Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/52—Compositions containing diazo compounds as photosensitive substances
  • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

• the invention relates to light-sensitive diazonium compounds of a new type and to diazotype material sensitized with these diazonium compounds.
• This 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 photodecomposition products which are completely or almost completely colourless, which when exposed to light show no staining, or hardly any, and which do not actively react with diazonium compounds to yield dyestuffs.
• Diazotype material sensitized with a diazonium compound of insufficient stability has poor keeping quality. Poor keeping quality may appear from a decrease of the concentration of the diazonium compound through gradual decomposition, so that in the course of time copies with azo-dyestuff images of poor density are obtained.
• diazonium com pounds 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 diazonium 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.
• R and R stand for alkyl groups with at most 4 C-atoms, and R for an alkyl group with at most 4 C-atoms or an aralkyl group with at most 7 C-atoms.
• lIIrX in which X is an anion, Y is a hydrogen or a halogen atom or an alkyl or alkoxy group, R stands for an alkyl group, R for an alkyl group with at most 3 C-atoms, and R for a cyclohexyl group.
• Diazotype material manufactured with diazonium compounds of the Formulae I, II and III is very attractive because of its high light-sensitivity. It may be one-component diazotype material or two-component diazotype material. Upon development with weakly alkaline phloroglucinol developers, such one-component diazotype material furnishes copies with brown azo-dyestutf images, and upon development with buffered weakly acid phloroglucinol developers (if the diazonium compound used has sutficiently high coupling activity to allow development with a weakly acid liquid) it yields copies with dark, often even black, azo-dyestuff images.
• diazonium compounds those according to g the Formulae II and III in which Y represents an etherified hydroxyl group, form a class apart. They have considerably lower light-sensitivity, but they show higher thermostability, i.e., they are better able to stand up to storage in a warm atmosphere.
• the other diazonium compounds according to the Formulae I, II and III are very interesting because of their higher light-sensitivity, but their thermostability is too low, so that diazotype materials sensitized with them will not stand up sufficiently to storage in warm rooms. When such materials are stored for some days at temperatures of 40-50 0, they already show a considerable reduction of the diazonium compound concentration.
• diazonium compounds of the following general Formula IV are provided.
• R stands for a substituted or nonsubstituted alkyl, branched alkyl, unsaturated alkyl, cycloalkyl or aralkyl group, COR for an acyl group, R for a substituted or non-substituted alkyl, branched alkyl, unsaturated alkyl, cycloalkyl, aralkyl or aryl group, and
• acyl is to be understood to mean the radical -COR where R may be a hydrogen atom or an organic radical of any of a great variety of types.
• R may be a hydrogen atom or an organic radical of any of a great variety of types.
• acyl thus has the meaning usually assigned to it in the literature concerning the diazotype process. See, e.g., British patent specifications Nos. 615,774, 347,430, and 539,031.
• Very suitable diazonium compounds for sensitizing diazotype materials according to the invention are those which satisfy the general Formula IV, in which X is an anion, R stands for a substituted or non-substituted alkyl, branched alkyl, unsaturated alkyl, cycloalkyl, aralkyl or aryl group, or a substituted or non-substituted alkoxy, branched alkoxy, unsaturated alkoxy, cycloalkoxy, aralkyloxy or aryloxy group, R for a substituted or nonsubstituted alkyl, branched alkyl, unsaturated alkyl, cycloalkyl, aralkyl or aryl group, R for a substituted or nonsubstituted alkyl, branched alkyl or aralkyl group, and R for a substituted or non-substituted alkyl, branched alkyl, aralkyl or cyclo
• the diazonium compounds according to the invention are very light-sensitive, and have higher coupling activity and greater thermostability than the corresponding diazonium compounds without the amino-substituent in the ortho-position.
• the azocoupling components commonly used in the diazotype process they yield both light-coloured and dark azo-dyestuffs.
• polyvalent phenols such as resorcinol and phloroglucinol they couple to form darker azo-dyestufis than do the diazonium compounds of the Formulae I, II and III.
• diazotype material sensitized with diazonium compounds according to the invention is very light-sensitive, has higher developing speed, and stands up better to high temperatures than comparable diazotype material sensitized with a corresponding compound without the amino-substituent in the ortho-position.
• the diazonium compounds according to the invention are suitable for sensitizing one-component diazotype material and two-component diazotype material and, on account of their good thermostability, they are also very suitable for use in heat-developable diazotype material, since their pyrolysis during the development of such material is relatively small.
• diazonium compounds according to the invention which have a light alkoxy group in the meta-position and a light tertiary amino group in the para-position, such as a dimethylamino, diethylamino, di(2'-hydroxyethyl) amino, or a morpholino, piperidino, or pyrrolidino group, are better suited for use in two-component diazotype materials, in which relatively slowly coupling diazonium compounds are generally preferred.
• the compounds with a N-alkyl- N-aralkylamino group or a N-alkyl-N-cycloalkylamino group in the para-position are better suited for the sensitization of one-component diazotype material, even of such material that is developed with the weakly acid buffered developers, which are greatly preferred because of their high keeping quality.
• Particularly attractive diazonium compounds are those according to the Formula IV in which X is an anion, R stands for a substituted or non-substituted alkyl group with at most 4 C-atoms, R for a substituted or non-substituted alkoxy group with at most 4 Catoms, R for a substituted or non-substituted phenyl group, R and R for substituted or non-substituted straight chain alkyl groups with at most 4 C-atoms.
• Diazotype material sensitized with these compounds has better keeping quality and higher developing speed than material which contains a diazonium compound according to the Formula III wherein Y is a halogen atom and R and R are alkyl groups.
• the said diazonium compounds according to the Formula III are used in practice on a large scale for sensitizing diazotype materials. Compared with these diazotype materials, the material of the present invention moreover yields copies which show a more attractive black azodyestuff image when a buffered weakly acid phloroglucinol developer is employed.
• Equally attractive diazonium compounds are those according to the Formula IV in which X is an anion, R R and R stand for alkyl groups with at most 4 C-atoms, R for a substituted or non-substituted alkoxy, benzyloxy, or phenoxy group, and R for a cyclohexyl group.
• Diazotype material sensitized with these compounds is also suitable for development with weakly acid buttered phloroglucinol developers and it also yields copies with fine black azo-dyestutf images, but in addition it is 15% more light-sensitive.
• diazonium compounds which can be used with good results in diazotype material according to the invention:
• the diazonium compounds can be used as diazonium salts, e.g. as diazonium chloride, sulfate, hydrogen sulfate or phosphate, or as metal chloride double salt, such as chlorozincate and chlorostannate, as diazonium borofluoride or as diazonium aryl sulfonate.
• diazotype material can be applied in the diazotype material individually, mixed together, or in admixture with diazonium compounds of other types. It goes Without saying that as the diazotype material according to the invention has a higher content of another diazonium compound it will present the specific advantages of the diazonium compounds according to the invention to a lesser degree.
• the familiar supports such as paper, tracing paper, printing-plate paper, tracing linen, opaque linen, synthetic paper, metal sheets, glass fibres, polyester film and the like,
• the conventional auxiliary agents can be used, e.g. acids, such as citric acid, tartaric acid, boric acid, and phosphoric 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; substances which serve to enhance the developing speed, such as glycerol, polyethylene glycol, urea, thiosinamine, and the like; surface-improving substances such as finely divided silicon dioxide (colloidal or non-colloidal), aluminum oxide, barium sulfate, and rice starch; binders such as gelatin, gum arabic, cellulose ethers, starch derivatives, polyvinyl alcohol; dispersions of synthetic resins, such as dispersions of cationic, non-ionic, and anionic polyvinyl acetate.
• acids such as citric acid, tarta
• the phloroglucinol developers which are used in the one-component diazotype process often vary as to their composition and acidity. Below, two Weakly acid phloroglucinol developers and one Weakly alkaline phloroglucinol developer are described which are employed in practice and are used for development in a number of the following examples.
• Developer A is a solution of 4 g. of phloroglucinol 0.1 g. of acetoacetanilide 3 ml. of sodium 2-ethylhexyl sulfate 15 g. of beet sugar 2.5 g. of benzoic acid 14 g. of sodium benzoate 135 g. of sodium formate in 1000 ml. of water.
• the pH of this liquid is approximately 5.8.
• Developer B is a solution of:
• the pH of this liquid is approximately 6.5.
• Developer C is a solution of:
• the pH of this liquid is approximately 9.
• Another strip of the sheets A and B is stored, in a closed, moisture-tight wrapping as commonly used for diazotype material, for some tens of hours in a room in which a temperature of about 50 C. prevails. After this the strips are imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out, and the strips are then developed in ammonia vapour.
• Strip A shows a strong purple image
• image B shows a faint violet-brown image, both on a white background.
• the diazonium compound used according to the invention was prepared as follows:
• 2,3-dichloronitrobenzene was converted into 3-chloro- Z-methoxynitrobenzene with sodium methanolate.
• the nitro group of this product was reduced to an amino group, which was tosylated.
• the 3-chloro-2-methoxy-N- tosylaniline was nitrated, methylated, and saponified.
• the 4-nitro-3-choloro-2-methoxy N methylaniline thus obtained, which melts at 128 C., was methylated again to 4 nitro-3-chloro 2 methoxy N,N dimethyl aniline.
• Another strip of the sheets A and B is stored, in a closed, moisture-tight wrapping as commonly used for diazotype material, for some tens of hours in a room in which a temperature of about C. prevails. After this the strips are imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out. The strips are developed in ammonia vapour. Strip A shows a strong brown image, strip B shows a faint brown image on a transparent background.
• the diazonium compound used according to the example was prepared as follows:
• the light-sensitive printing plate has excellent keeping quality. It is imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out.
• the image on the printing plate is developed by moistening the image side of the plate with a solution of:
• the plate shows a black image, which absorbs ink quite selectively. From the plate 50 good offset prints can be made.
• the diazonium compound obtained according to the example was prepared as follows:
• 2,3-dichloronitrobenzene was fused with 4-chlorophenol and potassium hydroxide.
• the 3-chloro-2-(4'-chlorophenoxy)nitrobenzene was reduced and tosylated to 3-chloro- 2-(4-chlorophenoxy)-N-p-tosylaniline.
• This product was methylated, saponified, and cyclohexylated to 3-chloro-2- (4-chlorophenoxy)-N-rnethyl-N cyclohexylaniline.
• This product was nitrated, its chlorine atom was replaced by a methylamino group and this group was acylated with ethyl chloromethanoate.
• EXAMPLE IV (A) White base paper for the diazotype process, of weight g./m. is sensitized with a solution containing:
• the copy on sheet A shows a blue-black image on a foggy grey background.
• the copy on sheet B also shows a blue-black image, but, on a bright white, completely bleached-out background.
• the diazonium compound used in sensitizing liquid A is less light-sensitive than the compound used in sensitizing liquid B.
• the new diazonium compounds used according to the example were prepared as follows:
• EXAMPLE V A dispersion of di(octadecylammonium)oxalate is prepared by grinding a mixture of:
• the paper thus pre-treated is sensitized with a solution containing:
• disulfonic acid 25 g. of oxalic acid g. of rice starch g. of polyvinyl alcohol (of the type Rhodoviol 4/ 20 P) 1 ml. of wetting agent on basis of polymerized ethylene oxide, Scurol 0 (from Rhone-Poulenc S.A.) in
• a sheet of the diazotype material thus obtained is imagewise exposed underneath a letter typed on one side until the diazonium compound underneath the image-free portions of the letter has completely bleached out. Then the sheet is developed by guiding it over a metal cylinder with a surface temperature of about C.
• the copy shows a strong violet image on a foggy violet background.
• the diazonium compound used in the example was prepared as follows:
• the copy on sheet B shows a very dark violet-brown image on a foggy violet-brown back 1 1 ground.
• the copies on the sheets C and D show a black image on a foggy brown-grey background.
• the copies on the sheets E and F show a black image on a foggy bluegrey background.
• a second strip of the sheets A, B, C, D, E, and F is stored for some days in a moisture-tight wrapping at a temperature of 50 C. Then the strips are imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out. The strips are then developed with developer C, with which paper A also gives complete development.
• strips B, C, D, E, and F show a much more intensive image than strip A because a large part of the diazonium compound on strip A has decomposed during storage.
• the diazonium compounds according to the invention used in the example were prepared as follows:
• the azo-dyestuff of 1-phenyl-3-methylpyrazolone-5 and the 4 dimethylamino-3-methoxy-2-N-methyl-N-ethoxycar-bonylamino benzene diazonium compound melts at 147 C.
• the azo-dyestulr' of 1-phenyl-3-methylpyrazolone- 5 and the 4 dimethylamino 3-rnethoxy-2-N-n-propyl- N ethoxycarbonylaminobenzene diazonium compound melts at 130 C.
• the azo-dyestutf of 1-phenyl-3-methylpyrazolone-S and the 4-dimethylamino-3-methoxy-2-N- isobutyl-N-ethoxycarbonylaminobenzene diazonium compound melts at 102104 C.
• a second strip of the sheets A, B, C, D, E, and F is stored for some days in a moisture-tight wrapping at a temperature of C. Then the strips are imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out. The strips are then developed with developer C, with which paper A also gives complete development.
• strips B, C, D, E, and F show a much more intensive image than strip A because a large part of the diazonium compound on strip A has decomposed during storage.
• the diazonium compounds C, D, E, and F were prepared as follows:
• EXAMPLE VIII White base paper for the diazotype process, of weight 50 g./m. was sensitized with a solution containing:
• a sheet of the diazotype paper thus obtained is imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has almost completely bleached out, and then developed with developer C.
• the copy shows a brown image on a white background.
• the copy is quite suitable as an intermediate for making further copies on diazotype paper.
• the diazonium compound used in the example was prepared as follows:
• each of the liquids a sheet of opaque linen for reproduction purposes is sensitized in such a way that, after drying, each of the sheets, marked A, B, and C respectively, contains approximately 0.45 millimole of diazonium compound per m.
• the strips are developed with developer B.
• the copies on the strips B and C develop more rapidly than the copy on strip A.
• the copy on strip A shows a dark violet-brown image on a white background
• the copies on the strips B and C show a black image on a white background.
• Strip A shows a less intensive azo-dyestuff image than the strips B and C in consequence of the pyrolysis of the diazonium compound during storage.
• the diazonium compounds B and C used in the example were prepared as follows:
• Diazonium compound C was prepared in an analogous way.
• EXAMPLE X White paper of weight g./m. coated on one side with a cellulose acetate film layer (approximately 50% by weight of combined acetic acid) having a thickness of approximately 10 microns, which layer has been affixed to the paper by means of an adhesive and has been deacylated to a depth of about 4 microns to an average 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), is impregnated on the de-acylated side of the cellulose acetate layer with the following solution:
• the diazotype material thus obtained is very light-sensitive.
• a sheet of this material is imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out, and is then developed with developer A.
• the copy shows a black image on a bright white background.
• the diazonium compound used in the example was prepared as follows:
• 2,3-dichloronitrobenzene was fused with 4-chlorophe- 1101 and potassium hydroxide.
• the 3-chloro-2-(4'-chloro phenoxy)nitrobenzene was reduced and then brought into reaction with epoxyethane.
• the 3-chloro-2-(4'-chlorophenoxy)-N,N-di(2'-hydroxyethyl)aniline thus obtained was acetylated, nitrated, and deacetylated.
• alkyl and its equivalent in alkoxy where not otherwise qualified inconsistently with the meaning here given, is meant to include non-branched, branched, saturated and/or unsaturated monovalent groups, or radicals, derived from aliphatic hydrocarbons, in any of which one or more of the hydrogen atoms normally present may have been replaced by a substituent suitable for light-sensitive diazonium compounds, such as a halogen atom, an amino group, an alkoxy group, or some other.
• cycloalkyl, aralkyl, aryl, cycloalkoxy, aralkoxy and aryloxy are meant to include groups, or radicals, of the character respectively denoted by these terms, in any of 15 which one or more of the hydrogen atoms normally present may have been replaced by such a substituent.
• X is an anion
• R is alkyl, cycloalkyl or aralkyl
• R is a hydrogen atom or an alkyl, cycloalkyl, aralkyl, aryl, alkoxy, cycloalkoxy, aralkoxy or aryloxy radical;
• R is alkyl, cycloalkyl, aralkyl or aryl
• R is alkyl or aralkyl
• R is akyl, cycloalkyl or aralkyl
• X is an anion
• R is an alkyl group having 1-4 C atoms or a cycloalkyl or a benzyl group
• R is hydrogen, an alkyl or alkoxy group having 1 to 4 C atoms, or a cycloalkyl, benzyl, phenyl, benzyloxy, or phenyloxy group;
• R is an alkyl group having 1-4 C atoms of a cycloalkyl, benzyl, or phenyl group;
• R is an alkyl group having 1-4 C atoms, a benzyl group or an alkoxycarbonyloxyalkyl group having more than 4 C atoms, and
• R is an alkyl group having 1-4 C atoms, a cycloalkyl or benzyl group, or an alkoxycarbonyloxyalkyl group having more than 4 C atoms; or
• R and R together with the nitrogen atom by which they attach to the phenyl nucleus carrying the diazonium group constitute a morpholino, piperazino, piperidino or pyrrolidino ring.
• R is alkyl, aralkl or cycloalkyl.
• R is an alkyl group having at most 4 C-atoms
• R is an alkoxy group having at most 4 C-atoms
• R is a phenyl group
• R and R each is a straight chain alkyl group having at most 4 C-atoms.
• R R and R each is an alkyl group having at most 4 C-atoms
• R is an alkoxy group having at most 4 C-atoms, or a benzyloxy or phenoxy group; and R is a cyclohexyl group.
• a diazonium compound according to claim 1 namely, a 4 N,N dimethylamino-3-alkoxy-2-N-benzyl- N-ethoXy-carbonylamino benzene diazonium compound.
• a diazonium compound according to claim 1 namely, a 4 N methyl-N-cyclohexylamino-3-alkoxy-2- N alkyl N ethoxycarbonylamino benzene diazonium compound.
• a diazonium compound according to claim 1 namely, a 4 N,N dialkylamino-3-chlorophenoxy-2-N- methyl-N-ethoxycarbonylamino benzene diazonium compound.
• a diazotype material comprising a support carrying a light-sensitive layer containing a diazonium compound as defined in claim 1.
• a diazotype material comprising a support carrying a light-sensitve layer containing a diazonium compound according to claim 1.
• a diazotype material comprising a support carrying a light-sensitve layer containing a diazonium compound according to claim 2.
• a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the substantial absence of an azo coupling component, a diazonium compound according to claim 1, wherein:
• R is an alkyl group having at most 4 C-atoms
• R is an alkoxy group having at most 4 C-atoms
• R is a phenyl group
• R and R each is a straight chain alkyl group having at most 4 C-atoms.
• a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the substantial absence of an azo coupling component, a diazonium compound according to claim 1, wherein, in the said formula:
• R R and R each is an alkyl group having at most 4 C-atoms
• R is an alkoxy group having at most 4 C-atoms, or a benzyloxy or phenoxy group; and R is a cyclohexyl group.
• a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the substantial absence of an azo coupling component, a diazonium compound as defined in claim 6.
• a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the substantial absence of an azo coupling component, a diazonium compound as defined in claim 5.
• a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the substantial absence of an azo coupling component, a diazonium compound as defined in claim 8.
• a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the substantial absence of an azo coupling component, a diazonium compound as defined in claim 9.
• a one-component diazotype material comprising FOREIGN PATENTS a support carrying a light-sensitve layer containing, in the 6 407 303 1/1965 Netherlands substantial absence of an azo coupling component, a 1005:899 9/1965 Great Britai'n.

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Citations (4)

• 0
  • NL NL132069D patent/NL132069C/xx active
• 1965
  • 1965-07-02 NL NL6508566A patent/NL6508566A/xx unknown
• 1966
  • 1966-06-08 FI FI1509/66A patent/FI43677B/fi active
  • 1966-06-09 DK DK297066AA patent/DK118381B/da unknown
  • 1966-06-09 GB GB25815/66A patent/GB1082889A/en not_active Expired
  • 1966-06-13 DE DE1966C0039343 patent/DE1547655B2/de active Granted
  • 1966-06-17 JP JP41038914A patent/JPS4928448B1/ja active Pending
  • 1966-06-27 AT AT614066A patent/AT271194B/de active
  • 1966-06-27 CH CH925066A patent/CH472695A/de not_active IP Right Cessation
  • 1966-06-28 US US561040A patent/US3520692A/en not_active Expired - Lifetime
  • 1966-06-28 SE SE08773/66A patent/SE348185B/xx unknown
  • 1966-06-29 BE BE683333D patent/BE683333A/xx not_active IP Right Cessation
  • 1966-07-01 ES ES0328588A patent/ES328588A1/es not_active Expired

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