JPS6230416B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improvement of a two-component type diazo copying material, and more specifically, it provides excellent preservability and developability before copying, and provides clear copied images with high sunlight fastness after copying. The present invention relates to a two-component copying material obtained. In conventional two-component type diazo copying materials in which the photosensitive layer on the support contains both a diazo compound and a coupling component, thiosulfur is added to the photosensitive layer in order to obtain a clear copy image with excellent sunlight fastness. Copying materials containing urea or its derivatives and zinc chloride are known. However, this type of copying material generally does not have good developability. This is because copying materials containing thiourea or its derivatives are prone to pre-coupling during storage due to oxidative decomposition of thiourea, etc. This is because it contains an acid stabilizer. In other words, when thiourea or its derivatives are used for the purpose of improving the sunlight fastness of reproduced images, a relatively large amount of acid stabilizer must be used to prevent precoupling. Deterioration in the developability of the material cannot be avoided. However, regardless of the developing method, it is desirable for diazo copying materials to be developed with as little alkali as possible in order to prevent pollution and save resources, so the above-mentioned deterioration in developability is inevitable. Must improve. An object of the present invention is to provide a two-component diazo copying material that has satisfactory storage stability, good developability, and is capable of forming copied images with clear sunlight fastness. The feature is that benzotriazole or a derivative thereof and a metal salt of an inorganic acid coexist in a photosensitive layer on a support containing a diazo compound and a coupling component. The benzotriazole or its derivative used in the present invention, in cooperation with a metal salt of an organic or inorganic acid, contributes to improving the clarity and sunlight fastness of reproduced images, but this is because the above compound is complexed with metal ions. It is presumed that this is because it effectively acts on the metal chelate formation of the azo dye. And benzotriazole and its derivatives are less susceptible to oxidative decomposition compared to conventional thiourea or its derivatives.
By adding a small amount of acid stabilizer, the shelf life of the copying material can be guaranteed, and the developability of the copying material is not particularly impaired. The benzotriazole derivatives of the present invention include alkylated, halogenated, or hydroxylated derivatives of benzotriazole, such as 5-methylbenzotriazole, 5-chlorobenzotriazole, 6-chlorobenzotriazole, 1-hydroxybenzotriazole, etc. Triazole, 5-methyl-1-hydroxybenzotriazole, and the like are specific examples of benzotriazole derivatives that can be used in the present invention. Each of these benzotriazole derivatives and benzotriazole can be used alone, as well as in combination with each other, or in combination with a derivative and benzotriazole. However, in any case, the total amount of benzotriazole and its derivatives present in the photosensitive layer is 0.1 to 2.0 g/m2, preferably 0.3 to 0.6 g/ ^m2 .
g/m ² range. On the other hand, metal salts of inorganic acids include Cu salts, Mg salts, Ca salts, Ba salts, and Zn salts of inorganic acids such as hydrochloric acid and sulfuric acid.
Salt, Cd salt, Hg salt, Al salt, Sn salt, Co salt, Ni salt, etc. can all be used. magnesium chloride,
Calcium chloride, zinc chloride, magnesium sulfate,
Zinc sulfate, aluminum sulfate, etc. are typical examples of metal salts useful in the present invention. In the present invention, two or more types of metal salts can be used together, or one type can be used alone, but in any case, the amount of metal salts present in the photosensitive layer is 0.1 to 2.0.
Preferably it is on the order of g/m ² . As the diazo compound, known diazonium salts that can be used in two-component diazo copying materials are used in the present invention. Examples of such diazonium salts are as follows. ◎Paraphenylenediamine N,N-substituted compound diazonium salt General formula (X: anion R′, R″: aliphatic hydrocarbon group Z, Y: group that can be introduced into the benzene nucleus) 4-Diazo-N,N-dimethylaniline 4-Diazo-N,N-diethylaniline 4-Diazo- N,N-ethyl-N-β-hydroxyethylaniline 4-diazo-N,N-bis-β-hydroxyaniline 4-diazo-N-methyl-N-β-hydroxyethylaniline 4-diazo-N-ethyl- N-β-hydroxypropylaniline 4-diazo-N-ethyl-N-(β-diethylamino)-ethylaniline 4-diazo-2-chloro-N,N-diethylaniline 4-diazo-2-methyl-N,N -diethylaniline 4-diazo-2-iodo-N,N-diethylaniline 4-diazo-2-trifluoromethyl-N,N
-Diethylaniline 4-Diazo-N-ethyl-N-benzylaniline 4-Diazo-N-methyl-N-benzylaniline ◎Aminohydroquinone ether diazonium salt General formula (R, R′ and R″: alkyl group or aryl group) 4-diazo-2,5-dibutoxy-N,N-diethylaniline 4-diazo-2,5-diethoxy-N-benzoylaniline 4-diazo-2 ,5-diethoxy-N-ethyl-N-benzoylaniline 4-diazo-2,5-dibenzyloxy-N-
Benzoylaniline 4-diazo-2-chloro-5-methoxy-N-
Benzoylaniline 4-Diazo-2,5-diethoxy-N-benzoylmethylaniline 4-Diazo-2,5-diethoxy-N-benzoyloxymethylaniline Others, 4-diazo-2,5-dioxyalkyl (or dioxy (aryl)-N-alkyl (or aryl) compounds and their derivatives ◎Aminodiphenyl, aminodiphenylamine and similar compound-based diazonium salts General formula: XN ₂ -R-A-R' and XN ₂ -R-A-A-N ₂ X (diarylamine [A: -NH-] diphenyl [A: single bond] diphenyl oxide [A: -O-]) (diarylmethane [A: -CH ₂ -] stilbene [A: -CH=CH-] ) Diaryl or arylalkyl sulfide paradiazodiphenylamine 4-diazo-2,5,4'-triethoxydiphenylamine 4-diazo-2,5,4-triethoxydiphenyl 4,4-bisdiazo-2, 2',5,5'-tetrahydroxydiphenylmethane bisdiazo-3,3'-dichloro-5,5'-dimethoxybenzidine 4-diazo-2,5-dimethoxyphenylethyl sulfide 4-diazo-2, 5-Diethoxy-4'-methyl-diphenylsulfide ◎Heterocyclic amine derivative diazonium salt General formula (A: O (morpholine type), S (thiomorpholine type), methylene group (phenylpiperidine type), single bond (phenylpyrrolidine type)) 4-Diazo-2,5-dibutoxy-N-phenylmorpholine 4 -Diazo-2,5-diethoxy-N-phenylmorpholine 4-diazo-2-methoxy-N-thiomorpholine 4-diazo-N-phenylpiperidine 4-diazo-N-phenylpyrrolidine 4-diazo-2, 5-n-butoxy-N-phenylpiperidine and others, 4-diazo-N-phenyl heterocyclic amine derivatives ◎ Orthophenylenediamine N,N-substituted compound derivatives and orthoaminophenol derivative diazonium salts 2-diazo- 4-methylmercapto-N,
N'-dimethylaniline 2-diazo-5-benzoylamino-N,
N'-dimethylaniline 2-diazo-1-naphthol-5-sulfonic acid Each of the diazonium salts listed above can be used as a sulfate, hydrochloride, or fluoroborate, as well as zinc chloride, tin chloride, ammonium sulfate, etc. It can also be used in the form of a double salt. As the coupling component of the present invention, any of the above-mentioned diazo compounds and compounds capable of coupling (couplers) can be used. Examples of such couplers include phenol derivatives, oxynaphthalene derivatives, compounds containing active methylene groups, and heterocyclic compounds, and specific examples thereof are as follows. ◎Phenol derivatives Pyrocatechol resorcinol Phloroglycine Pyrogallol resorcinol Monoglycol ether Resorcinol Glycol ether Meta-aminophenol Para-aminophenol Diethylaminophenol 2,5,6-Trimethylphenol 2-Hydroxymethylphenol β-(2-Hydroxyphenyl)-Propionic acid 2- (ω-phenylaminomethyl)-phenol β-(4-methyl-2-hydroxyphenyl)
-Glutaric acid 2,5-dimethyl-6-(N-dimethylaminomethyl)-phenol 1,3-dimethyl ether of pyrogallol N-lauryl-para-aminophenol N-acyl-meta-aminophenol metahydroxyacetanilide ortho-N- Hydrodiphenol-mono-guanidine Para-N-hydrodiphenol-bi-guanidine 2,5-dimethyl-4-morpholinomethylphenol 2-methyl-5-isopropyl-4-morpholinomethylphenol 4-morpholinemethylresorcinol monomethyl ether 3 ,3',5-trihydroxydiphenyl 3,3',5,5'-tetrahydroxydiphenyl 2,2',4,4'-tetrahydroxydiphenyl 2,4,4'-trihydroxydiphenyl- 2′-
Sulfonic acid 2,4,6,3',5'-pentahydroxydiphenyl 2,2',4,4'-tetrahydroxydiphenyl sulfide ◎Oxynaphthalene derivative 2,3-dioxynaphthalene β-naphthol n- Naphthol 1,6-dioxynaphthalene 2,7-dioxynaphthalene 2,3-hydroxynaphthalene-6-sulfonic acid 2-naphthol-3,6-disulfonic acid 2,7-dihydroxynaphthalene-3-sulfonic acid 2,8 -Dihydroxynaphthalene-6-sulfonic acid 1,8-dihydroxynaphthalene-8-sulfonic acid 1,8-aminonaphthol-5-sulfonic acid 2,7-dihydroxy-3,6-disulfonic acid 1,8-benzoylaminonaphthol- 2-Sulfonic acid 1,8-dihydroxynaphthalene-6-sulfonic acid 2-hydroxy-3-naphthoic acid-N-β-hydroxyethylamide 2-hydroxy-3-naphthoic acid-N,N-bis-β-hydroxyethyl Amide 8-hydroxy-2-naphthoic acid-hydroxyethylamide 1-(N-carboethoxymethylamino)-8
-Naphthol-4-sulfonic acid 5-(para-nitro)-benzamide-1-naphthol 1-hydroxynaphthyl-7-phenylguanidine 2-hydroxynaphthyl-8-biguanidine 1-naphthol-3-(N-β -hydroethyl)-sulfonamide 1-naphthol-3-(N-O-methoxyphenyl)-sulfonamide bis-[5-oxy-7-sulfonaphthyl(2)]
Amine N,N-bis[1-oxy-3-sulfonaphthyl(6)]-thiourea ◎Compound containing active methylene group 1-phenyl-3-methylpyrazolone(5)-acetoacetanilide 1-phenyl-3- Carboxypyrazolone - acetoacetic acid cyclohexylamide acetoacetic acid benzylamide cyanoacetanilide cyanoacetomorpholine ◎Heterocyclic compound 1-(3'-sulfoamide)-phenyl-3-methylpyrozolone-5 1-(4'-carboxy-ethyl phenyl)-3
-Dodecyl-pyrazolone-5 8-hydroxy-1,2-naphthiimidazole 2-methyl-4-hydroxybenzimidazole 7-methyl-4-hydroxybenzothiazole 1,7-dimethyl-4-hydroxy-benzotriazole 2 of the present invention Although component-type diazo copying materials use benzotriazole or its derivatives instead of conventional thiourea or its derivatives, this compound also undergoes oxidative decomposition to some extent and generates ammonia, so it is difficult to use the copying materials. In order to improve storage stability, it is preferable to incorporate known acid stabilizers such as citric acid, tartaric acid, oxalic acid, and boric acid into the photosensitive layer. However, precoupling can be sufficiently prevented with a smaller amount than in conventional copying materials, and therefore the developability of the diazo copying material of the present invention is not impaired. The present invention will now be described in more detail with reference to Examples. Example 1 N,N'-diethylaminobenzenediazonium chloride was used as the diazo compound and 2,3-dihydroxynaphthalene was used as the coupling component.
6-Sodium sulfonate was used, Table 1
Each photosensitive solution having the composition shown below was prepared.

[Table] The three types of photosensitive solutions mentioned above were applied to 68 g/m ² of diazo photosensitive paper base paper (approximately 10 ml/m ² coating amount) and dried to obtain three types of diazo copying materials. Next, each copying material is combined with a transparent original, exposed and developed using a diazo dry copying machine (Recopy SM-1500), and the maximum and minimum densities of the resulting copies are measured using a photovoltmeter to determine the developability of each copying material. The brownness of the copies was evaluated by the following method. (1) Developability: - Maximum density at incomplete development/Maximum density at complete development x 10
0 = Development rate (%) Incomplete development...When developing at the maximum speed of the copying machine used Complete development...When developing at the lowest speed of the copying machine used (2) Brownness: - Fade meter (Suga Test Instruments Co., Ltd.) company)
The copy is irradiated with light for 5 hours, and the copy density before and after irradiation is measured to determine the difference. In addition, each of the above three types of copy materials before exposure and development was left in a dark place at 50°C and 50% RH for 24 hours, and then exposed and developed in the same manner as above, and the maximum and minimum densities of the resulting copies were determined. The storage stability of each copying material was evaluated by measuring with a photovoltmeter and determining the amount of change from the maximum density and minimum density of copies obtained without being left in the dark. The results are shown in Table-2.

[Table] As is clear from the above, the copying material of the present invention is
While it has excellent developability and storage stability,
The copying material of Comparative Example 1, which uses thiourea, has poor storage stability, and the copying material of Comparative Example 2, in which the amount of tartaric acid is doubled in order to improve this problem, has significantly poor developability. Example 2 2,5-diethoxy-4- as a diazo compound
Each photosensitive solution having the composition shown in Table 3 was prepared using morpholinobenzenediazonium chloride zinc chloride double salt and 2-hydroxy-3-naphthoic acid morpholinoethylamide as a coupling component.

【table】

[Table] Next, each of these photosensitive solutions was coated on 68 g/m ² of diazo photosensitive paper base paper (approximately 10 ml/m ² coating amount) and dried to obtain two types of diazo copying materials. Next, using each of the obtained copying materials, the same test as in Example 1 was carried out using the same procedure, and the results shown in Table 4 were obtained. However, the copy machine used was a Ricopy Super Dry 205 instead of the Ricopy SM-1500.

[Table] As is clear from Table 4, the copying material of the present invention had excellent developability and storage stability, but the copying material of Comparative Example 3 had three times the amount of citric acid. Poor storage stability. As a precaution, the same photosensitive solution as Comparative Example 3 was prepared except that the amount of citric acid was changed to 1.0 g, and a copying material was prototyped using this photosensitive solution. However, the copying material had extremely severe pre-coupling and could not be put to practical use. Example 3 2,5-diethoxy-4- as a diazo compound
Morpholinobenzenediazonium boron tetrafluoride double salt is used as a coupling component of 2,2',4,4'-
A photosensitive solution having the composition shown in Table 5 was prepared using tetrahydroxydiphenyl sulfide.

[Table] Each of the two types of photosensitive liquids obtained was applied to a 70g/m ² tracing paper (approximately 20g/m 2 coating amount).
m ² ) and dried to prepare a second original copy material.
Next, the developability, brownness, and storage stability of both copying materials were evaluated.
Evaluation was performed in the same manner as in Example 1, and the results shown in Table 6 were obtained.

[Table] Table 6 shows that the copying material of Comparative Example 5 is unsatisfactory in terms of storage stability, while the copying material of Example 3 has excellent storage stability and has better developability than the copying material of Comparative Example 3. It shows that you are prepared.

Claims (1)

[Claims] 1. In a two-component diazo copying material in which the photosensitive layer on the support contains a combination of a diazo compound and a coupling component, the photosensitive layer contains benzotriazole or its alkylated, halogenated or hydroxylated derivative, and an inorganic acid. A two-component type diazo copying material characterized by coexisting with a metal salt.