US3676140A - Diazo recording - Google Patents

Diazo recording Download PDF

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Publication number
US3676140A
US3676140A US94575A US3676140DA US3676140A US 3676140 A US3676140 A US 3676140A US 94575 A US94575 A US 94575A US 3676140D A US3676140D A US 3676140DA US 3676140 A US3676140 A US 3676140A
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US
United States
Prior art keywords
group
benzothiazolium
stands
hydrogen
diazonium
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Expired - Lifetime
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US94575A
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English (en)
Inventor
Albert Lucien Poot
Henri Depoorter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/58—Coupling substances therefor

Definitions

  • R stands for an organic group introduced by quaternization
  • R stands for hydrogen, an alkyl group, a phenyl group, an alkoxy group, a halogen atom, an amino group, cyano, an alkoxycarbonyl group, an acyl group, or an alkylsulphonyl group,
  • R stands for hydrogen, a C -C alkyl group, an alkoxy group, cyano, cyanovinyl or a halogen atom,
  • R stands for hydrogen, halogen, a sulpho group or a sulphamyl group, the benzene ring of the benzothiazolium nucleus carrying at least one substituent other than hydrogen and being free of a methoxy group in the 6-position; and recording materials useful therein.
  • -A preferred benzothiazolium compound is 2,3,5,6-tetramethyl-benzothiazolium methylsulphate and a preferred diazonium compound p-diethylaminobenzene-diazonium tetraborofiuoride.
  • This invention relates to recording and reproduction of information and to the use of particular chemical compounds in the diazo recording process and material.
  • diazo recording process is based on the fact that certain diazo compounds, e.g. diazonium salts, can be decomposed information-wise by light under nitrogen evolution and remaining diazo compound can react with a so-called coupler to form a dye.
  • diazo compounds e.g. diazonium salts
  • the recording material contains a diazo compound and a coupler.
  • it contains an acid that prevents the premature reaction of the diazo compound and the coupler.
  • a volatile base such as ammonia. This neutralizes the acid and allows the remaining diazonium compound to combine with the coupler and to form a dye in the image areas.
  • the recording material contains only the diazo compound. After the recording material has been exposed image-wise to ultra-violet light, it is treated with an alkaline solution containing the coupler. The remaining diazo compound couples with the coupler in the non-exposed areas.
  • a coupler in the broader definition is a substance that bears an active or mobile hydrogen atom.
  • Normally used couplers are aromatic hydroxy compounds such as phenols and naphthols of which 2,3'-dihydroxynaphthalene-6-sulphonic acid is a typical example.
  • Couplers contain a reactive methyl or methylene group as described in the Belgian patent specification 459,543 filed Aug. 3, 1945 by Gevaert Photo- Producten NV. and United States patent specification 2,532,744 of James M. Straley, issued Dec. 5, 1950. Typical examples of the latter class are quaternary salts of 2-methyl quinoline, Z-methyl thiazole and Z-methylbenzothiazole, and N-methyl-Z-methylene-benzothiazoline.
  • the present invention more particularly relates to the use in diazotype recording of couplers that contain an active methyl group.
  • said couplers are used in the one-component as well as in the two-component diazo system.
  • said couplers combine a high coupling activity with a high shelf life of the recording material.
  • couplers according to the following general formula may be used with suitable diazonium compounds to form dyes that have a deep violet to neutral black colour:
  • X- represents an anion, e.g. a chloride, bromide, iodide, perchlorate, thiocyanate, benzene sulphonate, p-toluene sulphonate, methyl sulphate, ethyl sulphate or a propyl sulphate anion, but X is missing when the anion is already contained in the R group (betaine' salt form), e.g. as a group,
  • R stands for an organic group introduced by quaternization, e.g. an aliphatic group, including a cycloaliphatic group, a saturated aliphatic group, an unsaturated aliphatic group or one of said groups in substtiuted form, e.g. an alkyl group, more particularly a C -C alkyl group, an allyl group, a cycloalkyl group, e.g. a cyclopentyl or cyclohexyl group, a substituted cycloalkyl group, a substituted alkyl group, e.g.
  • a hydroxy alkyl group a carboxy alkyl group, a sulpho alkyl group, a sulphato alkyl group, a phospho alkyl group, a phosphoester substituted alkyl group, an acetoxyalkyl group, wherein the substituted alkyl group preferably contains from 1 to 4 carbon atoms, such as in 18- hydroxyethyl, fl-acetoxyethyl, sulphopropyl, sulphobutyl, phosphopropyl, sulphatopropyl, and sulphatobutyl, further the substituted alkyl group wherein M is hydrogen, an onium group or a metal atom; B represents a lower alkylene group such as a methylene, ethylene, propylene, or butylene group, and A represents a methylene group or,
  • a N-(methylsulphonyl)- carbarnylmethyl group a v-(acetylsulphamyl)-propyl, or a 5-(actylsulphamyD-butyl group)
  • an aromatically substituted alkyl group e.g. a benzyl group, a phenylethyl group, a substituted aralkyl group, e.g. a hydroxy benzyl group, a carboxy benzyl group, a sulpho benzyl group, a halogenated benzyl group, e.g. a bromobenzyl group, and
  • R stands for hydrogen, an alkyl group including a substituted alkyl group, e.g. a C C alkyl group e.g. methyl, a substituted alkyl group, e.g. benzyl, hydroxy methyl, sulphomethyl or trifluoromethyl, an alkoxy group e.g. methoxy, fluorine, bromine or iodine, amino including substituted amino, cyano, an alkoxycarbonyl group, an acyl group, e.g. an acetyl group, an alkylsulphonyl group, e.g. a methylsulphonyl group,
  • R stands for hydrogen, a C -C alkyl group, a substituted alkyl group, an alkoxy group, cyano, cyanovinyl, a halogen atom, e.g. fluorine, chlorine or bromine,
  • R stands for hydrogen, a halogen atom, e.g. fluorine, chlorine or bromine, sulpho or sulphamyl, the benzene ring of the benzothiazolium nucleus carrying at least one of the substituents enumerated for R R and R other than hydrogen and being free from a methoxy group in the 6-position.
  • a halogen atom e.g. fluorine, chlorine or bromine, sulpho or sulphamyl
  • 2-methyl-benzothiazolium compounds are known as starting materials for the preparation of methine dyes suited for the spectral sensitization of photographic silver halide emulsion materials.
  • methine dyes suited for the spectral sensitization of photographic silver halide emulsion materials.
  • preparation of 5-fluoro, S-trifiuoromethyl and S-cyano-Z-methyl-benzothiazoles and their quaternary salts in connection with the manufacture of cyanine dyes has been described by A. I. Kiprianov and L. M. Yagupolsky, Zhur. Obshchei Khim., 22, 2209-15 (1952) or J. Gen. Chem., 22, 2267- 2272 (1952).
  • betaine type salts according to the above general formula may e.g. proceed according to methods described in the United Kingdom patent specifications 886,270 filed June 24, 1957 by Gevaert Photo- Producten N.V., 886,271 filed June 20, 1957 by Gevaert Photo-Producten N.V., and 904,332 filed July 5, 1957 by Gevaert Photo-Producten N.V. and the French patent specification 1,149,769 filed May 14, 1956 by Agfa Wolfen.
  • the diazonium salts suitable for use according to the present invention can be defined as aromatic compounds bearing a diazo group, of which one valency is satisfied by a carbon atom from the aromatic nucleus and the other valency by an acidic ion.
  • Particularly suitable diazonium compounds are the stabilized diazonium salts, preferably the zinc chloride double salts and fluoroborates.
  • Exemplary diazonium salts are those prepared by diazotisation of amines listed in Table 2.
  • the benzothiazolium compounds containing a S-methyl group or a plurality of methyl groups on the benzene part of the benzothiazolium nucleus e.g. containing a methyl group in the 6- and 7-position of the benzothiazolium nucleus
  • the benzothiazolium compounds containing on the benzene part of the benzothiazolium nucleus at least one methyl group and at least one methoxy group e.g. containing simultaneously one methyl group in the or 6-position and one methoxy group in the 5- or 6- position of the benzothiazolium nucleus, are particularly suited to produce by coupling with a diazonium compound a dye with neutral black colour.
  • Diazonium compounds that are preferably used for obtaining a neutral black dye by coupling with the hemethiazolium compounds of the general formula are prepared by diazotisation of primary aromatic amines that in para-position with respect to the primary amino group contain a tertiary amino group such as a dialkylamino group, wherein the alkyl groups may be substituted.
  • Suitable supports or layers used in copying materials according to the present invention have liquid-absorbing characteristics as e.g. ordinary wood pulp paper or rag type paper but also textiles including fabrics made of cotton, cellulose acetate, regenerated cellulose, in other words all types of woven or felted materials, which can be impregnated with a solution containing one or more of the diazonium compounds and/ or couplers, may be used.
  • a transparent sheet is used as support, e.g. a water-impermeable resin sheet.
  • a transparent film-supports of use in silver halide photography When using a water-impermeable resin sheet as support the imaging chemicals are preferably applied into a hydrophilic colloid layer e.g. a gelatin-containing layer.
  • the radiation sensitive coating composition containing a diazonium compound may contain all kinds of other ingredients, e.g. wetting agents, substances generating a base on heating or a thermally activatable base releasing material, e.g. urea and the substances used for that purpose described, e.g. in the United Kingdom patent specification 983,363 filed May 8, 1961 by Nashua Corporation and the French patent specifications 1,376,708 and 1,376,709 both filed Sept. 17, 1963 by Et. Bauchet Co.,
  • optical brightening agents pigments, e.g. silica and antioxidants improving the whiteness of the areas, in which the diazonium compound has been destroyed.
  • Suitable antioxidants are thiourea, ascorbic acid and allyl isothiocyanate in concentrations ranging from 15 to 25 percent by weight in respect of the diazonium salts.
  • Preferred amounts of diazonium compound and conpler per sq. m. are in the range of 0.1 g. to 0.5 g. and 0.1 g. to 1.5 g. respectively.
  • a good storage stability of a coating composition containing a diazonium compound and a coupler according to the general formula can be obtained by using in admixture with said compounds an acid, e.g. citric acid, tartaric acid, boric acid, trichloroacetic acid, tribromoacetic acid, sulphosalicylic acid, phosphoric acid or 1,3,6-naphthalene trisulphonic acid disodium salt in an amount of to 200 percent by weight in respect of the diazonium salt.
  • an acid e.g. citric acid, tartaric acid, boric acid, trichloroacetic acid, tribromoacetic acid, sulphosalicylic acid, phosphoric acid or 1,3,6-naphthalene trisulphonic acid disodium salt.
  • EXAMPLE A coating composition was prepared by mixing the following ingredients until dissolution of the water-soluble compounds:
  • the composition was coated onto a paper base in a proportion of 19 g. per sq. m. and after drying through a line diapositive exposed with ultraviolet light in a common diazotype copying apparatus.
  • a dry or Wet diazo process which comprises the coupling of a diazo compound with a benzothiazolium compound corresponding to the following general formula:
  • X stands for an anion, but X" is missing when the anion is already contained in the R group,
  • R stands for hydrogen, an alkyl group, a phenyl group, an alkoxy group, a halogen atom, an amino group, cyano, an alkoxycarbonyl group, an acyl group, or an alkylsulphonyl group,
  • R stands for hydrogen, a C -C alkyl group, an alkoxy group, cyano, cyanovinyl or a halogen atom,
  • R stands for hydrogen, halogen, a sulpho group or a sulphamyl group, and wherein the benzene ring of the benzothiazolium nucleus carries at least one of the substituents enumerated for R R and R other than hydrogen and is free from a methoxy group in the 6-position.
  • a dry or wet diazo process according to claim 3, wherein the diazonium compound is of the zinc chloride double salt or fluoroborate type.
  • X- stands for an anion, but X" is missing when the I 10 cyano, an alkoxycarbonyl group an acyl group, or an alkylsulphonyl group,
  • R stands for hydrogen, a C -C alkyl group, an alkoxy group, cyano, cyanovinyl or a halogen atom,
  • R stands for hydrogen, halogen, a sulpho group or a sulphamyl group, and wherein the benzene ring of the benzothiazolium nucleus carries at least one of the substituents enumerated for R R and R other than hydrogen and is free from a methoxy group in the 6-position.
  • a diazotype recording material wherein the diazo compound has been prepared by diazotisation of a primary aromatic amine that in paraposition with respect to the primary amino group contains a tertiary amino group.
  • a diazot'ype recording material wherein the diazo compound is a diazonium salt of the zinc chloride double salt or fiuoborate type.
  • a diazo type recording material according to claim 8 wherein the diazonium salt corresponds to one of the following structural formulae:

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  • Chemical & Material Sciences (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)
  • Heat Sensitive Colour Forming Recording (AREA)
US94575A 1969-12-23 1970-12-02 Diazo recording Expired - Lifetime US3676140A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB6270869 1969-12-23

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US3676140A true US3676140A (en) 1972-07-11

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US (1) US3676140A (enrdf_load_stackoverflow)
JP (1) JPS4834765B1 (enrdf_load_stackoverflow)
BE (1) BE759935A (enrdf_load_stackoverflow)
CA (1) CA920580A (enrdf_load_stackoverflow)
DE (1) DE2061239A1 (enrdf_load_stackoverflow)
FR (1) FR2073027A5 (enrdf_load_stackoverflow)
GB (1) GB1332459A (enrdf_load_stackoverflow)
NL (1) NL7018257A (enrdf_load_stackoverflow)
SU (1) SU363264A3 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985562A (en) * 1973-05-18 1976-10-12 Agfa-Gevaert N.V. Diazo recording process and material
US4130426A (en) * 1974-04-22 1978-12-19 Fuji Photo Film Co., Ltd. Heat developable light-sensitive diazotype materials and process of use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985562A (en) * 1973-05-18 1976-10-12 Agfa-Gevaert N.V. Diazo recording process and material
US4130426A (en) * 1974-04-22 1978-12-19 Fuji Photo Film Co., Ltd. Heat developable light-sensitive diazotype materials and process of use

Also Published As

Publication number Publication date
GB1332459A (en) 1973-10-03
BE759935A (fr) 1971-06-07
NL7018257A (enrdf_load_stackoverflow) 1971-06-25
DE2061239A1 (de) 1971-07-01
FR2073027A5 (enrdf_load_stackoverflow) 1971-09-24
CA920580A (en) 1973-02-06
JPS4834765B1 (enrdf_load_stackoverflow) 1973-10-23
SU363264A3 (enrdf_load_stackoverflow) 1972-12-30

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