinobenzene,
4-Diazo-1-dimethylamino-3-carboxybenzene, 4-diazo-1-tolylmercapto-2,5-
Double salts of diazo compounds such as jetoxybenzene and 4-diazo-1,4-methoxybenzoylamino-2,5-jethoxybenzene and metal halides of chlorides (zinc chloride, cadmium chloride, tin chloride, etc.); Examples include salts of strong acids such as sulfuric acid, boron tetrafluoride, and hexafluorophosphoric acid of the diazo compound, but are not limited to these.

Examples of couplers include resorcinol, 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 soda, 2
, 3-dihydroxy-6-sulfonic acid sodium, 2,5-
Sodium dihydroxynaphthalene-6-sulfonate, 1-
Sodium hydroxynaphthalene-4-sulfonate, 1-amino-3-hydroxynaphthalene-3,6-disulfonamide, naphthol AS, naphthol AS-D, 2-hydroxynaphthalene-3-biguanide, 2-hydroxynaphthoic acid morpholinopropylamide , 2-hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid-N-dimethylaminopropylamide hydrochloride, 2
．． 2'.

Examples include 4,4'-tetrahydroxydiphenyl sulfoxide, but are not limited thereto.

In the present invention, in addition to the above-mentioned materials, various additives commonly used in diazo copying materials can be used, such as ethylene glycol, triethylene glycol, etc. as development accelerators; Naphthalene
Sodium monosulfonate, sodium naphthalene-disulfonate, sodium naphthalene-trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride, etc.; As antioxidants, thiourea, urea, etc.; As a dissolving agent. Caffeine, theophylline, etc.; as acid stabilizers citric acid, tartaric acid, sulfuric acid,
Oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. may be blended as appropriate, and a small amount of saponin may also be added. In addition, as an image density improver, starch,
Appropriate amounts of inorganic and organic fine particles such as clay and resin can be added. ” 4-

Claims (1)

[Claims] (1) Pre-coated resin layer and photosensitive layer were provided on the support 2
In the component type diazo copying material, the precoat resin layer comprises (a) at least one selected from acrylic esters and methacrylic esters, and (b) at least one selected from acrylonitrile and vinyl acetate. A two-component diazo copying material characterized by using a resin layer containing a copolymer resin as a main component.