Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/42—Singly bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • 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 diazotype material i.e. sheet material comprising a support carrying a layer of a diazonium compound, and more particularly to diazotype material containing a diazonium compound selected from a class of such compounds novel for the purpose.
• the diazotype material may, for example, be so-called onecomponent diazotype material which is developed with a liquid developer, so-called two-component diazotype material which is developed with the aid of ammonia vapour, or heat-developable diazotype material.
• the invention further relates to a new class of diazonium compounds of use in the production of the said diazotype material.
• diazotype process the diazonium compound 4-diazo-2,5-diethoxy-N-benzoylaniline has been applied on a large scale.
• Known materials are one-component diazotype material, two-component diazotype material, and heat-developable diazotype material, sensitized with this diazo compound. See British patent specification No. 347,430, British patent specification No. 815,005, and The Photographic Journal, 92B, 43-48 (1952).
• acyl group of these compounds vary widely.
• R is hydrogen, or a substituted or non-substituted organic radical, such as alkyl, aralkyl, aryl, alkoxy, aralkyloxy and aryloxy, or a substituted amido group.
• the 4-diazo-2,5-di(alkyl-, aralkyl-, or aryl)oXy-N- acylanilines have reasonable light-sensitivity and great coupling activity. The latter property makes them suitable for use in one-component diazotype material, and especially in one-component diazotype material that can be developed with weakly acid phloroglucinol developers. Compare: The Photographic Journal, 92B, 43-48 (1952).
• the azo-dyestufifs formed from the 4- diazo-2,5-di(alkyl-, aralkyl-, or aryl)oXy-N-acylanilines and phlorogl-ucinol, using the said weakly acid developers have rather low absorption for radiation from the near ultra-violet part of the spectrum, the radiation with the aid of which copies are made in the diazotype process.
• diazotype copies on translucent diazotype materials, sensitized with these diazonium compounds are not particularly suitable for use as so-called intermediate copies, from which further copies are made.
• Another known compound is the diazonium compound 4-diazo-2-alkoXy-N-benzoylaniline. This compound is not very light-sensitive and practically useless because of its poor stability. See Fiat Final Report 813, page 362.
• diazotype material which comprises a support sheet carrying a layer of a diazonium compound of the general Formula II NzX wherein X is an anion, R is an alkyl (i.e., non-branched or branched alkyl), cycloalkyl or aralkyl radical, CO-R is an acyl group, R is an acylamino, alkylsulphonamido, aralkylsulphonamido, arylsulphonamido, or triazinyl group, and R, an alkyl, branched alkyl, cycloalkyl, aralkyl or aryl radical.
• R is an alkyl (i.e., non-branched or branched alkyl), cycloalkyl or aralkyl radical
• CO-R is an acyl group
• R is an acylamino, alkylsulphonamido, aralkylsulphonamido, ary
• diazonium compounds as a new class of diazonium compounds, the compounds of general Formula II just set forth.
• the diazonium compounds of Formula II have considerably higher coupling activity and, with polyvalent phenols such as phloroglucinol and resorcinol, form azo-dyestufis with greater absorption for U.V. radiation than the corresponding 2,5-di(alkyl-, aralkyl-, or aryl)oxy compounds (which compounds will hereinafter be referred to as 2,5-di-RO compounds).
• diazotype material sensitized with these new diazonium compounds develops much more rapidly than diazotype material sensitized with the corresponding 2,5-di-RO compounds and, when polyvalent phenols are used as azo components, often yields copies with azo-dyestufis having better absorption for U.V. radiation.
• the diazotype material according to the invention preferably is a one-component diazotype material.
• the conventional weakly acid phloroglucinol developers it yields copies with dark-red to brown azo-dyestuff images; upon development with the conventional weakly alkaline phloroglucinol developers it yield copies with lighter-coloured, orange-red to brown azo-dyestuff images.
• a slowly coupling compound such as 7'-hydroxy-1,2',4,S-naphthimidazole, 2-hydroxynaphthalene-3,6-disulphonic acid, and 7-hydroXy-1-biguanidinonaphthalene, may be included as azo-coupling component.
• the diazotype material according to the invention may be heat-developable diazotype material, e.g. of the type described in British patent specification No. 815,005 and in British patent application No. 47,343/ 62.
• the diazotype material according to the invention may contain an opaque support, such as opaque white paper or opaque linen, or a transparent support, such as tracing paper, tracing linen, cellulose-ester foil, polyester foil, transparentized paper and the like.
• the diazonium compound may be applied direct to the support or may be present in a hydrophilic or hydrophobic film layer which may or may not be attached to the support by means of one or more sub-layers.
• diazonium compounds which can be applied in the diazotype material according to the invention 4-diazo S-N-acetyl N-methylamino 2-methoxy N-acetylaniline 4-diazo S-N-acetyl N-methylamino 2-4-chloro(phenoxy) N-acetylaniline 4-diazo -N-octanoyl N-methylamino Z-ethoxy N-acetylaniline 4-diazo S-N-acetyl N-ethylamino Z-methoxy N-phenacetylaniline 4-diazo 5-N-acetyl N-methylamino 2-n-propoxy N-benzoylaniline 4-diazo S-N-acetyl N-methylamino 2-methoxy N 2',4'-dichlorobenzoyl) aniline 4-diazo S-N-acetyl N-acetyl N-methylamino 2-methoxy N 2'
• nitrates and metal chloride double salts e.g. diazonium chlorozincates, chlorostannates), borofluorides, and the like. They can be applied separately in the diazotype material according to the invention or be mixed together.
• the diazotype material according to the invention can all be prepared by starting from the 4-chloro 2- aminophenolalkyl, branched alkyl, cycloalkyl, aralkyl, or aryl ethers.
• the 4 chloro 2-amino-phenolalkyl, branched alkyl, cycloalkyl, and aralkylethers can be obtained from 4-chlorophenol by introducing into this product a nitro group in ortho-position relative to the hydroxyl group, and etherifying the hydroxyl group and reducing the nitro group to an amino group.
• the 4-chloro 2-aminophenolaryl ethers are obtained by fusing 2,5-dichloronitrobenzene with a hydroxyaryl compound and potassium hydroxide and reducing the nitro group.
• the amino group of the 4-chloro Z-aminophenolalkyl, branched alkyl, cycloalkyl, aralkyl, or aryl ether is (a) acylated with e.g. a carbohalide or an ester or chloroformic acid, or
• the 4-acyl, 4-sulphonamido, or 4-triazinyl Z-N-acyl N- (alkyl, branched alkyl, cycloalkyl, or aralkyl)amino 5 (alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxynitrobenzene thus formed is reduced to the corresponding amine, and then a diazonium compound is produced from it in the usual way.
• a preferred form of diazotype material according to the invention is that containing a diazonium compound of the general Formula II, in which X is an anion, R stands for a non-branched alkyl group having at most five C- atoms, -COR for an acyl group, R for an acylamino or triazinyl group, and R for an alkyl, aralkyl or aryl radical.
• This diazotype material not only couples more actively, but has moreover considerably higher light-sensitivity than diazotype material sensitized with a corresponding 2,5-di-RO compound.
• a further preferred form of diazotype material according to the invention is one-component diazotype material containing a diazo compound of the general Formula III in which X is an anion and R stands for a non-branched alkyl group having at most five C-atoms, R for a hydrogen atom or an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group, R for an alkyl, alkoxy, benzyl, benzyloxy, phenyl, or phenoxy group, and R for an alkyl or benzyl radical.
• X is an anion and R stands for a non-branched alkyl group having at most five C-atoms
• R stands for a non-branched alkyl group having at most five C-atoms
• R stands for a non-branched alkyl group having at most five C-atoms
• R stands for a non-branched alkyl group having at most five C-atoms
• R stands for
• diazonium compounds according to the above general Formula HI are eminently suitable for use in transparent one-component diazotype material for development with weakly acid phloroglucinol developers.
• diazonium compounds those in which R is an alkoxy, benzyloxy or phenoxy group are outstanding; they are more stable that the corresponding diazonium compounds in which R is an alkyl, benzyl, or phenyl radical, and the azo-dyestuffs formed from them are darker and have better Water-fastness than those formed from the corresponding diazonium compounds referred to above, so that with the diazonium compounds in which R is an alkoxy, benzyloxy, or phenoxy group a diazotype material of good stability can be made, yielding copies with a fairly dark-brown azo-dyestulf image which shows no or only very little bleeding of the azo-dyestulf upon development.
• these diazonium compounds are eminently suitable for the sensitizing of transparent diazotype materials.-The copies show a dark, very legible image with good absorption for U.V. radiation, and thus are "very suitable for use as transparent intermediate originals.
• benzene diazonium compounds which have a N-acetyl N-methyl-a-mino group in ortho-position. Furthermore they may carry methyl or methoxy substituents. These diazonium compounds have practically no light-sensitivity and are very unstable, they couple actively, whilst forming light-coloured, yellow to red azo-dyestulfs. With these diazonium compounds no diazotype material that is suitable in practice can be made.
• the auxiliary agents commonly used in diazotype materials can be applied, e.g. acids, such as citric acid, tartaric acid, and boric acid; metal salts, such as zinc chloride, nickel sulphate and alum; stabilizers, such as benzene and naphthalene diand trisulphonic acids, p-phenol sulphonic acid and their Water-soluble salts, and urea; substances which increase the developing speed, such as glycerol; substances which improve the water-fastness and/ or the shade of the azo-dyestulf, such as 7'-hydroxy-1',2',4,5,-naphthimidazole and 2-hydroxymethyl benzimidazole; particles for improving the surface of the support, such as silica, aluminum oxide, rice starch ,and polyvinyl acetate particles; binders, such as polyvinyl alcohol, methylcellulose, and starch ethers.
• acids such as citric acid, tartaric acid, and boric acid
• the phloroglucinol developers which are used in the one-component diazotype process often vary as to their composition and acidity.
• Three weakly acid phloroglucinol developers and one weakly alkaline phloroglucinol developer are described below, which are employed in practice and which are used for development in the examples following hereafter.
• Developer A is a solution of: Phloroglucinol g 4 Acetoacetanilide g 0.1
• Developer C is a solution of:
• Example I White base paper of weight 80 g./m. for the diazotype process, which has been pre-c-oated with an aqueous silica dispersion and then dried, is sensitized with a liquid containing: 4-(4-methylphenyl)-sulphonylamino S-methoxy, 2-
• the dried light-sensitive material is image-wise exposed under a transparent Indian-ink drawing until the diazo compound under the image-free portions of the drawing has bleached out, and is then developed by guiding it over a heated roller having a temperature of about 140 C., the back of the sheet contacting the roller surface.
• the copy shows a red-brown image on a white background.
• the diazonium compound used in the example is prepared as follows: S-chloro 2-methoxyaniline is tosylated with p-tosyl chloride and then nitrated. The S-methoxy 4-p-tosylamino 2-chloro l-nitrobenzene is brought into reaction with monomethylamine, and the reaction product thus obtained is acetylated. The melting point of the 5-methoxy 4-p-tosylamino Z-N-acetyl N-methylamino l-nitrobenzene thus obtained is 190 C. This nitro compound is catalytically reduced to the corresponding amine, which is then diazotized. The resulting diazonium compound is obtained in the form of the zinc chloride double salt.
• Example II White base-paper of weight 50 g./m. for the diazotype process is transparentized in the usual way by treating it with a resin solution in an organic solvent and drying it, and is then sensitized with a solution of 4-benz0ylarnino Z-N-acetyl N-methylamino S-ethoxybenzene diazonium chloride, zinc chloride double salt g 50 Tartaric acid g" 3 Boric acid g 1 Sodium salt of naphthalene 1,3,6-trisulphonic acid g 40 Gum arabic g 2.5 Rice starch g 120 Vinnapas H.60 ml 40 Water ml 1000 A sheet of the dry light-sensitive material is imagewise exposed under a transparent pencil-drawing until the diazonium compound under the white portions of the original has largely bleached out and is then developed with the developer B described above, according to the socalled thin-layer method.
• the copy shows a brown image on a foggy light-brown background.
• the image has good absorption for U.V. radiation, so that the copy is very suitable for use as an intermediate original for making further copies on diazotype material.
• the diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and ethylated with ethyl bromide to form 2-nitro 4-chloro l-ethoxybenzene.
• the nitro group of this product is catalytically reduced, after which the free amino group is benzoylated.
• the 2-benzoylamino 4-chloro l-ethoxybenzene thus formed is nitrated, subsequently brought into reaction with monomethylamine, and then acetylated, by which means S-ethoxy 4-benzoylamino Z-N-acetyl N-methylamino l-nitrobenzene is obtained.
• the melting point of this nitro compound is l94-l95 C. After the nitro group of this compound has been catalytically reduced and the amine thus formed has been diazotized, the diazonium compound is obtained in the form of the zinc chloride double salt.
• Example 111 A cellulose acetate film layer of weight about 20 g./m. applied on natural tracing paper of weight about g./ m. is superficially hydrolysed to a depth of about 4 ,u. and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:
• a sheet of the dry transparent diazotype paper is imagewise exposed under a transparent ink drawing until all the diazo compound under the image-free portions of the original has bleached out and is then developed with developer B according to the thin-layer method.
• the transparent copy obtained shows a brown image, which has fairly good absorption for U.V. radiation.
• the diazonium compound used according to the example is prepared as follows: 5-ch1oro 2-methoxyaniline is benzoylated and then nitrated. The 5-chloro 4-nitro 2- methoxy N-benzoylaniline thus formed is brought into reaction with monomethylamine and then acetylated with hexanoyl chloride. The S-methoxy 4-benzoylamino 2-N- hexanoyl N-methylamino l-nitrobenzene melts at 117- 119 C. The nitro group of this compound is catalytically reduced and the amine thus formed is diazotized. The diazonium compound is obtained in the form of the zinc chloride double salt.
• Example IV A cellulose acetate film layer of weight about 20 g./m. applied on a natural tracing paper of weight about 80 g./m. is superficially hydrolysed to a depth of about 4 and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:
• a sheet of the dry transparent diazotype paper is imagewise exposed and developed as described in Example III.
• the copy thus obtained shows a violet-brown image that has good absorption for U.V. radiation.
• the diazonium compound used in the example is prepared as follows: 5-chloro 2-methoxyaniline is converted into 5-chloro 4-nitro2-methoxy N-benzoylaniline as described in Example III.
• Example V By immersion, transparent cloth type Sub./ 0/ 86 (from Red Bridge Book Cloth Company, Red Bridge, Ainsworth, Bolton, England) is coated with a layer of weight about 70 g. /m. of the following liquid:
• hydrophilic poylvinyl acetate layer is sensitized with a solution of:
• the hydrophilic light-sensitive layer obtained after drying contains about 0.9 millimol of diazonium compound per in. sensitized surface.
• a sheet of the transparent diazotype linen thus obtained is image-wise exposed and developed as described in Example II.
• the copy thus obtained shows a darkbrown azo-dyestuff image on a foggy light-brown back ground.
• the azo-dyestuff image has good absorption for U.V. radiation.
• the diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and ethylated with ethyl bromide ,to form 2-nitro 4-chloro l-ethoxybenzene.
• the nitro group of this compound is catalytically reduced, after which the amino group thus obtained is acetylated.
• the 2-acetylamino 4-chloro l-ethoxybenzene thus formed is nitrated, brought into reaction with monoethylamine, and then acylated with octanoyl bromide, by which reaction S-ethoxy 4-acetylamino 2-N- octanoyl N-methylamine l-nitrobenzene is obtained.
• the melting point of this compound is -127 C. After the nitro group of this compound has been reduced and the amine thus formed has been diazotized, the diazonium compound is obtained in the form of the zinc chloride double salt.
• Example VI A clear cellulose acetate film of 150 g./m. with an acetyl content of approximately 2.5 acetyl groups per unit of glucose of the cellulose acetate is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:
• the diazotype material thus obtained is very light-sensitive and has a high developing speed.
• a sheet of this diazotype material is exposed under a transparent India ink drawing until all the diazonium compound under the image-free portions of the drawing has bleached out, and is then developed with developer B.
• the copy shows a brown image on a crystal-clear background.
• the copy thus obtained is eminently suitable for use as an intermediate original for making further copies.
• the azo-dyestufr image has good absorption for U.V. radiation.
• the diazonium compound used in the example is prepared as follows: 5-chloro 2-rnethoxyaniline (HCl salt) is brought into reaction with dicyanodiamide, by which means 5-chloro Z-methoxy l-biguanidinobenzene is obtained. With the aid of acetic anhydride this compound is converted into 1-(5-chloro 2-methoxy phenyl) Z-amino 4-imino 6-methyl triazine (1,3,5), which compound is nitrated, after which the product thus obtained is brought into reaction with monomethylamine.
• Example VII A clear cellulose acetate film of weight 150 g./m. with an acetyl content of about 2.5 acetyl groups per unit of glucose of the cellulose acetate is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of:
• the hydrophilic light-sensitive layer obtained after drying contains about 0.5 millimol of diazonium compound per m. of the sensitized surface.
• a sheet of the diazotype material thus prepared is image-wise exposed and developed as described in Example III.
• the copy thus obtained shows a red-brown image on a crystal-clear background.
• the aZo-dyestuff image has good absorption for UV. radiation.
• the diazonium compound used in the example is prepared as follows: 4-methoxyaniline is nitrated to form 4- methoxy 3-nitroaniline, and With p-tosyl chloride this product is converted into 4-methoxy 3-nitro N-p-tosylaniline, which is methylated with dimethyl sulphate, after which it is hydrolysed to 4-methoxy 3-nitro N-methylaniline.
• This compound is acetylated and its nitro group is reduced, by which means Z-methoxy S-N-acetyl N- methylaminoaniline is obtained. This compound is brought into reaction with phosgene.
• N,N'-bis(2-methoxy 5- N-acetyl N-methylamino phenyl)urea is formed, from which, upon nitration, N,N'-bis(2-methoxy S-N-acetyl N-methylamino 4-nitrophenyl)urea is obtained, the latter compound melting at 279283 C.
• This nitro compound is converted into the above-mentioned diazonium salt in the usual way.
• Example VIII Transparent linen for the diazotype process, e. g. Winterbottom NFSB cloth (from The Winterbottom Book Cloth 00., Manchester 2, England), is sensitized with a solution of:
• a sheet of the diazotype linen thus obtained is imagewise exposed as described in Example 111 and developed with developer C.
• the copy obtained shows a brown azo-dyestuff image.
• the diazonium compound used in the example is prepared as follows: 5-chloro 2-methoxyaniline is phenacetylated and then nitrated. The 5-chloro 4-nitro Z-methoxy N-phenacetylaniline thus formed is brought into reaction with monoethylamine and then acetylated. The S-methoxy 4-phenacetylamino Z-N-acetyl N-ethylamino l-nitrobenzene melts at 158 C. The nitro group of this compound is reduced to amino group and the amine is diazotized. The diazonium compound is obtained in the form of the zinc chloride double salt.
• Example IX White base paper of weight g./m. for the diazotype process is sensitized with a liquid containing:
• Zinc chloride double salt of 4-benzoylamino S-methoxy Z-N-benzyloxycarbonyl N-rnethylamino ben- A sheet of the diazotype paper thus obtained is imagewise exposed under a transparent ink drawing until all the diazonium compound under the image-free portions of the drawing has bleached out and is then developed with developer A. The copy obtained shows a brown image on a clear white background.
• the diazonium compound used in the example is pre- Example X A cellulose acetate film layer of weight about 20 g./m.
• a sheet of dry the light-sensitive material is image-wise exposed under 'atransparent pencil drawing until the diazonium compound under the image-free portions of the original has largely bleached out and is then developed with developer B.
• the copy shows a brown image on a foggy light-brown background.
• the image has good absorption for UV. radiation, so that the copy is very suitable for use as an inter-mediate original.
• the diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and butylated with n-butyl bromide. The nitro group of the product obtained is reduced and the amino compound resulting therefrom is benzoylated. The Z-benzoylamino 4-chloro 1-butoxyben zene thus formed is nitrated, brought into reaction with" monomethylamine, and then acetylated. Thus butoxy 4-benzoylamino 2-N-acetyl N-:methylamino l-nitrobenzene is obtained, which compound .melts at 120- 122 C. From this nitro compound the above-mentioned a n Salt s. f m d,
• a sheet of the dry light-sensitive material is image-wise exposed under a transparent pencil drawing until the diazonium compound under the image-free portions of the original has largely bleached out and is then developed with developer D.
• the copy shows a brown image on a foggy light-brown background.
• the image has good ab sorption for UV. radiation, so that the copy is very suitable for use as an intermediate original.
• the diazonium compound used in the example is prepared as follows: S-chloro 2-methoxyaniline is acylated with the ethyl ester of chloro-fonnic acid and then nitr-ated. The S-ch'loro 4-nitro 2-methoxy N-ethoxycarbonylaniline thus formed is then brought into reaction with monomethylamine and acetylated. The 5-rnethoxy 4- ethoxycarbonylamino 2-N-acetyl N-methylamino l-nitrobenzene melts at 202-203" C. From this nitro compound the corresponding diazonium compound is prepared in the usual way, said compound being obtained in the form of the zinc chloride double salt.
• Example XII A transparentized rag paper, such as transparentized rag paper grade 506 (from Plastic Coating Corp, Holyoke, Mass., U.S.A.), is sensitized with a solution of:
• a sheet of the diazotype material thus obtained is image-wise exposed and developed as described in Example X.
• the copy shows a brown image on a foggy light-brown background
• the image has good absorption for UV. radiation and consequently is very suitable for use as an intermediate original.
• the diazonium compound used in the example is prepared as follows: S-methylamino 4-nitro Z-methoxy N- benzoylaniline (see Example IX) is brought into reaction with adipyl chloride, N,N'-dimethyl N,N'-bis(2'-nitro 4- methoxy. 5-benzoylaminophenyl) adipic diamide thus be ing formed, which compound melts at 229-231" C. The nitro groups of this compound are reduced, the amino groups diazotized, and the bis-diazonium compound is obtained in the form of the zinc chloride double salt.
• Example XIII White paper of weight 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 is aflixed to the paper by means of an adhesive and deacylated to a depth of-about 4 microns to an acetyl content calculated as combined acetic acid of on an average approximately 20% by weight (which corresponds to an average number of acyl groups per unit of glucose of the cellulose acetate of 0.7), is impregnated on the deacylated side of the cellulose acetate layer with the following solution:
• the diazotype material thus obtained is very lightsensitive.
• a sheet of it is image-wise exposed and developed as described in Example III.
• the copy shows a violetblack image on a white background.
• the diazonium compound used in the example is prepared as follows: 4-chlorophenol is nitrated and converted with n-propyl bromide into 2-nitro 4-chloro l-propoxybenzene. The nitro group of this compound is reduced and the amino compound thus formed is benzoylated.
• the 5- chloro 4-nitro 2-propoxy N-benzoylaniline is brought into reaction with monomet'hylamine and then acylated with the ethyl ester of chloro-formic acid to form S-propoxy 4- benzoylamino Z-N-ethoxycarbonyl N-methylamino l-nitrobenzene, which compound melts at 124126 C. From this nitro compound the diazonium chloride, zinc chloride double salt, is obtained in the usual way.
• Example XIV Sized natural tracing paper of weight 80 g./m. is sensitized with a liquid containing: 4-acetylamino 5-(4'-chloro)phenoxy Z-N-acetyl N- methylarninobenzene diazonium chloride, zinc chloride double salt g 63 Alum g 5 Rice Starch g 40 Gelatin g 2 Vinnapas H.60 ml 50 Water ml 950 and dried.
• a sheet of the dry light-sensitive material is image-wise exposed and developed as described in Example VIII.
• the copy shows a brown image on a transparent background.
• the image has good absorption for UV. radiation, so that the copy is very suitable for use as an intermediate original.
• the diazonium compound used in the example is prepared as follows: S-chloro 2(4-chloro)phenoxyaniline is acetylated and then nitrated. The 5(4-ch loro)phenoxy 4- acetylamino Z-chloro l-nitrobenzene thus formed is brought into reaction with monomethylarnine, after which the reaction product is acetylated. The melting point of the 5(4'-chloro)phenoxy 4 acetylamino 2-N-acetyl N-methy'lamine l-nitrobenzene thus prepared is 21 0212 C. This nitro compound is converted in the usual way into diazonium compound, which is obtained in the form of the zinc chloride double salt.
• Example XV Sized natural tracing paper is pre-coated with an aqueous dispersion of colloidal silica, in which anionic dispersed polyvinyl acetate, such as Setamul N28 (from Synthese N.V., Katwijk aan Zee, Netherlands) is present as a binder, and dried.
• the paper thus pre-coated is sensitized with a liquid containing:
• the diazonium compound used in the example is prepared as follows: S-chloro Z-methoxyaniline is successively benzoylated, nitrated, and brought into reaction with monomethylamine. The S-methoxy 4-benzoylamino Z-methylamino l-nitrobenzene thus obtained is acetylated. The nitro compound thus obtained melts at 206-208 C.
• the diazonium compound is prepared in the usual way, said compound being obtained in the form of the zinc chloride double salt.
• Example XVI White paper coated with a so-called baryta layer is sensitized with a solution containing:
• the copy shows a violet-red image on a white background.
• the diazonium compound used in the example is prepared as follows: S-chloro 2(4-chlorophenoxy)aniline is benzoylated and then nitrated.
• the 5-(4'-ch-loro)phenoxy 4-benzoylamino 2-chloro l-nitrobenzene is brought into reaction with monomethylamine, after which the reaction product is acetylated.
• the melting point of the 5-(4'-chloro)phenoxy 4-benzoylamino 2-N-acetyl N- methylamino l-nitirobenzene thus prepared is -182184 C. From [this nitro compound the diazonium compound is prepared in the usual way and obtained in the form of the zinc chloride double salt.
• Example XVII White base paper of weight g./m. for the diazotype process is sensitized with a liquid containing:
• a sheet of the diazotype material thus obtained is image-wise exposed as described in Example II and then developed with developer A.
• the copy shows a darkbrown image on a foggy brown background.
• Example II Another sheet is also exposed as described in Example II and then developed with developer D.
• the copy shows a brown image on a foggy light-brown background.
• the diazonium compound used in the example is prepared as follows: p-Chlorophenol is converted W t aid of cyclopenty ⁇ bromide into 4-chloro l cyclopentyh oxybenzene. This product is nitrated, the nitro group 18 subsequently reduced, and the amino group is benzoylated.
• the 2 -'beuzoy1amino 4-chlotro l-cyclopentyloxybem in which X is an anion; R is an alkyl, a cycloalkyl or an aralkyl radical; COR is an acyl group; R is an acylamino, an alkylsulphonamido, an aralkylsulphonamido, an arylsulphonamido or a 1,3,5 triazinyl group; and R is an alkyl, a cycloalkyl, an aralkyl or an aryl radical.
• Diazotype material according to claim 1, wherein R is a nonbranched alkyl group having at most five C- atoms; R is an acylamino or 2. 1,3,5 triazinyl group; and R is an alkyl, an aralkyl or an aryl radical.
• diazonium compound is a compound of the general formula:
• R is a nonbranched alkyl group having at most five C-atoms;
• R is a hydrogen atom or an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group;
• R is an alkyl, alkyloxy, benzyl, benzyloxy, phenyl or phenoxy group; and
• R is an alkyl or a benzyl radical.
• X is an anion
• R is an alkyl, a cycloalkyl or an aralkyl radical
• COR is an acyl group
• R is an acylamino, an alkylsulphonamido, an aralkylsulphonamido, an arylsulphonamid-o or a triazinyl group
• R is an alkyl, a cycloalkyl, an aralkyl or an aryl radical.
• R is a non branched alkyl group having at most five C-atoms; R is an acylamino or a triazinyl group; and R is an alkyl, aralkyl or aryl radical.
• R is a nonbranched alkyl group having at most five C-atoms;
• R is a hydrogen atom or an alkyl, an alkoxy, a benzyl, a benzyloxy, a phenyl or a phenoxy group;
• R is an alkyl, an alkyloxy, a benzyl, a benzyloxy, a phenyl or a phenoxy group; and
• R is an alkyl or a benzyl radical.
• R is an alkoxy, a benzyloxy' or a phenoxy group.

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• 0
  • NL NL121032D patent/NL121032C/xx active
  • NL NL288469D patent/NL288469A/xx unknown
  • DE DENDAT1251656D patent/DE1251656B/de active Pending
• 1964
  • 1964-01-15 DK DK20364AA patent/DK114878B/da unknown
  • 1964-01-16 FI FI0089/64A patent/FI40438B/fi active
  • 1964-01-20 SE SE658/64A patent/SE315496B/xx unknown
  • 1964-01-21 GB GB2596/64A patent/GB1045242A/en not_active Expired
  • 1964-01-27 US US340534A patent/US3338713A/en not_active Expired - Lifetime
  • 1964-01-30 BE BE643153D patent/BE643153A/xx unknown
  • 1964-01-31 ES ES295910A patent/ES295910A1/es not_active Expired
  • 1964-02-03 CH CH122664A patent/CH461267A/de unknown

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