US3769021A - Light-sensitive diazotype copying material - Google Patents

Abstract

A diazotype copying material having a light-sensitive coating containing a diazonium salt selected from the group consisting of 2,5-disubstituted derivatives of 4-dibenzylamino-benzene diazonium salt exhibits a very high sensitivity to light.

Description

te States Patent Saito et al.

[ Oct. 30, 1973 LIGHT-SENSITIVE DIAZOTYPE COPYING MATERIAL Related US. Application Data Continuation-impart of Ser. No. 659,609, Aug. 10, 1967, abandoned.

[30} Foreign Application Priority Data Aug. 26, 1966 Japan 41/55819 Nov. 29, 1966 Japan.... 41/77761 Nov. 29. 1966 Japan 41/77762 [52] US. Cl. 96/91 R, 260/141, 96/49 [51] Int. Cl G03c 1/54 [58] Field of Search 96/91.75, 49; 260/141, 142

[56] References Cited UNITED STATES PATENTS 3,272,630 9/1966 Rauhut et a1. 96/91 X 3,379,531 4/1968 Mizianty et a1. 96/91 3,432,301 3/1969 Rauhut et a1. 96/91 3,281,246 10/1966 Rauhut et al.. 96/91 3462,27] 8/1969 Rauhut et a1. 96/91 59,551 8/1969 Rauhut et a1. 96/91 42,652 5/1969 Hectors et al. 96/91 FOREIGN PATENTS OR APPLICATIONS 957,838 5/1964 Great Britain 96/91 R 919,037 2/1958 Great Britain 96/91 R 867,630 5/1961 Great Britain 915/91 R 1,110,835 4/1968 Great Britain 260/141 OTHER PUBLICATIONS Reproduction Paper News Bulletin, Andrew Paper & Chem. Co. Inc. No. 26, Sept. 1960.

Landau, R., Fascicules 1a8 (Les diazo), Distributed by Andrews Papers & Chem. Co. Inc., 1960, p. 30 relied on.

Primary Examiner-Charles L. Bowers, Jr. Attorney-Woodhams, Blanchard & Flynn [57] ABSTRACT A diazotype copying material having a light-sensitive coating containing a diazonium salt selected from the group consisting of 2,5-disubstituted derivatives of 4- dibenzylamino-benzene diazonium salt exhibits a very high sensitivity to light.

1 Claim, No Drawings LIGHT-SENSITIVE DIAZOTYPE COPYING MATERIAL CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of our copending application Ser. No. 659 609, filed Aug. 10, 1967, now abandoned.

BAOKGROUND OF THE INVENTION FIELD OF THE INVENTION DESCRIPTION OF THE PRIOR ART In the field of copying techniques which utilize diazonium compounds, there has been a demand, since the time such techniques were found, for copying materials high in light-sensitivity or, in other words, a demand for diazonium compounds having high sensitivity to light. This demand has been on the increase of late, because fluorescent lamps which are not only less expensive but also smaller in the total radiation energy than mercury lamps have become utilized widely as the light source for diazotype copying. In order to meet this increasing demand, there have been introduced various kinds of derivatives of p-aminobenzene diazonium compounds having relatively high sensitivity to light.

SUMMARY OF THE INVENTION OIJR wherein:

R is selected from the group consisting of a hydroxyl radical, an alkoxy or phenyl-substituted alkoxy radical having from one to four carbon atoms in the alkyl chain, a morpholino radical, a pyrrolidino radical, a piperidino radical, a piperazino radical and wherein R, and R are alkyl radicals having from one to four carbon atoms;

Y is selected from the group consisting of hydrogen, an alkyl radical having from one to four carbon atoms, an alkoxy radical having from one to four carbon atoms, a hydroxyl-substituted alkoxy radical having from one to four carbon atoms, and a morpholino-, pyrrolidino-, piperidinoor piperazino-substituted alkoxy radical having from one to four carbon atoms;

n is an integer between 1 and 4; and

X represents an anionic radical.

The diazonium compounds according to the present invention may be applied to one-component copying materials which are developed according to the moistdevelopment method, two-component copying materials which are developed according to the drydevelopment method and also to three-component copying materials which are developed according to the thermal development method. By the use of these diazonium compounds of the present invention, there are obtained copies of images varying in color such as black and blue, depending on the type of the azo coupling component used. According to the present invention, the light-sensitive copying layer is coated on a support such as paper, precoated paper and plastic foil which is used in ordinary diazotype copying materials. This copying layer may contain an additive such as an anti-yellowing agent and a stabilizer.

The diazonium compounds used in the present invention are prepared, in many cases, in the form of diazonium chloride or double salt of diazonium chloride and metal chloride, and in particular, they are obtained in the form of double salts of diazonium chloride and zinc chloride or double salts of diazonium chloride and cadmium chloride. In the present invention, however, the type of anion which is coupled to the diazonium cation is not critical. Diazonium compounds in the form of, for example, bromides, sulfates and fluoroborates may also be used in the present invention.

With respect to the general formula of the diazonium compounds of the present invention, the preferred alkyl radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl. The preferred alkoxy radicals include methoxy, ethoxy, n-propoxy, iso-propoxy and n-butoxy. The preferred N R2 radicals include N-methylamino, N-ethylamino, N,N- dimethylamino, N,N-diethylamino and, N,N-npropylamino.

As has been stated, the diazonium compounds of the present invention may be applied to one-component, two-component and three-component copying materials. The diazonium compounds show an increased coupling velocity and such compounds are particularly suitable for both one-component and two-component copying materials.

Hereunder are enumerated typical diazonium compounds which are used in the present invention. It should be understood, however, that the diazonium compounds which are usable in the present invention are not restricted to these compounds alone.

Formula 1 Formula 2 h C 1H4 O H2- Formula 3 Formula 4 Formula 5 CH3 i gag O C2H4N (C2115) HCl (124-129 C.) [4l0-415 m (l28-132 c.) 410 115 mu] (105-111 C.) [410-415 mp] (119-122 C.) [400-405 mp] NOTE: (Decomposition point), [ultraviolet absorption].

FORMULA l Seventy grams of S-(B-hydroxy) ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml of water. While holding the temperature of this solution between 90C. and 100C, 127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about five hours, the supernatant oil layer was removed and distilled under a reduced pressure of 1 mmHg. As a result, g of distillate boiling between 240C. and 255C. were obtained (This substance had a melting point between 665C. and 67.5C.). This distillate was coupled to a diazonium compound of p-nitroaniline to produce a dyestuff, with the yield being 57 g (The resulting substance has a melting point between 202C. and 204C). This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N-diacetyl-pdiaminobenzene to separate out. The obtained acetyl compound was subjected to hydrolysis, followed by diazotization in a known manner. The resulting diazonium compound was salted out with zinc chloride. Thus 15 g of 4-dibenzylamino-5-(B-hydroxy) ethoxy benzene diazonium chloride, zinc chloride double salt which was yellow in color were obtained. This double salt had a decomposition point between 123C. and 125C, and had a peak ofultraviolet absorption at 410 FORMULA 2 One hundred twenty-one grams of S-(B-benzyloxy) ethoxy aniline and 82 g of sodium acetate were dissolved in 50 ml of water. While holding the temperature of this solution between C. and C., 127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about six hours, the supernatant oil layer was removed and dissolved in 400 ml of toluene. The resulting solution was subjected to washing with water two or three times and to dehydration with anhydrous sodium sulfate. Then, hydrogen chloride gas was introduced into the solution, 1 15 g of chloride were separated from the solution (This chloride had a melting point between 210C. and 212C). This chloride was dissolved in acetic acid and coupled, in the presence of sodium chloride, to a diazonium compound of p-nitroaniline. The

resulting coupled compound was neutralized with additional sodium acetate, thereby producing a dyestuff, with the yield being 106 g (The resulting substance had a melting point between 210C. and 212C.). This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N-diacetyl-pdiaminobenzene to separate out. The obtained acetyl compound was subjected to hydrolysis, followed by diazotization by known manner, and salted out by zinc chloride. Thus 18 g of 4-dibenzylamino-5-(B-benzyloxy)ethoxybenzene diazonium chloride, zince chloride double salt which was yellow in color were obtained. This double salt had a decomposition point between 99C. and 102C. and a peak of ultraviolet absorption within the range of from 405 mu to 410 mu.

FORMULA 4 Eighty-two grams of 2-methyl-5-(B-hydroxy) ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml of water. While holding the temperature of this solution between 90C. and 100C., 127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about 7 hours, the supernatant oil layer was removed and distilled under a reduced pressure of 1 mmHg. As a result, 98 g of distillate boiling between 243C. and 248C. were obtained. This distillate was coupled to a diazonium compound of p-nitroaniline to produce a dyestuff, with the yield being 68 g (The resulting substance had a melting point between 197C. and 199C) This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N'-diacetyl-pdiaminobenzene to separate out. The obtained acetyl compound was subjected to hydrolysis, followed by diazotization by known manner, and was salted out by zinc chloride. Thus 18 g of 4-dibenzylamino-2-methyl- S-(B-hydroxy) ethoxybenzene diazonium chloride, zinc chloride double salt which was yellow in color were obtained. This double salt had a decomposition point between 124 C. and 129C., and had a peak of ultraviolet absorption within the range of from 410 my. to 415 mu.

FORMULA 5 One hundred and five grams of 2-methyl-5-(B- pyrrolidino) ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml of water. While maintaining the temperature of this solution between 90C. and 100C.,

127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about six hours, the supernatant oil layer was removed and dissolved in 400 ml of toluene. The resulting solution was subjected to washing with water two or three times and to dehydration with anhydrous sodium sulfate. Then, hydrogen chloride gas was introduced into the solution and 1 12 g of chloride were separated from the solution (This substance had a melting point between 178C. and 182C) This chloride was dissolved in acetic acid and coupled, in the presence of sodium chloride, with a diazonium compound of pnitroaniline to produce a dyestuff, with the yield being 105 g (The resulting substance had a melting point between 207C. and 209C.). This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N'-diacetyl-p-diaminobenzene to separate out.

The obtained acetyl compound was subjected to hydrolysis, followed by diazotization by known manner, and salted out by zinc chloride. Thus 28 g of 4- dibenzylamino-2-methyl-5-(B-pyrrolidino) ethoxybenzene diazonium chloride, zinc chloride double salt which was yellow in color were obtained. This double salt has a decomposition point between 128C. and 132C. and a peak of ultraviolet absorption within the range of 410 mg to 415 mu.

FORMULA 8 One hundred eleven grams of Z-methyl-S-(B- morpholino) ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml of water. While maintaining the temperature of this solution between C. and C., 127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about six hours, the supernatant oil layer was removed and dissolved in 400 ml of toluene. The resulting solution was subjected to washing with water two or three times and to dehydration with anhydrous sodium sulfate. Then, hydrogen chloride gas was introduced into the solution and 121 g of chloride were separated from the solution (This substance had a melting point between 185C. and 187C) This chloride was dissolved in acetic acid and coupled, in the presence of sodium acetate, with a diazonium compound of pnitroaniline to produce a dyestuff, with the yield being 1 12 g (The resulting substance had a melting point between 215C. and 218C.). This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N-diacetyl-p-diaminobenzene to separate out. The obtained acetyl compound was subjected to hydrolysis, followed by diazotization by known manner, and salted out by zinc chloride. Thus 28 g of 4- dibenzylamino-2-methyl-5-(,B-morpholino) ethoxybenzene diazonium chloride, zinc chloride double salt which was yellow in color were obtained. This double salt had a decomposition point between 118C. and 120C. and a peak of ultraviolet absorption within the range of 400 my. to 405 my" FORMULA 10 One hundred grams of 2,5-(B-hydroxy) ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml of water. While holding the temperature of this solution between 90C. and 100C., 127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about 5 hours, the supernatant oil layer was removed and distilled under a reduced pressure of 1 mmHg. As a result, 95 g of distillate boiling between 257C. and 261C. were obtained. This distillate was coupled to a diazonium compound of p-nitroaniline to produce a dyestuff, with the yield being 75 g (The resulting substance had a melting point between 208C. and 210C.). This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N-diacetyl-pdiaminobenzene to separate out. The obtained acetyl compound was subjected to hydrolysis, followed by diazotization by known matter, and salted out by zinc chloride. Thus 32 g of 4'-dibenzylamin0-2,5-(B- hydroxy) ethoxybenzene diazonium chloride, zinc chloride double salt which was yellow in color were obtained. This double salt had a decomposition point between l30C.'and 136C., and had a peak of ultraviolet absorption within the range offrom 405 mu to 410 mu.

FORMULA ll One hundred seventy-six grams of 2,5-di(;8- morpholino) ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml of water. While maintaining the temperature of this solution between 90C. and 100C., 127 g of benzyl chloride were added, in drops, to the solution while stirring. After the mixture was left to react for about six hours, the supernatant oil layer was removed and dissolved in 400 ml of toluene. The resulting solution was subjected to washing with water two or three times and to dehydration with anhydrous sodium sulfate. Then, hydrogen chloride gas was introduced into the solution and 131 g of chloride were separated from the solution (This substance had a melting point between 217C. and 219C). This chloride was dissolved in acetic acid and coupled, in the presence of sodium chloride, to a diazonium compound of pnitroaniline. The resulting coupled compound was neutralized with sodium acetate, thereby producing a dyestuff, with the yield being 125 g (The resulting substance had a melting point between 231C. and 233C This dyestuff was then reduced with hydrogen gas to an amino compound. This latter compound was reacted with acetic anhydride to cause N,N'-diacetyl-pdiaminobenzene to separate out. The obtained acetyl compound was subjected to hydrolysis, followed by diazotization by known manner, and salted out by zinc chloride. Thus 51 g of 4-dibenzylamino-2,5-(B- morpholino) ethoxybenzene diazonium chloride, zinc chloride double salt which was yellow in color were obtained. This double salt had a decomposition point between 135C. and 140C. and a peak of ultraviolet absorption within the range of 405 my. to 410 my" DESCRIPTION OF THE PREFERRED EMBODIMENTS I EXAMPLE l A white support for use in diazotype copying materials was precoated with an emulsion consisting of finely granular silica and vinyl acetate. Onto this precoated support was applied a solution having the following composition:

4-dibenzylamino-5-(B-hydroxy) ethoxy benzene diazonium chloride, zinc chloride double salt (refer to Formula 1) 1.3 g

Tartaric acid 0.4 g

Boric acid 0.1 g

Water 100 ml andthe sheet was dried.

An original was placed on the light'sensitive copying layer thus obtained and was exposed to light by the use of an illuminating apparatus employing a fluorescent lamp to form a latent image on the layer. This exposure was completed in a very short length of time. The copying layer carrying the latent image was developed in a solution having the following composition:

Thiourea 1.5 g

Phloroglucin 0.4 g

Benzoic acid 0.25 g

Sodium benzoate 1.5 g Sodium phosphate 1.5 g Water ml The developing solution had a pH of about 5.9. The development was carried out rapidly, and the obtained copy had an image of black in color. The half tone areas of the image obtained were consistent in color with the maximum density areas of this reproduced im age.

EXAMPLE-2 A support for use in ordinary diazotype lightscnsitive copying materials was coated with a sensitizing solution of the following composition:

4-dibenzylamino-2,S-(B-hydroxy) ethoxybenzene diazonium chloride, zinc chloride double salt (Refer to Formula 10) 1.5 g

Tartaric acid 6.0 g

Boric acid 1.0 g

Acetic acid 2.0 g

Water 100.0 g

Caffeine 0.5 g

Methyl cellulose 0.08 g

lso-propanol 3.0 g

2-hydroxy naphthalene-3-carboxylic acid-di-(Z'-hydroxyethyl) amide 3.0 g and the paper was dried. The coated layer was exposed to light in a manner similar to that described in Example l and the resulting layer was brought into contact with an ammonia gas having a high ammonia concentration to develop the image. The developed copy showed a deep blue image.

In case the development was performed by the use of an alkaline aqueous solution composed of:

Potassium metaborate 3 g Potassium carbonate 2 g Water 100 g in lieu of the aforementioned ammonia gas, a similar, satisfactory copy was obtained.

EXAMPLE 3 A solution consisting of:

Ethyleneglycol monomethylether 20 Formic acid 3 g Water 35 g Iso-propanol 40 g Citric acid 3 g Cresyl glutaric acid 2 g 4-dibenzylamino-2-methyl-S-(B-ethoxy) ethoxy benzene diazonium compound, zinc chloride double salt (Refer to Formula 6) 4 g was applied to an acetyl cellulose sheet and was dried. Development was conducted with an ammonia gas in a manner similar to that of Example 2, and a copy yellow in color was obtained. This copy could be used as a good intermediate original since it has a property to intensively absorb ultraviolet rays and the rays locating in the regions near thereof.

We claim:

1. A light-sensitive copying material for the diazotype process comprising a support and a photosensitive layer coated on said support, said layer comprising a diazonium compound having the formula:

\N Nix or? Q a (01mm 5 wherein:

R is selected from the group consisting of hydroxyl, alkoxy having from one to four carbon atoms, a group of the formula in which R, is alkylene having from one to four car- 5 bon atoms, aryloxy,

N and n is an integer between one and four; and

X represents an anionic radical.