JPH05692B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to two-component diazo copying materials containing two couplers which also act as anti-tarnish agents. Prior Art Conventionally, as a two-component type diazo copying material, for example, a diazo compound with the general formula (However, R ₁ and R ₂ represent a C ₁ to C ₄ alkyl group.) A compound using a water-soluble alkylphenol as a coupler was published in Japanese Patent Publication No. 37-1999.
This is proposed in Publication No. 10275. The diazo compound of the general formula used here has a high photodecomposition rate and is a preferred compound for improving the efficiency of copying operations, so it is generally widely used, but after development, its photodecomposition products remain on the background. However, it has the disadvantage that it oxidizes over time and turns into a colored substance, staining the scalp. Moreover, alkylphenols have low coupling properties and slow coupling speeds, and therefore reduce the developability of copying materials.Also, when a large amount of low coupling couplers is used to solve this problem (colors other than yellow) Similar to the case of diazo compounds (also used in large quantities when combined with a coupler that produces red or blue colors), over time the skin becomes colored and contaminated by ultraviolet rays, heat, etc. A similar drawback is the general formula for Katsupura. (However, R ₁ and R ₂ represent an alkyl group.) The compound represented by (US Patent No. 2946684), the general formula (However, R ₁ and R ₂ are alkyl groups, R ₃ is hydrogen, alkyl, β-hydroxyethyl, aralkyl, aryl, carboxy, carboethoxy, or carbopropoxy group, and R ₄ is hydrogen, alkyl, or carboethoxy group. ) (U.S. Patent No. 3139341) and general formula (However, R ₁ is an alkyl group, a hydroxyalkyl group,
An alkoxyalkyl group, an alkylaminoalkyl group or a cyclohexyl group, R ₂ and R ₃ represent an alkyl group. ) (U.S. Pat. No. 3,183,093). On the other hand, Tokko Akira
Publication No. 35-4833 has a general formula for Kupler. (However, R ₁ represents an alkylene group, an alkylene arylene alkylene group, or an isoalkylidene group, R ₂ and R ₃ represent hydrogen, an alkyl group, a sulfo group, or a halogen, p is 0 or an integer, and n is p
When is 0, it represents 1, and when p is an integer, it represents p+1. ) A diazo copying material using resorcinol ethers has been proposed. In the case of this diazo copying material, resorcinol ethers have higher coupling properties than water-soluble alkylphenols, so they have the advantage of better developability. It also has the disadvantage of large discoloration. Object The object of the present invention is to provide a two-component diazo copying material which has excellent developability, exhibits little background discoloration after development, and can therefore be stored as a copy for a long period of time. Structure The two-component diazo copying material of the present invention has (a) general formula () [However, R ₁ and R ₂ represent an alkyl group (alkyl preferably has 1 to 5 carbon atoms). ] A diazo compound represented by (b) General formulas () () and () (However, R ₃ and R ₄ represent an alkyl group (alkyl preferably has 1 to 4 carbon atoms), and R ₅ ,
R ₆ represents hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylaminoalkyl group (among the above groups, the total number of alkyl carbon atoms is preferably 1 to 10), a cyclohexyl group, or oxygen, It may form a ring together with sulfur, nitrogen or carbon atoms. ] [However, R ₇ and R ₈ represent an alkyl group (alkyl preferably has 1 to 4 carbon atoms), and R ₉ represents hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylaminoalkyl group (each of the above In the group, the total number of carbon atoms in alkyl is 1
~10 is preferred) or a cyclohexyl group. ] [However, R ₁₀ and R ₁₁ represent an alkyl group (alkyl preferably has 1 to 4 carbon atoms). ] At least one alkylphenol coupler represented by (c) general formula () [However, R ₁₂ is an alkylene group such as an ethylene group, a methylene group, a tetramethylene group, an alkylene phenylene alkylene group such as a methylene phenylene methylene group, an ethylene phenylene ethylene group, or an isoalkylidene group such as an isopropylidene group or an isobutylidene group. In the expression, R ₁₃ and R ₁₄ are hydrogen,
It represents an alkyl group (the number of carbon atoms in the alkyl group is preferably 1 to 6), a sulfo group, or a halogen, and p represents 0 or an integer (preferably 1 or less). ] It is characterized by containing a resorcinol ether coupler shown in the following. The present invention was developed in two-component type diazo copying materials, in order to solve the problem of background contamination caused by the commonly used diazo compound of the general formula (), as a result of studies on various discoloration inhibitors. It was discovered and completed that the combination of the coupler of () or () and the coupler of general formula () is extremely effective. In this way, the above two types of couplers act as discoloration inhibitors in the background area, and act as couplers in the image area. However, even when used alone, the effect as an anti-discoloration agent cannot be obtained.
Rather, it promotes discoloration. That is, a synergistic effect as an anti-discoloration agent can be obtained only by combining these two types of couplers. Also, regarding the action as a coupler, the general formula () () or ()
The coupling speed of the coupler is slower than that of the general formula (). Therefore, azo dye formation in the image area is carried out competitively between these two types of couplers, so that high developability and a constant variety of color tones are ensured. Specific examples of the diazo compound of general formula () used in the present invention include the following. 2,5-dimethoxy-4-morpholinobenzenediazonium 2,5-diethoxy-4-morpholinobenzenediazonium 2,5-di-n-propoxy-4-morpholinobenzenediazonium 2,5-di-n-butoxy-4-morpholino Benzenediazonium 2,5-di-n-pentoxy-4-morpholinobenzenediazonium 2,5-di-iso-propoxy-4-morpholinohenzenediazonium 2,5-di-iso-butoxy-4-morpholinobenzenediazonium These Diazo compounds are used in the form of salts such as chlorides, boron fluorides, hexafluorophosphates, bisulfates, and arylsulfonates. Specific examples of couplers of general formula ()() or () are as follows. 2,5-dimethyl-4-morpholinomethylphenol 2,5-diethyl-4-morpholinomethylphenol 2,5-dimethyl-4-diethylaminomethylphenol 2,5-dimethyl-4-pyrrolidinomethylphenol 3,5-dimethyl -6-morpholinomethylphenol 2,5-dimethyl-4-piperidinomethylphenol 2,4-dimethyl-6-[4'-methyl-4-piperazino-(1')-methyl]-phenol 2,5- Dimethyl-4-[4'-methyl-piperazino-(1')-methyl]-phenol 2,6-dimethyl-4-[4'-phenyl-piperazino-(1')-methyl]-phenol 3,5- Dimethyl-2-[4'-methyl-piperazino-(1')-methyl]-phenol 2,3-dimethyl-6-[4'-phenyl-piperazino-(1')-methyl]-phenol 2,5- Dimethyl-4-[4'-β-hydroxyethyl-piperazino-(1')-methyl]-phenol 2,5-dimethyl-4-[4'-benzyl-piperazino-(1')-methyl]-phenol 3 -Methyl-6-isopropyl-4-[4'-methyl-piperazino-(1')-methyl]-phenol 3-methyl-5-ethyl-2-[4'-phenyl-piperazino-(1')-methyl ]-phenol 2,6-dimethyl-4-[4'-benzyl-piperazino-(1')-methyl]-phenol 3,5-dimethyl-2-[2'-carboethoxy-piperazino-(1')- methyl]-phenol 2,5-dimethyl-4-[4'-ethyl-piperazino-(1')-methyl]-phenol 2,6-dimethyl-4-[4'-β-hydroxyethyl-piperazino-(1 ')-Methyl]-phenol 2,6-dimethyl-4-[3'-methyl-4'-phenylpiperazino-(1')-methyl]-phenol 2,6-dimethyl-4-[4'-Carboethoxy-piperazino-(1')-methyl]-phenol2,5-dimethyl-4-[4'-carboethoxy-piperazino-(1')-methyl]-phenol 3,6-dimethyl-2-[ 4'-Carbopropoxy-piperazino-(1')-methyl]-phenol 2,6-dimethyl-4-[4'-carbopropoxy-piperazino-(1')-methyl]-phenol 2,5-dimythyl-4 -[4'-Carbopropoxy-piperazino-(1')-methyl]-phenol N,N-bis(2,4-dimethyl-6-hydroxybenzyl)-amine N,N-bis(2,4-dimethyl- 6-hydroxybenzyl)-methylamine N,N-bis-(2,5-dimethyl-4-hydroxybenzyl)-methylamine N,N-bis-(2,4-dimethyl-6-hydroxybenzyl)-butylamine N ,N-bis-(2,5-dimethyl-6-hydroxybenzyl)-ethylamine N,N-bis(2,5-dimethyl-6-hydroxybenzyl)-cyclohexylamine N,N-bis-(2,4- dimethyl-6-hydroxybenzyl)-2'-diethylaminoethylamine N,N-bis-(2,4-dimethyl-6-hydroxybenzyl)-2'-hydroxyethylamine, N-bis-(3,5-dimethyl-4 -hydroxybenzyl)-methylamine, N-bis-(3,4-dimethyl-2-hydroxybenzyl)-methylamine N,N-bis-(2-methyl-5-tert-butyl-6-hydroxybenzyl)- Methylamine N,N-bis-(2,4-dimethyl-6-hydroxybenzyl)-ethylamine N,N-bis-(2-methyl-4-ethyl-6
-hydroxybenzyl)-methylamine N,N-bis-(2,5-dimethyl-6-hydroxybenzyl)-3'-methoxy-propylamine-(1') N,N-bis-(2,4-dimethyl -6-hydroxybenzyl)-2'-hydroxy-propylamine N,N-bis-(2,5-dimethyl-6-hydroxybenzyl)-2'-diethylaminoethylamine N,N-bis-(2,5-dimethyl -4-hydroxybenzyl)-piperazine N,N-bis-(2,4-dimethyl-6-hydroxybenzyl)-piperazine These couplers can also be used in the form of the hydrochloride. Further, specific examples of the coupler of general formula () are as follows. m,m'-ethylenedioxydiphenol m,m'-trimethylenedioxydiphenol m,m'-tetramethylenedioxydiphenol m,m'-pentamethylenedioxydiphenol m,m'-1- Melt trimethylenedioxydiphenol 6,6'-dimethyl-3,3'-trimethylenedioxydiphenol 4,4',6,6'-tetramethyl-3,3'-trimethylenedioxydiphenol m , m'-(p-phenylene dimethylene dioxy) diphenol 6,6'-dihexyl-3,3'-isopropylidene dioxydiphenol m, m'-ethylenedioxydiphenol/formaldehyde polycondensate Each of the above Generally, the amount of each component used is 1 part by weight of the diazo compound of the general formula ().
The coupler of formula () or () is preferably about 0.1 to 1 part by weight, and the coupler of general formula () is preferably about 0.1 to 1 part by weight. In addition to the above-mentioned components, the diazo copying material of the present invention may contain a coupler that develops colors such as red, brown, blue, and purple in order to adjust various color tones, but the coupling rate is determined by the general formula (). It is preferable to use something similar to a coupler. Examples of this type of coupler include resorcin, resorcin monoglycol ether, resorcin glycol ether, meta-aminophenol, para-aminophenol, diethylaminophenol, meta-hydroxyacetanilide, 4-morpholine methylresorcinol monomethyl ether, 3,3',5-trihydroxydiphenyl enyl, 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'-tetrahydroxydiphenylsulfide, 3,5-resorcinic acid ethanolamide, 2,4-resorcinic acid ethanolamide, α
-resorcinic acid, α-resorcinic acid methyl ester, 4-bromo-3,5-resorcinic acid, 4-bromo-3,5-resorcinic acid ethanolamide,
resorcin monohydroxyethyl ether, 2,
3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene-6-sulfonic acid, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene-3-
Sulfonic acid, 1,8-dihydroxynaphthalene-
6-sulfonic acid, 2,7-dihydroxynaphthalene-3,6-disulfonic acid, 2-hydroxy-3
-Naphthoic acid-N-β-hydroxyethylamide, 2-hydroxy-3-naphthoic acid-N,N-
Bis-β-hydroxyethylamide, 2-hydroxy-3-naphthoic acid-2'-methylanilide, 2
-Hydroxy-3-naphthoic acid-2'-methoxyanilide, 2-hydroxy-3-naphthoic acid-α-
Naphthylamide, 2-hydroxy-3-naphthoic acid-3'-nitroanilide, 2-hydroxynaphthalene-8-biguanidine, 1-naphthol-3-
(N-β-hydroxyethyl)-sulfonamide and the like. In addition, organic acids such as citric acid, tartaric acid, oxalic acid, malic acid, glutaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, boric acid, Adding inorganic acids such as sulfur, arylsulfonic acids such as benzenesulfonic acid, naphthalenesulfonic acid, and anthraquinonesulfonic acid, or alkali metal salts thereof, chlorides and sulfates of zinc, nickel, aluminum, magnesium, tin, etc. I can do it. Furthermore, as a binder, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polystyrene, polyethylene, polypropylene, polyvinyl alcohol, hydroxyethyl cellulose, cellulose acetate, cellulose butyrate,
Cellulose acetate propionate, cellulose nitrate, etc. can be added, and silica, alumina, clay, quartz powder, glass powder, starch, melamine resin, acetal resin, etc. can be added as fillers. To make the diazo copying material of the present invention, a photosensitive solution containing the aforementioned diazo compound, coupler, and various additives is coated on a support such as paper, plastic film, or synthetic paper and dried to form a photosensitive layer. good. In this case, a precoat layer containing a binder and a filler as main components may be provided on the support in advance. The development method applied to the diazo copying material of the present invention is the same as the conventional method, such as a dry method using ammonia gas or an organic solvent-based development method in which a basic substance such as amine or soda carbonate is dissolved with or without a small amount of water. An example is a semi-dry method in which a small amount of liquid is applied. Effect In the diazo copying material of the present invention, by using the coupler of the general formula (), () or () in combination with the coupler of the general formula (), background discoloration after development is prevented without reducing developability. This allows for long-term storage as a copy. The present invention will be explained below by way of examples. All parts are by weight. Example 1 5% of the surface of a 50μ thick polyester film
After treatment with an aqueous solution of trichloroacetic acid, a photosensitive solution having the following composition was applied and dried to produce a diazo copying material having a photosensitive layer with a thickness of 5 μm. Ethyl cellosolve 40 parts Methanol 20 parts Acetone 20 parts Cellulose butyrate acetate 25 parts Silica (Thyroid 244, manufactured by Fuji Davison)
10 parts Citric acid 2 parts Sulfosalicylic acid 0.5 parts 2,5-dimethyl-4-morpholinomethylphenol 1.0 parts m,m'-trimethylenedioxyphenol 2.0 parts Resorcinol 0.5 parts 2,5-diethoxy-4-morpholinobenzenediazonium. BF ₄ salt 4 parts Example 2 Ethyl cellosolve 40 parts Methanol 20 parts Acetone 20 parts Cellulose butyrate acetate 20 parts Vinyl chloride-vinyl acetate copolymer (Vinylite)
VAGH, manufactured by UCC) 5 parts Silica (Thyroid 65, manufactured by Fuji Davison) 10 parts Citric acid 3 parts 2,4-dimethyl-4-diethylaminomethylphenol hydrochloride 1.5 parts m,m'-ethylenedioxydiphenol 2.0 Part 2,2',4,4'-tetrahydroxydiphenylsulfide 0.5 parts 2,5-diethoxy-4-morpholinobenzenediazonium BF ₄ salt 4 parts A photosensitive solution was used in the same manner as in Example 1. Created diazo copying material. Example 3 Synthetic paper (YUPO TP-90, manufactured by Oji Yuka Synthetic Paper Co., Ltd.)
Apply a pre-coating solution with the following composition and dry it to a thickness of
A 5μ precoat layer was applied. Toluene 40 parts Methyl cellosolve 40 parts Cellulose butyrate acetate 20 parts Vinylite VAGH 5 parts Silica (Thyroid 244) 15 parts Next, a photosensitive liquid having the following composition was applied onto the precoat layer and dried to obtain a diazo copying material having a photosensitive layer with a thickness of 5μ. I made it. Methanol 50 parts Acetone 30 parts Ethyl cellosolve 20 parts Citric acid 3 parts N,N-bis-(2,4-dimethyl-6-hydroxybenzyl)-methylamine hydrochloride 2 parts m,m'-ethylenedioxydiphenol 1.5 parts 2-hydroxy-3-naphthoic acid-2'-methylanilide 0.7 parts 2,5-diethoxy-4-morpholinobenzenediazonium BF ₄ salt 2 parts 2,5-dibutoxy-4-morpholinobenzenediazonium BF ₄ salt 2 parts Comparative Example 1 A diazo copying material was prepared in the same manner as in Example 1 except that 2,5-dimethyl-4-morpholinomethylphenol was removed from the photosensitive solution. Comparative Example 2 A diazo copying material was prepared in the same manner as in Example 1 except that m,m'-trimethylenedioxydiphenol was removed from the photosensitive solution. Comparative Example 3 A diazo copying material was prepared in the same manner as in Example 2 except that m-hydroxyphenylurea was used instead of m,m'-ethylenedioxydiphenol in the photosensitive solution. Comparative Example 4 In Example 3, N,N-bis-
(2,4-dimethyl-6-hydroxybenzyl)-
A diazo copying material was prepared in the same manner except that methylamine hydrochloride was used. Among the above diazo copying materials, Examples 1 and 2
Copies were made using the dry developing method for Comparative Examples 1, 2, and 3, and copies were made using the semi-dry developing method for Example 3 and Comparative Example 4, and the performance was evaluated. The results shown in the table below were obtained. Ta.

[Table] A Macbeth transmission densitometer was used as the densitometer. As can be seen from the above results, the product of the present invention has a clean background without reducing the development speed, and in particular, there is little discoloration of the background over time, making it possible to store copies for a long period of time.

Claims (1)

[Claims] 1 (a) General formula () (However, R ₁ and R ₂ represent an alkyl group.) A diazo compound represented by (b) general formulas () () and () (However, R ₃ and R ₄ represent an alkyl group, and R ₅ ,
R ₆ represents hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylaminoalkyl group, a cyclohexyl group, or may form a ring together with oxygen, sulfur, nitrogen or carbon atoms. ) (However, R ₇ and R ₈ represent an alkyl group, and R ₉
is hydrogen, alkyl group, hydroxyalkyl group,
It represents an alkoxyalkyl group, an alkylaminoalkyl group or a cyclohexyl group. ) (However, R ₁₀ and R ₁₁ represent an alkyl group.) At least one alkylphenol coupler represented by (c) general formula () (However, R ₁₂ represents an alkylene group, an alkylenephenylene alkylene group, or an isoalkylidene group, R ₁₃ and R ₁₄ represent hydrogen, an alkyl group, a sulfo group, or a halogen, and p represents 0 or an integer.) A two-component diazo copying material, characterized in that it contains a resorcinol ether coupler.