US3459551A - Diazotype material - Google Patents

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US3459551A
US3459551A US547721A US3459551DA US3459551A US 3459551 A US3459551 A US 3459551A US 547721 A US547721 A US 547721A US 3459551D A US3459551D A US 3459551DA US 3459551 A US3459551 A US 3459551A
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diazonium
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Herbert Rauhut
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Keuffel and Esser Co
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Assigned to SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIATION FOR ITSELF AND AS AGENT FOR CITIBANK, N.A. A NATIONAL BANKING ASSOCIATION, BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING ASSOCIATION, CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF CHICAGO, A NATIONAL BANKING ASSOCIATION, CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING ASSOCIATION, CHEMICAL BANK, A BANKING INSTITUTION OF reassignment SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIATION FOR ITSELF AND AS AGENT FOR CITIBANK, N.A. A NATIONAL BANKING ASSOCIATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KEUFFEL & ESSER COMPANY A.N.J. CORP
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/06—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of alkaline solutions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

  • the present invention relates to a diazotype material and more particularly relates to improved photosensitive diazo components useful in diazotype reproduction material.
  • the diazo compounds which are most suitable are those containing lower alkyl groups attached to the basic nitrogen atom, while for the semi-wet process the best ones are those in which the basic nitrogen atom is attached to higher hydrocarbon radicals.
  • the substituents on the basic nitrogen atom affect not only coupling speed, but they also affect the light-sensitivity and keeping qualities of the diazo compounds and the light-sensitive layers prepared therewith.
  • the properties of the p-amino benzene diazo compounds depend also on substituents attached to the phenylene ring.
  • a substituent such as a methyl, methoxy, or carboxyl group in a position ortho to the diazonium group, brings about a considerable improvement in stability and at the same time a color shift toward blue.
  • Light-sensitivity is, however, lowered by these substituents.
  • the presence of an alkoxy group in a position meta to the diazonium group makes the diazo compound considerably more light-sensitive in relation to the unsubstituted compound, but the keeping qualities become poorer as a result.
  • this type of diazo compound is nevertheless important because of its high light-sensitivity and it finds practical use in cases where copies have to be prepared as quickly as possible.
  • 3,281,246 describes a group of alkylmercaptoand amino-substituted 3-alkoxy diazonium compounds.
  • Application Ser. No. 425,921, filed Jan. 15, 1965, describes a group of alkoxy-, alkylmercaptoand amino substituted 3 hydroxya-lkoxy diazonium com- 3,459,551 Patented Aug. 5, 1969 pounds.
  • diazo-type material having improved stability and light-sensitivity comprising substituted p-aminobenzene diazonium compounds with meta-substituents including a quarternary amino group as part of the hetero-atom.
  • the light-sensitive diazonium compounds of the present invention have the general formula:
  • R stands for 'an alkyl group with at the most four carbon atoms
  • R stands for an alkyl group with at the most four carbon atoms or an aralkyl group with at the most ten carbon atoms, or
  • R and R together with the nitrogen atom N to which they are attached, form a heterocyclic group which may bear one or several substituents,
  • R stands for an alkylene radical which contains at least 2 C-atoms and may also be substituted
  • R and R stand for alkyl or hydroxyalkyl, or
  • R and R together with the nitrogen atom to which they are attached, form an unsubstituted or substituted heterocyclic radical
  • R stands for alkyl or aralkyl
  • X stands for a hydrogen or halogen atom or an alkyl or alkoxy group
  • Y and Y each stand for the anion of an acid.
  • the p-aminobenzenediazonium salts according to the above mentioned general formula exhibit high light-sensitivity and excellent stability. Their substantivity is bet ter than that of the p-aminobenzenediazo compounds which characterize the reproduction material described in the above-mentioned copending applications. Diazotype material prepared with these diazonium compounds exhibit improved properties in respect of shelf life and advantages which show themselves during its processing and in the copies prepared from it.
  • Diazotype materials comprising the present diazonium compounds can be prepared in the usual manner and can be used to advantage in both the dry or semi-wet diazotype processes. Depending upon the azo coupler component selected, images of deep color can be prepared with great speed.
  • the p-aminobenzenediazo compounds corresponding to the general formula stated above have not yet been described in the literature. They are obtained according to processes which are described in the literature and in particular in the mentioned co-pending applications.
  • the p-tertiary-aminonitrobenzenes with a tertiary amino group in the ether group in the meta-position which are mentioned in these applications can be converted into the quaternary form by conventional methods with e.g. alkyl halides or aralkyl-halides or dialkylsulphates. Conversion of these quaternised compounds into diazo compounds is effected without difficulty.
  • the separation of the diazo compound is eifected in the form of its metal halide double salts or in other manner known in the art.
  • a photocopying base paper of the kind commonly used in diazotype processes one side of which is provided with a precoat consisting of colloidal silicic acid and polyvinyl acetate, is coated on the precoated surface with a solution which contains in parts by volume of water Parts by weight Citric acid 3.5 Boric acid 3.5 Thiourea 5.0 3.5-dihydroxy-4-bromobenzoic acid amide 1.2
  • Example 2 A photocopying base paper of the kind commonly used in diazotype processes, one side of which is provided with a precoat consisting of colloidal silicic acid and polyvinyl acetate, is coated on the precoated surface with a solution which contains in 100 parts by volume of water Parts by weight Citric acid 4.0 Thiourea 5.0 Aluminum sulphate 3.0 Sodium 1,3,6-naphthalenetrisulphonate 3.5
  • the reproduction paper has very good shelf life.
  • the resulting reproduction paper is imagewise exposed in the normal manner under a transparent original and then developed with ammonia vapour. Blue images on a White back ground are obtained.
  • the diazo compound used (that of Formula III) is prepared in manner analogous to that stated for the diazo compound described in Example 1. However, in this case the 2-chloro-5-nitrophenol is reacted with epichlorohydrin instead of with ethylene bromide.
  • a diazotype reproduction material comprising a support and a photosensitive composition coated thereon, said composition comprising a photosensitive diazonium compound having the general formula:
  • R is an alkylene group having two to four carbon atoms or beta-hydroxypropylene
  • R is an alkyl group having one to four carbon atoms, and R is an alkyl having one to four carbon atoms or aralkyl, or R and R together with the nitrogen, form a pyrrolidine, piperidino, or morpholino p;
  • R is an alkyl or hydroxyalkyl group and R is an alkyl or hydroxyalkyl group, or R and R together with the nitrogen, form an unsubstituted or substituted 5- or 6-membered heterocyclic group;
  • R is an alkyl having one to four carbon atoms, or
  • X is a hydrogen or halogen atom, or an alkyl or alkoxy group
  • Y and Y are each an anion of an acid.
  • diazoniurn compound is the zinc chloride double salt of 3,4- pyrroldino-benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3,4- pyrrolidino-benzene diazonium chloride.
  • diazonium compound is the cadmium chloride double salt of 1-ethoxy-4-morpholino-5benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3,4 (N-ethyl-N-butyl)-amino-benzene diazonium chloride.
  • diazonium compound is the cadmium chloride double salt of 3,4- pyrrolidino-benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3,4- piperidino-benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 2-chloro- 3,459,551 7 8 4-(N-methyl-N-benzyl) amino 5 benzene diazonium 3,281,246 10/1966 Rauhut et a1 96-- 91 chloride. 3,343,960 9/1967 Sus 9691 13.
  • said diazonium compound is the zinc chloride double salt of 3,4- NORMAN G. TORCHIN, Primary EXamiHBl diethylamino-benzene diazoniurn chloride. 5 BOWERS, Assistant Examiner References C1ted USI CL- XIR. UNITED STATES PATENTS 260141, 142, 567 3,272,630 9/1966 Rauhut et a1 96-91 XR

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  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrrole Compounds (AREA)
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Description

United States Patent K Int. Cl. G03c 1/54; C07c 113/04 US. Cl. 96-91 13 Claims ABSTRACT OF THE DISCLOSURE Diazotype material of improved stability and light sensitivity includes a 3-quaternary ammonium-alkoxy substituted p-phenylene diamine derived diazonium compound.
The present invention relates to a diazotype material and more particularly relates to improved photosensitive diazo components useful in diazotype reproduction material.
In copying papers and other diazotype materials that have been sensitized with diazo compounds, the den'vatives of unilaterally diazotized p-phenylene diamine have been used as the photosensitive components. These diazonium compounds have a tertiary amino group of basic character and they have been used successfullyfor both the dry process and the semi-wet process.
For the dry process the diazo compounds which are most suitable are those containing lower alkyl groups attached to the basic nitrogen atom, while for the semi-wet process the best ones are those in which the basic nitrogen atom is attached to higher hydrocarbon radicals.
The substituents on the basic nitrogen atom affect not only coupling speed, but they also affect the light-sensitivity and keeping qualities of the diazo compounds and the light-sensitive layers prepared therewith.
In considerable measure the properties of the p-amino benzene diazo compounds depend also on substituents attached to the phenylene ring. a substituent such as a methyl, methoxy, or carboxyl group in a position ortho to the diazonium group, brings about a considerable improvement in stability and at the same time a color shift toward blue. Light-sensitivity is, however, lowered by these substituents. The presence of an alkoxy group in a position meta to the diazonium group makes the diazo compound considerably more light-sensitive in relation to the unsubstituted compound, but the keeping qualities become poorer as a result. Despite their poor stability, this type of diazo compound is nevertheless important because of its high light-sensitivity and it finds practical use in cases where copies have to be prepared as quickly as possible.
It has been found that the stability of this general type of meta-substituted diazonium compound can be improved without loss of light-sensitivity through the use of hetero-atom substituents in the alkoxy group in the position meta to the diazonium group. Some useful improvements in such diazonium compounds have been disclosed in related copending US. patent applications owned by the assignee of the present invention. U.S. application Ser. No. 311,220, filed Sept. 24, 1963, now US. Patent No. 3,272,630 describes a group of alkoxy-aryloxyand tertiary amino-substituted 3-alkoxy diazonium compounds. Application Ser. No. 414,878, filed Nov. 30, 1964, now U.S. Patent No. 3,281,246 describes a group of alkylmercaptoand amino-substituted 3-alkoxy diazonium compounds. Application Ser. No. 425,921, filed Jan. 15, 1965, describes a group of alkoxy-, alkylmercaptoand amino substituted 3 hydroxya-lkoxy diazonium com- 3,459,551 Patented Aug. 5, 1969 pounds. Application Ser. No. 547,738 filed May 5, 1966, describes a group of alkoxy-substituted 3-alkoxy-4-hydroxyalkylamino-diazonium compounds.
Now, according to the present invention, there is provided diazo-type material having improved stability and light-sensitivity comprising substituted p-aminobenzene diazonium compounds with meta-substituents including a quarternary amino group as part of the hetero-atom. The light-sensitive diazonium compounds of the present invention have the general formula:
wherein R stands for 'an alkyl group with at the most four carbon atoms,
R stands for an alkyl group with at the most four carbon atoms or an aralkyl group with at the most ten carbon atoms, or
R and R together with the nitrogen atom N to which they are attached, form a heterocyclic group which may bear one or several substituents,
R stands for an alkylene radical which contains at least 2 C-atoms and may also be substituted,
R and R stand for alkyl or hydroxyalkyl, or
R and R together with the nitrogen atom to which they are attached, form an unsubstituted or substituted heterocyclic radical,
R stands for alkyl or aralkyl,
X stands for a hydrogen or halogen atom or an alkyl or alkoxy group,
Y and Y each stand for the anion of an acid.
The p-aminobenzenediazonium salts according to the above mentioned general formula exhibit high light-sensitivity and excellent stability. Their substantivity is bet ter than that of the p-aminobenzenediazo compounds which characterize the reproduction material described in the above-mentioned copending applications. Diazotype material prepared with these diazonium compounds exhibit improved properties in respect of shelf life and advantages which show themselves during its processing and in the copies prepared from it.
Diazotype materials comprising the present diazonium compounds can be prepared in the usual manner and can be used to advantage in both the dry or semi-wet diazotype processes. Depending upon the azo coupler component selected, images of deep color can be prepared with great speed.
The p-aminobenzenediazo compounds corresponding to the general formula stated above have not yet been described in the literature. They are obtained according to processes which are described in the literature and in particular in the mentioned co-pending applications. The p-tertiary-aminonitrobenzenes with a tertiary amino group in the ether group in the meta-position which are mentioned in these applications can be converted into the quaternary form by conventional methods with e.g. alkyl halides or aralkyl-halides or dialkylsulphates. Conversion of these quaternised compounds into diazo compounds is effected without difficulty.
- The separation of the diazo compound is eifected in the form of its metal halide double salts or in other manner known in the art.
In the table are set forth the formulae of some diazo compounds by which the reproduction material according to the invention is characterized. In the examples, typical preparation of some of these compounds and preparation, in the usual manner, of diazotype materials employing the same are described. The weight and volume units in the examples may be nominally considered as milliliters and grams.
A photocopying base paper of the kind commonly used in diazotype processes, one side of which is provided with a precoat consisting of colloidal silicic acid and polyvinyl acetate, is coated on the precoated surface with a solution which contains in parts by volume of water Parts by weight Citric acid 3.5 Boric acid 3.5 Thiourea 5.0 3.5-dihydroxy-4-bromobenzoic acid amide 1.2
Diazo compound from triethylbeta-(5-amino-2-pyrrolidino-phenoxyethyl)-ammonium chloride in the form of the zinc chloride double salt (Formula 1) 2.4
parts by weight of 2-chloro-5-nitrophenol are dissolved in 400 parts by volume of methylglycol and 220 parts by volume of ethylenebromide and heated to the boil, with stirring. Under reflux, a solution of 24 parts by weight of sodium hydroxide in 250 parts by volume of water is added dropwise to the methylalcoholic solution in 3 hours. After further stirring for two hours under reflux the reaction mixture is filtered with suction while hot, the filtrate concentrated to dryness in vacuo, and the residue treated with water, filtered with suction and dried. Yield: 165 parts by weight with a melting point of 71- 75 C.
305 parts by weight of 2-ch1oro-5-nitrophenyl-beta bromoethylether with 385 parts by weight of anhydrous diethylamine and 60 parts by volume of water are heated to the boil, with stirring. After boiling for two hours the reaction mixture is poured into ice water, filtered with suction and washed thoroughly with ice water. While the 395 parts by weight of reaction product which are obtained are still moist, there are poured over it 450 parts by volume of pyrrolidine and 30 parts by volume of water and the mixture is heated to the boil, with stirring. After the mixture has been stirred for about three hours under reflux, 180 parts by volume of pyrrolidine are distilled off. The residue is poured into the ice water, filtered with suction and washed thoroughly with water. Yield of 5 nitro 2 pyrrolidinophenyl beta diethylaminoethylether: 325 parts by weight, with a melting point of 39 C. After recrystallization from petroleum ether the melting point of 42 C. is obtained.
160 parts by weight of S-nitro-2-pyrrolidinophenyl-betadiethylaminoether are dissolved in 100 parts by volume of acetone. This solution is heated to the boil, with stirring, and there are added to it dropwise 75 parts by volume of ethyl iodide. After stirring for a further hour under reflux the reaction mixture is cooled, filtered with suction, digested with acetone and dried. Yield: 95 g. with a melting point of 197 C.
30 parts by Weight of the triethyl-beta-(S-nitro-Z- pyrrolidino-phenoxyethyl)-ammonium iodide thus prepared are hydrogenated with hydrogen in 200 parts by volume of methanol in the presence of active nickel catalyst. The amino compound formed, after filtering off the catalyst and evaporation of the solvent, is dissolved, without purification, in 80 parts by volume of water and 20 parts by volume of hydrochloric acid and diazotised at 0-10 C. with 33 parts by volume of 2 N sodium nitrite solution. After dilution of the diazotising mixture with 100 parts by volume of water the mixture is filtered over carbon. An aqueous solution of 15 parts by weight of zinc chloride is added to it and salting out is efiected with sodium chloride. Yield: 11 parts by weight of the compound of Formula I after dissolving in water and precipitating by adding sodium chloride solution.
Example 2 A photocopying base paper of the kind commonly used in diazotype processes, one side of which is provided with a precoat consisting of colloidal silicic acid and polyvinyl acetate, is coated on the precoated surface with a solution which contains in 100 parts by volume of water Parts by weight Citric acid 4.0 Thiourea 5.0 Aluminum sulphate 3.0 Sodium 1,3,6-naphthalenetrisulphonate 3.5
and then dried.
The reproduction paper has very good shelf life.
The resulting reproduction paper is imagewise exposed in the normal manner under a transparent original and then developed with ammonia vapour. Blue images on a White back ground are obtained.
The diazo compound used (that of Formula III) is prepared in manner analogous to that stated for the diazo compound described in Example 1. However, in this case the 2-chloro-5-nitrophenol is reacted with epichlorohydrin instead of with ethylene bromide.
The foregoing examples have been presented for the purpose of illustration and should not be taken to limit the invention. It will be apparent that the present invention is capable of numerous variations which will be included within the scope of the appended claims.
What is claimed is:
1. A diazotype reproduction material comprising a support and a photosensitive composition coated thereon, said composition comprising a photosensitive diazonium compound having the general formula:
wherein:
(a) R is an alkylene group having two to four carbon atoms or beta-hydroxypropylene;
(b) R is an alkyl group having one to four carbon atoms, and R is an alkyl having one to four carbon atoms or aralkyl, or R and R together with the nitrogen, form a pyrrolidine, piperidino, or morpholino p;
(c) R; is an alkyl or hydroxyalkyl group and R is an alkyl or hydroxyalkyl group, or R and R together with the nitrogen, form an unsubstituted or substituted 5- or 6-membered heterocyclic group;
(d) R is an alkyl having one to four carbon atoms, or
benzyl;
(e) X is a hydrogen or halogen atom, or an alkyl or alkoxy group; and
(f) Y and Y are each an anion of an acid.
2. Material according to claim 1 wherein said diazoniurn compound is the zinc chloride double salt of 3,4- pyrroldino-benzene diazonium chloride.
3. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3,4- pyrrolidino-benzene diazonium chloride.
4. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3,4- pyrrolidino-benzene diazonium chloride.
5. Material according to claim 1 wherein said diazonium compound is the cadmium chloride double salt of 1-ethoxy-4-morpholino-5benzene diazonium chloride.
6. Material according to claim 1 wherein said diazonium compound is the 3,4-morpholino-benzene diazonium borofluoride.
7. Material according to claim 1 wherein said diazonium compound is the Zinc chloride double salt of 3,4- pyrrolidino-benzene diazonium chloride.
8. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3,4 (N-ethyl-N-butyl)-amino-benzene diazonium chloride.
9. Material according to claim 1 wherein said diazonium compound is the cadmium chloride double salt of 3,4- pyrrolidino-benzene diazonium chloride.
10. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3,4- piperidino-benzene diazonium chloride.
11. Material according to claim 1 wherein said diazonium compound is the cadmium chloride double salt of 2- methyl-4-morpholino-5-benzene diazonium chloride.
12. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 2-chloro- 3,459,551 7 8 4-(N-methyl-N-benzyl) amino 5 benzene diazonium 3,281,246 10/1966 Rauhut et a1 96-- 91 chloride. 3,343,960 9/1967 Sus 9691 13. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3,4- NORMAN G. TORCHIN, Primary EXamiHBl diethylamino-benzene diazoniurn chloride. 5 BOWERS, Assistant Examiner References C1ted USI CL- XIR. UNITED STATES PATENTS 260141, 142, 567 3,272,630 9/1966 Rauhut et a1 96-91 XR
US547721A 1962-09-26 1966-05-05 Diazotype material Expired - Lifetime US3459551A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DEK47829A DE1226879B (en) 1962-09-26 1962-09-26 Light-sensitive copying material with p-phenylenediamine derivative diazotized on one side as a light-sensitive substance
DEK0051523 1963-12-03
DEK0051880 1964-01-18
DEK56061A DE1289425B (en) 1962-09-26 1965-05-08 Photosensitive copying material which, as photosensitive substance, contains at least one derivative of p-phenylenediamine which is diazotized on one side and has an alkoxy group in the m-position to the diazo group
DEK56060A DE1289736B (en) 1962-09-26 1965-05-08 Photosensitive copying material which contains as photosensitive substance at least one derivative of p-phenylenediamine which is diazotized on one side and has an alkoxy group in the m-position to the diazo group

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US3459551A true US3459551A (en) 1969-08-05

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US311220A Expired - Lifetime US3272630A (en) 1962-09-26 1963-09-24 Light-sensitive reproduction material containing unilaterally diazotized p-phenylene-diamine derivatives as the light sensitive substance
US425921A Expired - Lifetime US3432301A (en) 1962-09-26 1965-01-15 Reproduction material
US547738A Expired - Lifetime US3462271A (en) 1962-09-26 1966-05-05 Diazotype material
US547721A Expired - Lifetime US3459551A (en) 1962-09-26 1966-05-05 Diazotype material

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US311220A Expired - Lifetime US3272630A (en) 1962-09-26 1963-09-24 Light-sensitive reproduction material containing unilaterally diazotized p-phenylene-diamine derivatives as the light sensitive substance
US425921A Expired - Lifetime US3432301A (en) 1962-09-26 1965-01-15 Reproduction material
US547738A Expired - Lifetime US3462271A (en) 1962-09-26 1966-05-05 Diazotype material

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US (4) US3272630A (en)
BE (3) BE651969A (en)
CH (3) CH439960A (en)
DE (5) DE1226879B (en)
DK (2) DK116488B (en)
FI (2) FI44335B (en)
GB (4) GB1001493A (en)
NL (6) NL140344B (en)
SE (5) SE301420B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634090A (en) * 1968-09-03 1972-01-11 Keuffel & Esser Co Light sensitive one-component diazotype material
US3769021A (en) * 1966-08-26 1973-10-30 Ricoh Kk Light-sensitive diazotype copying material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL297944A (en) * 1962-09-26
US3379531A (en) * 1965-03-30 1968-04-23 Gen Aniline & Film Corp Two-component heat developing diazotypes
JPS5115858B2 (en) * 1972-04-17 1976-05-20
FR2400221A1 (en) * 1977-08-09 1979-03-09 Kodak Pathe PHOTOSENSITIVE DIAZONIUM COMPOUND USEFUL, IN PARTICULAR, FOR PREPARING LITHOGRAPHIC PRINTING BOARDS, PROCESS FOR PREPARING THIS COMPOUND AND PLATE PRESENSITIZED WITH THIS COMPOUND
CH661501A5 (en) * 1982-01-26 1987-07-31 Oreal COMPOUNDS DERIVATIVE FROM AMINO-3 PROPANOL-2 FOR USE IN DYEING HAIR, PREPARATION METHOD THEREOF, DYE COMPOSITION CONTAINING THE SAME, AND HAIR DYEING METHOD THEREOF.
ATE439131T1 (en) * 2001-08-30 2009-08-15 Chemocentryx Inc BICYCLIC COMPOUNDS AS INHIBITORS OF CHEMOKINE BINDING TO US28
DE102013220789A1 (en) * 2013-10-15 2015-04-16 Henkel Ag & Co. Kgaa Antiperspirant cosmetic products containing aromatic sulfonic acids

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US3272630A (en) * 1962-09-26 1966-09-13 Keuffel & Esser Co Light-sensitive reproduction material containing unilaterally diazotized p-phenylene-diamine derivatives as the light sensitive substance
US3281246A (en) * 1964-11-30 1966-10-25 Keuffel & Esser Co Diazotype reproduction material
US3343960A (en) * 1963-09-14 1967-09-26 Keuff & Esser Company Coupling components for lightsensitive diazo coatings

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US2529464A (en) * 1946-09-23 1950-11-07 Gen Aniline & Film Corp Diazotype composition containing n-hydroxyethyl-m-toluidine-p-diazos
US2552354A (en) * 1947-04-16 1951-05-08 Gen Aniline & Film Corp Diazotype layers containing diazos of n-(2-hydroxypropyl)-phenylenediamines
BE600885A (en) * 1960-03-04
BE629326A (en) * 1962-03-09

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272630A (en) * 1962-09-26 1966-09-13 Keuffel & Esser Co Light-sensitive reproduction material containing unilaterally diazotized p-phenylene-diamine derivatives as the light sensitive substance
US3343960A (en) * 1963-09-14 1967-09-26 Keuff & Esser Company Coupling components for lightsensitive diazo coatings
US3281246A (en) * 1964-11-30 1966-10-25 Keuffel & Esser Co Diazotype reproduction material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3769021A (en) * 1966-08-26 1973-10-30 Ricoh Kk Light-sensitive diazotype copying material
US3634090A (en) * 1968-09-03 1972-01-11 Keuffel & Esser Co Light sensitive one-component diazotype material

Also Published As

Publication number Publication date
BE651969A (en) 1965-02-18
NL140344B (en) 1973-11-15
GB1122249A (en) 1968-07-31
NL141657B (en) 1974-03-15
BE680701A (en) 1966-11-07
NL297944A (en)
SE329331B (en) 1970-10-05
GB1062918A (en) 1967-03-22
CH468024A (en) 1969-01-31
FI44191B (en) 1971-06-01
FI44335B (en) 1971-06-30
SE340042B (en) 1971-11-01
DE1249682B (en) 1967-09-07
SE340043B (en) 1971-11-01
SE327134B (en) 1970-08-10
SE301420B (en) 1968-06-04
DE1226879B (en) 1966-10-13
DE1249683B (en) 1967-09-07
US3272630A (en) 1966-09-13
NL6605723A (en) 1966-11-10
NL6606212A (en) 1966-11-10
BE656466A (en) 1965-05-31
NL149294B (en) 1976-04-15
DE1289736B (en) 1969-02-20
US3432301A (en) 1969-03-11
US3462271A (en) 1969-08-19
NL6413684A (en) 1965-11-25
NL6414808A (en) 1965-07-19
GB1001493A (en) 1965-08-18
CH468025A (en) 1969-01-31
GB1122104A (en) 1968-07-31
CH439960A (en) 1967-07-15
DK114170B (en) 1969-06-02
DE1289425B (en) 1969-02-13
DK116488B (en) 1970-01-12

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