US3695885A - Heat developable diazotype copying material - Google Patents

Heat developable diazotype copying material Download PDF

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Publication number
US3695885A
US3695885A US43968A US3695885DA US3695885A US 3695885 A US3695885 A US 3695885A US 43968 A US43968 A US 43968A US 3695885D A US3695885D A US 3695885DA US 3695885 A US3695885 A US 3695885A
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United States
Prior art keywords
copying material
coupler
group
carbon atoms
aqueous solution
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Expired - Lifetime
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US43968A
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English (en)
Inventor
Shoji Maryama
Tadashi Saito
Tomiaki Asami
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Individual
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Individual
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Priority claimed from JP1747570A external-priority patent/JPS4917291B1/ja
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/52Compositions containing diazo compounds as photosensitive substances
    • G03C1/58Coupling substances therefor
    • G03C1/585Precursors

Definitions

  • a heat developable diazotype copying material comprising a support and a light-sensitive layer formed onto one surface of said support, said layer containing a coupler which activated during the heat development of the copying material and at least two kinds of diazonium compounds forming a black azo dye as a result of a reaction between said coupler and said idazonium compounds.
  • the present invention relates to a diazotype copying material capable of forming a desired black copied-image through heat development.
  • the conventional heat developable diazotype copying materials may be divided broadly into three categories as follows by the components of the light-sensitive layer thereof and the pattern of the heat development process applicable thereto.
  • the object of the present invention is to provide a heat developable diazotype copying material of the foregoing category (c), and particularly materials which are capable of effecting the coupling of a copied image in black color tone.
  • the coupler constituting one component of the lightsensitive layer applicable in the present invention includes such compounds as expressed by the following general formula:
  • R and R each is a radical selected from the group consisting of hydrogen, alkyl radicals having 1 to 6 carbon atoms, benzyl, bromine, chlorine, iodine, acetyl, and w-carboxyalkyl radicals having 1 to 4 carbon atoms; and R is a radical selected from the group consisting of hydrogen, hydroxyl radical alkyl radical having 1 to 2 carbon atoms, alkyl-sulfonyloxy (--0--SO -alkyl) radicals in which the alkyl group has 1 to 4 carbon atoms, carboalkoxyoxy radicals in which the alkyl group has 1 to 4 carbon atoms, acylacyoxy o (-OO-acyl)t radicals having 7 to 9 carbon atoms, alkylacyloxy radicals having 2 to 12 carbon atoms, w-hydroxyalkyl radicals having 1 to 3 carbon atoms, w-hydroxyalkyloxy radicals having 1 to 3 carbon atoms and alkoxy
  • R is a radical selected from the group consisting of hydrogen, hydroxyl radical, alkyl radicals having 1 to 2 carbon atoms, alkoxyl radicals having 1 to 4 carbon atoms, sulfonyloxy (-O-SO radical, alky1-sulfonyloxy (OSO -alky1) radical in which the alkyl group has 1 to 4 carbon atoms, carbamoyl radical, carbamoyloxy radical, carboalkoxyloxy radicals in which the alkoxyl group has 1 to 4 carbon atoms, acyloxyl radicals in which the acyl group has 2 to 9 carbon atoms, alkyl-acyloxyl radicals having 2 to 12 carbon atoms, w-hydroxyalkyl radicals having 1 to 3 carbon atoms and w-hydroxyalkyloxy radicals having 1 to 3 carbon atoms.
  • C O O H Y is a member selected from the group consisting of wherein:
  • R represents a radical selected from the group consisting of hydrogen, alkyl radicals having 1 to 4 carbon atoms, hydroxyethyl radical, hydroxypropyl radical and acetyl radical
  • X is a member selected from the group consisting of Cl-' /2ZnCl wherein:
  • R" is a radical selected from the group consisting of hydrogen, cyclohexyl radical, alkyl radicals having 1 to 4 carbon atoms, hydroxyalkyl radicals having 2 to 4 carbon atoms, cyano radical and aralkyl radicals hav- 5 ing 7 to 11 carbon atoms, such as R' is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, aralkyl radicals having 7 to 11 carbon atoms, such as cyclohexyl radical, hydroxyalkyl radicals having 2 to 4 carbon atoms and benzoyl radical; and X is the radical identical with that of said X expressed in the general Formula I.
  • R" and R""' each is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, hydroxylalkyl radical having 2 to 3 carbon atoms and benzyl radical;
  • X is the radical identical with that of X expressed in the general Formula I.
  • X" and Y are the radicals identical with that of X and Y, respectively, expressed in the general Formula I;
  • R and R each is a radical selected from the group consisting of alkoxyl radicals having 1 to 4 carbon atoms, halogens and hydrogen.
  • Diazonium compounds of benzoyl amide group expressed by the following general Formula 1V:
  • R and R each is a radical selected from the group consisting of alkoxyl radicals having 1 to 4 carbon atoms, halogens and hydrogen;
  • R is a radical selected from the group consisting of hydrogen and alkyl radicals having 1 to 3 carbon atoms; and X" is the radical identical with that of X expressed in the general Formula I.
  • a coupler expressed by the above-mentioned general formula usually forms a purple azo dye or a blue azo dye as a result of a coupling reaction between said coupler and a diazonium compound generally employed for conventional diazotype copying materials, but in case where a coupling reaction is effected between said coupler and a member selected from the group consisting of diazonium compounds expressed by the foregoing general Formulas I and I along with a member selected from the group consisting of diazonium compounds expressed by the foregoing general Formulas II, III or IV, there is formed a black azo dye. And, in case where a coupling reaction is effected between said coupler and a single member selected from the group consisting of diazonium compounds expressed by said general Formula I or general Formula I, there is formed a yellow azo dye.
  • the present invention stems from the knowedge obtained through observation and study of the coupling reaction effected by means of varieties of combinations of diazonium compounds and coupler. At least one member as illustrated by Formulas I and I must be contained in the light-sensitive layer of the copying material. Diazonium compounds expressed by the general Formulas II through IV represent the optimum examples,
  • any other diazonium compound generally employed in this field of art and capable of forming a blue azo dye or a purple azo dye as a result of coupling reaction between a coupler expressed by the foregoing general formula and said diazonium compound is also applicable in the present invention.
  • an organic acid such as citric acid, tartaric acid, etc. as the acid component contributing to the preservability of the copying material
  • thiourea contributing to the prevention of fading as well as the preservability of the copying material
  • so-called coupling assistant such as guanidine sulfate, pentaerythritol, O- methyl-isothiourea, guanylurea, etc. contributing to accelerating the coupling
  • guanidine sulfate pentaerythritol, O- methyl-isothiourea, guanylurea, etc. contributing to accelerating the coupling
  • alkali metal or alkaline earth metal salt of an organic acid such as sodium citrate, calcium citrate, magnesium citrate, sodium tartrate, calcium tartarate, calcium gluconate, etc. may be employed as a assistant dissolving agent to accelerate dissolution of the foregoing coupler in preparing a solution for use in forming the light-sensitive layer.
  • the intended copying material By applying an aqueous solution comprising the above mentioned components dissolved therein onto one surface of a support such as paper, an acetate film, a polyester film, a synthetic paper, etc. and drying thereafter, the intended copying material can be obtained.
  • the thus obtained heat developable diazotype copying material of the present invention is characterized not only by the production of a distinct black-color image when employed for actual copying but also by the fact that the light-sensitive layer has a satisfactory heat-resisting property.
  • the decomposition temperatures of diazonium compounds expressed by the general Formula I or I' are comparatively higher than those of conventional diazonium compounds and are in the range of from 150 to 200 C.
  • the decomposition loss of the diazonium compound at the time of heat development is relatively small and a highly concentrated color development can be obtained. That is, since the copying material of the present invention employs a specifically selected diazonium compound as set forth above, even if the coupling is effected at a temperature in the range of from 150 to 200 (3., there will occur no loss of the diazonium compound due to heating, and a highly concentrated color development can be expected. Moreover, the copied image formed by the copying material of the present invention, that is, the dye produced thereby has excellent interceptive property for ultarviolet rays.
  • n N -morgmon An aqueous solution comprising the foregoing components was applied onto the surface of a support consisting of paper precoated with silica, starch, polyvinyl acetate emulsion, etc. and dried at. a temperature in the range of from 100 to C. After superposing the original thereon, the thus treated support was exposed by means of a mercury lamp or a fluorescent lamp in conventional method and subsequently developed by heating at 170 Crfor 5 seconds. As a result, there was obtained a distince yellow-color image formed on a white background.
  • COMPARATIVE EXAMPLE 3 The below-mentioned aqueous solution (A) and aqueous solution (B) were respectively treated in the same manner as in Comparative Example 1, and subsequently by treating the resultant two kinds of copying materials in the same way as in Comparative Example 1, heat development was effected. As a result, there was obtained a yellow-color image formed on a White background in both cases.
  • Aqueous solution (A) Aqueous solution (8) Components:
  • EXAMPLE 3 Aqueous solution (a) 1 Formula C O O H 9 Formula Subsequent to applying the foregoing aqueous solution (a) onto a support consisting of paper pre-coated in the same manner as in Comparative Example 1, and drying, the coated surface was further coated with the foregoing aqueous solution (b) and dried again, whereby a heat developable diazotype copying material was prepared. The image-forming property and the color of image of this copying material proved equal to that of Example 1. In those cases where the coupler employed for the foregoing aqueous solution (a) was replaced by a member selected from the below-mentioned Group-B of couplers, the effect was the same as in the present example.
  • Aqueous solution (b) Components:
  • Aqueous solution (b) Components:
  • Aqueous solution (b) Components:
  • the total molar quantity of diazonium compounds in the compositions of this invention is normally from about 0.2 to 1, based on the molar quantity of coupling compound, and the ratio of blue or purple color-producing diazonium compound to yellow color-producing diazonium compound is in the range of from about 0.2 to 2.0 mols per 1 mol of yellow color-producing diazonium compound.
  • a black line heat developable diazotype copying material comprising a support and a light-sensitive layer formed onto one surface of said support wherein said layer contains:
  • Coupler As the only coupler present a coupler selected from the group consisting of compounds having the general formula radicals in which the alkyl group has 1 to 4 carbon atoms, arylacyoxy radicals having 7 to 9 carbon atoms, lalkylacyloxy radicals having 2 to 12 carbon atoms, w-hydroxylalkyl radicals having 1 to 3 carbon atoms,
  • R" is a radical selected from the group consisting of hydrogen, cyclohexyl radical, alkyl radicals having 1 to 4 carbon atoms, hydroxyalkyl radicals having 2 to 4 carbon atoms, cyano radical and aralkyl radicals having 7 to 11 carbon atoms;
  • R' is a radical selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, aralkyl radicals having 7' to 11 carbon atoms, cyclohexyl radical, hydroxyalkyl radicals having 2 to 4 carbon atoms and benzoyl radical; and
  • X is the radical identical with that of said X expressed in the general Formula I;
  • X" is the radical identical with that of said X expressed in the general Formula I; and general Formula III V1! wherein R and R each is a radical selected from the 15 group consisting of alkoxyl radicals having 1 to 4 carbon atoms, halogens and hydrogen; R is a radical selected from the group consisting of hydrogen and alkyl radicals having 1 to 3 carbon atoms; and X' is the radical identical with that of said X expressed in the general Formula I.
  • a diazotype copying material according to claim 1, wherein said light-sensitive layer further contains an organic acid, thiourea and a member selected from the group consisting of guanidine sulfate, pentaerythritol, O-methyl-isothiourea and guanylurea.
  • a diazotype copying material according to claim 1, wherein said light-sensitive layer further contains a small amount of a salt selected from the group consisting of sodium citrate, calcium citrate, magnesium citrate, sodium tartrate, calcium tartrate and calcium gluconate.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is a compound of the group C OOH COOH HO- OH HO- OH Br- -C2H Ol- (CHz)3CH3 C O OH O OH C O OH 5.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is HO OH Br- C2 5 6.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO OH C1- (CH2)aCHa 7.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO OH 8.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO OH 9.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is COOH HO- OH 10.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is HO OH CHQCHQCOOH 12.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is a compound of the group coon coon coon no on no on no on I I Br Cl CH:
  • a heat developable diazotype copying material of claim 1 wherein the coupler is coon 00011 no or: no 011 I Br arm 01 Br 5 17.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is COOH COOH
  • a heat developable diazotype copying material of claim 1 wherein the coupler is OOOH HO- OH Cl Br 22.
  • a heat developable diazotype copying material of claim 1 wherein the coupler is a compound of the group C O OH ('30 OH O O OH HO OH HO OH HO- OH I 9 Br Br 01- (J1 Br Br CH: 47H: H;

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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)
US43968A 1969-06-07 1970-06-05 Heat developable diazotype copying material Expired - Lifetime US3695885A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4474569 1969-06-07
JP1747570A JPS4917291B1 (enExample) 1970-02-28 1970-02-28

Publications (1)

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US3695885A true US3695885A (en) 1972-10-03

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US (1) US3695885A (enExample)
DE (1) DE2018908C3 (enExample)
FR (1) FR2056231A5 (enExample)
GB (1) GB1307314A (enExample)
NL (1) NL7006018A (enExample)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252884A (en) * 1979-08-14 1981-02-24 James River Graphics, Inc. Negative-working diazotype photoreproduction
US4289839A (en) * 1976-10-22 1981-09-15 James River Graphics, Inc. Negative image diazography formulation with acid labile coupler, diazonium compound and carboxylic acid anhydride
US4411979A (en) * 1981-01-28 1983-10-25 Ricoh Company, Ltd. Diazo type thermosensitive recording material
US4421839A (en) * 1979-08-03 1983-12-20 Dai Nippon Printing Co., Ltd. Heat-sensitive and photofixing recording sheet with diazosulfonate and acidic coupling agent therefore
US4659644A (en) * 1983-12-22 1987-04-21 Ricoh Company, Ltd. Diazo-type thermosensitive recording material with hydrazone coupler and chelating metal compound

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2495343B1 (fr) * 1980-12-02 1987-02-20 Regma Materiaux diazotypes thermodeveloppables contenant un precurseur d'activateur liberant lors du chauffage une base forte. procede de diazotypie mettant en oeuvre ces materiaux

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4289839A (en) * 1976-10-22 1981-09-15 James River Graphics, Inc. Negative image diazography formulation with acid labile coupler, diazonium compound and carboxylic acid anhydride
US4421839A (en) * 1979-08-03 1983-12-20 Dai Nippon Printing Co., Ltd. Heat-sensitive and photofixing recording sheet with diazosulfonate and acidic coupling agent therefore
US4252884A (en) * 1979-08-14 1981-02-24 James River Graphics, Inc. Negative-working diazotype photoreproduction
US4411979A (en) * 1981-01-28 1983-10-25 Ricoh Company, Ltd. Diazo type thermosensitive recording material
US4659644A (en) * 1983-12-22 1987-04-21 Ricoh Company, Ltd. Diazo-type thermosensitive recording material with hydrazone coupler and chelating metal compound

Also Published As

Publication number Publication date
DE2018908A1 (de) 1970-12-17
FR2056231A5 (enExample) 1971-05-14
NL7006018A (enExample) 1970-12-09
GB1307314A (en) 1973-02-21
DE2018908C3 (de) 1975-10-16
DE2018908B2 (de) 1975-03-13

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