US3442652A - Diazonium compounds and diazotype material - Google Patents

Diazonium compounds and diazotype material Download PDF

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US3442652A
US3442652A US535316A US3442652DA US3442652A US 3442652 A US3442652 A US 3442652A US 535316 A US535316 A US 535316A US 3442652D A US3442652D A US 3442652DA US 3442652 A US3442652 A US 3442652A
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diazonium
diazotype
group
alkyl
compound
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Adrianus Marie Petrus Hectors
Bernardus Hubertus Huibers
Carel Jacobus Knoester
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Chemische Fabriek L Van der Grinten NV
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Grinten Chem L V D
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    • 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

  • Particularly suitable for one-component diazotype layers are compounds having in the ortho position an alkylthio group containing at most three C atoms, in the meta position a non-branched alkoxy group containing at most four C atoms, and in the para position a N-alkyl-N-cyclohexylamino group wherein the N-alkyl group contains at most three C atoms.
  • the invention relates to new diazonium compounds and to diazotype material sensitized therewith.
  • diazotype material may be so-called one-component diazotype material which is developed with a liquid containing an azocoupling component, so-called two-component diazotype material which is developed with the aid of ammonia vapour, or heat-developable diazotype material.
  • diazonium compounds for sensitizing diazotype material should have good stability and give colourless photo-decomposition products.
  • Diazotype material sensitized with diazonium compounds according to Formulae 1 and 2 has high lightsensitivity. It may be one-component diazotype material or two-component diazotype material. In fresh condition this diazotype material furnishes copies with strong azodyestulf images, but when it has been kept in a warm atmosphere for some time, only copies with a dull image are obtained. This is due to decomposition of the diazonium compound under the influence of heat. Moreover, the completely exposed background of the copies is somewhat stained.
  • diazonium compounds also are very light-sensitive; however, they have higher coupling activity than the compounds according to the Formulae l and 2, and consequently are more suitable for application in one-component diazotype material which is developed with weakly acid buffered phloroglucinol developers.
  • diaizotype materials which have been sensititzed with a diazonium compound according to Formulae 1 and 2
  • one-component diazotype material sensitized with a. diazonium compound according to Formula 3 yields copies whose completely exposed background is slightly stained.
  • Diazotype material sensitized with such diazonium compounds stains strongly when bleached out, so that copies produced with this material show a strongly stained background.
  • R is an alkyl or branched alkyl group
  • R is an alkyl, branched alkyl, unsaturated alkyl, cycloalkyl, aralkyl or aryl group
  • R is an alkyl, branched alkyl or aralkyl group
  • R is an alkyl, branched alkyl, cycloalkyl or aralkyl group.
  • the substituents R12 R R and R may carry further substituents.
  • the diazonium compounds according to the invention are very light-sensitive and yield both light-colored and dark azo-dyestulfs with the azo-coupling components commonly used in the diazotype process. They are more stable and they bleach out more brightly (i.e., with no, or less, stain) then the diazonium compounds according to the Formulae 1, 2, 3 and 4. Consequently, diazotype materials sensitized with diazonium compounds according to the invention have higher keeping quality and yield copies which have a brighter completely exposed background than corresponding diazotype material sensitized with a diazonium compound according to the Formulae 1, 2, 3 and 4.
  • diazonium compounds can be used in the form of their diazonium salts, such as the chloride and the sulfate, in the form of metal chloride double salts, such as the chlorozincate, chloromanganate, and chlorostannate, or as diazonium borofiuoride or diazonium aryl sulfonate.
  • diazotype material can be applied in diazotype material individually, mixed together, or in admixture with diazonium compounds of other types. It goes without saying that a diazotype material according to the invention, according as it has a higher content of another diazonium compound, will present the specific advantages of the diazonium compounds according to the invention to a less degree.
  • the familiar supports such as paper, tracing paper, transparentized paper, tracing linen, opaque linen, synthetic paper, metal plates, glass fibre, polyester film, and the like, can be sensitized.
  • the diazonium compound may or may not be incorporated in a hydrophilic or hydrophobic film layer.
  • the diazonium compounds with a low-carbon dialkylamino group in the para-position and a low-carbon alkoxy group in the meta-position are suitable in particular for application in two-component diazotype materials.
  • the diazonium compounds carrying in the para-position a higher-carbon dialkylamino group, a N-alkyl-N-aralkylamino, and a N-alkyl-N-cycloalkylamino group, as well as those with an aralkyloxy and an aryloxy group in the meta-position, are suitable especially for use in one-component diazotype layers.
  • the materials with a one-component diazotype layer are developed with the aid of a liquid containing an azo-coupling component.
  • Preferred diazonium compounds according to the invent1on are those carrying an alkylthio group having at most three C-atoms in the ortho-position, an unbranched alkoxy group having at most four C-atoms in the metaposition, and a N-alkyl-N-cyclohexylamino group in which the N-alkyl group contains at most three C-atoms in the para-position with respect to the diazonium group.
  • One-component diazotype material sensitized with these compounds is very light-sensitive and has good keeping quality. It bleaches out bright white, and upon development with the conventional alkaline phloroglucinol developers it yields copies with very dark, almost black azodyestuff images, which copies show very little yellowing when exposed to light.
  • the conventional auxiliary agents can be used, e.g. acids, such as citric acid, tartaric acid, and boric acid; stabilizers, such as benzene and naphthalene sulfonic acids, p-phenolsulfonic acid, and their water-soluble salts; metal salts, such as zinc chloride, magnesium chloride, nickel sulfate, and alum; materials which serve to enhance the developing speed, such as glycerol, polyethylene-glycol, urea, thiosinamine, and the like; surface-improving agents, such as finely divided silicon dioxide (colloidal or non-colloidal), aluminium oxide, barium sulfate and rice starch; binders, such as gelatin, gum arabic, cellulose ethers, starch, jder' ivatives, polyvinyl alcohol; dispersions of syniheticfresins, such as dispersions of cationic, non-ionic,
  • hloroglucinol developers which are used in the one-component diazotype process often vary as 'totheir composition and acidity. Below, one weakly acid ,phloroglucinol developer and one weakly alkaline phloro'glucinol developer are described which are used for development in the following examples.
  • Developer A is a solution of:
  • developer B is a solution of:
  • the pH of this liquid is approximately 9.5.
  • the following examples will serve to illustrate the invention.
  • EXAMPLE I A sheet of white base paper for the diazotype process, of weight 80 g./m. was sensitized with a liquid containing 4-N-methyl-N-benzylamino-3-methoxy 2 methylthiobenzene diazonium chloride, stannic chloride (B) Another sheet of white base paper for the diazotype process, of weight 80 g./m. was sensitized with a liquid containing 4-N-methyl-N- benzylamino 3 methoxybenzene diazonium chloride, zinc chloride double salt g Tartaric acid g 5 Aqueous polyvinyl acetate dispersion (Vinnapas H. 60) ml 30 Water ml 1000 and dried.
  • Diazotype paper A had better keeping quality than diazotype paper B.
  • the diazonium compound according to the invention used in this example was prepared as follows:
  • 2,3-dichlororiitrobenzene was converted with sodium methanolate into 3-chloro-2-methoxynitrobenzene.
  • the nitro group of the latter compound was reduced to an amino group.
  • the amino group was tosylated.
  • the product thus obtained was nitrated to 4-nitro-3-chloro-2-methoxy- N-tosylaniline, which was methylated, saponified, and benzylated.
  • the 4-N-methyl-N-benzylamino-3-methoxy-2- chloronitrobenz'ene thus prepared was brought into reaction with methyl mercaptan. From 4-N-methyl-N-benzylamino-3-methoxy-2 methylthionitrobenzene the diazonium chlorostannate was obtained in the usual way by reduction and diazotization.
  • EXAMPLE II A sheet of white base paper for the diazotype process, of weight g./m. was sensitized with a liquid con taining 4-dimethylamino-3-(4 chlorophenoxy) 2 ethylthiobenzene diazonium chloride, zinc chloride double salt g 25 Citric acid g 5 Saponin g 0.2 Water ml 1000 and dried.
  • the diazotype paper thus obtained was very light-sensitive.
  • a sheet of this material was imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed with developer A.
  • the copy thus obtained showed, on a white background, an image which is called black in the diazotype art.
  • the diazonium compound used in this example was prepared as follows:
  • the 4 dimethylamino- 3- (4'-chlorophenoxy)-2-chloronitrobenzene thus prepared was brought into reaction with ethylmercaptan, and from the 4-dimethylamino-3-(4'-chlorophenoxy)-2 ethylthionitrobenzene the diazonium chlorozincate was obtained in the usual way by reduction and diazotization.
  • EXAMPLE III White base paper for the diazotype process, of weight 80 g./m. pre-treated with non-colloidal silica, was sensitized with a solution containing 4 dimethylamino 3 isobutoxy 2 ethylthioben- A sheet of the two-component diazotype paper thus obtained was irnagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed in ammonia vapour.
  • the copy showed a blue-violet image on a bright white background.
  • the diazonium compound used in this example was prepared as follows:
  • 2,3-dichloronitrobenzene was converted into 3-chloro- 2-isobutoxynitrobenzene. Its nitro group was reduced to an amino group. The amino group was tosylated. The product thus obtained was nitrated to 4-nitro-3-chloro-2- isobutoxy-N-tosylaniline, methylated, saponified, and methylated again.
  • the 4-dimethylamino-3-isobutoxy-2 chloronitrobenzene thus produced was brought into reaction with ethylmercaptan, and from the 4-dimethylamino-3-isobutoxy-2-ethylthionitrobenzene the diazonium chlorostannate was obtained in the usual way by reduction and diazotization.
  • EXAMPLE IV White base paper for the diazotype process, of weight 80 g./m. was coated with a layer of approximately 4 g./m. of finely divided di(hexadecylammonium) oxalate.
  • This layer was sensitized with a solution containing 4 dimethylamino 3 methoxy 2 (2' hydroxyethyl) -thibenzene diazonium chloride, zinc chlo-
  • the heat-developable diazotype paper thus obtained was imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed by guiding it over a heated roller, the surface temperature of which was approximately 150 C.
  • the copy showed a violet image on a white background.
  • the diazonium compound used in this example was prepared as follows:
  • EXAMPLE V White base paper for the diazotype process, of weight 80 g./m. was sensitized with a solution containing 4 N methyl N cyclohexylamino 3 methoxy- 2-ethy1thiobenzene diazonium chloride, stannic chloride double salt g Tartaric acid Aqueous polyvinyl acetate dispersion (Vinnapas H. 60) ml
  • the sensitizing liquid contains, instead of said compound, an equivalent quantity of the corresponding diazonium compound without the ethylthio- 2-substituent, the diazotype paper thus obtained bleaches out less white and has poorer keeping quality.
  • the diazonium compound used in this example was EXAMPLE VI White paper of weight 150 g./m.'-, coated on one side with a cellulose acetate film layer (approximately 50% by weight of combined acetic acid) of a thickness of approximately 10 microns, which layer had been affixed to thev paper by means of an adhesive and had been deacylated to a depth of about 4 microns to an acetyl content, calculated as combined acetic acid, of approximately 20% by weight (which corresponds to an average number of acyl groups per glucose unit of the cellulose acetate of 0.7), was impregnated on the de-acylated side of the cellulose acetate layer with the following solution:
  • the copy showed a black image on a bright white background.
  • the diazonium compound used in this example was prepared as follows:
  • 4-nitro-3-chloro-2-methoxy-N-methylaniline was benzylated.
  • the 4-nitro-3-chloro-2-methoxy-N-methyl-N-benzylaniline was brought into reaction with isobutylmercaptan, and from the 4-N-methyl-N-benzylamino-3- methoxy-24sobutylthionitrobenzene the diazonium salt was obtained in the usual way by reduction and diazotization.
  • EXAMPLE VII White base paper for the diazotype process, of weight g./m. was sensitized with a solution containing:
  • the diazonium compound used in this example was prepared as follows:
  • 2,3-dichloronitrobenzene was converted into 3-chloro- 2-(4-chlorophenoxy) nitrobenzene.
  • the nitro group was reduced to an amino group, which was converted with epoxyethane into a di(2'-hydroxyethyl)amino group, from which a bis(2'-acetoxyethyl)amino group was obtained with acetic anhydride.
  • the product thus prepared was nitrated.
  • the 4-nitro-3-chloro-2-(4'-chlorophenoxy)- N,N-di-(2'-acetoxyethyl)aniline thus formed was saponified, then brought into reaction with ethylrnercaptan and acetylated again. From the 4-di(2-acetoxyethyl)-amino- 3-(4'-chlorophenoxy)-2-ethylthionitrobenzene the diazonium salt was prepared in the usual way by reduction and diazot
  • the light-sensitive planographic printing plate thus obtained was exposed underneath a negative original until the diazonium compound underneath the image-free portions of the original had completely bleached out, and was then developed by rubbing the light-sensitive side of the plate with a solution containing:
  • a sheet of the very light-sensitive transparent paper was imagewise exposedunderneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed with developer B.
  • the copy showed a brown image on a bright background and was well suited for making further copies on diazotype material.
  • the diazonium compound used in this example was prepared as follows:
  • 3-chloro-2-methoxynitrobenzene was de-etherified to 3- chloro-2-hydroxynitrobenzene, which was converted into 3-chloro-Z-allyloxynitrobenzene by reaction with allyl bromide.
  • the nitro group of this compound was reduced and the amino group obtained was dimethylated.
  • the 3- chloro-2-allyloxy-N,N-dimethylaniline was nitrated to 4- dimethylamino 3 allyloxy-2chloronitrobenzene, which was brought into reaction with ethylmercaptan.
  • the product thus obtained was reduced, and from the amino compound the diazonium salt was obtained in the usual way.
  • a sheet of the very light-sensitive diazotype paper thus obtained was imagewise exposed and developed as in Example I.
  • the copy showed a brown image on a bright white background.
  • the diazonium compound used in this example was prepared as follows:
  • 3-chloro-2-hydroxynitrobenzene was converted into 3- chloro-2-benzyloxynitrobenzene by reaction with benzyl chloride.
  • the nitro group of this product was reduced and the amino group thus obtained was dimethylated.
  • the 3-chloro-2-benzyloxy N,N dimethylaniline was nitrated to 4-dimethylamino-3-benzyloxy-2-chloronitrobenzene, the chloride atom being then replaced by an ethylthio group.
  • the product thus obtained was reduced, and from the amino compound the diazonium salt was obtained in the usual way.
  • the diazonium compound used in this example was prepared as follows:
  • 2,3-dichloronitrobenzene was converted into 3-chloro- 2 (2 ethoxyethoxy)nitrobenzene by reaction with 2- ethoxyethanolate.
  • the nitro group was reduced to an amino group and the amino group was dimethylated.
  • the 3-chloro-2-(2'-ethoxyethoxy) N,N dimethylaniline thus prepared was nitrated and the chlorine atom was then replaced 'by an ethylthio group by reaction with ethyl mercaptan. From the nitro compound the diazonium salt was obtained in the usual way by reduction and diazotization.
  • R is a lower alkyl or a branched lower alkyl group
  • R is a lower alkyl, a branched lower alkyl, a lower alkenyl, a cycloalkyl, a benzyl or a phenyl group,
  • R is a lower alkyl, a branched lower alkyl or a benzyl group
  • R is a lower alkyl, a branched lower alkyl, a cycloalkyl or a benzyl group.
  • a compound according to claim 1 namely a 4- (alkyl) (cyclohexyl)amino 3 alkoxy-Z-alkylthiobenzene diazonium compound.
  • a compound according to claim 1 namely, a 4- dialkylamino-3-aryloxy 2 alkylthiobenzene diazonium compound.
  • a compound according to claim 1 namely, a 4- dialkylamino-3-aralky1oxy-2 alkylthiobenzenc diazonium compound.
  • a compound according to claim 1 namely, a 4- (methyl) (cyclohexyl) amino-3-methoxy 2 ethylthiobenzene diazonium compound.
  • a compound according to claim 1 namely, a 4- (methyl) (benzyl)amino-3-methoxy-2-alkylthiobenzene diazonium compound.
  • a compound according to claim 1 namely, a 4- dimethylamino- 3 chlorophenoxy 2 ethylthiobenzene diazonium compound.
  • Diazotype material comprising a support carrying a light-sensitive layer containing a diazonium compound as defined in claim 1.
  • One-component diazotype material comprising a support carrying a light-sensitive layer containing a diazonium compound as defined in claim 2.

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Description

United States Patent US. Cl. 96-31 13 Claims ABSTRACT OF THE DISCLOSURE Diazotype material having high light-sensitivity and which couples with usual azo coupling components to form strong images having non-stained backgrounds and good keeping qualities is obtained by providing and utilizing in the light-sensitive layer a new para-(tertiary) amino-2- (alkyl or branched alkyl) thio-3-(alkyl, branched alkyl, alkenyl, cycloalkyl, benzyl or phenyl) oxy-benzene diazonium compound in which one of the tertiary amino substituents is alkyl, branched alkyl or benzyl and the other is alkyl, branched alkyl, cycloalkyl or benzyl. Particularly suitable for one-component diazotype layers are compounds having in the ortho position an alkylthio group containing at most three C atoms, in the meta position a non-branched alkoxy group containing at most four C atoms, and in the para position a N-alkyl-N-cyclohexylamino group wherein the N-alkyl group contains at most three C atoms.
The invention relates to new diazonium compounds and to diazotype material sensitized therewith. Such diazotype material may be so-called one-component diazotype material which is developed with a liquid containing an azocoupling component, so-called two-component diazotype material which is developed with the aid of ammonia vapour, or heat-developable diazotype material.
Besides having good light-sensitivity and suitable coupling activity, diazonium compounds for sensitizing diazotype material should have good stability and give colourless photo-decomposition products.
If the photo-decomposition product is coloured, copies made on the diazotype material completely exposed show a stained background. This is especially disturbing when the support of the diazotype material is white paper or when the support is transparent and the copy is to serve as 2211111 intermediate for further copying on diazotype materi In recent years very light-sensitive diazonium compounds have come into use for sensitizing diazotype materials. These compounds are chiefly benzene diazonium compounds having a tertiary amino group in the paraposition with respect to the diazo group and an etherified hydroxyl group in the meta-position, and possibly a further substituent, such as alkoxy, alkyl, or halogen, in the para-position with respect to the etherified hydroxyl group.
British patent specification 867,629 describes diazonium compounds of the following general formula,
( NzX 3,442,652 Patented May 6, 1969 in which X is an anion, R and R stand for alkyl groups having at most 4 C-atoms, and R for an alkyl group having at most 4 C-atoms or an aralkyl group having at most 7 C-atoms.
, British patent specification 888,598 describes diazonium compounds of the following general formula,
( NzX in which X is an anion, Y is a hydrogen or halogen atom or an alkyl or alkoxy group, R stands for an alkyl group, R5 for an alkyl group having at most 3 C-atoms, and R for a cyclohexyl group.
Diazotype material sensitized with diazonium compounds according to Formulae 1 and 2 has high lightsensitivity. It may be one-component diazotype material or two-component diazotype material. In fresh condition this diazotype material furnishes copies with strong azodyestulf images, but when it has been kept in a warm atmosphere for some time, only copies with a dull image are obtained. This is due to decomposition of the diazonium compound under the influence of heat. Moreover, the completely exposed background of the copies is somewhat stained.
British patent specification 919,037 describes diazonium compounds of the following general formula,
( N zX in which X is an anion, Y is, for example, a hydrogen or a halogen atom or a methyl, alkoxy, or phenoxy group, R stands for a substituted or non-substituted phenyl group, and R and R for an alkyl, cycloalkyl, or aralkyl substituent, which is either substituted or non-substituted. R and R together with the nitrogen atom may also form a heterocyclic ring.
These diazonium compounds also are very light-sensitive; however, they have higher coupling activity than the compounds according to the Formulae l and 2, and consequently are more suitable for application in one-component diazotype material which is developed with weakly acid buffered phloroglucinol developers.
Like diaizotype materials which have been sensititzed with a diazonium compound according to Formulae 1 and 2, one-component diazotype material sensitized with a. diazonium compound according to Formula 3 yields copies whose completely exposed background is slightly stained.
Dutch patent application 6406974 describes diazonium compounds of the following general formula,
( NzX Ru-S ORro N in which represents a morpholino, piperazino, piperidino, or pyrrolodino ring, while R and R represent alkyl, aralkyl, or aryl groups.
Diazotype material sensitized with such diazonium compounds stains strongly when bleached out, so that copies produced with this material show a strongly stained background.
It is an object of the present invention to provide novel diazonium compounds and diazotype material sensitized therewith in which the disadvantages referred to above are minimized or even eliminated.
According to the first feature of the present invention there are provided diazonium compounds of the following general formula,
( NzX in which X is an anion, R is an alkyl or branched alkyl group, R is an alkyl, branched alkyl, unsaturated alkyl, cycloalkyl, aralkyl or aryl group, R is an alkyl, branched alkyl or aralkyl group, and R is an alkyl, branched alkyl, cycloalkyl or aralkyl group. The substituents R12 R R and R may carry further substituents.
The diazonium compounds according to the invention are very light-sensitive and yield both light-colored and dark azo-dyestulfs with the azo-coupling components commonly used in the diazotype process. They are more stable and they bleach out more brightly (i.e., with no, or less, stain) then the diazonium compounds according to the Formulae 1, 2, 3 and 4. Consequently, diazotype materials sensitized with diazonium compounds according to the invention have higher keeping quality and yield copies which have a brighter completely exposed background than corresponding diazotype material sensitized with a diazonium compound according to the Formulae 1, 2, 3 and 4.
The following is a list, though not a complete one, of diazonium compounds according to the invention which can be used with good results in a diazotype material:
4-diazo-3 -ethylthio-2-cyclopentoxy-N,N-dimethylaniline 4-diazo-3-ethylthio-2-benzyloxy-N,N-dimethylaniline 4-diazo-3-ethylthio-2-(4-chlorophenoxy)-N,N-dimethylaniline 4-diazo-3-ethylthio-2-ethoxy-N,N-diethylaniline 4-diazo-3 -ethylthio-2-n-propoXy-N,N-diethylaniline 4-diazo-3-ethylthio-2-methoxy-N,N-di-(2'-chloroethyl) aniline 4-diazo -3 -ethylthio-2-methoxy-N,N-di- (2'-hydroxyethyl) aniline 4-diazo-3-ethylthio-2-meth oxy-N,N-di- (2-acetoxyethyl aniline 4-diazo-3 -ethylthio-2- (4'-chlorophenoxy) -N,N-di- (2-acetoxyethyl aniline 4-diazo-3 -ethylthio-2-methoxy-N,N-di-n-butyl aniline 4-diazo-3-ethylthio-2-methoxy-N-methyl-N-cyclohexylaniline 4-diazo-3 -ethylthio -2-ethoxy-N-methyl-N-cyclohexylaniline 4-diazo-3-ethylthio -2-ethoxy-N-ethyl-N-cyclohexylaniline 4-diazo-3 -methylthio-2-propoXy-N-methyl-N-cyclohexylaniline 4-diazo-3 -ethylthio-Z-methoxy-N-methyl-N-benzylaniline 4-diazo-3-ethylthio-2-n-butoxy-N-methyI-N-henzylaniline 4-diazo-3 -ethylthio-2-methoxy-N-n-butyl-N-benzylaniline 4-diazo-3 -ethylthio-2-meth oxy-N-isobutyl-N-benzylaniline 4-diazo-3-ethylthio-2-methoxy-N-ethyl-N- (2',6'-dichlorobenzyl aniline 4-diazo-3 -ethyl thio2-methoxy-N,N-dib enzyl aniline 4-diazo-3 -ethylthio-2-meth oxy-N-b enzyl-N-cyclohexylaniline.
These diazonium compounds can be used in the form of their diazonium salts, such as the chloride and the sulfate, in the form of metal chloride double salts, such as the chlorozincate, chloromanganate, and chlorostannate, or as diazonium borofiuoride or diazonium aryl sulfonate.
They can be applied in diazotype material individually, mixed together, or in admixture with diazonium compounds of other types. It goes without saying that a diazotype material according to the invention, according as it has a higher content of another diazonium compound, will present the specific advantages of the diazonium compounds according to the invention to a less degree.
With the diazonium compounds according to the invention the familiar supports, such as paper, tracing paper, transparentized paper, tracing linen, opaque linen, synthetic paper, metal plates, glass fibre, polyester film, and the like, can be sensitized. The diazonium compound may or may not be incorporated in a hydrophilic or hydrophobic film layer.
The diazonium compounds with a low-carbon dialkylamino group in the para-position and a low-carbon alkoxy group in the meta-position are suitable in particular for application in two-component diazotype materials. The diazonium compounds carrying in the para-position a higher-carbon dialkylamino group, a N-alkyl-N-aralkylamino, and a N-alkyl-N-cycloalkylamino group, as well as those with an aralkyloxy and an aryloxy group in the meta-position, are suitable especially for use in one-component diazotype layers. The materials with a one-component diazotype layer are developed with the aid of a liquid containing an azo-coupling component.
Preferred diazonium compounds according to the invent1on are those carrying an alkylthio group having at most three C-atoms in the ortho-position, an unbranched alkoxy group having at most four C-atoms in the metaposition, and a N-alkyl-N-cyclohexylamino group in which the N-alkyl group contains at most three C-atoms in the para-position with respect to the diazonium group.
One-component diazotype material sensitized with these compounds is very light-sensitive and has good keeping quality. It bleaches out bright white, and upon development with the conventional alkaline phloroglucinol developers it yields copies with very dark, almost black azodyestuff images, which copies show very little yellowing when exposed to light.
In the diazotype material according to the invention the conventional auxiliary agents can be used, e.g. acids, such as citric acid, tartaric acid, and boric acid; stabilizers, such as benzene and naphthalene sulfonic acids, p-phenolsulfonic acid, and their water-soluble salts; metal salts, such as zinc chloride, magnesium chloride, nickel sulfate, and alum; materials which serve to enhance the developing speed, such as glycerol, polyethylene-glycol, urea, thiosinamine, and the like; surface-improving agents, such as finely divided silicon dioxide (colloidal or non-colloidal), aluminium oxide, barium sulfate and rice starch; binders, such as gelatin, gum arabic, cellulose ethers, starch, jder' ivatives, polyvinyl alcohol; dispersions of syniheticfresins, such as dispersions of cationic, non-ionic, and anionic polyvinyl acetate; and substances which serve to stabilize the background of the copies, such as thiourea.
The hloroglucinol developers which are used in the one-component diazotype process often vary as 'totheir composition and acidity. Below, one weakly acid ,phloroglucinol developer and one weakly alkaline phloro'glucinol developer are described which are used for development in the following examples.
Developer A is a solution of:
G. Phloroglucinol 6.5 Resorcinol 4 Thiourea Sodium dibutylnaphthalene sulfonate 2 Sodium formate 14 Sodium benzoate 22 Trisodium citrate (2 aq.) 49 Citric acid 1.2
in 1000 ml. of water.
The pH of this liquid is approximately 6.5. Developer B is a solution of:
' G. Thiourea 30 Phloroglucinol 5.4 Resorcinol 6.5 Potassium hydroquinone monosulfonate 1 Sorbitol 5 Beet sugar 15 Potassium tetraborate (5 aq.) 50 Sodium isopropylnaphthalene sulfonate 1.5
in 1000 ml. of water.
The pH of this liquid is approximately 9.5. The following examples will serve to illustrate the invention.
EXAMPLE I (A) A sheet of white base paper for the diazotype process, of weight 80 g./m. was sensitized with a liquid containing 4-N-methyl-N-benzylamino-3-methoxy 2 methylthiobenzene diazonium chloride, stannic chloride (B) Another sheet of white base paper for the diazotype process, of weight 80 g./m. was sensitized with a liquid containing 4-N-methyl-N- benzylamino 3 methoxybenzene diazonium chloride, zinc chloride double salt g Tartaric acid g 5 Aqueous polyvinyl acetate dispersion (Vinnapas H. 60) ml 30 Water ml 1000 and dried.
Both diaztoype papers were very light-sensitive. Diazotype paper A had better keeping quality than diazotype paper B.
A strip of each sheet was imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the'image-free portions of the drawing had completely bleached out. Both strips were then developed with developer B. Thus two copies with a brown image on a white background were obtained. The background of copy A was whiter than that of copy B.
The diazonium compound according to the invention used in this example was prepared as follows:
2,3-dichlororiitrobenzene was converted with sodium methanolate into 3-chloro-2-methoxynitrobenzene. The nitro group of the latter compound was reduced to an amino group. The amino group was tosylated. The product thus obtained was nitrated to 4-nitro-3-chloro-2-methoxy- N-tosylaniline, which was methylated, saponified, and benzylated. The 4-N-methyl-N-benzylamino-3-methoxy-2- chloronitrobenz'ene thus prepared was brought into reaction with methyl mercaptan. From 4-N-methyl-N-benzylamino-3-methoxy-2 methylthionitrobenzene the diazonium chlorostannate was obtained in the usual way by reduction and diazotization.
EXAMPLE II A sheet of white base paper for the diazotype process, of weight g./m. was sensitized with a liquid con taining 4-dimethylamino-3-(4 chlorophenoxy) 2 ethylthiobenzene diazonium chloride, zinc chloride double salt g 25 Citric acid g 5 Saponin g 0.2 Water ml 1000 and dried.
The diazotype paper thus obtained was very light-sensitive.
A sheet of this material was imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed with developer A. The copy thus obtained showed, on a white background, an image which is called black in the diazotype art.
The diazonium compound used in this example was prepared as follows:
With 4-chlorophenol and potassium hydroxide, 2,3-dichloronitrobenzene was converted into 3-chloro-2-(4'- chlorophenoxy) nitrobenzene. Its nitro group was reduced to an amino group. The amino group was tosylated. The product thus obtained was nitrated to 4-nitro-3-chloro-2- (4-chlorophenoxy)-N-tosylaniline, which was methylated, saponified, and methylated again. The 4 dimethylamino- 3- (4'-chlorophenoxy)-2-chloronitrobenzene thus prepared was brought into reaction with ethylmercaptan, and from the 4-dimethylamino-3-(4'-chlorophenoxy)-2 ethylthionitrobenzene the diazonium chlorozincate was obtained in the usual way by reduction and diazotization.
EXAMPLE III White base paper for the diazotype process, of weight 80 g./m. pre-treated with non-colloidal silica, was sensitized with a solution containing 4 dimethylamino 3 isobutoxy 2 ethylthioben- A sheet of the two-component diazotype paper thus obtained was irnagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed in ammonia vapour.
The copy showed a blue-violet image on a bright white background.
The diazonium compound used in this example was prepared as follows:
2,3-dichloronitrobenzene was converted into 3-chloro- 2-isobutoxynitrobenzene. Its nitro group was reduced to an amino group. The amino group was tosylated. The product thus obtained was nitrated to 4-nitro-3-chloro-2- isobutoxy-N-tosylaniline, methylated, saponified, and methylated again. The 4-dimethylamino-3-isobutoxy-2 chloronitrobenzene thus produced was brought into reaction with ethylmercaptan, and from the 4-dimethylamino-3-isobutoxy-2-ethylthionitrobenzene the diazonium chlorostannate was obtained in the usual way by reduction and diazotization.
EXAMPLE IV White base paper for the diazotype process, of weight 80 g./m. was coated with a layer of approximately 4 g./m. of finely divided di(hexadecylammonium) oxalate.
This layer was sensitized with a solution containing 4 dimethylamino 3 methoxy 2 (2' hydroxyethyl) -thibenzene diazonium chloride, zinc chlo- The heat-developable diazotype paper thus obtained was imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed by guiding it over a heated roller, the surface temperature of which was approximately 150 C.
The copy showed a violet image on a white background.
The diazonium compound used in this example was prepared as follows:
3 chloro 2 methoxyaniline was tosylated, nitrated, methylated, saponified, and methylated again. The 4-dimethylamino-3-methoxy-2-chloronitrobenzene thus prepared was brought into reaction with 2-hydroxyethylmercaptan. From the nitro compound thus obtained the diazonium salt was obtained in the usual way by reduction and diazotization.
EXAMPLE V White base paper for the diazotype process, of weight 80 g./m. was sensitized with a solution containing 4 N methyl N cyclohexylamino 3 methoxy- 2-ethy1thiobenzene diazonium chloride, stannic chloride double salt g Tartaric acid Aqueous polyvinyl acetate dispersion (Vinnapas H. 60) ml When the above-mentioned sensitizing liquid contains, instead of said compound, an equivalent quantity of the corresponding diazonium compound without the ethylthio- 2-substituent, the diazotype paper thus obtained bleaches out less white and has poorer keeping quality.
The diazonium compound used in this example was EXAMPLE VI White paper of weight 150 g./m.'-, coated on one side with a cellulose acetate film layer (approximately 50% by weight of combined acetic acid) of a thickness of approximately 10 microns, which layer had been affixed to thev paper by means of an adhesive and had been deacylated to a depth of about 4 microns to an acetyl content, calculated as combined acetic acid, of approximately 20% by weight (which corresponds to an average number of acyl groups per glucose unit of the cellulose acetate of 0.7), was impregnated on the de-acylated side of the cellulose acetate layer with the following solution:
4 N methyl N benzylamino 3 methoxy 2- isobutylthiobenzene diazonium chloride, zinc chlo- The diazotype material thus obtained was very lightsensitive. A sheet of this material was imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed with developer A.
The copy showed a black image on a bright white background.
The diazonium compound used in this example was prepared as follows:
4-nitro-3-chloro-2-methoxy-N-methylaniline was benzylated. The 4-nitro-3-chloro-2-methoxy-N-methyl-N-benzylaniline was brought into reaction with isobutylmercaptan, and from the 4-N-methyl-N-benzylamino-3- methoxy-24sobutylthionitrobenzene the diazonium salt was obtained in the usual way by reduction and diazotization.
EXAMPLE VII White base paper for the diazotype process, of weight g./m. was sensitized with a solution containing:
4 di(2' acetoxyethyl)amino 3 (4 chlorophenoxy)-2-ethylthiobenzene diazonium chloride, zinc chloride double salt g.. 30
Tartaric acid g 5 Aqueous polyvinyl acetate dispersion (Vinnapas H. 60) ml an equivalent quantity of the corresponding compound without the ortho-substituent, the diazotype paper thus obtained has poorer keeping quality and bleaches out with a somewhat more pronounced stain.
The diazonium compound used in this example was prepared as follows:
2,3-dichloronitrobenzene was converted into 3-chloro- 2-(4-chlorophenoxy) nitrobenzene. The nitro group was reduced to an amino group, which was converted with epoxyethane into a di(2'-hydroxyethyl)amino group, from which a bis(2'-acetoxyethyl)amino group was obtained with acetic anhydride. The product thus prepared was nitrated. The 4-nitro-3-chloro-2-(4'-chlorophenoxy)- N,N-di-(2'-acetoxyethyl)aniline thus formed was saponified, then brought into reaction with ethylrnercaptan and acetylated again. From the 4-di(2-acetoxyethyl)-amino- 3-(4'-chlorophenoxy)-2-ethylthionitrobenzene the diazonium salt was prepared in the usual way by reduction and diazotization.
EXAMPLE VIII An ofiset-printing plate of paper was sensitized with a liquid containing:
4 N methyl N benzylamino 3 methoxy 2- ethylthiobenzene diazonium chloride, zinc chloride double salt g 25 Ethanol ml 100 Water .ml 900 and dried.
The light-sensitive planographic printing plate thus obtained was exposed underneath a negative original until the diazonium compound underneath the image-free portions of the original had completely bleached out, and was then developed by rubbing the light-sensitive side of the plate with a solution containing:
200 g. of sodium 2 acetoacetaminonaphthalene-6,8 disulfonate in 1000 ml. of water.
EXAMPLE IX Sized natural tracing paper, of weight 80 g./m. was sensitized with a solution containing:
4 dimethylamino-3-allyloxy-Z-ethylthiobenzene diazonium chloride, stannic chloride double salt g 35 Tartaric acid 2 5 Ethanol (96%) ml 300 Water ml 700 and dried.
A sheet of the very light-sensitive transparent paper was imagewise exposedunderneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing had completely bleached out, and was then developed with developer B.
The copy showed a brown image on a bright background and was well suited for making further copies on diazotype material.
The diazonium compound used in this example was prepared as follows:
3-chloro-2-methoxynitrobenzene was de-etherified to 3- chloro-2-hydroxynitrobenzene, which was converted into 3-chloro-Z-allyloxynitrobenzene by reaction with allyl bromide. The nitro group of this compound was reduced and the amino group obtained was dimethylated. The 3- chloro-2-allyloxy-N,N-dimethylaniline was nitrated to 4- dimethylamino 3 allyloxy-2chloronitrobenzene, which was brought into reaction with ethylmercaptan. The product thus obtained was reduced, and from the amino compound the diazonium salt was obtained in the usual way.
EXAMPLE X White base paper for the diazotype process, of weight 60 g./m. was sensitized with a solution containing:
4-dimethylamino-3-benzyloxy-Z-ethylthiobenzene diazonium chloride, zinc chloride double salt ..g 35 Tartaric acid g 5 Aqueous polyvinyl acetate dispersion (Vinnapas H. 60) ml 30 Water ml 1000 and dried.
A sheet of the very light-sensitive diazotype paper thus obtained was imagewise exposed and developed as in Example I. The copy showed a brown image on a bright white background.
The diazonium compound used in this example was prepared as follows:
3-chloro-2-hydroxynitrobenzene was converted into 3- chloro-2-benzyloxynitrobenzene by reaction with benzyl chloride. The nitro group of this product was reduced and the amino group thus obtained was dimethylated. The 3-chloro-2-benzyloxy N,N dimethylaniline was nitrated to 4-dimethylamino-3-benzyloxy-2-chloronitrobenzene, the chloride atom being then replaced by an ethylthio group. The product thus obtained was reduced, and from the amino compound the diazonium salt was obtained in the usual way.
EXAMPLE XI Sized natural tracing paper, of weight g./m. was sensitized with a liquid containing:
4-dimethylamino-3-(2'-ethoxyethoxy)-2-ethyl thiobenzene diazonium chloride, stannic chloride A sheet of the very light-sensitive transparant material thus obtained was imagewise exposed and developed as in Example III. The copy obtained showed a yellow-brown image on a bright background and was eminently suitable for making further copies on diazotype material.
The diazonium compound used in this example was prepared as follows:
2,3-dichloronitrobenzene was converted into 3-chloro- 2 (2 ethoxyethoxy)nitrobenzene by reaction with 2- ethoxyethanolate. The nitro group was reduced to an amino group and the amino group was dimethylated. The 3-chloro-2-(2'-ethoxyethoxy) N,N dimethylaniline thus prepared was nitrated and the chlorine atom was then replaced 'by an ethylthio group by reaction with ethyl mercaptan. From the nitro compound the diazonium salt was obtained in the usual way by reduction and diazotization.
The present invention is not to be considered restricted to particulars of any of the compounds, materials or examples hereinabove described except as may be required by a fair construction of the appended claims, for various modifications and substitutions of equivalent nature will become available to those skilled in the art upon consideration of the nature of this invention.
11 What is claimed is: 1. A light-sensitive diazonium compound of the general formula,
in which X is an anion,
R is a lower alkyl or a branched lower alkyl group,
R is a lower alkyl, a branched lower alkyl, a lower alkenyl, a cycloalkyl, a benzyl or a phenyl group,
R is a lower alkyl, a branched lower alkyl or a benzyl group, and
R is a lower alkyl, a branched lower alkyl, a cycloalkyl or a benzyl group.
2. A diazonium compound according to claim 1, wherein alkylamino-3-alkoxy-2-alkylthiobenzene diazonium compound.
6. A compound according to claim 1, namely a 4- (alkyl) (cyclohexyl)amino 3 alkoxy-Z-alkylthiobenzene diazonium compound.
7. A compound according to claim 1, namely, a 4- dialkylamino-3-aryloxy 2 alkylthiobenzene diazonium compound.
8. A compound according to claim 1, namely, a 4- dialkylamino-3-aralky1oxy-2 alkylthiobenzenc diazonium compound.
9. A compound according to claim 1, namely, a 4- (methyl) (cyclohexyl) amino-3-methoxy 2 ethylthiobenzene diazonium compound.
10. A compound according to claim 1, namely, a 4- (methyl) (benzyl)amino-3-methoxy-2-alkylthiobenzene diazonium compound.
11. A compound according to claim 1, namely, a 4- dimethylamino- 3 chlorophenoxy 2 ethylthiobenzene diazonium compound.
12. Diazotype material comprising a support carrying a light-sensitive layer containing a diazonium compound as defined in claim 1.
13. One-component diazotype material comprising a support carrying a light-sensitive layer containing a diazonium compound as defined in claim 2.
References Cited FOREIGN PATENTS 6,406,974 12/ 1964 Netherlands. 6,407,303 l/ 1965 Netherlands.
NORMAN G. TORCHIN, Primary Examiner.
C. BOWERS, Assistant Examiner.
US. Cl. X.R.
US535316A 1965-03-24 1966-03-18 Diazonium compounds and diazotype material Expired - Lifetime US3442652A (en)

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Cited By (4)

* 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
US3775131A (en) * 1970-06-19 1973-11-27 Oce Van Der Grinten Nv Diazonium compounds and diazotype materials containing them
US3868255A (en) * 1969-07-23 1975-02-25 Gaf Corp Diazonium salts and diazotype materials
US3970460A (en) * 1973-03-28 1976-07-20 Multitec Ag Diazotype composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6406974A (en) * 1963-06-18 1964-12-21
NL6407303A (en) * 1963-07-06 1965-01-07

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6406974A (en) * 1963-06-18 1964-12-21
NL6407303A (en) * 1963-07-06 1965-01-07

Cited By (4)

* 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
US3868255A (en) * 1969-07-23 1975-02-25 Gaf Corp Diazonium salts and diazotype materials
US3775131A (en) * 1970-06-19 1973-11-27 Oce Van Der Grinten Nv Diazonium compounds and diazotype materials containing them
US3970460A (en) * 1973-03-28 1976-07-20 Multitec Ag Diazotype composition

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