JPH08262619A - Heat developed type diazo copying material and method of encapsulating coupler used for this material - Google Patents

Abstract

PURPOSE: To provide heat developed type diazo copying material having high coloring property and an excellent shelf life by encapsulating a coupler with alkali soluble resin as a partition wall. CONSTITUTION: A coupler is used being micro-capsuled with a styrene-acrylic acid copolymer or the mixture of a styrene-acrylic acid copolymer and an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer as a capsule wall. This micro-capsule is produced by dissolving the coupler in a water insoluble organic solvent together with acetic acid and mixing it in the ammonium solution styrene-acrylic acid copolymer of alkali soluble resin or the mixed solution of the styrene-acrylic acid copolymer and isobutylene- maleic anhydride copolymer or styrene-maleic anhydride copolymer. Heat developed type diazo copying material with high image density and an excellent shelf life can thereby be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable diazo copying material in which a latent image is formed on a transparent or semi-transparent original by superposing the latent image thereon and then developing the latent image with heat. The present invention also relates to a heat-sensitive recording material capable of being optically fixed.

[0002]

2. Description of the Related Art Heat developable diazo copying materials are generally
A photosensitive layer containing a diazo compound, a coupling component and a color-forming aid as main components is provided on a support such as paper or film, and urea, sodium trichloroacetate or the like is used as the color-forming aid. This type of diazo copying material is 1
Development is performed by heating at 80 to 200 ° C. The developing mechanism uses an alkali that is decomposed and generated by heating. Further, as an attempt to develop at low temperature, a heat-fusible substance such as higher fatty acid amide is used as a color-forming aid,
The developing mechanism utilizes activation of the diazo compound and the coupling component by heating and melting.

However, in the conventional case, pre-coupling gradually progressed during storage, and undesired coloring sometimes occurred. Therefore, JP-A-57-42042, JP-A-57-45094, and JP-A-57-1
No. 25091 discloses the presence of any one of a diazo compound, a coupling component and an alkali generator in the form of discontinuous particles to prevent contact between the components,
Although methods to prevent precoupling have been proposed,
In this method, in order to obtain high thermal sensitivity, it is necessary to reduce the particle size of each particle, which causes a problem of poor raw storability.

Further, Japanese Patent Publication No. 4-75147 proposes an encapsulation technique in which only a diazo compound is contained as a core substance in a microcapsule, and polyurethane or polyurea is used as a partition wall around the core substance in a polymerization reaction. However, since the partition wall becomes a thermosetting resin and an alkali generator must be used in order to obtain thermal sensitivity, and since the diazo compound is included, the surrounding polyurethane and polyurea resin shield the ultraviolet rays. Therefore, there is a fatal defect that the capacity of the light source of the copying machine is increased.

On the other hand, Japanese Patent Laid-Open No. 57-44141 proposes an in-liquid drying method in which a partitioning agent is a non-polar wax to encapsulate a coupling component. Since the coupling reaction at the time of melting was suppressed, there were many problems in practical use.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation, and has a high color developability and an excellent raw storability which are not found in conventional heat developable diazo copying materials. It is intended to provide a diazo copying material.

[0007]

According to the present invention, a diazo compound, a coupler, an alkaline-soluble resin and a sensitizer are provided in a single layer on a support, or a layer and a coupler containing the diazo compound are provided. A heat-developable diazo copying material provided by laminating layers containing an alkali-soluble resin and a sensitizer, wherein the coupler is encapsulated with the following alkali-soluble resin (a) or (b) as a partition wall. A heat developable diazo copying material is provided. (A) Styrene-acrylic acid copolymer (b) Styrene-acrylic acid copolymer and isobutylene-
Maleic anhydride copolymer or a mixture with a styrene-maleic anhydride copolymer. Further, there is provided a heat-developable diazo copying material characterized by using a higher fatty acid amide having 10 to 20 carbon atoms or an N-substituted higher fatty acid amide as the sensitizer. Also,
A method for encapsulating a coupler used in a heat-developable diazo copying material is characterized in that both a coupler and acetic acid are dissolved in a water-insoluble solvent, and this is mixed with an ammonium solution (a) or (b) of an alkali-soluble resin described below. Provided. (A) Ammonium solution of styrene-acrylic acid copolymer (b) Ammonium solution of styrene-acrylic acid copolymer and ammonium solution of isobutylene-maleic anhydride copolymer or ammonium solution of styrene-maleic anhydride copolymer Mixed with.

The present invention will be described in detail below. As described above, the heat-developable diazo copying material of the present invention comprises a coupler (a) styrene-acrylic acid copolymer or (b) styrene-acrylic acid copolymer and isobutylene-maleic anhydride copolymer or styrene-anhydride. A mixture with a maleic acid copolymer is used as a capsule wall after being microencapsulated, whereby a heat developable diazo copying material having a high image density and excellent raw storability can be obtained.
The microcapsules used in the present invention are produced by dissolving both the coupler and acetic acid in a water-insoluble organic solvent, and mixing this with an ammonium solution (a) or (b) of an alkali-soluble resin described below. (A) Ammonium solution of styrene-acrylic acid copolymer (b) Ammonium solution of styrene-acrylic acid copolymer and ammonium solution of isobutylene-maleic anhydride copolymer or ammonium solution of styrene-maleic anhydride copolymer Mixed with.

The microcapsules used in the present invention are emulsified and dispersed in a W / O type, a coupler and an organic acid are allowed to coexist inside the oil, and an acidic component is eluted from the inside to hydrophobize the alkali-soluble resin and coat it as a partition wall. To act. The particle size distribution of the microcapsules used in the present invention is a distribution of 1 μm to 10 μm, and D50 in the range of 3 μm to 8 μm has good thermal response sensitivity and does not break due to pressure.

The partition wall resin of the microcapsule of the present invention is melted by heating and is not directly involved in the coupling reaction, but it is eutectic after being heated with the sensitizer of the present invention, and the molten coupler comes into contact with the diazonium salt for coupling. The reaction proceeds.

Since the eutectic point of the sensitizer and the coupler in the present invention can be presumed to be the place of the coupling reaction,
In the present invention, a sensitizer that promotes the production of a naphtholate anion, which is the rate-determining factor in the coupling reaction, for example, has 10 carbon atoms.
To 22 higher fatty acid amides and N-substituted higher fatty acid amides are preferably used. Specific examples of the higher fatty acid amide include lauric acid amide, myristyl acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, eicoic acid amide, and elaidic acid amide. Specific examples of the fatty acid amide include N-methylol stearic acid amide, N-methylol caproic acid amide, N-methylol lauric acid amide, and N-methylol behenic acid amide. With these higher fatty acid amides and N-substituted higher fatty acid amides, naphthol-based, phenol-based, and active methylene-based couplers rapidly eutecticize. That is, the eutectic point is 80 ° C to 150 ° C by the DSC method.
It is achieved by selecting a specific coupler adjusted to the range of. The eutectic point is measured by thermal analysis and is highly versatile.
This is possible with the SC method and an endothermic peak appears.

More specifically, the present invention will be described in more detail. As the coupling component, a naphthol AS type coupler is mainly used, and it can be used in combination with any of those for general two-component type diazo copying materials. For example, resilcin, phloroglucin,
2,5-dimethyl-4-morpholinomethylphenol,
3-hydroxycyanoacetanilide, parasulfoacetanilide, 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonamide, 2,2-dihydroxynaphthalene, 2,7-dihydroxynaphthalene-
Sodium 3,6-disulfonate, 2,3-dihydroxy-
Sodium 6-sulfonate, 2,5-dihydroxynaphthalene-sodium sulfonate, 1-hydroxynaphthalene-4
-Sodium sulfonate, 1-amino-3-hydroxynaphthalene-3,6-disulfonamide, naphthol AS-
D, 2-hydroxynaphthalene-3-biguanide, 2
-Hydroxynaphthoic acid morpholinopropylamide, 2
-Hydroxynaphthoic acid ethanolamide, 2-hydroxynaphthoic acid-N, N-dimethylaminopropylamide hydrochloride, 2,4,2 ', 4'-tetrahydroxydiphenyl, 2,4,2', 4'-tetrahydroxy Examples thereof include diphenyl, 2,4,2 ', 4'-tetrahydroxydiphenyl sulfoxide and the like.

Examples of the alkali-soluble resin used in the present invention include casein, polyacrylic acid, modified PVA, CMC,
Gum arabic, isobutylene-maleic anhydride copolymer, diisobutene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, ethylene-acrylic acid copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid A copolymer is mentioned. More specifically, Tg is 5
A styrene-acrylic acid copolymer having a molecular weight of 3500 to 10000 from 0 ° C to 95 ° C is preferable, and a styrene-acrylic acid copolymer alone or isobutylene-
Particularly preferred is a maleic anhydride copolymer or a mixture with a styrene-maleic anhydride copolymer.

Since the method for producing the capsules of the present invention is carried out by the phase separation method, it is difficult to use Tg and molecular weight regions other than those mentioned above. When Tg and the molecular weight are high, the coverage of the capsule wall is lowered and the phase separation cannot be performed well. Further, when Tg and the molecular weight are low, coarsening progresses due to aggregation due to blocking between the capsule walls.

The water-insoluble organic solvent used for preparing the capsule liquid of the present invention includes tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, Dicyclohexyl phthalate,
Examples thereof include butyl oleate, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate and the like.

A specific production method by the heating phase separation method used in the present invention is to add an amount of ammonia water which can be dissolved in an alkali-soluble resin and to dissolve it by stirring while heating at 50 ° C. Next, the naphthol-based coupler and acetic acid are both dissolved in an organic solvent such as a phthalate ester-based solvent. The amount of acetic acid at this time is adjusted to the oxidation number of the styrene-acrylic acid copolymer.
Next, the resulting mixture is mixed with an alkali-soluble resin solution which is twice the amount of the organic solvent in which the coupler has been dissolved, and stirred with a commercially available homomixer to obtain an emulsion. After stirring this liquid at a liquid temperature of 60 ° C. for 30 minutes,
Confirm that the pH has reached 7 and make the end point. The capsule particle size at this time depends on the stirring speed, but is almost determined by the particle size of the core agent. The obtained microcapsule dispersion was measured by a commercial laser diffraction particle size distribution and D50 was calculated to be 5 μm.
To 10 μm. As a result of observing the shape of the capsule on a glass plate with an electron microscope, it was found that the core substance was in a continuous particle state in which it was encapsulated in a styrene-acrylic acid copolymer. This encapsulation method has an advantage that it can be manufactured at a lower cost than the interfacial polymerization method or the like.

In the heat-developable diazo copying material of the present invention, a precoat layer containing fine particle powder and a resin is provided on a support, and a photosensitive layer is provided thereon to improve photosensitivity and image density. Can be higher Further, it is possible to further improve the photosensitivity by dividing the photosensitive layer into a diazo layer and a coupler layer. As the layer structure, a diazo photosensitive layer may be provided on the coupler layer, and fine particle powder, for example, inorganic fine particle powder, organic fine particle powder can be used in the layer, and silica is a specific example of the inorganic fine particle powder.
There are alumina, kaolin, talc, titanium, calcium carbonate, aluminum hydroxide, magnesium hydroxide and the like, and as the organic fine particle powder, styrene resin particles, urea-formalin condensation resin particles, benzoguanamine resin particles and the like can be mixed.

The fine particle powder used in the precoat layer is
The same inorganic fine particle powder and organic fine particle powder as described above can be used. Specific examples of the inorganic fine particle powder include silica, alumina, kaolin, talc, titanium, calcium carbonate, aluminum hydroxide and magnesium hydroxide. Examples of the powder include styrene resin particles, urea-formalin condensation resin particles, and benzoguanamine resin particles. When silica is used, its specific surface area is 150 to 20.
It is preferable to set it in the range of 0 m ² / g. The effect is due to the maximum pore volume of the silica fine particles and adsorbs the molten substance that has been melted by heat to improve the abrasion resistance of the image portion formed as a result. If the specific surface area exceeds 200 m ² / g, the effect is poor.

As a resin for binding these powders,
Polyvinyl alcohol, polyacrylamide, casein, gelatin, starch and its derivatives, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and other water-soluble resins, polyvinyl acetate, polyacrylic acid ester, vinyl chloride-acrylic acid ester copolymerization It is a combination of various emulsion resins of ethylene-vinyl acetate copolymer.

The diazo compounds used in the present invention have the general formula ArN ²⁺ X ^- is a diazonium salt represented by (wherein, Ar represents an aromatic moiety substituted or unsubstituted, A
rN ²⁺ represents a diazonium salt, and X ⁻ represents an acid anion. )

Specific examples of the diazo compound include, for example, 4
-Diazo-N, N-dimethylaniline, 4-diazophenylmorpholine, 4-diazo-N, N-dibutylaniline, 4-diazo-2,5-dimethoxyphenylmorpholine, 4-diazo-2,5-diethoxyphenyl Morpholine, 4-diazo-2,5-dipropoxyphenylmorpholine, 4-diazo-2,5-dibutoxyphenylformoline, 4-diazo-2,5-dibutoxy-N-benzyl-N-ethylaniline, 4- Diazo-2,5-dibutoxy-N, N-dibutylaniline, 4-diazo-2,5-
Dibutoxy-N-benzyl-N-oxyethylaniline, 4-diazo-2,5-dibutoxyphenylpiperazine, 4-diazo-2,5-diethoxyphenylpyrrolidine, 4-diazo-2,5-dipropoxyphenylpyrazine Beridine, 4-diazo-2,5-diethoxy-N, N-dimethylaniline, 4-diazo-1-benzoylamino-
2,5-dibutoxybenzene, 4-diazo-1- (4 '
-Methoxybenzoylamino) -2,5-dimethoxybenzene, 4-diazo-1- (4'-methoxybenzoylamino) -2,5-diethoxybenzene, 4-diazo-
1- (4'-methyldibenzoylamino) -2,5-dipropoxybenzene, 4-diazo-1- (3'-chlorobenzoylamino) -2,5-diethoxybenzene, 4
-Diazo-1- (3'-methoxybenzoylamino)-
2,5-dibutoxybenzene, 4-diazo-1- (3 '
-Methyldibenzoylamino) 2,5-dimethoxybenzene, 4-diazo-1-phenylmercapto-2,5-
Dipropoxybenzene, 4-diazo-1- (4'-toluylmercapto) -2,5-diethoxybenzene, 4-
Diazo-1- (4'-methoxyphenylmercapto)-
2,5-dibutoxybenzene, 4-diazo-1- (4 '
-Chlorophenylmercapto) -2,5-dimethoxybenzene, 4-diazo-1- (3'-toluylmercapto) -2,5-diethoxybenzene, 4-diazo-1-
(3'-Methoxyphenylmercapto) -2,5-dipropoxybenzene, 4-diazo-1- (2'-toluylmercapto) -2,5-dibutoxybenzene, 4-diazo-1-phenoxy-2,5 -Dibutoxybenzene, 4
-Diazo-1- (4'-methoxyphenoxy) -2,5
-Double salts of zinc chloride, cadmium chloride, tin chloride such as diethoxybenzene, and salts of inorganic acids such as sulfuric acid, hexafluorophosphoric acid, and tetrafluoroboric acid of the diazo compound.

In the present invention, the above-described diazo compound is applied as an aqueous solution or a dispersion without a binder or using a binder. As the binder, polyvinyl alcohol, polyacrylamide, casein, gelatin, starch and its derivatives, water-soluble resins such as polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose,
Various emulsion resins such as polyvinyl acetate, polyacrylic acid ester, chloride-vinyl acrylic acid ester copolymer, ethylene-vinyl acetate copolymer and the like can be used. Further, when a diazo compound which is poorly soluble in water is dissolved in an organic solvent and applied, a resin soluble in an organic solvent may be used as a binder. Examples of such a resin include vinyl chloride-based resins. , Vinyl acetate-based, vinyl chloride-vinyl acetate-based copolymer, vinyl acetate-vinylidene chloride-based copolymer, polystyrene-based, butyral-based, polycarbonate-based, acrylic acid derivative-based resins and the like.

The above-mentioned coupling component is applied as an aqueous solution or dispersion without a binder or using a binder. As the binder, polyvinyl alcohol, polyacrylamide, casein, gelatin, starch and its derivatives, polyvinylpyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose,
Water-soluble resins such as hydroxyethyl cellulose, various emulsion resins such as polyvinyl acetate, polyacrylic acid ester, vinyl chloride-acrylic acid ester copolymer, and ethylene-vinyl acetate copolymer can be used. Further, in the coupler layer, a water-soluble or water-insoluble basic substance or a substance capable of generating an alkali upon heating is used as a color-forming assistant. Specific examples of the coloring aid include, for example, sodium hydroxide, potassium carbonate, sodium hydrogen carbonate, sodium acetate, ammonium acetate, ammonium chloride, ammonium sulfate, ammonium citrate, stearylamine, urea, thiourea, allylurea, allylthiourea. , Methylthiourea, ethylenethiourea, sodium trichloroacetate, guanidine trichloroacetate, morphonium trichloroacetate, guanidine carbonate, guanidine sulfate, aminoguanidine sulfate, 1,2,3-triphenylguanidine, 1,2-ditolylguanidine , 1,2-dicyclohexylguanidine, imidazole, benzimidazole, 2-heptadecylimidazole, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-
4-methylimidazole, 2-undecylimidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, N, N'-dibenzylpiperazine, 4,4 '
-Dithiomorpholine, 2-aminobenzothiazole and the like. These color forming aids can be used in combination of two or more kinds.

In the heat-developable diazo copying material of the present invention, in addition to the color-forming component, various additives that are applied to ordinary diazo heat-sensitive recording materials, and naphthalene-sodium monosulfonate and naphthalene-disulfone as storability improvers. Sodium acid, sodium naphthalene-trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride and the like can be used. Further, it is possible to use thiourea and urea as antioxidants, caffeine and theophylline as solubilizers, and citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid and the like as acid stabilizers, etc. A small amount of saponin can be added. Further, when the heat-developable diazo copying material of the present invention is used as a light-fixing type heat-sensitive recording material, a filler can be added for the purpose of preventing sticking to a thermal head and improving runnability. Examples of such fillers include styrene resin fine particles, urea-formalin condensate resin fine particles, aluminum hydroxide, magnesium hydroxide, calcium carbonate, titanium, talc, kaolin,
Examples thereof include organic and inorganic solid fine particles such as silica and alumina, and metal soaps can also be used for the same purpose.

The heat-developable diazo copying material of the present invention can be advantageously applied to various other fields of heat-sensitive recording, in particular, as output recording paper for facsimiles and electronic calculators which require high-speed recording. In the case of the present invention, the characters and images recorded on the surface of the recording paper can be fixed by decomposing unreacted diazo compound by exposing after image formation by heating. Further, the heat-sensitive recording material of which this is a light-fixing type utilizes its fixability,
It can be applied to the recording of necessity 6 on securities, gift certificates, admission tickets, certificates, slips, and the like, and their creation.

[0026]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples. In addition, "part" which shows an addition amount represents a "weight part."

<Preparation of Coupler Capsule Liquid A> 3.45 parts of 2-hydroxy-3-naphthoic acid anilide and 0.85 parts of acetic acid were dissolved in 24 parts of tricresyl phosphate. Next, the above coupler solution was mixed with 50 parts of an aqueous solution of styrene-ammonium acrylate, which is an alkali-soluble resin, and
An emulsion was obtained by stirring at 12,000 to 10,000 rpm for 3 minutes with a commercially available homomixer. Next, this emulsion is heated to 60 ° C.
The mixture was warmed to 30 ° C. and stirred weakly for 30 minutes, and when the pH of the dispersion became 7, the end point was reached.

<Preparation of Coupler Capsule Liquid B> 2-Hydroxy-3-naphthoic acid morpholinopropylamide 3.45 parts acetic acid 0.85 parts tricresyl phosphate 24
Dissolved in part. Next, 2% of an ammonium aqueous solution of isobutylene-maleic anhydride copolymer was mixed with an aqueous solution of ammonium styrene-acrylic acid copolymer, and 50 parts of an alkali-soluble resin solution having a total concentration of 5% was mixed with the above coupler solution. In the subsequent steps, the capsule liquid was prepared by the same operation as the preparation of the coupler capsule liquid A.

<Preparation of Coupler Capsule Solution C> 2.45 parts of 2-hydroxy-3-naphthoic acid anilide and 0.85 parts of acetic acid were dissolved in 24 parts of tricresyl phosphate. Next, 2% of an aqueous solution of ammonium styrene-maleic anhydride copolymer was mixed with an aqueous solution of ammonium styrene-acrylic acid copolymer to prepare an alkali-soluble resin solution 50 having an overall concentration of 5%.
The above coupler liquid was mixed in parts. In the subsequent steps, the capsule liquid was prepared by the same operation as the preparation of the coupler capsule liquid A.

Example 1 The above-mentioned coupler capsule liquids A, B and C were respectively applied to a general high-quality paper so that the weight after drying was 3.5 g / m ² to form a coupler layer. Next, the following diazo photosensitive solution was applied to the coupler layer so as to have an adhesion amount of 0.8 g / m ² after drying to prepare the heat developable diazo copying materials A ₁ , B ₁ and C ₁ of the present invention. . <Diazo Photosensitive Solution-1> 4-diazo-1- (4'-toluylmercapto-2,5-diethoxybenzene chloride 1/2 zinc chloride double salt 1.0 part tartaric acid 0.5 part polyvinyl alcohol (10% aqueous solution ) 20 parts Calcium carbonate 2.0 parts Water 76.5 parts

Example 2 To 50 parts of each of the coupler capsule liquids A, B and C, 30 parts of a stearic acid amide dispersion liquid (concentration of solid content: 30%) was added, and after coating and drying on general high-quality paper, 6.5 g / m ² The heat-developable diazo copying materials A ₂ , B ₂ and C ₂ of the present invention were prepared by applying the diazo photosensitizing solution described in Example 1 to the coating amount and then coating and drying it at a coating amount of 0.8 g / m ² . .

Example 3 The coupler-capsule coated paper obtained in Example 2 was coated and dried with the following base-containing photosensitive solution at a coating amount of 0.8 g / m ² , and the heat-developable diazo copying material A of the present invention was applied. ₃ , B ₃ , and C ₃ were produced. <Diazo Photosensitive Solution-2> 4-diazo-1- (4'-toluylmercapto-2,5-diethoxybenzene chloride 1/2 zinc chloride double salt 1.0 part tartaric acid 0.5 part polyvinyl alcohol (10% aqueous solution ) 20 parts Calcium carbonate 2.0 parts Triphenylguanidine 20% dispersion liquid (average particle size 3 μm) 2.0 parts Water 74.5 parts

Example 4 3.45 parts of 2-hydroxy-3-naphthoic acid morpholinopropylamide and 0.85 part of acetic acid were dissolved in 24 parts of tricresyl phosphate. Next, 2% of an ammonium aqueous solution of isobutylene-maleic anhydride copolymer was mixed with an aqueous solution of ammonium styrene-acrylic acid copolymer, and 50 parts of an alkali-soluble resin solution having a total concentration of 5% was mixed with the above coupler solution. In the subsequent steps, 70 parts of the coupler capsule liquid was added to the photosensitive liquid of Example 1 to prepare a mixed liquid of the coupler liquid and the diazo liquid. <Coupler diazo photosensitive solution> 4-diazo-1- (4'-toluylmercapto-2,5-diethoxybenzene chloride 1/2 zinc chloride double salt 1.0 part Tartaric acid 0.5 part Polyvinyl alcohol (10% aqueous solution) 20 parts Calcium carbonate 2.0 parts Water 76.5 parts Coupler Capsule Liquid B 70 parts The above-mentioned coupler diazo photosensitive solution is applied to a general high-quality paper, dried and then applied to an adhesion amount of 7.3 g / m ² , followed by heat development of the present invention. A type diazo copying material was prepared.

Example 5 The heat-developable diazo copying material of the present invention was prepared in the same manner as in Example 4, except that the coupler capsule liquid A was used in place of the coupler capsule liquid B of the coupler diazo photosensitive liquid prepared in Example 4. It was made.

Comparative Example 1 10 g of 2-hydroxy-3-naphthoic acid anilide was used as PV.
Disperse in 50 g of A10% aqueous solution with a ball mill for 24 hours,
A coupler layer was formed by coating an ordinary fine paper in an amount of 3.5 g / m ^{2 in} terms of dry weight. Next, the diazo photosensitive solution of Example 1 was applied to the coupler layer to give a dry weight of 0.8 g / m ^2.
Was applied to obtain a heat-developable diazo copying material.

Comparative Example 2 2-hydroxy-3-naphthoic acid morpholinopropylamide (10 g) was dispersed in 50 g of a 10% PVA aqueous solution by a ball mill for 24 hours, and coated on general fine paper to give a dry weight of 3.5 g.
It was applied to the amount of deposition of / m ² to form a coupler layer. Next, the diazo photosensitive solution of Example 1 was applied to the coupler layer to a coating amount of 0.8 g / m ² in terms of dry weight to obtain a heat developable diazo copying material.

Comparative Example 3 <Preparation of Coupler Capsule Liquid> 2-Hydroxy-3-
3.45 parts of naphthoic acid anilide and 3: 1 adduct of xylylene diisocyanate and trimethylolpropane 18
Parts were dissolved in 24 parts tricresyl phosphate. Next, the above coupler solution was mixed with 50 parts of a 5% aqueous solution of polyvinyl alcohol, and the mixture was heated at 20 ° C. with a commercially available homomixer from 12,000 to 1: 1.
The mixture was stirred at 0000 rpm for 3 minutes to obtain an emulsion having an average particle size of 5 μm. Next, 100 parts of water was added to this emulsion and the mixture was heated to 60 ° C. and slightly stirred for 2 hours to obtain an emulsion dispersion. Then, this coupler capsule solution was applied to a general high-quality paper at a dry weight of 3.5 g / m ² to form a coupler layer, and then the diazo photosensitive solution of Example 1 was applied to the coupler layer at a dry weight. The heat-developable diazo copying material was obtained by applying the coating amount of 0.8 g / m ² .

Comparative Example 4 <Preparation of Coupler Capsule Liquid> 2-Hydroxy-3-
3.45 parts of naphthoic acid morpholinopropylamide and 0.85 part of acetic acid were dissolved in 24 parts of tricresyl phosphate. Next, 50 parts of gelatin was adjusted to a resin concentration of 5% and the above coupler solution was mixed. Subsequent steps produced the capsule liquid by the same operation as the preparation of the coupler capsule liquid A. Next, this coupler solution was applied to general high-quality paper to give a dry weight of 3.
After forming the coated coupler layer deposition amount of 5 g / m ^2, coated thermal development diazo copying material coating weight of 0.8 g / m ² at a coating dry weight diazo photosensitive solution of Example 1 in the coupler layer Got

The heat-developable diazo copying material obtained as described above was used as Copiart 100 (manufactured by Fuji Photo Film Co., Ltd.).
The copying scale 4 was used to form an exposed portion and a light-shielded portion, and the image was developed at a developing temperature of about 130 ° C. The obtained recorded image was measured for blue density and non-image density with a Macbeth reflection densitometer. Next, in order to evaluate the preservability of the diazo copying material before development, it was stored in a constant temperature bath at 50 ° C. for 72 hours, and the change amount from before storage was measured by a Macbeth reflection densitometer for blue density and non-image density. The results are shown in Table 1.

[0040]

[Table 1]

From Table 1, it is clear that the examples have a high image density and are excellent in raw storage stability. It is also preferable that the capsule wall is made of styrene-acrylic acid copolymer alone, but styrene- Acrylic acid copolymer and isobutylene
Even more excellent image density can be obtained when a maleic anhydride copolymer or a mixture with a styrene-maleic anhydride copolymer is used. On the other hand, it can be seen that even if the coupler is directly added to the coupler layer or used as a capsule, the comparative example in which the capsule wall has polyurethane or gelatin has poor raw storability.

[0042]

INDUSTRIAL APPLICABILITY As described above, the heat-developable diazo copying material of the present invention has a high image density and excellent raw storability. Further, the heat developable diazo copying material of the present invention is
Since the coupler as described above is obtained by the heating phase separation method, it can be manufactured at a lower cost than the interfacial polymerization method or the like.

Claims (3)

[Claims] 1. A diazo compound, a coupler, and a support on a support.
In a heat-developable diazo copying material, which is provided by incorporating an alkali-soluble resin and a sensitizer in one layer, or by laminating a layer containing a diazo compound and a layer containing a coupler, an alkali-soluble resin and a sensitizer. A heat-developable diazo copying material, wherein the coupler is encapsulated with the following alkali-soluble resin (a) or (b) as a partition wall. (A) Styrene-acrylic acid copolymer (b) Styrene-acrylic acid copolymer and isobutylene-
A mixture with a maleic anhydride copolymer or a styrene-maleic anhydride copolymer. 2. The heat developable diazo copying material according to claim 1, wherein a higher fatty acid amide having 10 to 20 carbon atoms or an N-substituted higher fatty acid amide is used as a sensitizer. 3. A heat-developable diazo copying material characterized in that both a coupler and acetic acid are dissolved in a water-insoluble organic solvent, and this is mixed with an ammonium solution (a) or (b) of the following alkali-soluble resin. Encapsulation method for the coupler used. (A) Ammonium solution of styrene-acrylic acid copolymer (b) Ammonium solution of styrene-acrylic acid copolymer and ammonium solution of isobutylene-maleic anhydride copolymer or ammonium solution of styrene-maleic anhydride copolymer Mixed with.