JPH08278593A - Heat developable diazo copying material - Google Patents

Abstract

(57) [Summary] [Object] To provide a heat-developable diazo copying material which has high color development and high developability and is excellent in raw storage stability. [Structure] A heat-developable diazo copying material containing a diazo compound, a coupler, a basic substance and a eutectic agent on a support, containing coupler particles treated by reacting the surfaces of the coupler particles with isocyanate and a sulfonamide compound. A heat-developable diazo copying material characterized in that

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 exposing the latent image with heat. The present invention also relates to a heat-sensitive recording material, particularly a heat-sensitive recording material capable of being optically fixed.

[0002]

2. Description of the Related Art A heat-developable diazo copying material generally comprises a photosensitive layer containing a diazo compound, a coupling component and a color-forming aid as a main component on a support such as paper or film. , Sodium trichloroacetate, etc. are used. This type of diazo copying material is 180 ℃ ~
Development is performed by heating at 200 ° C., and the developing mechanism uses an alkali that is decomposed and generated by heating. Further, in an attempt of low-temperature development, a heat-fusible substance such as higher fatty acid amide is used as a color-forming aid, and the development mechanism uses activation of a diazo compound and a coupling component by heating and melting. However, in the conventional case, pre-coupling gradually progressed during storage, and undesired coloring was sometimes caused. For this reason, JP-A-57-4204
2, JP-A-57-45094 and JP-A-57-12509
As disclosed in Japanese Patent Publication No. 1 etc., by allowing any one of the diazo compound, the coupling component and the basic substance to exist in the form of discontinuous particles, contact between the components is prevented and pre-coupling is prevented. Although it has been proposed to prevent it, there is a problem that the desired raw storability cannot be obtained if the particle size is reduced in order to obtain high heat sensitivity and color density. Further, as disclosed in Japanese Patent Publication No. 4-75147, an encapsulation technique has been proposed in which only a diazo compound is contained as a core substance in a microcapsule, and polyurethane and polyurea are used as partition walls around the core substance in a polymerization reaction. However, since the diazo compound is included, the surrounding polyurethane and polyurea resins block ultraviolet rays, which leads to an increase in the capacity of the light source of the copying machine, and JP-A-61-210688.
As disclosed in the publication, there is a problem that the desired storability cannot be obtained unless the unencapsulated diazo compound is removed. Further, as disclosed in JP-A-57-44141, an in-liquid drying method has been proposed in which a coupling component is encapsulated using a non-polar wax as a partitioning agent, but the diaphragm is a non-polar wax. Since the coupling reaction at the time of heat melting was suppressed, there were many problems in practical use. As described above, it is very difficult to achieve compatibility between high color developability, developability and raw storability in the conventional heat-developable diazo copying material, and it is not so excellent in manufacturing suitability for microencapsulation of diazo component. Is.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable diazo copying material which eliminates the above-mentioned drawbacks of the prior art, has high color-forming property, developability, and excellent raw storage stability. To do.

[0004]

The object of the present invention is to provide a surface of coupler particles in a heat-developable diazo copying material containing a diazo compound, a coupler, a basic substance and a eutectic agent on a support. A heat-developable diazo copying material characterized by containing a coupler particle treated with an isocyanate and a sulfonamide-based compound "," a heat containing a diazo compound, a coupler, a basic substance and a eutectic agent on a support. In the development type diazo copying material, the thermal development is characterized in that the surface of the coupler particle contains a coupler particle and a sulfonamide compound which are treated by reacting the surface of the coupler particle with an isocyanate, and the surface treated coupler particle has a median diameter of 15 μm or less. Type diazo copying material "," Heat development type containing diazo compound, coupler, basic substance and eutectic agent on support A heat-developable diazo copy, characterized in that, in an azo copying material, the coupler particle surface contains a coupler particle which has been treated by reacting with an isocyanate and a sulfonamide compound, and the isocyanate reacted with the coupler particle surface is an aliphatic isocyanate. material",
"In a heat-developable diazo copying material containing a diazo compound, a coupler, a basic substance and a eutectic agent on a support,
Heat-developable diazo copying material characterized in that it contains coupler particles obtained by reacting the surfaces of coupler particles with isocyanate and a sulfonamide compound, and the basic substance is water-insoluble or sparingly soluble "and" on a support ". In a heat-developable diazo copying material containing a diazo compound, a coupler, a basic substance and a eutectic agent, the coupler particles are treated by reacting the surfaces of the coupler particles with an isocyanate, and the sulfonamide compound is contained, and the coupler is eutecticized. The melting point of the eutectic agent to be used is in the range of 80 ° C. to 150 ° C.

Thus, the present invention provides a surface of coupler particles in a heat-developable diazo copying material in which a recording layer containing a diazo compound, a coupler, a basic substance and a eutectic agent is provided on a support. It is characterized in that it contains a coupler particle treated by reacting with an isocyanate and a sulfonamide compound. As a result of various studies to achieve the above-mentioned object, the inventors of the present invention have incorporated the coupler particles obtained by reacting the surface of the coupler particles with an isocyanate and a sulfonamide compound to improve the preservability of raw photosensitive paper, especially the background fog. It has been found that the developability (heat sensitivity) is improved without deteriorating. The present invention has been made based on this. The present invention will be described in detail below.

As described above, the heat-developable diazo copying material of the present invention is most characterized in that it contains the coupler particles obtained by reacting the surfaces of the coupler particles with an isocyanate and the sulfonamide compound. The present inventors considered that the pre-coupling that occurs during the storage of the photographic light-sensitive paper is suppressed by making the hydrogen atom of the hydroxyl group on the coupler particle surface difficult to dissociate. As a method of achieving this, the present inventors have reacted with hydroxyl groups of the coupler, and when the compound is heated and fused, the isocyanate dissociates with the coupler and the dissociation product has a coupling ability. It was examined to suppress the background fog. A method of treating the coupler in a mixed solvent of a solvent in which the coupler is dissolved and a coupler in which the dissolved coupler is capable of reacting with an isocyanate and a solvent in which the coupler particles are not dissolved has been studied, but the copying material by this method is
It was found that the color development during high-speed development was inferior. It was understood that this is because the particle size was increased due to precipitation of the reaction product with isocyanate on the surface of the coupler particles, and that the isocyanate dissociation reaction during heat dissolution was slower than the coupling reaction. Therefore, as a result of studying a sensitizer that accelerates this dissociation reaction and does not deteriorate the shelf life of the photosensitive paper, it was found that the desired developability (heat sensitivity) can be obtained by incorporating a sulfonamide compound with the surface-treated coupler particles.
Was found to achieve. Here, when the median diameter of the surface-treated coupler particles is larger than 15 μm,
There was little effect on developability (heat sensitivity). It was found that this is because the particle system, that is, the specific surface area of the particles has a higher contribution to the coupling reaction during development than the dissociation reaction rate. Therefore, the median diameter of the surface-treated coupler particles is preferably 15 μm or less.
It was also found that aliphatic isocyanates are more effective in terms of shelf life than aromatic aromatic isocyanates. Furthermore, it is preferable that the basic substance, which is one of the color forming aids, is sparingly water-soluble or water-insoluble. This is because in the surface-treated coupler particles, the reaction product of the isocyanate and the coupler has a property of being easily dissociated in an alkaline aqueous solution, and the water-soluble basic substance having an effect on the color developability in the coupler particle dispersion liquid. This is because the coupler particle dispersion is made strongly alkaline and the reaction product is dissociated, so that the desired storability cannot be obtained. Therefore, it is desirable that the basic substance is sparingly water-soluble or water-insoluble. Further, the melting point of the eutectic agent which is eutectic with the coupler is preferably 80 ° C. or higher in consideration of the dry fog during drying, and low temperature development (100
150 ° C. or less is preferable in consideration of (˜140 ° C.).

Now, the main components used in the present invention will be described. The diazo compound used in the present invention is a diazonium salt represented by the general formula ArN ₂ + X-.
(In the formula, Ar represents a substituted or unsubstituted aromatic moiety, ArN ₂ + represents a diazonium salt, and X- represents an acid anion.) Specific examples of the diazo compound include 4-diazo-N, N-
Dimethylaniline, 4-diazophenylmorpholine, 4
-Diazo-N, N-dibutylaniline, 4-diazo-
2,5-dimethoxyphenylmorpholine, 4-diazo-
2,5-diethoxyphenylmorpholine, 4-diazo-
2,5-dipropoxyphenylmorpholine, 4-diazo-2,5-dibutoxyphenylmorpholine, 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-ethoxyaniline, 4-diazo-2,5
-Dibutoxyphenylpiperazine, 4-diazo-2,5
-Diethoxyphenylpyrrolidine, 4-diazo-2,5
-Dipropoxyphenylpiperidine, 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'-methoxybenzoylamino) -2,5-dipropoxybenzene, 4-
Diazo-1- (3′-chlorobenzoylamino) -2,
5-Diethoxybenzene, 4-diazo-1- (3'-methoxybenzoylamino) -2,5-dibutoxybenzene, 4-diazo-1- (3'-methoxybenzoylamino) -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'-toluyl) Mercapto) -2,5-dibutoxybenzene, 4-diazo-1-phenoxy-2,5
A double salt of a chloride such as dibutoxybenzene and 4-diazo-1- (4′-methoxyphenoxy) -2,5-diethoxybenzene and a metal chloride such as zinc chloride, cadmium chloride and tin chloride; Examples thereof include salts of inorganic acids such as sulfuric acid, hexafluorophosphoric acid, and tetrafluoroboric acid of diazo compounds.

The diazo compound is applied as an aqueous solution or dispersion without using a binder or with a binder. In the present invention, polyvinyl alcohol as a binder, polyacrylamide, casein, gelatin, starch and its derivatives, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose,
Water-soluble resins such as ethyl cellulose, hydroxyethyl cellulose, polyvinyl acetate, polyacrylic acid ester,
Vinyl chloride-acrylic acid ester copolymer, ethylene-
Various emulsion resins such as vinyl acetate copolymer can be used. In addition, when a poorly water-soluble diazo liquid component is dissolved in an organic solvent and applied, a resin soluble in an organic solvent may be used as a binder, and examples thereof include vinyl chloride-based, vinyl acetate-based, and vinyl chloride-based resins. -Vinyl acetate-based copolymer, vinyl acetate-vinylidene chloride-based copolymer, polystyrene-based,
Butyral-based, polycarbonate-based, acrylic acid-derivative-based resins and the like can be used.

In the present invention, as the coupling component, all those used in general two-component type diazo copying materials can be used, but the eutectic agent and 80 ° C. to 150 ° C.
Therefore, a naphthol AS-based coupler that is relatively easy to eutectic is desirable. For example, naphthol AS, naphthol AS-D,
Naphthol AS-BO, Naphthol AS-BS, Naphthol AS-E, Naphthol AS-G, Naphthol AS-
LB, naphthol AS-OL, naphthol AS-SW,
Naphthol AS-TR etc. can be mentioned.

Examples of the sulfonamide compounds used in the present invention include p-toluenesulfonamide, o-toluenesulfonamide, benzenesulfonamide, etc., but if they are organic sulfonamide compounds, they are not limited thereto. There is no such thing. However, p-toluenesulfonamide is particularly effective.

Examples of the eutectic agent used in the present invention include higher fatty acid amides having 10 to 20 carbon atoms and N-substituted higher fatty acid amides. Specifically, lauric acid amide, myristyl acid amide, palmitic acid are used. Amide, stearic acid amide, arachidic acid amide, behenic acid amide,
Eicoic acid amide, elaidic acid amide, N-methylol stearic acid amide, N-methylol caproic acid amide, N
Examples include methylol lauric acid amide and N-methylol behenic acid amide.

These coupling components are applied as a dispersion without using a binder or using a binder. As binder, polyvinyl alcohol,
Polyacrylamide, casein, gelatin, starch and its derivatives, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, ethylcellulose,
Water-soluble resins such as hydroxyethyl cellulose, polyvinyl acetate, polyacrylic acid esters, vinyl chloride-acrylic acid ester copolymers, various emulsion resins such as ethylene-vinyl acetate copolymers, polyacrylic acid, modified PV
A, CMC, gum arabic, isobutylene-maleic anhydride copolymer, diisobutene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, ethylene-acrylic acid copolymer, styrene-acrylic acid copolymer, Examples thereof include styrene and methacrylic acid copolymers, and these resins can be used in combination of two or more kinds.

In the coupler layer, water-soluble as a color-forming aid,
A hardly soluble or water insoluble basic substance or a substance which generates an alkali upon heating is used. Specific examples of the color forming aid used in the present invention 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,
Among these, those which are sparingly soluble in water or insoluble in water are more desirable. 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 sodium naphthalene monosulfonate and naphthalenedisulfonic acid as storage stability improvers. Sodium, sodium naphthalene trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride and the like can be used. Further, thiourea, urea, etc. can be used as an antioxidant, caffeine, theophylline acid, etc. can be used as a solubilizer, and in addition, a small amount of saponin can be added for the purpose of stabilizing the dispersion of components used, defoaming, etc. . When it is used as a light-fixing type heat-sensitive recording material, a filler such as styrene resin fine particles, urea-formalin condensate resin fine particles, aluminum hydroxide or hydroxide is used for the purpose of preventing sticking to the thermal head and improving running property. Organic or inorganic solid particles such as magnesium, calcium carbonate, titanium, talc, kaolin, silica and alumina can be added. Metal soaps can also be used for the same purpose.

The heat-developable diazo copying material of the present invention can be advantageously applied not only to the heat-developable copying material, but also to various heat-sensitive recording fields, particularly recording sheets for facsimiles and electronic computers which require high-speed recording. Moreover, in the case of the present invention, the characters and images recorded on the surface of the recording paper can be fixed by forming an image by heating and then decomposing the unreacted diazo compound by exposure. Further, the recording material of the present invention can be applied to the recording and preparation of necessary items for securities, gift certificates, entrance tickets, certificates, slips, etc. by utilizing its fixing property. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" indicating the addition amount
Represents "parts by weight".

[0016]

【Example】

Preparation of surface-treated coupler particles Surface-treated coupler particles (A) Naphthol AS 10.0 parts Octadecyl isocyanate 0.5 parts Dimethylformamide 10.0 parts Toluene 78.5 parts The above coupler dispersion is heated at 50 ° C. for 10 hours. Coupler particles (A) surface-treated by filtration, vacuum drying, washing with toluene, filtration, and vacuum drying three times.
(HORIBA's LA-700 measurement median diameter 10μ
m) was obtained. Surface-treated coupler particles (B) Naphthol AS 10.0 parts Octadecyl isocyanate 1.0 part Dimethylformamide 10.0 parts Toluene 78.0 parts The above coupler dispersion is heated at 50 ° C. for 10 hours, then filtered and vacuum dried. Coupler particles (B) which have been subjected to surface treatment by repeating washing with toluene, filtration and vacuum drying three times.
(HORIBA's LA-700 measurement median diameter 20μ
m) was obtained. Surface-treated coupler particles (C) Naphthol AS 10.0 parts Phenylisocyanate 0.5 parts Dimethylformamide 10.0 parts Toluene 78.5 parts The above coupler dispersion is heated at 50 ° C. for 10 hours, then filtered and vacuum dried. Coupler particles (C) which have been subjected to surface treatment by repeating washing with toluene, filtration and vacuum drying three times.
(HORIBA's LA-700 measurement median diameter 10μ
m) was obtained.

(Example 1) Surface-treated coupler particles (A) 3.0 parts Behenamide 20% dispersion 25.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Paratoluene sulfonamide 5.0 parts Polyvinyl alcohol Aqueous solution (10%) 10.0 parts Guanidine carbonate 1.0 part Water 51.0 parts (Example 2) Surface-treated coupler particles (A) 3.0 parts Behenamide 20% dispersion 25.0 parts Styrene-acrylic Ammonium acid salt 5.0 parts Paratoluene sulfonamide 5.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Benzimidazole 1.0 parts Water 51.0 parts (Example 3) Surface-treated coupler particles (C) 3 0.0 parts Behenic acid amide 20% dispersion liquid 25.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Paratoluene sulfonamide 5.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Benzimidazole 1.0 parts Water 51.0 parts (Comparative Example 1) Naphthol AS (median diameter 4 μm) 3.0 parts Behenamide 20% dispersion 25 0.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Paratoluene sulfonamide 5.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Guanidine carbonate 1.0 parts Water 51.0 parts (Comparative Example 2) Surface treatment Coupler particles (A) 3.0 parts Behenamide 20% dispersion 25.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Guanidine carbonate 1.0 part Water 55. 0 part (Comparative Example 3) Surface-treated coupler particles (A) 3.0 parts Behenamide 20% dispersion 25.0 parts Styrene-acrylic Ammonium acid salt 5.0 parts Para-tert-butylphenol 5.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Guanidine carbonate 1.0 part Water 51.0 parts (Comparative Example 4) Surface-treated coupler particles (B ) 3.0 parts Behenamide 20% dispersion 25.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Paratoluene sulfonamide 5.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Guanidine carbonate 1.0 Parts Water 51.0 parts (Comparative Example 5) Surface-treated coupler particles (A) 3.0 parts Ethylenebiscapric acid amide 20% dispersion 25.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Paratoluene sulfonamide 5 0.0 parts Polyvinyl alcohol aqueous solution (10%) 10.0 parts Benzimidazole 1.0 parts Water 51.0 parts (Comparative Example 6) Surface-treated coupler particles (A) 3.0 parts Ricinoleic acid amide 20% dispersion 25.0 parts Styrene-acrylic acid ammonium salt 5.0 parts Paratoluene sulfonamide 5.0 parts Polyvinyl alcohol aqueous solution (10 %) 10.0 parts Benzimidazole 1.0 parts Water 51.0 parts (Diazo liquid component) 4-diazo-2,5-dibutoxyphenyl morpholine chloride / 1/2 zinc chloride 1.5 parts Tartaric acid 0.5 Parts Isopropanol 1.0 parts Polyvinyl alcohol (10%) 10.0 parts Silica 2.0 parts Saponin 0.1 parts Water 84.9 parts The above diazo solution is applied to a high-quality paper with a wire bar and dried to give a solid content of 1 It was set to be 0.0 g / m ² . After forming the diazo layer by coating, the above coupler liquid components (Example 1), (Example 2), (Example 3), (Comparative Example 1),
(Comparative Example 2), (Comparative Example 3), (Comparative Example 4), (Comparative Example 5), and (Comparative Example 6) were coated and dried so that the solid content adhesion amount was 3.5 g / m ^2, and heat development was performed. A type diazo copying material was prepared. However, with respect to (Comparative Example 6), the photosensitive paper was not evaluated because a dry fog occurred when the coupler liquid component was applied. The heat-developable diazo copying material obtained as described above was changed to COPIART100 (manufactured by Fuji Photograph Co., Ltd., development temperature: about 1).
The photosensitivity was measured with a copying scale 4 (20 ° C.). The developability was compared by (density value when developed with copy scale 8 / density value when developed with copy scale 2). Then, the unexposed / completely exposed sample was developed on the copy scale 4, and the color-developed portion (unexposed portion) and the background portion (completely exposed portion) obtained were measured as the densities of the initial sample with a Macbeth reflection densitometer. Next, in order to check the raw storability of the photosensitive paper, 5
The sample was stored in a 0 ° C. packaged state for 72 hours and subjected to a forced deterioration test. After the deterioration test, the densities of the colored portion and the background portion were measured as in the initial sample. The results are shown in Table 1.

[0018]

[Table 1]

[0019]

As is clear from the above detailed and specific description, the heat-developable diazo copying material of the present invention contains coupler particles obtained by reacting the surfaces of the coupler particles with isocyanate and a sulfonamide compound. By doing so, the effect of excellent raw storability is exhibited without lowering the color developability and developability.

Claims (5)

[Claims] 1. A heat-developable diazo copying material containing a diazo compound, a coupler, a basic substance and a eutectic agent on a support, wherein the coupler particles are treated by reacting the surfaces of the coupler particles with an isocyanate and a sulfonamide compound. A heat-developable diazo copying material characterized by containing. 2. The heat-developable diazo copying material according to claim 1, wherein the surface-treated coupler particles have a median diameter of 15 μm or less. 3. The heat-developable diazo copying material according to claim 1, wherein the isocyanate reacted with the surface of the coupler particle is an aliphatic isocyanate. 4. The heat developable diazo copying material according to claim 1, wherein the basic substance is water-insoluble or sparingly soluble. 5. The heat-developable diazo copying material according to claim 1, wherein the melting point of the eutectic agent for eutecticizing the coupler is in the range of 80 ° C. to 150 ° C.