JP3741821B2 - Thermal development type diazo copy material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat-developable diazo copy material in which a latent image is formed by exposing it on a transparent or semi-transparent document, and then developing the latent image with heat. About. Further, the present invention relates to a heat-developable diazo copying material for a second original drawing which has a high light-shielding property as a second original drawing and has no background fog even after being stored for a long period of time.
[0002]
[Prior art]
The diazo second original drawing sheet is widely used to prevent contamination of the original drawing when copying an industrial drawing or to save the rewriting time when correcting the drawing.
As a method of forming an image on the diazo second original sheet, a so-called dry method in which development is performed through an atmosphere filled with ammonia gas and water vapor, or a small amount of alkaline developer is applied to the diazo photosensitive surface of the second original sheet. There is a so-called semi-dry method for developing by doing so. The dry method has a problem of odor due to the use of ammonia as a developer, and a copying machine becomes large in order to prevent ammonia from leaking outside. The semi-dry method can be made more compact than a dry-type copying machine, but has a problem that it takes time to replenish and dispose of the developer because it uses a developer, and it cannot be immediately added because it is still wet immediately after copying. The present invention relates to a thermal development method that does not use a developing solution which is a problem in these development methods, but the coupling component conventionally used for the second original drawing has a high water solubility, so this material was used. If the copy material is stored for a long period of time, background fogging will occur. Further, as disclosed in JP-A-57-44141, JP-A-59-190866, etc., any one of diazo compounds, coupling components and alkali generators is encapsulated to isolate them from other components. In particular, a second original drawing sheet using microcapsules encapsulating a diazo compound is disclosed in Japanese Patent Laid-Open No. 3-44633. However, these methods also sufficiently satisfy raw storage and thermal coloring properties. Not a thing. Further, since the diazo compound that forms the latent image is formed into a particulate capsule, the resolving power is lower than that of a photosensitive paper on which a normal diazo compound is dissolved and applied.
[0003]
[Problems to be solved by the invention]
The present invention maintains a light-shielding property equivalent to that of a conventional dry type or wet type, is a heat development method that does not have a defect due to the use of a conventional developer, and does not cause background fog that is a problem in this method. Provided is a heat-developable diazo copying material for a second original drawing that develops a black color with excellent long-term raw storage.
[0004]
[Means for Solving the Problems]
  According to the present invention, first, a photosensitive layer containing a diazo compound on a support, a coupler component, and a coupler layer containing a copolymer having a carboxylic acid and / or dicarboxylic anhydride as a constituent component as a monomer.ProvidedIn diazo copying materials,SaidA compound represented by the following general formula (I) as a coupler component:The following general formula (II)A heat-developable diazo copying material comprising a compound represented by the formula:
[Chemical 1]
(In the formula, X represents a cyano group, an acetyl group, a benzoyl group, or a —COOR group, and R represents an alkyl group, an aryl group, or a benzyl group.)
[Chemical formula 2]
(Wherein R₁Represents a substituted or unsubstituted aryl group. )
The secondtwoOn one side of a transparent or translucent support,A photosensitive layer containing a diazo compound;SaidA coupler component represented by the general formula (I), a photosensitive thermosensitive layer comprising a coupler layer containing a copolymer having a carboxylic acid and / or dicarboxylic anhydride as a constituent component as a monomer;SaidA photosensitive layer containing a diazo compound on the opposite side of the support;SaidIt is characterized by providing a light and heat sensitive layer comprising a coupler layer represented by the general formula (II) and a coupler layer containing a copolymer having carboxylic acid and / or dicarboxylic anhydride as a constituent component as a monomer.As described in the firstA heat developable diazo copying material is provided.
  FirstthreeIn addition,the above1st or 1stAs described inIn the invention,SaidCoupler layer or / andSaidThere is provided a heat-developable diazo copying material characterized in that the photosensitive layer contains a water-soluble guanidine derivative.
  FirstFourIn addition,the above1st or 1stAs described inIn the invention,SaidCoupler layer or / andSaidThere is provided a heat-developable diazo copying material, wherein the photosensitive layer contains a heat-fusible substance having a melting point of 60 to 150 ° C.
  FirstFiveIn addition,the above1st or 1stAs described inIn the present invention, there is provided a heat-developable diazo copying material, wherein the copolymer resin is a styrene-acrylic acid copolymer.
  FirstSixIn addition,the above1st or 1stAs described inIn the present invention, the copolymer resin is a mixture of a styrene-acrylic acid copolymer and an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer. Is provided.
[0005]
The heat-developable diazo copying material of the present invention is excellent in the light-shielding property of an image when a color is developed because the coupling component of the general formula (I) is used, and this and the coupling component of the general formula (II) By combining, a black tone image is given. The heat-developable diazo copy material of the present invention is excellent in long-term storage as compared with the conventional second original drawing.
[0006]
In the present invention, a sufficiently excellent diazo copying material can be formed with the above-described configuration. However, in order to easily adjust the color tone balance when using a plurality of coupling components having different coupling speeds, Contains a photosensitive layer containing a diazo compound on one side of a transparent support, a coupler component represented by the above general formula (I), and a copolymer containing carboxylic acid and / or dicarboxylic anhydride as a monomer as a monomer A photosensitive layer comprising a coupler layer, a photosensitive layer containing a diazo compound on the opposite side of the support, a coupler component represented by the general formula (II), a carboxylic acid and / or dicarboxylic anhydride as a monomer It is preferable to provide a light and heat sensitive layer comprising a coupler layer containing a copolymer containing a product as a constituent.
Further, a heat-developable diazo copying material having improved heat developability can be obtained by incorporating a water-soluble guanidine derivative and a heat-fusible substance having a melting point of 60 to 150 ° C. into the coupler layer and / or the photosensitive layer.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In general, since a diazo copying material is coated with a solution in which a diazo compound is dissolved and dried, a high-resolution image can be obtained. In dry or wet type photosensitive paper, an acid aid is added even if the diazo compound and the coupler component are in contact with each other, so pre-coupling during storage is prevented. Since a developer (ammonia or organic amine) that neutralizes the agent is not used, similarly, if an acidic auxiliary is used, color development will cease. Therefore, a method for preventing pre-coupling by another method is required. For this reason, the coupling component uses a compound insoluble in water to reduce contact with the diazo compound. However, since this is not sufficient in practice, the present invention employs a method of coating the coupler particles with a resin capable of forming a film.
[0008]
When a copolymer resin containing carboxylic acid and / or dicarboxylic anhydride as a monomer as a monomer, preferably its ammonium salt, is used as a coating liquid for coating and dried, a water-insoluble film is formed around the coupler component. , Contact with the diazo compound is prevented, and pre-coupling during storage is prevented.
[0009]
According to the study by the present inventors, in order to obtain a second original drawing sheet having a high light shielding property, the coupler component is a dye having absorption in the absorption wavelength region of the diazo compound in the spectrum when coupled with the diazo compound. The coupler component that forms such a dye is a compound having an active methylene group, and tends to cause background fogging because of its faster coupling speed than a general naphthol coupler. Therefore, in order to suppress background fogging, it has been found that a coupler component having a lower solubility in water is effective, and as a result of intensive studies, the compound represented by the general formula (I) is incorporated into water. The present invention is completed by grasping that it has low color solubility and excellent color-shielding properties for the second original drawing. It came to that. Also for black color development, the compound represented by the general formula (I) has two coupling positions, one forms a yellow image and the other forms a magenta image. Therefore, the general formula (II) When combined with a compound represented by the formula, it has been confirmed that black color is developed.
[0010]
In addition, in order to improve heat developability, it is a common method to use a basic substance such as an inorganic alkali or an organic amine as a color developing accelerator, but they inhibit film formation of the coating resin and are being stored. In some cases, a background fog may occur. On the contrary, a weakly basic substance such as urea has almost no background fog, but color development is insufficient. According to the study by the present inventors, these problems are solved when a water-soluble guanidine salt is used as a color development accelerator, and the background fogging hardly occurs even in raw storage while maintaining the color developability. It has been confirmed.
[0011]
Hereinafter, the present invention will be described in more detail.
Examples of the copolymer resin containing carboxylic acid and / or dicarboxylic anhydride as a monomer used in the present invention include, for example, styrene-acrylic acid copolymer, isobutylene-maleic anhydride copolymer, and styrene-anhydride. A maleic acid copolymer or the like is used, but a styrene-acrylic acid copolymer having a Tg of 60 ° C. or higher is preferable from the viewpoint of preservability.
[0012]
It is also preferable to use a mixture of a styrene-acrylic acid copolymer and an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer. When these mixed resins are used, compared with the case where a single resin is used, pre-coupling during storage is further suppressed while maintaining the color developability, and background fogging is reduced.
[0013]
The reason is not clear, but when the aqueous solution of ammonium salt of styrene-acrylic acid copolymer and aqueous solution of isobutylene-maleic anhydride copolymeric ammonium salt are mixed, gelation may occur and the solution may become cloudy. Observed and due to this phenomenon, when the resin mixed aqueous solution in which the coupler component is dispersed is applied and dried on the support, gelation is promoted along with evaporation of ammonia and water, and a firm film is formed around the coupler component. I guess that.
[0014]
The mixing ratio of the resin is 0.01 to 2 parts by weight such as isobutylene-maleic anhydride copolymer or styrene-maleic anhydride copolymer, preferably 0.1 to 1 part by weight of the styrene-acrylic acid copolymer. 1 part by weight.
Usually, the above copolymer resin is dissolved in an aqueous ammonia solution and used as an ammonium salt.
[0015]
The amount of the copolymer resin used is 0.1 to 1 part by weight of the coupler component.
10.0 parts by weight, preferably 0.5 to 4.0 parts by weight.
[0016]
Examples of the water-soluble guanidine salt used in the present invention include guanidine carbonate, guanidine acetate, guanidine formate, guanidine phosphate, guanidine sulfamate, and guanidine malate.
[0017]
Moreover, the usage-amount is 0.1-10 weight part with respect to 1 weight part of coupler components, Preferably it is 0.2-3.0 weight part.
[0018]
In the present invention, it is preferable to use a heat-fusible substance having a melting point of 60 to 150 ° C. in order to promote thermal response. The heat-fusible substance is a substance having an action of dissolving the coupler component or the above resin when melted. For example, alcohol derivatives such as 2-tribromoethanol, 2,2-dimethyltrimethylene glycol and 1,2-cyclohexanediol, waxes such as paraffin wax, microcrystalline wax, montanic acid wax, carnauba wax, monostearin, tristearin, etc. Higher fatty acid esters, higher alcohols such as polyethylene glycol, polyethylene oxide, and behenyl alcohol, higher polyhydric alcohols, higher ketones, and the like. In particular, since the organic acid amide derivative represented by the following general formula has a large dissolving action when melted, the coupling reaction proceeds efficiently and color development is promoted.
R₂-CONH-R_Three
(R₂Represents an alkyl or aryl group having 8 to 22 carbon atoms, R_ThreeRepresents hydrogen, an alkyl group having 1 to 18 carbon atoms or an aryl group.
[0019]
Specific examples include higher fatty acid amide derivatives such as lauric acid amide, stearic acid amide, behenic acid amide, stearic acid methylol amide, ethylene bis stearic acid amide, benzoic acid stearyl amide, 2-naphthoic acid lauryl amide, myristic acid anilide. , Stearic acid anilide and the like.
[0020]
In the present invention, the background fogging during storage has been improved by the above configuration. However, for example, when a pressure such as rubbing is applied to the photosensitive surface, a phenomenon occurs in which only the portion is covered during storage. In order to prevent this phenomenon, a copolymer resin containing carboxylic acid and / or dicarboxylic anhydride as a monomer and / or a melting point of 60 to 150 as a monomer between a layer containing a diazo compound and a layer containing a coupler component. It is effective to provide an intermediate layer containing a heat-fusible substance at 0 ° C. Here, the above-mentioned materials can be used as the copolymer resin containing carboxylic acid and / or dicarboxylic acid anhydride as a monomer and the thermofusible substance polymer compound having a melting point of 60 to 150 ° C. By using the intermediate layer having this configuration, it is possible to prevent rubbing and fogging due to the above pressure without impairing thermal responsiveness.
[0021]
As a coupling component represented with general formula (I) used by this invention, the following are mentioned, for example.
[0022]
[Table 1]
[0023]
In addition, as the coupling component represented by the general formula (II) used in the present invention,For example, 2-hydroxy-3-naphthoic acid anilide (naphthol AS)2-hydroxy-3-naphthoic acid-4'-methylphenylamide (naphthol AS-D), 2-hydroxy-3-naphthoic acid-4'-methoxyphenylamide, 2-hydroxy-3-naphthoic acid-4'-chlorophenyl Amides, 2-hydroxy-3-naphthoic acid-2'-methylphenylamide and the like. In the present invention, a coupler that is insoluble or hardly soluble in water is preferable for storage, and specific examples include naphthol AS and naphthol AS-D. Further, when the coupler component of this system is mixed with an organic acid amide derivative which is a heat-fusible substance and DSC is measured, eutectic formation is observed and it is presumed that the compatibility is good.
[0024]
In the present invention, the coupler component is used in an amount of 0.1 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, based on 1 part by weight of the diazo compound. When the amount is less than 0.1 parts by weight, the color development is insufficient. On the other hand, when the amount is more than 5.0 parts by weight, undesirable fog occurs during storage. The heat fusible substance is used in an amount of 0.1 to 10.0 parts by weight, preferably 0.5 to 5.0 parts by weight, based on 1 part by weight of the coupler component. When the amount is less than 0.1 parts by weight, color development is insufficient. Conversely, when the amount is more than 10 parts by weight, the feel is deteriorated.
[0025]
The diazo compound used in the present invention has the general formula ArN₂ ⁺X^-(Wherein Ar represents a substituted or unsubstituted aromatic moiety, ArN₂ ⁺Represents a diazonium cation 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-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 dibutoxyphenylpiperazine, 4-diazo-2,5-diethoxyphenylpyrrolidine, 4 -Diazo-2,5-dipropoxyphenylpiperidine, 4-diazo-2,5-diethoxy-N, N-dimethyl Nilin, 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'-methylcybenzoylamino) -2,5-dipropoxybenzene, 4-diazo-1- (3'-chlorobenzo) Iamino) -2,5-diethoxybenzene, 4-diazo-1- (3'-methoxybenzoylamino) -2,5-dibutoxybenzene, 4-diazo-1- (3'-methylcybenzoylamino) ) -2,5-dimethoxybenzene, 4-diazo-1-phenylmercapto-2,5-dibropoxybenzene, 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 chlorides such as diethoxybenzene, such as zinc chloride, cadmium chloride and tin chloride, and acid anions such as sulfuric acid, hexafluorophosphoric acid and tetrafluoroboric acid And salt of the salt.
[0026]
As the support in the heat-developable diazo second original drawing sheet of the present invention, a transparent or semi-transparent material such as paper, synthetic paper or plastic film can be used, but a single-sided or double-sided matte plastic film is preferred.
As the plastic film, a material with little deformation with respect to heating in the development process and a material excellent in dimensional stability is preferable, for example, polyethylene terephthalate, polybutylene terephthalate, polyester film such as polycarbonate, cellulose film such as cellulose triacetate, Examples thereof include polyolefin films such as polyethylene, polypropylene, and polystyrene, and polyimide films.
[0027]
The thickness of the support is suitably 20 to 200 μm. As the mat processing, there are a method of roughening the surface with sand plast or embossing, or a method of etching the surface with acid or the like. There is also a method of providing a mat layer composed of a layer containing a binder and fine particle powder. The latter is excellent for the purpose of increasing the image density and photosensitivity or improving the writability, and as the fine particle powder used in the mat layer, either inorganic fine particle powder or organic fine particle powder can be used. Specific examples of the inorganic fine particle powder include silica, alumina, kaolin, talc, titanium, calcium carbonate, aluminum hydroxide, magnesium hydroxide, and the like. Specific examples of the organic fine particle powder include styrene resin particles, urea-formalin condensation. Product resin particles, benzocoguanamine resin particles, and the like.
[0028]
As the binder, water-soluble resins such as polyvinyl alcohol, polyacrylamide, casein, gelatin, starch and derivatives thereof, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyester, polyvinyl acetate, polyacrylate, Various emulsion resins such as vinyl chloride-acrylic acid ester copolymer and ethylene-vinyl acetate copolymer are used.
[0029]
In the present invention, a binder is used when a photosensitive layer or coupler layer coating solution is coated on a support. Such binders include polyvinyl alcohol, polyacrylamide, casein, gelatin, starch and derivatives thereof, water-soluble resins such as polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, polyester, polyvinyl acetate, and polyacrylic. Various emulsion resins such as acid ester, vinyl chloride-acrylic acid ester copolymer, and ethylene-vinyl acetate copolymer can be used. In addition, after applying the coupler layer solution first, the photosensitive layer solution may be applied thereon, or the layers may be formed in the reverse order.
[0030]
In the heat-developable diazo copying material of the present invention, in addition to the color forming component described above, various additives applied to ordinary diazo type heat-sensitive recording materials, and sodium phthalene-monosulfonate and naphthalene-disulfone as preservative improvers. Sodium acid, sodium naphthalene-trisulfonate, sulfosalicylic acid, cadmium sulfate, magnesium sulfate, cadmium chloride, zinc chloride and the like can be used.
Antioxidants such as thiourea and urea, solubilizers such as caffeine and theophylline, acid stability such as citric acid, tartaric acid, sulfuric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc. A small amount of saponin can be added.
[0031]
In addition, when used as a second original sheet for photo-fixing type thermal recording, a filler may be added or a protective layer may be provided for the purpose of preventing sticking to the thermal head and improving running performance. Examples of the filler include organic and inorganic solid fine particles such as styrene resin fine particles, urea-formalin condensate resin fine particles, aluminum hydroxide, magnesium hydroxide, calcium carbonate, titanium, talc, kaolin, silica, and alumina. . In the present invention, metal soaps can also be used for the same purpose.
[0032]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0033]
referenceExample 1
  A coupler dispersion composed of the following composition was prepared, applied to the surface of a 75 μm PET film matted on one side using a wire bar and dried, and the adhesion amount was 8 g / m.²The coupler layer was formed.
    (Compound 1) dispersion (20%) 10 g
    30 g of styrene-ammonium acrylate copolymer aqueous solution (20%)
    (John Crill 679 manufactured by Johnson Polymer Co., Ltd.)
    30 g stearic acid amide dispersion (20%)
    Silica powder 1g
    Polyvinyl alcohol aqueous solution (10%) 10g
    Guanidine carbonate 1.5g
    100g of water
  On the above coupler layer, a photosensitive layer solution having the following composition is applied and dried using a wire bar, and the adhesion amount is 0.8 g / m.²The photosensitive layer was formed.
    4-diazo-1-morpholino-2,5-dibutoxybenzene
    Chloride ・ 1/2 zinc chloride 1.2g
    Tartaric acid 1g
    Caffeine 2g
    Isopropanol 5g
    Saponin 0.1g
    92.9g of water
  As above,Reference example 1A heat-developable diazo second original sheet was prepared.
[0034]
referenceExample 2
  referenceInstead of the styrene-ammonium acrylate copolymer aqueous solution (20%) of the coupler layer coating liquid of Example 1, a styrene-ammonium maleate anhydride copolymer aqueous solution (20%) (SMA-3000 manufactured by Kuraray Co., Ltd.) was used. The same operation was performed except that (Compound 3) was used instead of (Compound 1).Reference example 2A heat-developable diazo second original sheet was prepared.
[0035]
Example1
  A coupler dispersion composed of the following composition was prepared, applied to the surface of a 75 μm PET film matted on one side using a wire bar and dried, and the adhesion amount was 8 g / m.²The coupler layer was formed.
    Naphthol AS dispersion (20%) 10g
    (Compound 4) dispersion (20%) 10 g
    30 g of styrene-ammonium acrylate copolymer aqueous solution (20%)
    (John Crill 679 manufactured by Johnson Polymer Co., Ltd.)
    Isobutylene-ammonium maleate anhydride
    Copolymer aqueous solution (20%) 10g
    Stearamide dispersion (20%) 30g
    Silica powder 1g
    Polyvinyl alcohol aqueous solution (10%) 10g
    Guanidine carbonate 1.5g
    100g of water
  Above the coupler layerreferenceThe photosensitive layer solution of Example 1 was applied and dried using a wire bar, and the adhesion amount was 0.8 g / m.²The heat-developable diazo second original drawing sheet of the present invention was prepared.
[0036]
Example2
  A coupler dispersion composed of the following composition was prepared, applied to the surface of a 75 μm PET film matted on one side using a wire bar and dried, and the adhesion amount was 8 g / m.²The coupler layer was formed.
    Naphthol AS dispersion (20%) 10g
    (Compound 5) dispersion (20%) 10 g
    30 g of styrene-ammonium acrylate copolymer aqueous solution (20%)
    (John Crill 679 manufactured by Johnson Polymer Co., Ltd.)
    Isobutylene-ammonium maleate anhydride
    Copolymer aqueous solution (20%) 10g
    Stearamide dispersion (20%) 30g
    Silica powder 1g
    Polyvinyl alcohol aqueous solution (10%) 10g
    Guanidine carbonate 1.5g
    100g of water
  Above the coupler layerreferenceThe photosensitive layer solution of Example 1 was applied and dried using a wire bar, and the adhesion amount was 0.8 g / m.²The photosensitive layer was formed. Next, a coupler dispersion liquid having the following composition is prepared on the opposite side of the coated surface, applied and dried using a wire bar, and an adhesion amount of 8 g / m.²The coupler layer was formed.
    (Compound 5) dispersion (20%) 10 g
    30 g of styrene-ammonium acrylate copolymer aqueous solution (20%)
    (John Crill 679 manufactured by Johnson Polymer Co., Ltd.)
    Isoprene-ammonium maleate anhydride
    Copolymer aqueous solution (20%) 10g
    Stearamide dispersion (20%) 30g
    Silica powder 1g
    Polypinyl alcohol aqueous solution (10%) 10g
    Guanidine carbonate 1.5g
    100g of water
  Above the coupler layerreferenceThe photoreceptor solution of Example 1 was applied and dried using a wire bar, and the adhesion amount was 0.8 g / m.²The heat-developable diazo second original drawing sheet of the present invention was prepared.
[0037]
Comparative Example 1
  referenceA heat-developable diazo copying material was obtained in the same manner except that acetoacetolinide was used instead of compound-1 in the coupler layer dispersion of Example 1.
[0038]
When the above-described heat-developable diazo second original drawing sheet was superimposed on the original and exposed and developed with the copy art 100 manufactured by Fuji Photo Film, a yellow, black-green or black image was obtained. Next, the exposed and developed second original drawing sheet was used as a manuscript, and was copied onto a Ricoh Co., Ltd. SDE photosensitive paper and copied using a Ricoh Co., Ltd. SD-750 copier. The density of the image area was measured with a Macbeth densitometer 914. Further, SDE photosensitive paper was copied with an SD-750 copying machine without exposure and with development alone. The density of the image area at that time was also measured in the same manner. The ratio of the former density value to the latter density value was defined as the degree of light shielding. In order to test the raw storability, each sample was left to stand in an environment of 50 ° C. and 50% RH for 24 hours to be forcibly deteriorated and then taken out. It was measured. Without compulsorily degrading, this was compared with the density of the background portion measured in the same manner. The results are shown in Table 2.
[0039]
[Table 2]
*referenceExamples 1 and 2 and Comparative Example 1 are yellow filters.1,2The developed images of the second original image were black green and black, respectively, and the images were easily identified and measured with a black filter.
[0040]
【The invention's effect】
  The thermally developable diazo second original drawing sheet of the present invention is equivalent to a conventional dry or wet type.Light shielding andMaintains initial image quality and image reliability, is a heat development system that does not suffer from problems due to the use of conventional developers, and does not cause background fog, which is a problem with this system, and has excellent long-term raw storage stability TheColor blackIs.

Claims (6)

A diazo copying material comprising a photosensitive layer containing a diazo compound on a support, a coupler component, and a coupler layer containing a copolymer having a carboxylic acid and / or dicarboxylic anhydride as a constituent component as a monomer. A heat-developable diazo copying material comprising, as components, a compound represented by the following general formula (I) and a compound represented by the following general formula (II).
(In the formula, X represents a cyano group, an acetyl group, a benzoyl group, or a —COOR group, and R represents an alkyl group, an aryl group, or a benzyl group.)
(Wherein R ₁ Represents a substituted or unsubstituted aryl group. ) Copolymer comprising a photosensitive layer containing a diazo compound on one side of a transparent or translucent support, a coupler component represented by the general formula (I), and a carboxylic acid and / or dicarboxylic acid anhydride as a monomer A photosensitive layer comprising a coupler layer containing a photosensitive layer containing a diazo compound on the opposite side of the support, a coupler component represented by the general formula (II), and a carboxylic acid and / or dicarboxylic acid as a monomer. 2. The heat-developable diazo copying material according to claim 1, further comprising a photosensitive heat-sensitive layer comprising a coupler layer containing a copolymer containing an acid anhydride as a constituent component. The heat-developable diazo copying material according to claim 1 or 2, wherein the coupler layer or / and the photosensitive layer contain a water-soluble guanidine derivative. The heat-developable diazo copying material according to claim 1 or 2, wherein the coupler layer and / or the photosensitive layer contains a heat-fusible substance having a melting point of 60 to 150 ° C. 3. The heat-developable diazo copying material according to claim 1, wherein the copolymer resin is a styrene-acrylic acid copolymer. 3. The copolymer resin according to claim 1, wherein the copolymer resin is a mixture of a styrene-acrylic acid copolymer and an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer. Thermal development type diazo copy material.