US3676138A - Formation of dyes suited for reproduction purposes - Google Patents

Formation of dyes suited for reproduction purposes Download PDF

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Publication number
US3676138A
US3676138A US94574A US3676138DA US3676138A US 3676138 A US3676138 A US 3676138A US 94574 A US94574 A US 94574A US 3676138D A US3676138D A US 3676138DA US 3676138 A US3676138 A US 3676138A
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US
United States
Prior art keywords
group
diazonium
diazo
quaternary salt
compound
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US94574A
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English (en)
Inventor
Albert Lucien Poot
Henri Depoorter
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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

  • the quaternary salt is substituted on the nitrogen atom of the benzthiazolium nucleus with a CH Y group in which Y is an electron-withdrawing group such as in a --CH CONHSO CH group; and recording materials useful therein.
  • This invention relates to the formation of dyes, to recording and reproduction of information and to the use of particular chemical compounds in the diazo recording process.
  • the 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.
  • the remaining diazo compound can react with a so-called coupler to form a dye.
  • the recording material contains a diazonium compound and a coupler in intimate contact therewith in the same layer.
  • it contains an acid that prevents the premature reaction of the diazonium 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 diazonium compound. After the recording material has been exposed imagewise to ultra-violet light, it is treated with an alkaline solution containing the coupler. The remaining diazonium compound couples with the coupler in the non-exposed areas.
  • Usual couplers are aromatic hydroxy compounds such as phenols and naphthols of which 2,3-dihydroxynaphthaleen-6-sulphonic acid is a typical example.
  • Couplers contain a reactive methyl or methylene group as described in Belgian patent specification 459,543 filed Aug. 3, 1945 by Gevaert Photo-Producten NV. and US. patent specification 2,532,744 of James M. Straley, issued Dec. 5, 1950.
  • Typical examples of the latter class are quaternary salts of Z-methylquinoline, Z-methylthiazoline and 2-methylbenzothiazole, and N-methyl-Z-methylene-benzothiazoline.
  • diazotype printing it is very diflicult to obtain a black print with one diazonium compound and one coupler.
  • dyes with a neutral black colour tone can be produced by the coupling of a diazonium compound with a quaternary salt of 2-methyl-5,6- dimethoxybenzothiazole and/or a quaternary salt of 2- methylbenzothiazole the carbon atoms of which in the 5- and 6-position make part of a fused ring closed by a -0CH -O- or -OCH -CH -O- group.
  • Quarternary salts that are preferably used in the recording process and materials according to the present invention correspond to one of the following general Formulae I and II:
  • R represents a substituent 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 substituted 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. an aromatically substituted alkyl group, e.g.
  • a benzyl group a phenyl ethyl group, a substituted aralkyl group, e.g. a carboxybenzyl group, a sulphobenzyl group, a halogenated benzyl group, e.g. a bromo-benzyl group, a hydroxy-benzyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulphoalkyl group, a
  • sulphatoalkyl group a phosphoalkyl group, a phosphoester-substituted alkyl group, an acetoXy-alkyl group, wherein the alkyl group preferably contains from 1 to 4 carbon atoms, such as in fi-hydroXyethyl, B-acetoxyethyl, sulphopropyl, sulphobutyl, phosphopropyl, propyl sulphate, and butyl sulphate, further the substituted alkyl group A-(
  • a sulphocarbomethoxymethyl group an w-sulphocarbopropoxymethyl group, a p-(w-sulphocarbobutoxy)-benzyl group
  • A represents a lower alkylene group such as methylene, ethylene, propylene
  • B represents an alkyl group, an
  • n 1 or 2
  • 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 if the anion is already contained in the R group (betaine salt form).
  • the quaternary 2-methyl-5,6-dimethoxy-benzothiazolium compounds can be prepared by quarternization of the corresponding bases.
  • benzothiazolium compound the following receipt is given:
  • the benzothiazole compound having the following structural formula ⁇ CCH3 CH2 I and its quaternary salts can be prepared according to J. D. Kendall and H. G. Suggate, J. Chem. Soc. 1503 (1949).
  • a neutral black dye by coupling
  • the couplers used according to the present invention preferably diazonium compounds are used, 'Which are prepared by diazotation of primary aromatic amines containing in para-position with respect tothe primary amino group a tertiary amino group such as a dialkylamino group.
  • Typical examples of such amines are p-aniino-N,N-diethylaniline and p-amino-N-ethyl-N-benzylaniline.
  • the initial colour obtained with said couplers on coupling with diazo 69 is violet to dark violet and turns into neutral black on storage.
  • the quaternary salts of 2 methyl 5,6-dimethoxybenzothiazole can be used successfully in the one-component as well as in the two-component diazo system.
  • Said quaternary salts can further be used in a so-called thermodiazo process.
  • a recording material containing such a quaternary salt as coupler, a diazonium compound, a pH-reducing compound to prevent premature coupling, and optionally a compound forming or releasing a base on heating is (l) exposed information-wise to electromagnetic radiation that decomposes information-wise the diazonium compound and (2) is overall heated, whereby coupling takes place in accordance with the non-exposed portions of the recording material.
  • Diazo recording materials according to the present invention contain the diazonium compound preferably in a flexible sheet or supported flexible layer.
  • 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.
  • a transparent sheet is used as support, e.g. a water-impermeable resin sheet.
  • the imaging chemicals are preferably incorporated 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 1,37 6,- 709 both filed Sept. 17, 1963, by Et. Bauchet Co., further 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 to 25 percent by weight in respect of the diazonium salts.
  • Preferred amounts of diazonium compound and coupler per sq. m. are in the ranges 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 general Formula I can be obtained by using an 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 100 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.
  • diazo compounds includes the diazonium salts prepared by diazotation of an aromatic amine but also the diazonium salts produced from diazo sulphonates, which compounds may also be employed in a diazo recording process according to the present invention.
  • EXAMPLE 1 A coating composition was prepared by mixing the following ingredients until dissolution of the water-soluble compounds thereof: p-Diethylaminobenzene diazonium tetrafluoroborate (diazo 69) g 6 2-methyl 3 methylsulphonylcarbamylmethyl 5,6-
  • composition was coated onto a paper base in a proportion of 19 g. per sq. m. and after drying exposed 6 through a line diapositive with ultraviolet light in a common diazotype copying apparatus.
  • the colour formed initially was violet and turned rapidly into neutral black.
  • the colour formed initially was violet and after a few .minutes turned into neutral black.
  • Example 1 was repeated but instead of the benzothiazolium compound a same amount of coupler according to the general Formula I was used, where p-Diethylaminobenzene diazonium tetrafluoroborate (diazo 69) g 1.5 g 2 Citric acid g 10 Naphthalene-trisulphonicacid trisodium salt g 2 25% aqueous solution of naphthalene-trisulphonic acid disodium salt ml 14 Urea g 5 Saponine g 0.1 Ethylene glycol ml 5 Water, up to ml.
  • the colour formed initially was dark violet and turned into neutral black on storage.
  • a diazo recording process which comprises the coupling in alkaline medium of a diazonium compound with s o moo ⁇ H CH3 4 fiT X- o 11300 N L X wherein R represents an aliphatic group including a cycloaliphatic group, a saturated aliphatic group, an unsaturated aliphatic group or one of said groups in substituted form n represents 1 or 2, and
  • X represents an anion, but X- is missing when the anion is already contained in the R group.
  • diazonium compound is a diazonium salt prepared by diazotation of a primary aromatic amine that contains a tertiary amino group in para-position with respect to the primary amino group.
  • a photosensitive recording material comprising a self-supporting sheet or supported layer containing a diazonium compound and a quaternary salt of 2-methyl-5,6- dimethoxybenzothiazole and/or a quaternary salt of 2- methylbenzothiazole wherein the carbon atoms of the 5- and 6-position make part of a fused ring closed by a 01' group.
  • a photosensitive recording material according to claim 9, wherein the quaternary salt corresponds to one of the following general formula:
  • O s H3 00 TUBE CH3 H 00 is X or L X- 111 o y wherein R represents an aliphatic group including a cycloaliphatic group, a saturated aliphatic group, an unsaturated aliphatic group, or one of said groups in substituted form,
  • n 1 or 2
  • X'- represents an anion, but X- is missing when the anion is already contained in the R-group.
  • R in the general formula stands for the group -CH Y, wherein Y represents an electron-withdrawing group.

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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)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
US94574A 1969-12-03 1970-12-02 Formation of dyes suited for reproduction purposes Expired - Lifetime US3676138A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5909369 1969-12-03

Publications (1)

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US3676138A true US3676138A (en) 1972-07-11

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US (1) US3676138A (enrdf_load_stackoverflow)
JP (1) JPS4841202B1 (enrdf_load_stackoverflow)
BE (1) BE759710A (enrdf_load_stackoverflow)
CA (1) CA968211A (enrdf_load_stackoverflow)
CH (1) CH569986A5 (enrdf_load_stackoverflow)
DE (1) DE2059192A1 (enrdf_load_stackoverflow)
FR (1) FR2072685A5 (enrdf_load_stackoverflow)
GB (1) GB1328801A (enrdf_load_stackoverflow)
NL (1) NL7017685A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130426A (en) * 1974-04-22 1978-12-19 Fuji Photo Film Co., Ltd. Heat developable light-sensitive diazotype materials and process of use
US5407777A (en) * 1991-11-20 1995-04-18 Fuji Photo Film Co., Ltd. Diazo-type recording material comprising a 1-phenyl-3-pyrazolidone(phenidone) as an anti-oxidant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6180548A (ja) * 1984-09-27 1986-04-24 Canon Electronics Inc 磁気デイスク装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130426A (en) * 1974-04-22 1978-12-19 Fuji Photo Film Co., Ltd. Heat developable light-sensitive diazotype materials and process of use
US5407777A (en) * 1991-11-20 1995-04-18 Fuji Photo Film Co., Ltd. Diazo-type recording material comprising a 1-phenyl-3-pyrazolidone(phenidone) as an anti-oxidant

Also Published As

Publication number Publication date
DE2059192A1 (de) 1971-06-09
NL7017685A (enrdf_load_stackoverflow) 1971-06-07
JPS4841202B1 (enrdf_load_stackoverflow) 1973-12-05
CA968211A (en) 1975-05-27
CH569986A5 (enrdf_load_stackoverflow) 1975-11-28
BE759710A (nl) 1971-06-02
FR2072685A5 (enrdf_load_stackoverflow) 1971-09-24
GB1328801A (en) 1973-09-05

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