Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
  • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/52—Compositions containing diazo compounds as photosensitive substances
  • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

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

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Paper (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=5754132

Family Applications (1)

Country Status (12)

Cited By (1)

• 1969
  • 1969-12-17 DE DE1963252A patent/DE1963252C3/de not_active Expired
• 1970
  • 1970-12-07 NL NL7017820A patent/NL7017820A/xx unknown
  • 1970-12-14 BE BE760332A patent/BE760332A/fr unknown
  • 1970-12-14 AT AT1123070A patent/AT305763B/de not_active IP Right Cessation
  • 1970-12-14 ZA ZA708408A patent/ZA708408B/xx unknown
  • 1970-12-14 US US00098061A patent/US3736143A/en not_active Expired - Lifetime
  • 1970-12-15 ES ES386487A patent/ES386487A1/es not_active Expired
  • 1970-12-15 GB GB59439/70A patent/GB1282799A/en not_active Expired
  • 1970-12-15 SE SE7016971A patent/SE385877B/xx unknown
  • 1970-12-16 CA CA100785A patent/CA924710A/en not_active Expired
  • 1970-12-17 JP JP45113548A patent/JPS4840418B1/ja active Pending
  • 1970-12-17 FR FR7045522A patent/FR2073899A5/fr not_active Expired

Also Published As

Similar Documents

Legal Events