US3432301A - Reproduction material - Google Patents

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US3432301A
US3432301A US425921A US3432301DA US3432301A US 3432301 A US3432301 A US 3432301A US 425921 A US425921 A US 425921A US 3432301D A US3432301D A US 3432301DA US 3432301 A US3432301 A US 3432301A
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group
parts
compound
diazonium
pyrrolidino
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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

  • said layer comprising a diazonium compound having the formula:
  • X represents the members required to complete a heterocyclic ring selected from the group consisting of S-membered and 6-membered heterocyclic rings
  • X is selected from the group consisting of hydrogen and alkyl
  • R and R are members of one of the groups selected from Group A in which R;., is alkyl up to 4 carbon atoms and hydroxyalkyl with up to 4 carbon atoms, and R is hydrogen, alkyl up to 4 carbon atoms, and hydroxyalkyl with up to 4 carbon atoms
  • Group B in which R and R are members of the same 5- or 6-membered heterocyclic ring, and Y is the anion of an acid.
  • the present invention relates to a reproduction material and more particularly refers to a photosensitive diazotype reproduction material.
  • diazo compounds In copying papers and other copying foils that have been sensitized with diazo compounds, the derivatives of unilaterally diazotized p-phenylene diamine have been used as the photosensitive elements. These diazonium compounds have a tertiary amino group of basic character and they have been used successfully for both the dry process and the semi-wet 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 or a ring structure.
  • 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 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 3,432,301 Patented Mar. 11, 1969 of diazo compound is nevertheless important because of its high light-sensitivity and they find practical use in cases where copies have to be prepared as quickly as possible.
  • the light-sensitive reproduction material contains as light-sensitive substance provided by the invention at least one derivative of unilaterally diazotized p-phenylene diamine corresponding to the general formula:
  • R and R are members selected from the groups consisting of: group A wherein R is an alkyl group containing up to 4 carbon atoms, and R is a member selected from the group consisting of alkyl groups containing up to 4 carbon atoms and aralkyl groups with up to 10 carbon atoms; and group B wherein R and R are members of the same heterocyclic group; where Z is a member selected from the group consisting of alkoxy, arylated alkoxy, aryloxy, alkylthio and the group wherein R and R are members selected from the groups consisting of: group C wherein R is selected from the group consisting of hydrogen, alkyl groups containing up to 4 carbon atoms, hydroxy alkyl groups having up to 4 carbon atoms and R is a member selected from the group consisting of alkyl groups containing up to 4 carbon atoms, hydroxy alkyl groups containing up to 4 carbon atoms and aralkyl groups with up to 10' carbon atoms; and group D
  • One kind of the light-sensitive reproduction material in accordance with the present invention contains as light-sensitive substance a diazonium compound of the following formula:
  • X represents the members required to complete a heterocyclic ring selected from the group consisting of S-membered and 6-membered heterocyclic rings
  • X is selected from the group consisting of hydrogen and alkyl
  • R and R4 are members of one of the groups selected from Group A in which R and R are selected from the group consisting of hydrogen, alkyl up to 4 carbon atoms
  • Reproduction materials utilizing the present invention can be used both for the dry and for the semi-wet processes. According to the coupler used, dark colors such as deep brown or violet can be prepared with great speed.
  • one object of the present invention is to provide a light-sensitive, diazotype reproduction material utilizing a diazonium compound which can be used for the dry and for the semi-wet processes.
  • Another object is to provide a light-sensitive, diazotype reproduction material which has excellent photosensitivity, good stability, and good compatibility with additives and stabilizers.
  • the diazo compounds are generally used as the diazonium chloride in the form of double salts with metal halides such as zinc chloride or cadmium chloride. Other forms such as sulfates, phosphates or borofluorides may also be used.
  • the diazo compounds were simply obtained according to methods known in the literature particularly where the compounds contain a heterocyclic ring in the para position to the diazo group.
  • 2-chloro-5-nitrophenol e.g. was etherified with epichlorhydrin in the presence of an alkali, and the epoxide ring in the ether side chain was split and substituted by suitable agents.
  • the nuclear chlorine atom was replaced by a heterocyclic base containing a secondary nitrogen atom, the nitro compound reduced, and the product diazotized.
  • the starting material may be o-nitrophenol which is etherified in the above explained manner.
  • the nitro compound thus obtained is reduced and dialkylated according to one of the methods which are commonly known for reducing and dialkylating respectively.
  • the substitution of an amino group in the para position of the dialkylamino group is achieved by coupling with a diazo compound to form an azo dyestufi and subsequent reductive splitting of the azo group of the dyestuff; instead of coupling, a nitroso or a nitro group may be substituted to the benzene nucleus by a known method with subsequent reduction of the nitroso or nitro group.
  • the amino group is finally converted into the diazo group by the application of nitrous acid.
  • the formulas of some of the new diazonium compounds according to the present invention are in the table.
  • the melting points in degrees centigrade of the nitro compounds (nitro group in the p-position to the NR R group) which are the basic materials for these diazonium salts are: (1) 94 C., (2) 92 C., (3) 92 C., (4) 198 C. (as HCl salt), (5) 108-109" C., (6) 131 C., (7) 78-79 C., (8) 101 C.
  • the figures 1 to 8 correspond to the figures of the formulas in the table.
  • the sensitized raw paper was exposed behind a transparent master and developed with ammonia. Blue images on a white background were obtained.
  • the reproduction paper had an excellent shelf life.
  • the diazo compound employed was obtained by the following procedure. 173 parts by weight of 2-chloro-5- nitrophenol were dissolved in 250 parts by volume of methyl glycol, 176 parts by weight of epichlorhydrin were added and heated nearly to the boiling point. Then 100 parts by volume of 40% soda were gradually dropped into the solution without further heating. After addition of the soda, the mixture was refluxed for one hour. Then the warm solution was filtered, 100 parts by volume of water were added, cooled and the residue was drawn 01?. The latter was dried and recrystallized from methanol. The yield was 183 parts by weight melting at 93 C.
  • Example 2 A reproduction paper conventionally used for diazotype I purposes having on one side a precoating of colloidal silica and polyvinyl acetate was coated on the pretreated surface with a solution containing:
  • Example 1 per 100 parts by volume of water. The process according to Example 1 was followed and red images on a white background were obtained.
  • the diazo compound was obtained by the following procedure. parts by weight of 2-chloro-5-nitropheny1- glycidylether were heated with 60 parts by volume of din-propylamine during three hours on a steam bath. Then ice water was added and the precipitated product was drawn off and dried. The crude yield was parts by weight melting at 41-42" C. Further processing was effected with good yields analogous to the method described in Example 1.
  • a diazotype reproduction material which comprises a support and a photosensitive layer coated on said support, said layer comprising a diazonium compound having the formula:
  • X represents the members required to complete a heterocyclic ring selected from the group consisting of S-membered and 6-membered heterocyclic rings
  • X is selected from the group consisting of hydrogen and alkyl
  • R and R are members of one of the groups selected from: Group A in which R is alkyl up to 4 carbon atoms and hydroxyalkyl with up to 4 carbon atoms, and R is hydrogen, alkyl up to 4 carbon atoms, and hydroxyalkyl with up to 4 carbon atoms
  • Group B in which R; and R are members of the same 5- or 6-membered heterocyclic ring
  • Y is the anion of an acid.
  • a diazotype reproduction material which comprises a support and a photosensitive layer coated on said support, said layer comprising a diazonium compound selected from the group consisting of 4-pyrrolidino-3-(gamma-diethyl-amino beta hydroxypropoxy) -benzene diazonium chloride; 6-methyl-4-pyrrolidino-3- gamma-diethylamino-betahydroxy-propoxy)-benzene diazonium chloride; 4-pyrrolidino-3- gamma-pyrrolidino-beta-hydroxypropoxy)-benzene diazonium chloride; 4-morpholino-3 gamma-morpholino-beta-hydroxypropoxy)-benzene diazonium chloride; 4-pyrrolidino-3-(gamma-n-butylaminobeta-hydroxypropoxy)-benzene diazonium chloride; 4-pyrrolidino-3-(gamma-hydroxyethylamino-bet
  • a material in accordance with claim 1 in which said diazonium compound is 4-pyrrolidino-3-(gamma-di-ethylamino-beta-hydroxy-propoxy)-bcnzene diazonium chloride.
  • diazonium compound is 4-pyrrolidino-3-(gamma-n-butylamino-beta-hydroxy-propoxy)-benzene diazonium chloride.
  • a material in accordance with claim 1 in which said diazonium compound is 4-pyrrolidino-3-(gamma-dihydroxyethylarnino-bcta-hydroxy propoxy)-benzene diazonium chloride.
  • diazonium compound is 4-pyrrolidino-3-(gamma-di-npropylamino beta-hydroxy-propoxy)-benzene diazonium chloride.

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  • Organic Chemistry (AREA)
  • 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)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Pyrrole Compounds (AREA)

Description

United States Patent 7 Claims Int. Cl. G03c 1/54; C07c 113/04 ABSTRACT OF THE DISCLOSURE A diazotype reproduction material which comprises a support and a photosensitive layer coated on said support,
said layer comprising a diazonium compound having the formula:
in which X represents the members required to complete a heterocyclic ring selected from the group consisting of S-membered and 6-membered heterocyclic rings, X is selected from the group consisting of hydrogen and alkyl, R and R are members of one of the groups selected from Group A in which R;., is alkyl up to 4 carbon atoms and hydroxyalkyl with up to 4 carbon atoms, and R is hydrogen, alkyl up to 4 carbon atoms, and hydroxyalkyl with up to 4 carbon atoms; and Group B in which R and R are members of the same 5- or 6-membered heterocyclic ring, and Y is the anion of an acid.
The present invention relates to a reproduction material and more particularly refers to a photosensitive diazotype reproduction material.
In copying papers and other copying foils that have been sensitized with diazo compounds, the derivatives of unilaterally diazotized p-phenylene diamine have been used as the photosensitive elements. These diazonium compounds have a tertiary amino group of basic character and they have been used successfully for 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 semiwet process the best ones are those in which the basic nitrogen atom is attached to higher hydrocarbon radicals or a ring structure.
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 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 3,432,301 Patented Mar. 11, 1969 of diazo compound is nevertheless important because of its high light-sensitivity and they find practical use in cases where copies have to be prepared as quickly as possible.
It has now been found that the stability can be improved in many compounds of the last-named type without loss of light-sensitivity, and even with improvement in light-sensitivity by the introduction of hetero-atoms in form of hydroxyl and amino groups into the alkoxy group. The light-sensitive reproduction material contains as light-sensitive substance provided by the invention at least one derivative of unilaterally diazotized p-phenylene diamine corresponding to the general formula:
X where R and R are members selected from the groups consisting of: group A wherein R is an alkyl group containing up to 4 carbon atoms, and R is a member selected from the group consisting of alkyl groups containing up to 4 carbon atoms and aralkyl groups with up to 10 carbon atoms; and group B wherein R and R are members of the same heterocyclic group; where Z is a member selected from the group consisting of alkoxy, arylated alkoxy, aryloxy, alkylthio and the group wherein R and R are members selected from the groups consisting of: group C wherein R is selected from the group consisting of hydrogen, alkyl groups containing up to 4 carbon atoms, hydroxy alkyl groups having up to 4 carbon atoms and R is a member selected from the group consisting of alkyl groups containing up to 4 carbon atoms, hydroxy alkyl groups containing up to 4 carbon atoms and aralkyl groups with up to 10' carbon atoms; and group D wherein R and R are members of the same heterocyclic group; X is a member selected from the group consisting of hydrogen, halogen and methyl; and Y is the anion of an acid.
The present invention is closely related to the invention described in our co-pending application Ser. No. 311,220 filed Sept. 24, 1963, now US. Patent 3,272,630, issued Sept. 13, 1966 and should be considered in the light of the disclosure contained therein. In our co-pending application referred to, a reproduction material had been described comprising a sheet-like support and a light-sensitive diazotype layer coated on said support, which layer comprises a light-sensitive diazonium compound of nearly the above formula.
One kind of the light-sensitive reproduction material in accordance with the present invention contains as light-sensitive substance a diazonium compound of the following formula:
in which X represents the members required to complete a heterocyclic ring selected from the group consisting of S-membered and 6-membered heterocyclic rings, X is selected from the group consisting of hydrogen and alkyl, and R and R4 are members of one of the groups selected from Group A in which R and R are selected from the group consisting of hydrogen, alkyl up to 4 carbon atoms,
3 and hydroxy alkyl with up to 4 carbon atoms, and Group B in which R and R are members of the same heterocyclic ring.
Reproduction materials utilizing the present invention can be used both for the dry and for the semi-wet processes. According to the coupler used, dark colors such as deep brown or violet can be prepared with great speed.
Therefore one object of the present invention is to provide a light-sensitive, diazotype reproduction material utilizing a diazonium compound which can be used for the dry and for the semi-wet processes.
Another object is to provide a light-sensitive, diazotype reproduction material which has excellent photosensitivity, good stability, and good compatibility with additives and stabilizers.
Other objects will become apparent during the course of the following specification.
The diazo compounds are generally used as the diazonium chloride in the form of double salts with metal halides such as zinc chloride or cadmium chloride. Other forms such as sulfates, phosphates or borofluorides may also be used.
The diazo compounds were simply obtained according to methods known in the literature particularly where the compounds contain a heterocyclic ring in the para position to the diazo group. In such a case 2-chloro-5-nitrophenol e.g. was etherified with epichlorhydrin in the presence of an alkali, and the epoxide ring in the ether side chain was split and substituted by suitable agents. Subsequently the nuclear chlorine atom was replaced by a heterocyclic base containing a secondary nitrogen atom, the nitro compound reduced, and the product diazotized.
If the diazo compound used is a p-dialkylamino-benzenediazonium compound, the starting material may be o-nitrophenol which is etherified in the above explained manner. The nitro compound thus obtained is reduced and dialkylated according to one of the methods which are commonly known for reducing and dialkylating respectively. The substitution of an amino group in the para position of the dialkylamino group is achieved by coupling with a diazo compound to form an azo dyestufi and subsequent reductive splitting of the azo group of the dyestuff; instead of coupling, a nitroso or a nitro group may be substituted to the benzene nucleus by a known method with subsequent reduction of the nitroso or nitro group. The amino group is finally converted into the diazo group by the application of nitrous acid.
It should be understood that the products obtained according to the present process may also be obtained according to difierent reaction sequences.
Detailed descriptions of the properties and of the production of various compounds are given by the examples wherein the volume unit is milliliters and the weight unit is 1 gram. The formulas of some of the new diazonium compounds according to the present invention are in the table. The melting points in degrees centigrade of the nitro compounds (nitro group in the p-position to the NR R group) which are the basic materials for these diazonium salts are: (1) 94 C., (2) 92 C., (3) 92 C., (4) 198 C. (as HCl salt), (5) 108-109" C., (6) 131 C., (7) 78-79 C., (8) 101 C. The figures 1 to 8 correspond to the figures of the formulas in the table.
mol-znoll-nor Lil -ZI I 0-CHi-CHOH-CH2-NH-C4HD NaCl-ZnClz-HCI NaCl-ZnCh-HCI Zh'll Example 1 Citric acid 4.0 Thiourea 5.0 Aluminium sulfate 3.0 1,3,6-naphthalene trisulfonic acid sodium salt 3.5 2,7-dihydroxy naphthalene-3,6-disulfonic acid sodium salt 2.4 Zinc chloride 1.0 Diazo product of 1-amino-4-pyrrolidino-3-(gammahydroxy ethyl-amino-beta-hydroxy-propoxy) benzene in the form of its zinc chloride double salt of hydrochloric acid (Formula 6) 2.3
per 100 parts by volume of water. After drying the sensitized raw paper was exposed behind a transparent master and developed with ammonia. Blue images on a white background were obtained. The reproduction paper had an excellent shelf life.
The diazo compound employed was obtained by the following procedure. 173 parts by weight of 2-chloro-5- nitrophenol were dissolved in 250 parts by volume of methyl glycol, 176 parts by weight of epichlorhydrin were added and heated nearly to the boiling point. Then 100 parts by volume of 40% soda were gradually dropped into the solution without further heating. After addition of the soda, the mixture was refluxed for one hour. Then the warm solution was filtered, 100 parts by volume of water were added, cooled and the residue was drawn 01?. The latter was dried and recrystallized from methanol. The yield was 183 parts by weight melting at 93 C.
45 parts by volume of 2-chloro-5-nitro-phenyl glycidyl ether in 100 parts by volume of dioxane were dropped while cooling with ice into a solution of 120 parts by weight of ethanolamine in 100 parts by volume of dioxane under agitation within two hours. Then the solution was maintained fifteen hours at room temperature, poured on water, the residue drawn 01f and dried. The crude yield was 55 parts -by weight of 1-nitro-4-chloro-3-(gamma-hydroxy ethyl-amino-beta-hydroxy-propoxy)-benzene melting at 132133 C.
55 parts by weight of this intermediate product were heated to boiling temperature with 70 parts by volume of pyrrolidine and parts by volume of water during three hours, poured on water, drawn oil and recrystallized from methanol. The yield was 40 parts by weight of 1-nitro-4- pyrrolidino-3-(gamma hydroxy ethylamino beta-hydroxy-propoxy)-benzene melting at 131 C.
40 parts by weight of 1-nitro-4-pyrrolidino-3-(gammahydroxy-ethylamino-beta hydroxy propoxy)-benzene in 86 parts by volume of concentrated hydrochloric acid and 40 parts by volume of water were reduced while cooled with ice with zinc dust to 1-amino-4-pyrrolidino-3- (gamma-hydroxyethylamino-beta hydroxy propoxy)- benzene. The filtered solution was added to 37 parts by volume of hydrochloric acid and diazotized with 62 parts by volume of 2 N sodium nitrite solution under cooling with ice. The precipitated diazo compound was reprecipitated from a mixture of water and sodium chloride. The yield was 50 parts by weight.
Example 2 A reproduction paper conventionally used for diazotype I purposes having on one side a precoating of colloidal silica and polyvinyl acetate was coated on the pretreated surface with a solution containing:
6 3,5-dihydroxy-4-bromo-benzoic-2-diethylamino anilide Zinc chloride Diazo compound of 1-amino-4-pyrrolidino-3-(gamama-di-n-proylamino-beta hydroxy-propoxy)-benzene in the form of its zinc chloride double salt of hydrochloric acid (Formula 7) 2.2
per 100 parts by volume of water. The process according to Example 1 was followed and red images on a white background were obtained.
The diazo compound was obtained by the following procedure. parts by weight of 2-chloro-5-nitropheny1- glycidylether were heated with 60 parts by volume of din-propylamine during three hours on a steam bath. Then ice water was added and the precipitated product was drawn off and dried. The crude yield was parts by weight melting at 41-42" C. Further processing was effected with good yields analogous to the method described in Example 1.
Similar results were obtained if the compounds of the Formulas 1-5 and 8 were used which may be obtained analogously to the compound of Formula 6. In Formula 5, the N-n-butyl compound and in Formula 7 the N-di-npropyl compound were used.
It is apparent that the described examples are capable of many variations and modifications. All such variations and modifications are to be included within the scope of the present invention.
What is claimed is:
1. A diazotype reproduction material which comprises a support and a photosensitive layer coated on said support, said layer comprising a diazonium compound having the formula:
in which X represents the members required to complete a heterocyclic ring selected from the group consisting of S-membered and 6-membered heterocyclic rings, X is selected from the group consisting of hydrogen and alkyl, R and R are members of one of the groups selected from: Group A in which R is alkyl up to 4 carbon atoms and hydroxyalkyl with up to 4 carbon atoms, and R is hydrogen, alkyl up to 4 carbon atoms, and hydroxyalkyl with up to 4 carbon atoms; and Group B in which R; and R are members of the same 5- or 6-membered heterocyclic ring, and Y is the anion of an acid.
2. A diazotype reproduction material which comprises a support and a photosensitive layer coated on said support, said layer comprising a diazonium compound selected from the group consisting of 4-pyrrolidino-3-(gamma-diethyl-amino beta hydroxypropoxy) -benzene diazonium chloride; 6-methyl-4-pyrrolidino-3- gamma-diethylamino-betahydroxy-propoxy)-benzene diazonium chloride; 4-pyrrolidino-3- gamma-pyrrolidino-beta-hydroxypropoxy)-benzene diazonium chloride; 4-morpholino-3 gamma-morpholino-beta-hydroxypropoxy)-benzene diazonium chloride; 4-pyrrolidino-3-(gamma-n-butylaminobeta-hydroxypropoxy)-benzene diazonium chloride; 4-pyrrolidino-3-(gamma-hydroxyethylamino-betahydroxy-propoxy)-benzene diazonium chloride; 4-pyrrolidino-3- gamma-di-n-propylamino-beta-hydroxypropoxy)-benzene diazonium chloride; and 4-pyrrolidino-3-(-gamma-di-hydroxyethylamino-beta hydroxy-propoxy)-benzene diazonium chloride.
3. A material in accordance with claim 1 in which said diazonium compound is 4-pyrrolidino-3-(gamma-di-ethylamino-beta-hydroxy-propoxy)-bcnzene diazonium chloride.
4. A material in accordance with claim 1 in which said diazonium compound is 4-pyrrolidino-3-(gamma-n-butylamino-beta-hydroxy-propoxy)-benzene diazonium chloride.
5. A material in accordance with claim 1 in which said diazonium compound is 4-pyrrolidino-3-(gamma-dihydroxyethylarnino-bcta-hydroxy propoxy)-benzene diazonium chloride.
6. A material in accordance with claim 1 in which said diazonium compound is 4-pyrrolidino 3 (gamma-hydroxyethylaminmbeta hydroxy propoxy)-benzene diazonium chloride.
diazonium compound is 4-pyrrolidino-3-(gamma-di-npropylamino beta-hydroxy-propoxy)-benzene diazonium chloride.
References Cited UNITED STATES PATENTS 3,272,630 9/1966 Rauhut et a1. 9691 XR 3,281,245 10/1966 Werner et a1 9691 3,281,246 10/1966 Rauhut et a1 96-91 10 J. TRAVIS BROWN, Primary Examiner.
C. BOWERS, Assistant Examiner.
US. Cl. X.R.
7. A material in accordance with claim 1 in which said 15 260-141
US425921A 1962-09-26 1965-01-15 Reproduction material Expired - Lifetime US3432301A (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
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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US547721A Expired - Lifetime US3459551A (en) 1962-09-26 1966-05-05 Diazotype material

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CH (3) CH439960A (en)
DE (5) DE1226879B (en)
DK (2) DK114170B (en)
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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
US20030114423A1 (en) * 2001-08-30 2003-06-19 Chemocentryx, Inc. Arylamines as inhibitors of chemokine binding to US28

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1249683B (en) * 1962-09-26 1967-09-07 Kalle Aktiengesellschaft, Wiesbaden Biebrich Photosensitive copying material with p-phenylenediamine derivative diazotized on one side as a photosensitive substance
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
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.
DE102013220789A1 (en) * 2013-10-15 2015-04-16 Henkel Ag & Co. Kgaa Antiperspirant cosmetic products containing aromatic sulfonic acids

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
US3281246A (en) * 1964-11-30 1966-10-25 Keuffel & Esser Co Diazotype reproduction material
US3281245A (en) * 1962-03-09 1966-10-25 Keuffel & Esser Co Diazotype material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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
BE600885A (en) * 1960-03-04
DE1255486C2 (en) * 1963-09-14 1973-04-19 Kalle Ag Two component diazotype material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3281245A (en) * 1962-03-09 1966-10-25 Keuffel & Esser Co Diazotype material
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 (6)

* 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
US20030114423A1 (en) * 2001-08-30 2003-06-19 Chemocentryx, Inc. Arylamines as inhibitors of chemokine binding to US28
US20030149055A1 (en) * 2001-08-30 2003-08-07 Chemocentryx Bicyclic compounds as inhibitors of chemokine binding to US28
US6821998B2 (en) 2001-08-30 2004-11-23 Chemocentryx, Inc. Arylamines as inhibitors of chemokine binding to US28
US7101894B2 (en) 2001-08-30 2006-09-05 Chemocentryx, Inc. Bicyclic compounds as inhibitors of chemokine binding to US28
EP1465488A4 (en) * 2001-08-30 2007-04-18 Chemocentryx Inc Arylamines as inhibitors of chemokine binding to us28

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DK114170B (en) 1969-06-02
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US3459551A (en) 1969-08-05
DE1289736B (en) 1969-02-20
DE1249683B (en) 1967-09-07
FI44335B (en) 1971-06-30
FI44191B (en) 1971-06-01
NL149294B (en) 1976-04-15
SE329331B (en) 1970-10-05
DK116488B (en) 1970-01-12
CH439960A (en) 1967-07-15
NL6414808A (en) 1965-07-19
DE1249682B (en) 1967-09-07
DE1226879B (en) 1966-10-13
NL6413684A (en) 1965-11-25
NL6605723A (en) 1966-11-10
SE327134B (en) 1970-08-10
US3272630A (en) 1966-09-13
GB1062918A (en) 1967-03-22
US3462271A (en) 1969-08-19
BE680701A (en) 1966-11-07
CH468024A (en) 1969-01-31
SE340043B (en) 1971-11-01
SE340042B (en) 1971-11-01
SE301420B (en) 1968-06-04
NL6606212A (en) 1966-11-10
GB1122249A (en) 1968-07-31
NL140344B (en) 1973-11-15
BE651969A (en) 1965-02-18
GB1001493A (en) 1965-08-18
NL141657B (en) 1974-03-15
GB1122104A (en) 1968-07-31
NL297944A (en)

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