US3462271A - Diazotype material - Google Patents

Diazotype material Download PDF

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US3462271A
US3462271A US547738A US3462271DA US3462271A US 3462271 A US3462271 A US 3462271A US 547738 A US547738 A US 547738A US 3462271D A US3462271D A US 3462271DA US 3462271 A US3462271 A US 3462271A
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diazonium
amino
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alkyl
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Herbert Rauhut
Oskar Sus
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Keuffel and Esser Co
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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.
  • diazo compounds In copying papers and other diazotype materials that have been sensitized with diazo compounds, the derivatives of unilaterally diazotized p-phenylenediamine have been used as the photosensitive components. These diazonium compounds have a tertiary amino group of basic character and they have been used successfully for both the dry process and the semiwet process.
  • the diazo compounds which are most suitable are those containing lower alkyl groups attached to the basic nitrogen atom, while for the semiwet 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-aminobenzene 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.
  • diazotype material having improved stability and light sensitivity comprising substituted p-aminobenzene diazonium compounds which are meta-substituted with alkoxy, aryloxy, or aralkoxy groups and additionally by hydroxyalkyl substituent in the p-amino group.
  • the lightsensitive diazonium compounds of the present invention have the general formula:
  • R is an alkylene group which contains at least 2 C-atoms, R is an alkylene group,
  • R is an alkyl, aralkyl, or hydroxyalkyl
  • Z is an alkoxy, aralkoxy, aryloxy, or the group wherein R is hydrogen, or an alkyl or hydroxyalkyl,
  • R is alkyl, hydroxyalkyl, or aralkyl, or
  • X is hydrogen or a halogen or a methyl group
  • Y is an anion of an acid.
  • hydroxyalkyl radicals present in the diazo compounds defined above are preferably monohydroxyalkyl groups but may, however, also contain more than one hydroxyl group.
  • alkyl or .alkylene radicals radicals with up to four carbon atoms are preferred.
  • R and R are aralkyl groups
  • the benzyl group is preferred, which may optionally contain one or several low alkyl radicals or, on the nucleus, other substituents inert in the reaction.
  • the diazotype material according to the present invention exhibits particularly good stability with very good light sensitivity.
  • the diazo compounds which characterize the material have good compatibility with additives and stabilizers such as, e.g., citric acid, thiourea, zinc chloride, naphthalene-1,3,6-trisulfonic acid.
  • additives and stabilizers such as, e.g., citric acid, thiourea, zinc chloride, naphthalene-1,3,6-trisulfonic acid.
  • the material according to the invention can be prepared both as two-component material for the so-called dry process and as onecomponent material for the so-called semiwet process.
  • the dry process twocomponent material diazo compounds which at the amino group on the nucleus bear a low hydroxyalkyl radical besides a second such radical or a low alkyl radical and, for the semiwet process one-component material, diazo compounds which hear, at the amino group on the nucleus, at higher alkyl or hydroxyalkyl or aralkyl radical as a substituent in addition to the hydroxyalkyl radical which is always necessary.
  • the coupling dyes from the diazo compounds which are hydroxyalkylated at the amino nitrogen are, in general, not so sensitive to changes in pH value, are more bluish, and in continuous tones are of the same color as in the full shades.
  • the diazo compounds which characterize the reproduction material according to the invention are new and are in general used as diazonium chloride in the form of the double salts with metal halides, for example zinc chloride or cadmium chloride. However, they may also be used in other precipitation forms, e.g., as sulfates, phosphates, borofluorides, for the preparation of the light-sensitive coatings.
  • the hydroxyalkyl group is best introduced with the aid of alkylene oxide, e.g., ethylene oxide or propylene oxide. Other methods of preparation may also be effectively employed.
  • the present diazo compounds are used to prepare diazotype materials in the usual manner as typically shown in the examples. Dry or semiwet developing processes may be employed according to the material prepared and, depending upon the azo coupler components selected, dye images of various colors may be rapidly formed.
  • the sensitized base paper is imagewise exposed under a transparent original and developed with a solution which contains in each 100 cc. of water:
  • Phloroglucinol 0.330 Trisodium citrate 9.600 Sodium benzoate 2.420 Adipic acid 1.975 Sodium chloride z 5.700 Sodium salt of a dialkylnaphthalene sulfonic acid 0.200
  • Continuous tones are also of the same hue as the full shades.
  • Example 2 A photocopying base paper of the kind commonly used in diazotype processes and having a precoat consisting of colloidal silicic acid and polyvinyl acetate is coated on the precoated side with a solution which contains in 100 cc. of water:
  • the sensitized base paper is imagewise exposed under a transparent original and developed with ammonia. Bluish red lines on a white background are obtained.
  • 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 2 to 4 carbon atoms or a beta-hydroxypropylene group
  • R is an alkylene group, having 2 to 4 carbon atoms
  • R is an alkyl group having 1 to 3 carbon atoms, benzyl,
  • Z is an alkoxy having 2 to 4 carbon atoms, phenoxy,
  • R is an alkyl having 1 to 3 carbon atoms, or hydroxyalkyl group, and R is an alkyl having 1 to 3 carbon atoms, or benzyl;
  • X is hydrogen or a halogen or a methyl group
  • Y is an anion of an acid.
  • diazonium compound is the zinc chloride double salt of 2-chloro- 4-(N-beta-hydroxypropyl-N-benzyl)-amino-5-[beta (methoxy)ethoxy]benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 2-methyl-4- (N-hydroxyethyl-N-ethyl)amino-S-[delta-(N methyl N- benzylamino)butoxy]benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3-[beta- (butoxy)ethoxy]-4 (N-beta hydroxybutyl N methyl) aminobenzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3-[gamma-(diethylamino)propoxy]-4-(N-hydroxyethyl N benzyl)aminobenzene diazonium chloride.
  • diazoniurn compound is the zinc chloride double salt of 2-chloro- 4-(N-hydroxyethyl-N-hydroxyethyl amino-S- [beta (phen0xy)ethoxy] benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3-[beta- (benzyloxy)ethoxy]-4-(N-hydroxyethyl N propyl)aminobenzene diazonium chloride.
  • diazonium compound is the cadmium chloride double salt of 2-methyl-4-(N-hydroxyethyl-N-ethyl)amino-5-[ gamma (N hydroxyethyl-N-propyl amino)propoxy]benzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3-[be tahydroxy-gamma-(N-diethylamino)propoxy] 4 (N hydroxyethyl-N-ethyl)aminobenzene diazonium chloride.
  • diazonium compound is the zinc chloride double salt of 3-[betahydroxy-gamma-(N-diethylamino)propoxy] 4 (N hydroxyethyl-N-benzyl)aminobenzcne diazonium chloride.

Description

United States Patent U.S. CI. 9691 11 Claims ABSTRACT OF THE DISCLOSURE Diazotype material of improved stability and light sensitivity is provided through the use of p-phenylenediamine diazonium compounds which are meta-substituted with alkoxy substituents and which additionally bear a hydroxyalkyl substituent in the p-amino group.
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 derivatives of unilaterally diazotized p-phenylenediamine have been used as the photosensitive components. These diazonium compounds have a tertiary amino group of basic character and they have been used successfully for both the dry process and the semiwet 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 semiwet 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-aminobenzene 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 compounds can be improved without loss of light sensitivity through the use of heteroatom 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 U.S. patent applications owned by the assignee of the present nivention. U.S. application Ser. No. 311,220, filed Sept. 24, 1963, now U.S. Patent No. 3,272,630, describes a group of .alkoXy-, aryloxy-, and tertiary amino-substituted 3-alkoxydiazonium compounds. Application Ser. No. 414,878, filed Nov. 30, 1964, now U.S. Patent No. 3,280,246 describes a group of alkylmercaptoand amino-substituted 3-alkoxy- 3,462,271 Patented Aug. 19, 1969 "ice diazonium compounds. Application Ser. No. 425,921, filed Jan. 15, 1965, describes a group of alkoxy-, alkylmercaptoand amino-substituted 3-hydroxyalkoxydiazonium compounds. Application Ser. No. 547,721, filed May 5, 1966, describes a group of quaternary aminosubstituted 3-alkoxydiazonium compounds.
Now, according to the present invention, there is provided diazotype material having improved stability and light sensitivity comprising substituted p-aminobenzene diazonium compounds which are meta-substituted with alkoxy, aryloxy, or aralkoxy groups and additionally by hydroxyalkyl substituent in the p-amino group. The lightsensitive diazonium compounds of the present invention have the general formula:
wherein R is an alkylene group which contains at least 2 C-atoms, R is an alkylene group,
R is an alkyl, aralkyl, or hydroxyalkyl,
Z is an alkoxy, aralkoxy, aryloxy, or the group wherein R is hydrogen, or an alkyl or hydroxyalkyl,
R is alkyl, hydroxyalkyl, or aralkyl, or
R and R together with the nitrogen, for an unsubstituted or substituted 5- or 6-membered heterocyclic group,
X is hydrogen or a halogen or a methyl group, and
Y is an anion of an acid.
The hydroxyalkyl radicals present in the diazo compounds defined above, including the hydroalkyl groups standing in some cases in place of the symbols R R and R used in the general formula, are preferably monohydroxyalkyl groups but may, however, also contain more than one hydroxyl group. Of the alkyl or .alkylene radicals, radicals with up to four carbon atoms are preferred.
Where R and R are aralkyl groups, the benzyl group is preferred, which may optionally contain one or several low alkyl radicals or, on the nucleus, other substituents inert in the reaction.
The diazotype material according to the present invention exhibits particularly good stability with very good light sensitivity. The diazo compounds which characterize the material have good compatibility with additives and stabilizers such as, e.g., citric acid, thiourea, zinc chloride, naphthalene-1,3,6-trisulfonic acid. The material according to the invention can be prepared both as two-component material for the so-called dry process and as onecomponent material for the so-called semiwet process. Preferably, there are used for the dry process twocomponent material diazo compounds which at the amino group on the nucleus bear a low hydroxyalkyl radical besides a second such radical or a low alkyl radical and, for the semiwet process one-component material, diazo compounds which hear, at the amino group on the nucleus, at higher alkyl or hydroxyalkyl or aralkyl radical as a substituent in addition to the hydroxyalkyl radical which is always necessary.
By the presence of hydroxyl groups at the alkali radicals which are attached to the amino group on the nucleus, solubility is increased compared with the compounds which have no hydroxyl group there. Moreover, the coupling dyes from the diazo compounds which are hydroxyalkylated at the amino nitrogen are, in general, not so sensitive to changes in pH value, are more bluish, and in continuous tones are of the same color as in the full shades.
It is observed that it is not advantageous to use diazo compounds in which all alkyl groups are hydroxylated. Apart from the fact that the solubility of the diazo compounds is so increased that they are difficult to precipitate and their preparation is therefore attended by difiiculties, the water fastness of the coupling dyes formed from these compounds is unsatisfactory.
The diazo compounds which characterize the reproduction material according to the invention are new and are in general used as diazonium chloride in the form of the double salts with metal halides, for example zinc chloride or cadmium chloride. However, they may also be used in other precipitation forms, e.g., as sulfates, phosphates, borofluorides, for the preparation of the light-sensitive coatings.
Some of the present diazo compounds are shown in the table.
no-onn-rhomQ I IBOI'ZHOh-HOI 7 The preparation of the diazo compounds according to the above general formula is effected according to methods Which are known in the literature and which are also stated in the above-mentioned copending applications, but using for example hydroxylated alkyl halides instead of alkyl halides for the alkylation of the amino group on the nucleus. It has, however, proved expedient toefiect the introduction of the hydroxyalkyl group into the amino group on the nucleus by alkylation with hydroxylated alkyl halides before introducing a higher alkyl group or an aralkyl group. If the amino group concerned is already substituted with an alkyl or aralkyl group, the hydroxyalkyl group is best introduced with the aid of alkylene oxide, e.g., ethylene oxide or propylene oxide. Other methods of preparation may also be effectively employed.
The present diazo compounds are used to prepare diazotype materials in the usual manner as typically shown in the examples. Dry or semiwet developing processes may be employed according to the material prepared and, depending upon the azo coupler components selected, dye images of various colors may be rapidly formed.
EXAMPLE 1 Citric acid 0.50
g Sodium naphthalene-1,3,6-trisulfonate g 3.60 Saponin g 0.05 Isopropanol cc 5.00
Zinc chloride double salt of the diazo compound from l-amino 4 (hydroxyethylbenzyl)amino- 3-[fi-(methoxy)ethoxy] 6 chlorobenzene (Formula I) g 2.00
After drying, the sensitized base paper is imagewise exposed under a transparent original and developed with a solution which contains in each 100 cc. of water:
Borax 2.5
Sodium carbonate 3.0 Sodium chloride 2.0
Thiourea 5.0 Sodium isopropylnaphthalene sulfonate 0.1 Resorcinol 0.6 Phloroglucinol 0.6
High-contrast brown images on a white background are obtained.
If the base paper sensitized in the manner described above is treated, after exposure under an original, with a solution which contains in each 100 cc. of water:
Phloroglucinol 0.330 Trisodium citrate 9.600 Sodium benzoate 2.420 Adipic acid 1.975 Sodium chloride z 5.700 Sodium salt of a dialkylnaphthalene sulfonic acid 0.200
neutral black images on a white background are obtained. Continuous tones are also of the same hue as the full shades.
Example 2 A photocopying base paper of the kind commonly used in diazotype processes and having a precoat consisting of colloidal silicic acid and polyvinyl acetate is coated on the precoated side with a solution which contains in 100 cc. of water:
G. Tartaric acid 10.0 Boric acid 3.0
Thiourea 2.5 7-hydr0xynaphthimidazole 2.0
Zinc chloride double salt of the diazo compound from l-amino 4 (hydroxyethylbenzyl)amino- 3-[B-(methoxy)ethoxy] 6 chlorobenzene (Formula I) 1.93
After drying, the sensitized base paper is imagewise exposed under a transparent original and developed with ammonia. Bluish red lines on a white background are obtained.
The foregoing examples have been presented for the purpose of illustration and should not be taken to limit the scope of the present invention. It will be apparent that the described examples are capable of many variations and modificationsall such variations and modifications are to be included within the scope of the present invention as set forth in the appended claims.
What is claimed is:
1. Diazotype reproduction material comprising a support and a photosensitive composition coated thereon, said composition comprising a photosensitive diazonium compound having the general formula:
HORr- YI-R:
l lzY wherein:
R is an alkylene group having 2 to 4 carbon atoms or a beta-hydroxypropylene group;
R is an alkylene group, having 2 to 4 carbon atoms;
R is an alkyl group having 1 to 3 carbon atoms, benzyl,
or hydroxyalkyl group;
Z is an alkoxy having 2 to 4 carbon atoms, phenoxy,
benzyloxy, or the group wherein R is an alkyl having 1 to 3 carbon atoms, or hydroxyalkyl group, and R is an alkyl having 1 to 3 carbon atoms, or benzyl;
X is hydrogen or a halogen or a methyl group; and
Y is an anion of an acid.
2. Material according to claim 1 wherein said diazonium composed is the zinc chloride double salt of 2-chloro- 4-(N-hydroxyethyl-N-benzyl)amino-5 [beta (methoxy) ethoxy]benzene diazonium chloride.
3. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 2-chloro- 4-(N-beta-hydroxypropyl-N-benzyl)-amino-5-[beta (methoxy)ethoxy]benzene diazonium chloride.
4. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 2-methyl-4- (N-hydroxyethyl-N-ethyl)amino-S-[delta-(N methyl N- benzylamino)butoxy]benzene diazonium chloride.
5. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3-[beta- (butoxy)ethoxy]-4 (N-beta hydroxybutyl N methyl) aminobenzene diazonium chloride.
6. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3-[gamma-(diethylamino)propoxy]-4-(N-hydroxyethyl N benzyl)aminobenzene diazonium chloride.
7. Material according to claim 1 wherein said diazoniurn compound is the zinc chloride double salt of 2-chloro- 4-(N-hydroxyethyl-N-hydroxyethyl amino-S- [beta (phen0xy)ethoxy] benzene diazonium chloride.
8. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3-[beta- (benzyloxy)ethoxy]-4-(N-hydroxyethyl N propyl)aminobenzene diazonium chloride.
9. Material according to claim 1 wherein said diazonium compound is the cadmium chloride double salt of 2-methyl-4-(N-hydroxyethyl-N-ethyl)amino-5-[ gamma (N hydroxyethyl-N-propyl amino)propoxy]benzene diazonium chloride.
10. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3-[be tahydroxy-gamma-(N-diethylamino)propoxy] 4 (N hydroxyethyl-N-ethyl)aminobenzene diazonium chloride.
11. Material according to claim 1 wherein said diazonium compound is the zinc chloride double salt of 3-[betahydroxy-gamma-(N-diethylamino)propoxy] 4 (N hydroxyethyl-N-benzyl)aminobenzcne diazonium chloride.
References Cited UNITED STATES PATENTS 2,529,464 11/1950 Von Glahn et al 96-91 2,552,354 5/1951 Von Glahn et al 96-91 3,272,630 9/1966 Rauhut et a1. 9691 XR 3,281,246 10/1966 Rauhut et al 969l NORMAN G. TORCHIN, Primary Examiner C. BOWERS, Assistant Examiner US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,462 ,271 August 19 1969 Herbert Rauhut et a1.
It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 71, "U. S. Patent No. 3,280,246" should read U. S. Patent No. 3,281,246
Signed and sealed this 9th day of December 1969.
(SEAL) Attest:
Edward M. Fletcher, Jr. J
Attesting Officer Commissioner of Patents
US547738A 1962-09-26 1966-05-05 Diazotype material Expired - Lifetime US3462271A (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
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
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

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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
US547721A Expired - Lifetime US3459551A (en) 1962-09-26 1966-05-05 Diazotype material
US547738A Expired - Lifetime US3462271A (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
US547721A Expired - Lifetime US3459551A (en) 1962-09-26 1966-05-05 Diazotype material

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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)

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US3769021A (en) * 1966-08-26 1973-10-30 Ricoh Kk Light-sensitive diazotype copying material
US4284705A (en) * 1977-08-09 1981-08-18 Eastman Kodak Company Photosensitive diazo salt compositions and lithographic plate comprising same

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NL297944A (en) * 1962-09-26
US3379531A (en) * 1965-03-30 1968-04-23 Gen Aniline & Film Corp Two-component heat developing diazotypes
DE1793342C3 (en) * 1968-09-03 1979-05-23 Hoechst Ag, 6000 Frankfurt Fluorine-containing benzene diazonium compounds and their use in diazotype material
JPS5115858B2 (en) * 1972-04-17 1976-05-20
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.
EP1465488A4 (en) * 2001-08-30 2007-04-18 Chemocentryx Inc Arylamines 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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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
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

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NL261709A (en) * 1960-03-04
BE629326A (en) * 1962-03-09
DE1255486C2 (en) * 1963-09-14 1973-04-19 Kalle Ag Two component diazotype material

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
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
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

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
US4284705A (en) * 1977-08-09 1981-08-18 Eastman Kodak Company Photosensitive diazo salt compositions and lithographic plate comprising same

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NL6413684A (en) 1965-11-25
SE327134B (en) 1970-08-10
BE651969A (en) 1965-02-18
NL6606212A (en) 1966-11-10
NL149294B (en) 1976-04-15
BE656466A (en) 1965-05-31
CH439960A (en) 1967-07-15
DE1249683B (en) 1967-09-07
CH468024A (en) 1969-01-31
GB1122249A (en) 1968-07-31
DE1289736B (en) 1969-02-20
SE301420B (en) 1968-06-04
NL140344B (en) 1973-11-15
FI44191B (en) 1971-06-01
SE329331B (en) 1970-10-05
GB1001493A (en) 1965-08-18
FI44335B (en) 1971-06-30
BE680701A (en) 1966-11-07
US3272630A (en) 1966-09-13
SE340042B (en) 1971-11-01
NL6414808A (en) 1965-07-19
DE1289425B (en) 1969-02-13
DE1226879B (en) 1966-10-13
US3459551A (en) 1969-08-05
GB1122104A (en) 1968-07-31
SE340043B (en) 1971-11-01
DK114170B (en) 1969-06-02
NL297944A (en)
NL6605723A (en) 1966-11-10
DE1249682B (en) 1967-09-07
US3432301A (en) 1969-03-11
CH468025A (en) 1969-01-31
DK116488B (en) 1970-01-12
GB1062918A (en) 1967-03-22
NL141657B (en) 1974-03-15

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