US3736143A - Light-sensitive diazonium compounds and diazotype materials - Google Patents

Light-sensitive diazonium compounds and diazotype materials Download PDF

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US3736143A
US3736143A US00098061A US3736143DA US3736143A US 3736143 A US3736143 A US 3736143A US 00098061 A US00098061 A US 00098061A US 3736143D A US3736143D A US 3736143DA US 3736143 A US3736143 A US 3736143A
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amino
chloro
diazonium
benzene diazonium
melting point
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H Frommeld
S Scheler
A Brauninger
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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
    • C07D295/04—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
    • 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

  • Benzene diazonium compounds carrying a tertiary amino group in 4-position to the diazonium group have been used as light-sensitive substances in the diazotype field for a relatively long time.
  • These compounds may contain further substituents in the benzene ring, preferably in the 2- and 5 or 2- and 3-positions to the diazonium group, e.g. acylamino groups, alkoxy groups or halogen atoms.
  • the properties of the said compounds which make them suitable for the diazotype field are substantially determined by the said substituents.
  • Diazonium compounds for one-component diazotype materials are repeatedly described in the literature.
  • Dutch published patent application No. 6,610,037 discloses compounds carrying a halogen atom in the 2- and 3-positions to the diazonium group
  • British patent specification No. 1,082,889 discloses compounds carrying an acylamino group in 2-position to the diazonium group and an alkoxy radical in 3-position.
  • the coupling speed of all these compounds is not sufiicient for the present requirements, since one-component diazotype materials have increasingly been preferred which can be developed with weakly acid developers.
  • French patent specification No. 93,482 discloses compounds carrying an acylamino group in 2-position and a phenoxy radical in 5-position. These compounds couple somewhat more rapidly, but their coupling speed is not entirely satisfactory in an acid medium. Furthermore, they have the disadvantage that they generally form azo dyestutr's which have a relatively poor absorption in the ultraviolet range of the spectrum.
  • the present invention provides benzene diazonium compounds deriving from the unilaterally diazotized pphenylenediamine, which are characterized by the general formula:
  • R ⁇ /R2 N R4- Ra Ra RflOn 0C N NzX wherein R and R are alkyl, aralkyl or cycloalkyl radicals or,
  • R and R are hydrogen or halogen, one of which is hydrogen;
  • R and R are alkyl, aralkyl, cycloalkyl or aryl radicals
  • n 0 or 1
  • X is an anion
  • the diazonium compounds of the invention are distinguished from the known compounds by an increased coupling speed, good light-sensitivity and stability.
  • the compounds of the invention preferably are used in one-component diazotype material.
  • This material has a satisfactory light-sensitivity and can be developed with alkaline as well as with weakly acid buttered developer solutions.
  • the advantage of the high coupling speed of the diazonium compounds of the invention plays an important part in development in a neutral or weakly acid medium since at such a pH value development generally is performed more slowly.
  • the compounds of the invention may also be used in two-component diazotype materials which are developed by ammonia vapor or by heating.
  • R and R may be alkyl, aralkyl or cycloalkyl radicals which may be unsaturated or, in known manner, carry further substituents, e.g. halogen, hydroxy or amino groups.
  • substituents e.g. halogen, hydroxy or amino groups.
  • alkyl groups of 1 to 4 carbon atoms Preferably used are alkyl groups of 1 to 4 carbon atoms, aralkyl groups of 7 to 10 carbon atoms and clycloalkyl groups of 5 to 7 carbon atoms.
  • R and R together with the tertiary nitrogen atom, form a heterocyclic radical this radical may derive, eg from pyrrolidine, piperidine, piperazine, N-methylpiperazine, N acylpiperazine, thiomorpholine, morpholine, hexamethyleneimine, and the like, and again be substituted.
  • the mode of action of these radicals is known in the diazotype field.
  • halogen atom R or R is chlorine. But also other compounds may be used in which R or R is bromine, fluorine or iodine.
  • the acylated secondary amino group includes the acyl radical COO -R which may derive from an aliphatic or aromatic carboxylic acid (11:0) as well as from a carbonic acid semiester (11:1), an urethane grouping resulting with the aminonitrogen atom.
  • R and R may be alkyl, aralkyl, cycloalkyl, and aryl radicals. Preferably used are alkyl groups with 1 to 7, aralkyl groups with 7 to 10, and cycloalkyl groups with 5 to 7 carbon atoms.
  • the radicals R and R may also be substituted. Preferred substituents are alkoxy groups, halogen atoms or substituted amino groups.
  • X is one of the anions usual in the diazotype field, which form stable diazonium salts.
  • the diazonium salt may be present, [for example, as a chloride, sulphate, tetrafluoroborate, hexafluorophosphate or as a double salt with zinc chloride, tin tetrachloride, cadmium chloride, and the like.
  • benzene diazonium compounds of the invention are:
  • the melting points'referred to above are of the corresponding nitro compounds which are reduced and diazotized to form the indicated diazonium compounds.
  • 2,5-dichloro-aniline is acetylated, nitrated and deacetylated.
  • 2,5-dichloro-4nitro-aniline is then alkylated, e.g. methylated.
  • a primary amine e.g. butyl amine
  • 2 chloro-4-nitro-5-buty1amino-N,N-dimethyl-aniline is obtained, which is then acylated, reduced and diazotized.
  • the starting material is 3,4-dichloro-aniline, which is acetylated, nitrated and deacetylated.
  • 3,4-dichloro-6-nitro-aniline is reacted, for example, with morpholine and, via a subsequent Sandmeyer reaction, 2,5-dichloro 4 morpholinonitrobenzene is obtained.
  • the reaction with 'y-methoxypropylamino for example, yields 2-nitro-4-chloro-5-morpholino-N-y-methoxy-propyl) aniline which is reacted with chloroformic acid ethyl ester and then reduced and diazotized.
  • the base of the diazotype material produced with the compounds of the invention may be opaque, such as paper, linen, coated papers and metallic materials or translucent, such as coated and uncoated tracing papers or transparent, such as for example cellulose acetate, polyester or polycarbonate films.
  • the diazonium compound preferably is incorporated together with the usual additives into a hydrophilic film layer which has been applied to the surface of the hydrophobic base.
  • a transparent base e.g. natural transparent paper, transparentized paper, tracing cloth or polyester film, which carries on the surface a hydrophilic film layer,
  • the base is transparent or at least translucent, particularly the diazotype material produced therewith is very suitable for the production of intermediate originals.
  • the light-sensitive layer of the diazotype material may contain the usual additives, e.g. acids, such as citric acid, tartaric acid, boric acid, sulph'osalicylic acid, stabilizers, such as naphthalene- 1,3,6-trisulphonic acid and its water-soluble salts, antioxidants, such as thiourea, metal salts, such as aluminum sulphate, binders, such as gelatin, gum arabic and synthetic resin as well as silica dispersions.
  • acids such as citric acid, tartaric acid, boric acid, sulph'osalicylic acid, stabilizers, such as naphthalene- 1,3,6-trisulphonic acid and its water-soluble salts, antioxidants, such as thiourea, metal salts, such as aluminum sulphate, binders, such as gelatin, gum arabic and synthetic resin as well as silica dispersions.
  • acids such as citric acid, tartaric acid, boric acid
  • Example 1 White photoprinting base paper is provided with a precoat of finely divided silica and polyvinyl acetate and then coated with a solution of 0.5 g. of citric acid 3.5 g. of the sodium salt of naphthalene-1,3,6-trisulphonic acid, and
  • the pH value of the solution is about 6.
  • the copies have strong brown-violet lines which become visible immediately upon the application of the developer liquid.
  • Example 2 Natural transparent paper is coated with a solution of:
  • the material is exposed to light under an opaque line drawing and the latent image is developed according to the so-called thin-layer method by applying the following solution:
  • the pH value is about 7.0.
  • Example 3 Transparent paper is lacquered with acetyl cellulose and the lacquer layer is superficially hydrolyzed up to a depth of about 3.5 After the removal of the chemicals used for hydrolysis by washing with water, the hydrophilic surface is sensitized with the following solution:
  • Example 1 The material is exposed to light under an original and developed with the solution indicated in Example 1.
  • the copy obtained has violet lines on a transparent background and is very suitable as an intermediate original. Similarly good results are obtained with the compounds Nos. 26, 34 and 37.
  • Example 4 White photoprinting base paper is provided with a precoat of rice starch and polyvinyl acetate and then sensitized with a solution of:
  • citric acid 4.0 g. of the sodium salt of naphthalene-1,3,6-trisulphonic acid, and I 2.0 g. of 2-(N-cyclohexyl-N-acetyl-amino)-3-chloro-4-dimethylamino-benzene diazonium chloride, zinc chloride double salt (No. 6)
  • an unexposed strip is developed according to the so-called thinlayer method in a grooved-roller machine with the developer of Example 1 and, immediately upon leaving the machine, cut into three parts. Further development is stopped on Part I 15 seconds, and on Part II 30 seconds after the application of the developer by exposure to a strong light source, whereas Part III, for achieving the maximum color density, is passed a second time through the developing machine. In the case of this material, after 15 seconds 89% and after 30 seconds 96% of the maximum density are achieved.
  • Example 5 White photoprinting base paper is coated with a solution of:
  • the pH value of this liquid is about 9.5.
  • Example 6 White photoprinting base paper is provided with a precoat from rice starch and polyvinyl acetate and then coated with a solution of 0.3 g. of gum arabic 0.5 g. of citric acid 0.02 g. of saponin, and
  • Transparent paper lacquered with acetyl cellu'ose is superficially hydrolyzed to a depth of about 3.0, and the hydrophilic surface thus obtained is coated with a solution of:
  • the image areas of the copy obtained with Material A1 have a transmission of 6.5% at 405 nm. Under the same conditions the image areas of the copy obtained with Material B1 have a transmission of 13.0%.
  • R is methyl or ethyl
  • R is alkyl of 1-4 carbon atoms, cyclohexyl, or benzyl; or
  • R and R together with the nitrogen atom form a piperidine, piperazine, pyrrolidine, morpholine, or
  • R and R are hydrogen, chlorine, or bromine, one of which is hydrogen, the other being halogen;
  • R is alkyl of 1-7 carbon atoms, aralkyl of 7-10 carbon atoms, cyclohexyl, or (B-piperidino)-ethyl;
  • R is acetyl, ethoxy carbonyl, chloroacetyl, benzyloxycarbonyl, or benzoyl;
  • X is an anion
  • Diazotype material comprising a support having a coating thereon of a composition consisting essentially of a light-sensitive diazonium compound according to claim 1.

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Abstract

DIAZOTYPE MATERIAL OF INCREASED LIGHT-SENSITIVITY AND RATE OF DYE IMAGE DEVELOPMENT IS OBTAINED WITH AN ORTHOACYLAMINO - META - HALO-PARA-AMINO BENZENE DIAZONIUM COMPOUND. ONE-COMPONENT MATERIAL CAPABLE OF RAPID NEUTRAL DEVELOPMENT MAY BE PREPARED, AS WELL AS TWOCOMPONENT MATERIAL WHEN UTILIZING COUPLERS OF LOWER ACTIVITY.

Description

United States Patent 3,736,143 LIGHT-SENSITIVE DIAZONIUM COMPOUNDS AND DIAZOTYPE MATERIALS Hans-Dieter Fromrneld, Wiesbaden-Biebrich, Siegfried Scheler, Wiesbaden-Schierstein, and Arno Brauninger, Wiesbaden-Biebrich, Germany, assignors to Keufiel & Esser Company, Morristown, N .J.
No Drawing. Filed Dec. 14, 1970, Ser. No. 98,061 Claims priority, application Germany, Dec. 17, 1969, P 19 63 252.1 Int. Cl. G03c 1/54 U.S. Cl. 96-91 R 2 Claims ABSTRACT OF THE DISCLOSURE Diazotype material of increased light-sensitivity and rate of dye image development is obtained with an orthoacylamino meta halo-para-amino benzene diazonium compound. One-component material capable of rapid neutral development may :be prepared, as Well as twocomponent material when utilizing couplers of lower activity.
BACKGROUND OF THE INVENTION Benzene diazonium compounds carrying a tertiary amino group in 4-position to the diazonium group have been used as light-sensitive substances in the diazotype field for a relatively long time. These compounds may contain further substituents in the benzene ring, preferably in the 2- and 5 or 2- and 3-positions to the diazonium group, e.g. acylamino groups, alkoxy groups or halogen atoms. The properties of the said compounds which make them suitable for the diazotype field are substantially determined by the said substituents.
It is also known that, for the production of one-component diazotype materials, rapidly coupling diazonium compounds are preferably used, since only then the dyestuif formation during development occurs at a reasonable speed. If the dyestuif formation occurs too slowly, the water-soluble diazonium compound diliuses during development from the non-exposed into the exposed portions of the reproduction material. Undersirable blurred lines are then obtained.
Diazonium compounds for one-component diazotype materials are repeatedly described in the literature. Dutch published patent application No. 6,610,037 discloses compounds carrying a halogen atom in the 2- and 3-positions to the diazonium group, British patent specification No. 1,082,889 discloses compounds carrying an acylamino group in 2-position to the diazonium group and an alkoxy radical in 3-position. The coupling speed of all these compounds is not sufiicient for the present requirements, since one-component diazotype materials have increasingly been preferred which can be developed with weakly acid developers. The same applies to compounds carrying an alkylmercapto group in Z-position and a halogen atom in 3-position to the diazonium group.
French patent specification No. 93,482 discloses compounds carrying an acylamino group in 2-position and a phenoxy radical in 5-position. These compounds couple somewhat more rapidly, but their coupling speed is not entirely satisfactory in an acid medium. Furthermore, they have the disadvantage that they generally form azo dyestutr's which have a relatively poor absorption in the ultraviolet range of the spectrum.
A still higher coupling speed is exhibited by the compounds carrying an acylamino group in 2-position to the diazonium group and an alkoxy group in 5-position and in which, contrary to the above compounds, the 4-position is occupied by a thioether or acylamino radical ICC rather than a tertiary amino group (British patent specifications Nos. 1,064,129, and 1,045,242; U.S. patent application Ser. No. 883,302 and German published patent application No. 1,256,065). These compounds have the disadvantage, however, that they are relatively insensitive to light.
SUMMARY OF THE INVENTION The present invention provides benzene diazonium compounds deriving from the unilaterally diazotized pphenylenediamine, which are characterized by the general formula:
R{\ /R2 N R4- Ra Ra RflOn 0C N NzX wherein R and R are alkyl, aralkyl or cycloalkyl radicals or,
together with the nitrogen atom, a heterocyclic radical;
R and R, are hydrogen or halogen, one of which is hydrogen;
R and R are alkyl, aralkyl, cycloalkyl or aryl radicals;
n stands for 0 or 1; and
X is an anion.
The diazonium compounds of the invention are distinguished from the known compounds by an increased coupling speed, good light-sensitivity and stability.
The compounds of the invention preferably are used in one-component diazotype material. This material has a satisfactory light-sensitivity and can be developed with alkaline as well as with weakly acid buttered developer solutions. The advantage of the high coupling speed of the diazonium compounds of the invention, of course, plays an important part in development in a neutral or weakly acid medium since at such a pH value development generally is performed more slowly.
In combination with very slowly coupling azo components, e.g. 7' hydroxy 1,2,4,5 naphthimidazole or 2-hydroxy 8 biguanidino-naphthalene, the compounds of the invention may also be used in two-component diazotype materials which are developed by ammonia vapor or by heating.
DESCRIPTION OF THE INVENTION In the compounds of the invention, R and R may be alkyl, aralkyl or cycloalkyl radicals which may be unsaturated or, in known manner, carry further substituents, e.g. halogen, hydroxy or amino groups. Preferably used are alkyl groups of 1 to 4 carbon atoms, aralkyl groups of 7 to 10 carbon atoms and clycloalkyl groups of 5 to 7 carbon atoms. If R and R together with the tertiary nitrogen atom, form a heterocyclic radical, this radical may derive, eg from pyrrolidine, piperidine, piperazine, N-methylpiperazine, N acylpiperazine, thiomorpholine, morpholine, hexamethyleneimine, and the like, and again be substituted. The mode of action of these radicals is known in the diazotype field.
For economical reasons and because of the easy accessibility, the preferably selected halogen atom R or R is is chlorine. But also other compounds may be used in which R or R is bromine, fluorine or iodine.
In the compounds of the invention the acylated secondary amino group includes the acyl radical COO -R which may derive from an aliphatic or aromatic carboxylic acid (11:0) as well as from a carbonic acid semiester (11:1), an urethane grouping resulting with the aminonitrogen atom.
R and R may be alkyl, aralkyl, cycloalkyl, and aryl radicals. Preferably used are alkyl groups with 1 to 7, aralkyl groups with 7 to 10, and cycloalkyl groups with 5 to 7 carbon atoms. The radicals R and R may also be substituted. Preferred substituents are alkoxy groups, halogen atoms or substituted amino groups.
X is one of the anions usual in the diazotype field, which form stable diazonium salts. The diazonium salt may be present, [for example, as a chloride, sulphate, tetrafluoroborate, hexafluorophosphate or as a double salt with zinc chloride, tin tetrachloride, cadmium chloride, and the like.
Examples of the benzene diazonium compounds of the invention are:
( 1 2-(N-methyl-N-acetyl-amino) -3-chloro-4-dimethylamino-benzene diazonium hydrogen sulphate (melting point 121 C.)
(2) 2- N-methyl-N-ethoxycarbonyl-amino -3-chloro- 4-dimethylamino-benzene diazonium hydrogen sulphate (melting point 75 C.)
(3 2- N-propyl-N-ethoxycarbonyl-amino -4-dimethylamino-S-chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 82 C.)
(4) 2-N-propyl-Nbenzyloxycarbonyl-amino)-4-dimethylarnino-S-chloro-benzene diazonium tetrafluorobor ate (oil) (5 2- (N-cyclohexyl-N-acetyl-amino -4-dimethylamino- S-chloro-benzene diazonium tetrafiuoroborate (melting point 138 C.)
(6) 2- (N-cyclohexylacetylamino)-3-chloro-4- dimethylamino-benzene diazonium chloride, zinc chloride double salt (melting point 88 C.)
(7) 2- (N-cyclohexyl-N-ethoxycarbonyl-amino)-4- dimethylamino-S-chloro-benzene diazonium tetrafluoroborate (melting point 83 C.)
(8) 2- (N-n-butyl-N-acetyl-amino -4-dimethylamino- S-chloro-benzene diazonium tetrafluoroborate oil) (9) 2- (N-benzyl-N-acetyl-amino)-4-dimethylamino5- chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 83 C.)
(10) 2-(N-benzyl-N-acetyl-amino)-3-chloro-4-dimethylamino-benzene diazonium tetrafluoroborate (melting point 114 C.)
( 1 1) 2- (N-benzyl-N-ethoxycarbonyl-amino -4-dimethylarnino-S-chloro-benzene diazonium tetrafluoroborate (melting point 69 C.)
( 12) 2- (N-benzyl-N-ethoxycarb onyl-amino -3-chloro- 4-dimethylamino-benzene diazonium tetrafluoroborate (melting point 93 C.)
( 13) 2- [N- j3-phenyl-ethyl -N-ethoxycarbonylamino]-4-dimethylamino-5-chloro-benzene diazonium chloride, zinc chloride double salt (melting point 91 to 92 C.)
( 14) 2- N-methyl-N-ethoxycarbonyl-amino -4- (N- methyl-N-n-butylamino) -5-chloro-benzene diazonium tetrafiuoroborate 15) 2- (N-methyl-N-acetyl-amino) -4- N-methyl-N- cycloheXyl-arnino)-5-chloro-benzene diazonium chloride, Zinc chloride double salt (melting point 120 to 121 C.)
( 16) 2- N-rnethyl-N-ethoxycarbonyl-amino) -4- (N- methyl-N- cycloh exyl-amino -5-chlorobenzene diazonium tetrafiuoroborate (oil) 17 2- (N-methyl-N-acetyl-amino) -4- (N-methylbenzyl-amino) -5-chloro-benzene diazonium chloride, zinc chloride double salt (oil) (18) 2-(N-cyclohexyl-N-acetyl-amino)-4-diethylamino-S-chloro-benzene diazonium tetrafluoroborate (melting point 112 to 113 C.)
( 19) 2- (N-cyclohexyl-N-chloroacetyl-amino) -4-diethylamino-S-chloro-benzene diazonium tetrafluoroborate (melting point 93 to C.)
(20) 2-(N-cyclohexyl-N-ethoxycarbonyl-amino)-4- diethylamino-S-chloro-benzene diazonium tetrafluoroborate (melting point to 106 C.)
(21 2- (N-benzyl-N-ethoxycarbonyl-amino) -3- chloro-4-diethylaminobenzene diazonium tetrafluoroborate (melting point 76 to 78 C.)
(22) 2-(N-methyl-N-acetyl-amino)-4-pyrrolidino-5- chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 140 to 142 C.)
(23 2- (N-cyclohexyl-N-acetyl-amino) -4-pyrrolidino- S-chloro-benzene diazonium chloride, zinc chloride double salt (melting point 167 C.)
(24) 2-(N-cyclohexyl-N-ethoxycarbonyl-amino)-4-pyrrolidino-5-chloro-benzene diazonium chloride, zinc chloride double salt (melting point 128 C.)
(25 2- (N-benzyl-N-ethoxycarbonyl-amino) -4-pyrrolidino-S-chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 114 C.)
(26 2- N-methyl-N-acetyl-amino) -4-piperidino-5 chloro-benzene diazonium tetrafluoroborate (melting point 130 to 131 C.)
(27) 2-(N-methyl-N-ethoxycarbonyl-amino)-4-piperidino-S-chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 71 to 72 C.)
(28 2- (N-propyl-N-acetyl-amino) -4-pi=peridino-5- chloro-benzene diazonium chloride, tin tetrachloride double salt (29) 2 [N (,B-diethylamino-ethyl)N-acetyl-amino]-4- piperidino-S-chloro-benzene diazonium hexafluorophosphate hexafiuorophosphoric acid (30) 2 [N (6 piperidino-ethyl)-N-aoetyl-arnino]-4- piperidino-S-chloro-benzene diazonium hexafluorophosphate hexafluorophosphoric acid (31) 2 (N methyl N acetyl-amino)-4-(4'-methylpiperidino) 5 chloro-benzene diazonium tetrafluor borate (melting point 129 to 130 C.)
(32) 2 (N-methyl-N-acetyl-amino)-4- (3-methyl-piper idino)-5-ch1oro-benzene diazonium chloride, tin tetrachloride double salt (33) 2 (N methyl-N-ethoxycarbonyl-amino)-4-heptamethyleneimino-S-chloro-benzene diazonium hydrogen sulphate (melting point 95 to 96 C.)
(34) 2 (N methyl N-acetyl-amino)-4-morpholino-5- chloro-benzene diazonium hydrogen sulphate (melting point 126 to 128 C.) V 1 (35) 2 (N-methyl-N-acetyl-amino) 4- morpholino-S- bromo-benzene diazonium chloride, Zinc chloride double salt (melting point to 127 C.) (36) 2 (N methyl-N-benzoyl-amino)-4 morpho1ino-5- chloro-benzene diazonium chloride, zinc chloride, sodium chloride salt (melting point 122 to 125 C.)
(37) 2 (N-methyl-N-ethoxycarbonyl-amino)-4 morpho- 1ino-5-chloro-benzene diazonium hydrogen sulphate (melting point 99 to 100 C.)
(38) 2 [N ('y-methoxy-propyl)-N-benzyloxycarbonylamino] -4-morpholino-5-chloro-benzene diazonium chloride, tin tetrachloride double salt (39) 2 (N-cyclohexyl-N-acetyl-amino)-4-morpholino-5- chloro-benzene diazonium hydrogen sulphate (melting point 185 C.)
(40) 2 (N-cyclohexyl-N-ethoxycarbonyl-amino)-4-morpholino-S-chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 181 C.)
(41) 2 (N-benzyl-N-acetyl-amino) 4 morpholino-S- chloro-benzene diazonium chloride, zinc chloride double salt (melting point 132 C.)
(42) 2 (N-benzyl-N-ethoxycarbonyl-amino)-4-morpholino-5-chloro-benzene diazonium tetrafiuoroborate (melting point 138 C.)
(43) 2 [N (4' methoxy-phenyl)-N-acetyl-amino]-4- morpholino-S-chloro-benzene diazonium chloride, tin tetrachloride double salt (melting point 170 to 171 C.)
(44) 2 (N methyl-N-acetyl-amino)-4-(3'-methyl-morpholino) 5 chloro-benzene diazonium hydrogen sulphate (melting point 198 to 200 C.)
(45) 2 -(N methyl-N-acetyl-amino) -4-(3,5-dimethylmorpholino) 5 chloro-benzene diazonium hydrogen sulphate (melting point 131 to 134 C.)
(46) 2 (N methyl-N-acetyl-amino)-4- (N-methyl-piperazino)-5-chloro-benzene diazonium chloride, zinc chloride double salt (melting point 178 to 180 C.)
The melting points'referred to above are of the corresponding nitro compounds which are reduced and diazotized to form the indicated diazonium compounds.
For the preparation of the diazonium compounds of the invention, 2,5-dichloro-aniline is acetylated, nitrated and deacetylated. 2,5-dichloro-4nitro-aniline is then alkylated, e.g. methylated. By the reaction with a primary amine, e.g. butyl amine, 2 chloro-4-nitro-5-buty1amino-N,N-dimethyl-aniline is obtained, which is then acylated, reduced and diazotized.
According to a second method of synthesis, the starting material is 3,4-dichloro-aniline, which is acetylated, nitrated and deacetylated. 3,4-dichloro-6-nitro-aniline is reacted, for example, with morpholine and, via a subsequent Sandmeyer reaction, 2,5-dichloro 4 morpholinonitrobenzene is obtained. The reaction with 'y-methoxypropylamino, for example, yields 2-nitro-4-chloro-5-morpholino-N-y-methoxy-propyl) aniline which is reacted with chloroformic acid ethyl ester and then reduced and diazotized.
The base of the diazotype material produced with the compounds of the invention may be opaque, such as paper, linen, coated papers and metallic materials or translucent, such as coated and uncoated tracing papers or transparent, such as for example cellulose acetate, polyester or polycarbonate films. When the surface of the base is hydrophobic as in the case of plastic films, the diazonium compound preferably is incorporated together with the usual additives into a hydrophilic film layer which has been applied to the surface of the hydrophobic base.
An excellent djazotype material is obtained with the use of a transparent base, e.g. natural transparent paper, transparentized paper, tracing cloth or polyester film, which carries on the surface a hydrophilic film layer,
which has been produced by superficial hydrolysis of a lacquer layer from cellulose ester or polyvinyl ester.
When the base is transparent or at least translucent, particularly the diazotype material produced therewith is very suitable for the production of intermediate originals.
In addition to the diazonium compound of the invention and, possibly, a coupling compound, the light-sensitive layer of the diazotype material may contain the usual additives, e.g. acids, such as citric acid, tartaric acid, boric acid, sulph'osalicylic acid, stabilizers, such as naphthalene- 1,3,6-trisulphonic acid and its water-soluble salts, antioxidants, such as thiourea, metal salts, such as aluminum sulphate, binders, such as gelatin, gum arabic and synthetic resin as well as silica dispersions.
PREFERRED EMBODIMENTS.
Example 1 White photoprinting base paper is provided with a precoat of finely divided silica and polyvinyl acetate and then coated with a solution of 0.5 g. of citric acid 3.5 g. of the sodium salt of naphthalene-1,3,6-trisulphonic acid, and
1.7 g. of 2-(N-methyl N-acetyl-amino)-4-(N-methyl-N-cyclohexyl-amino)-5-chloro-benezne diazonium chloride, zinc chloride double salt (No. 15)
in ml. of water and dried.
After imagewise exposure to light, development is carried out with the following solution;
0.33 g. of phloroglucin 9.6 g. of trisodium citrate 2.4 g. of sodium benzoate 0.2 g. of adipic acid 2.0 g. of sodium adipate 5.7 g. of sodium chloride 0.2 g. of the sodium salt of a dialkyl naphthalene sulphonic acid as the wetting agent in 100 ml. of Water.
The pH value of the solution is about 6.
The copies have strong brown-violet lines which become visible immediately upon the application of the developer liquid.
Example 2 Natural transparent paper is coated with a solution of:
0.5 g. of citric acid 3.0 g. of the sodium salt of naphthalene-1,3,6-trisulphonic acid 0.02 g. of saponin, and
3.4 g. of 2-(N-methyl-N-acetyl-amino)-4-(4'-methylpiperidino) 5 chlorobenzene diazonium tetrafluoroborate (No. 31)
30 ml. of water and 20 ml. of isopropanol and dried.
The material is exposed to light under an opaque line drawing and the latent image is developed according to the so-called thin-layer method by applying the following solution:
0.06 g. of phloroglucin 0.4 g. of resorcin 1.5 g. of sodium benzoate 5.0 g. of trisodium citrate 1.0 g. of sodium formate 1.0 g. of thiourea 0.1 g. of the sodium salt of an alkyl naphthalene sulphonic acid as the wetting agent in 100 ml. of water.
The pH value is about 7.0.
7 Immediately upon the application of the developer, the developed image is visible in dark brown lines wh1ch absorb ultraviolet light very well. The copy obtained is thus excellently suitable as an intermediate original for making further copies. Similarly good results are obtained with the compounds Nos. 5, 8, 44 and 45.
Example 3 Transparent paper is lacquered with acetyl cellulose and the lacquer layer is superficially hydrolyzed up to a depth of about 3.5 After the removal of the chemicals used for hydrolysis by washing with water, the hydrophilic surface is sensitized with the following solution:
0.5 g. of citric acid 4.0 g. of the sodium salt of naphthalene-1,3,6-trisulphonic acid 0.1 g. of saponin, and
4.0 g. of 2-(N-benzyl-N-ethoxycarbonyl-amino)-3-chloro- 4-dimethyl-amino-benzene diazonium tetrafluoroborate 85 ml. of water and 15 ml. of isopropanol.
The material is exposed to light under an original and developed with the solution indicated in Example 1. The copy obtained has violet lines on a transparent background and is very suitable as an intermediate original. Similarly good results are obtained with the compounds Nos. 26, 34 and 37.
Example 4 White photoprinting base paper is provided with a precoat of rice starch and polyvinyl acetate and then sensitized with a solution of:
0.5 g. of citric acid 4.0 g. of the sodium salt of naphthalene-1,3,6-trisulphonic acid, and I 2.0 g. of 2-(N-cyclohexyl-N-acetyl-amino)-3-chloro-4-dimethylamino-benzene diazonium chloride, zinc chloride double salt (No. 6)
in 100 ml. of water.
When the diazotype material thus obtained is imagewise exposed to light and developed with the developer described in Example -1, copies with broken-violet lines on a white background are obtained. 1
For the determination of the development speed, an unexposed strip is developed according to the so-called thinlayer method in a grooved-roller machine with the developer of Example 1 and, immediately upon leaving the machine, cut into three parts. Further development is stopped on Part I 15 seconds, and on Part II 30 seconds after the application of the developer by exposure to a strong light source, whereas Part III, for achieving the maximum color density, is passed a second time through the developing machine. In the case of this material, after 15 seconds 89% and after 30 seconds 96% of the maximum density are achieved.
When a material containing, instead of theindicated diazonium compound, an equimolar quantity of the double salt of 2,3-dichloro-4-dimethylamino-benzene diazonium chloride and zinc chloride is treated in the same manner with the same developer, after 15 seconds 57% and after 30 seconds 76% of the maximum color density are achieved. When using 2-ethylmercapto-3-chloro-4-dimethylamino-benzene diazonium tetrafluoroborate instead of the indicated diazonium compound, the corresponding values are 38% after 15 seconds and 55%. after 30 seconds, when using 2-(N-cyclohexyl-N-acetylamino)- 3-methoxy-4-dimethylamindbenzene diazonium tetrafluoro-borate, the corresponding values are 56 ,after 15 seconds and 74% after 30 seconds.
8 Example 5 White photoprinting base paper is coated with a solution of:
0.5 g. of tartaric acid 3.5 g. of the sodium salt of naphthalene-l,3,6-trisulphonic acid, and
2.2 g. of 2-(N-cyclohexyl-N-ethoxycarbonyl-amino)-4- pyrrolidino-5-chloro-benzene diazonium chloride, zinc chloride double salt (NO. 24)
in m1. of water and dried.
After imagewise exposure to light, the material is developed with a solution of:
0.6 g. of phloroglucin 0.6 g. of resorcin 1.5 g. of thiourea 7.2 g. of potassium tetraborate 0.8 g. of potassium hydroxide 0.1 g. of the sodium salt of isopropyl naphthalene sulphonic acid in 100 ml. of water.
The pH value of this liquid is about 9.5.
Copies with red-brown lines are obtained. Similarly good results are obtained when using the compounds Nos. 13, 14, 18 and 23.
Example 6 White photoprinting base paper is provided with a precoat from rice starch and polyvinyl acetate and then coated with a solution of 0.3 g. of gum arabic 0.5 g. of citric acid 0.02 g. of saponin, and
1.76 g. of 2-(N-cyclohexyl-N-ethoxycarbonyl-amino)-4- dimethylamino 5 chloro-benzene diazonium tetrafluoroborate (No. 7)
in 100 ml. of Water and dried (Material A). i
By exposure to light under an original and development with a solution of:
0.4 g. of phloroglucin 0.1. g. of acetoacetanilide 0.25 g. of benzoic acid 1.5 g. of sodium benzoate 15.0 g. of sodium formate, and
0.1 g. of the sodium salt of the mono-(Z-ethyl-hexyl) ester of sulphuric acid in 100 ml. of water, which has a pH value of about 5.8, copies with strong violet lines are obtained.
If the developing speed is determined as described in Example 4, after 5 seconds 87% and after 10 seconds 91% of the maximum density are achieved.
If the diazonium compound of the invention is replaced by an equimolar quantity of 2-(N-cyclohexyl)- N-ethoxycarbonyl-amino)-4-dimethylamino-5- (4 chlo ro-phenoxy)-benzene diazonium hydrogen sulphate described in French Pat. 93,482 (Material B), the corresponding values are 76% after 5 seconds and 86% after 10 seconds. Material A of this example upon development thus needs half the time for achieving 87% of the maximum density than Material B.
Transparent paper lacquered with acetyl cellu'ose is superficially hydrolyzed to a depth of about 3.0, and the hydrophilic surface thus obtained is coated with a solution of:
0.5 g. of citric acid 0.1 g. of saponin, and
3.5 g. of 2-(N-cyclohexyl-N-ethoxycarbonyl-amino)-4- dimethylamino-5-chloro-benzene diazonium tetrafluoroborate (No. 7)
ml. of isopropanol, and 90 ml. of water and dried (Material A1).
Upon exposure to light under an original and development with the above developer, a transparent copy with dark violet lines is obtained which is excellently suitable as an intermediate original for making further copies because the dyestuff has a good absorption for actinic light.
For comparison purposes the same base was coated with a solution containing an equimolar quantity of the above-noted prior compound (Material B1). By exposure to light and development with the same developer, copies with blue-black lines are obtained, which have a much poorer absorption for actinic light.
As compared with the fully exposed background of the copy, the image areas of the copy obtained with Material A1 have a transmission of 6.5% at 405 nm. Under the same conditions the image areas of the copy obtained with Material B1 have a transmission of 13.0%.
What is claimed is:
1. A light-sensitive diazonium compound of the general formula:
wherein R is methyl or ethyl, and
R is alkyl of 1-4 carbon atoms, cyclohexyl, or benzyl; or
R and R together with the nitrogen atom form a piperidine, piperazine, pyrrolidine, morpholine, or
heptamethyleneimino;
R and R are hydrogen, chlorine, or bromine, one of which is hydrogen, the other being halogen;
R is alkyl of 1-7 carbon atoms, aralkyl of 7-10 carbon atoms, cyclohexyl, or (B-piperidino)-ethyl;
R is acetyl, ethoxy carbonyl, chloroacetyl, benzyloxycarbonyl, or benzoyl; and
X is an anion.
2. Diazotype material comprising a support having a coating thereon of a composition consisting essentially of a light-sensitive diazonium compound according to claim 1.
References Cited UNITED STATES PATENTS 3,520,692 7/1970 Knoester et al 96- 91 R 3,416,925 12/1968 Sus et al. 96-91 R 3,547,637 12/1970 Scheler et al 96-75 X 3,261,684 7/1960 Wilders et al 96-49 3,311,475 3/1967 Van Loon et al 96-91 R 3,338,713 8/1967 Hendrickx et a1. 96-91 R 3,028,240 4/1962 Werner et a1. 96-91 R 3,463,639 8/1969 Baltazzi 96-91 R 3,560,215 2/1971 Knoester et a1. 96-91 R 2,980,534 4/1961 Printy et a1. 96-49 X 3,497,355 2/1970 Mizianty 96-91 R 3,615,578 10/1971 Hectors et al 96-91 R FOREIGN PATENTS 1,534,978 6/1968 France 96-91 R OTHER REFERENCES Dinaburg, M. S., Photosensitive Diazo Compounds, The Focal Press, 1964, pp. -62 and 71.
Kosar, 1., Light-Sensitive Systems, J. Wiley & Sons, 1965, pp. -196197.
CHARLES L. BOWERS, JR., Primary Examiner US. Cl. X.R.
US00098061A 1969-12-17 1970-12-14 Light-sensitive diazonium compounds and diazotype materials Expired - Lifetime US3736143A (en)

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Publication number Priority date Publication date Assignee Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970460A (en) * 1973-03-28 1976-07-20 Multitec Ag Diazotype composition

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