[go: up one dir, main page]

US3298834A - Diazotype photoprinting material susceptible to thermal development - Google Patents

Diazotype photoprinting material susceptible to thermal development Download PDF

Info

Publication number
US3298834A
US3298834A US292098A US29209863A US3298834A US 3298834 A US3298834 A US 3298834A US 292098 A US292098 A US 292098A US 29209863 A US29209863 A US 29209863A US 3298834 A US3298834 A US 3298834A
Authority
US
United States
Prior art keywords
acid
naphthalene
light
heating
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US292098A
Inventor
Jr Robert I Eldred
Mckinney John Joseph
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.)
GAF Chemicals Corp
R Q O HOLDING CO Inc
Original Assignee
General Aniline and Film Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US284364A priority Critical patent/US3326686A/en
Priority to US292114A priority patent/US3166422A/en
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US292097A priority patent/US3301679A/en
Priority to US292115A priority patent/US3255011A/en
Priority to US292066A priority patent/US3294534A/en
Priority to US292098A priority patent/US3298834A/en
Priority to GB21014/64A priority patent/GB1063132A/en
Priority to NL6406013A priority patent/NL6406013A/xx
Priority to BE648593D priority patent/BE648593A/xx
Priority to FR976481A priority patent/FR1405427A/en
Application granted granted Critical
Publication of US3298834A publication Critical patent/US3298834A/en
Assigned to R Q O HOLDING COMPANY INC reassignment R Q O HOLDING COMPANY INC ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GAF CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives

Definitions

  • Two-component diazotype material comprises a supporting sheet, such as paper or film, having in a surface coating or layer, an azo coupling component and a stabilized light-sensitive diazonium compound, stablized against premature coupling by inclusion of an acid stabilizer.
  • a supporting sheet such as paper or film
  • an azo coupling component and a stabilized light-sensitive diazonium compound, stablized against premature coupling by inclusion of an acid stabilizer.
  • the light-sensitive diazonium compound On exposure of such coating to actinic light under an opaque pattern on a translucent background, the light-sensitive diazonium compound is destroyed in the light-struck areas, and upon subsequent exposure to an alkaline developing medium such as gaseous ammonia, the acid stabilizer is neutralized and the residual diazonium compound couples with the azo coupling component to form an azo dye image corresponding to the opaque pattern of the original.
  • Diazotype photoprinting material containing such reagents can be developed after exposure to light under an opaque pattern by heating at a temperature causing the aforesaid conversion or decomposition.
  • the alkaline reaction product formed thereby neutralizes the acid stabilizer and causes imagewise coupling of the residual diazonium compound with the azo coupling component.
  • 2,653,- 091 discloses inclusion in a two-component diazotype photoprinting layer of trichloroacetic acid as a stabilizer and an alkali metal, ammonium or nitrogen base salt of said acid as a heat sensitive alkali generating compound, said salt being decomposed on heating to yield an alkaline carbonate which promotes coupling.
  • Acid stabilizers included in two-component diazotype material are usually organic acids such as citric acid, tartaric acid or the like.
  • the stability of the photoprinting material aiforded by such stabilizers tends, how ever, to be reduced by the presence of the neutral to acid reagents which form an alkaline compound upon heating and this causes a critical reduction of the shelf life of the heat developable photoprinting material. While this effect can be reduced by increasing the amount of acid stabilizer, this has the disadvantage of impairing the development properties or requiring increased amounts of the heat-sensitive alkali generating reagents.
  • the quantity of naphthalene sulfonic acid salt employed is preferably at least 5% of the other non-volatile ingredients of the sensitizing composition. Suitable proportions range up to about 25% of the other non-volatile ingredients of the sensitizing composition.
  • the concentration of the naphthalene sulfonic acid salt in the sensitizing solution generally ranges from 1 to 10% by weight.
  • the sensitizing compositions of this invention may contain as light-sensitive stable diazonium compounds, those listed in U.S.P. 2,501,874 and in the article by Van der Grinten in the Photographic Journal, volume 92-3 (1952), page 46. They are especially diazonium compounds derived from N-monoand N-disubstituted pphenylenediamines, e.g., the diazotization products of:
  • Azo coupling components which can be incorporated in the photoprinting materials of the invention are:
  • Heat responsive reagents having an acid to neutral reaction at room temperatures, but which are adapted on heating to temperatures between and 200 C. to yield an alkaline reacting component for neutralization of the acid stabilizer in the light-sensitive photoprinting material of the invention include the monoalkali metal salts of strong organic acids which are decomposed on heating to form basic compounds, such as the monoalkali metal salts of malonic, maleic or oxalic acids; alkali metal salts of aliphatic mono-carboxylic acids and especially the alkali metal (Na, K) and nitrogen base sats of trichloroacetic acid.
  • reagents commonly employed in diazotype photoprinting materials for example hygroscopic agent such as glycerin; and wetting agents such as saponin, lauryl sulfate, keryl benzene sulfonate or oleyl-N-methyltaurine.
  • finely divided or colloidal silica or alumina aqueous dispersions or colloidal solutions of organic film-forming binders, such as colloidally water-soluble polyvinyl alcohol, methyl cellulose, hydroxy ethyl cellulose, gelatin or the like or latex-like dispersions or resins such as polyvinyl acetate, polyvinyl chloride, polyvinyl chlorideacetate, polyvinylidene chloride, apolyacryl-onitrile or polymethylmethacrylate.
  • organic film-forming binders such as colloidally water-soluble polyvinyl alcohol, methyl cellulose, hydroxy ethyl cellulose, gelatin or the like or latex-like dispersions or resins such as polyvinyl acetate, polyvinyl chloride, polyvinyl chlorideacetate, polyvinylidene chloride, apolyacryl-onitrile or polymethylmethacrylate.
  • the components of the sensitizing composition are preferably incorporated in a single solution or suspension, and applied in a single coating step to the base.
  • the latter may be paper or film, such as polyethylene-terephthalate (Mylar) and similar plastic materials which are capable of withstanding the elevated development temperatures.
  • Mylar polyethylene-terephthalate
  • the various components of the sensitizing compositions can be applied in successive coatings, one containing for example, the diazonium salt and another, the alkali generating heat-sensitive acid to neutral reagent, the azo coupling component being incorporated in either of the two layers.
  • Materials coated in accordance with the invention are developed after exposure to actinic light under an opaque pattern by heating at temperatures between 100 and 200 C. or preferably between 120 and 160 C. at which decomposition or conversion of the acid to neutral heat sensitive reagent to an alkaline reacting material occurs, causing coupling of the residual diazonium compound With the azo coupling component in the areas corresponding to the opaque pattern to form an azo dye image thereof.
  • Diazotype photoprinting materials containing naphthalene sulfonic acid salts in accordance with the present invention are characterized by superior shelf life and stability to decomposition in storage, without impairment of the rate and effectiveness of the heat development.
  • Example I The following composition was coated on a paper base sheet and dried:
  • a similar composition from which the naphthalene-1,3,6-trisulfonic acid salt was omitted was also coated on a paper sheet and dried.
  • the dried materials were exposed under an opaque pattern to actinic light, and developed by passing the sheet over a cylinder heated at from 150 to 175 C. Similar development of an azo dye image was obtained with both materials.
  • the two materials were then subjected to forced aging, and again tested as indicated above for making a photoprint of an opaque pattern.
  • the results demonstrated that the material containing the naphthalene-trisulfonic acid salt was characterized by superior shelf life as compared with the material lacking said salt.
  • Example II The procedures of Example I were repeated, except that for naphthalene-1,3,6-trisodium sulfonate, there was substituted an equal amount of naphthalene-2,7-disodium sulfonate. The results obtained were substantially the same as in the preceding example.
  • Example 111 Paper was coated with the following sensitizing composition:
  • Finely-divided silica (average particle size; 3-6
  • compositions as well as one in which naphthalene-1,3,6-trisodiurn sulfonate is omitted were tested for photoprinting, and found to give substantially equal results on heat development. After forced aging, it was found that the material containing naphthalenetrisodium sulfonate was characterized by greatly superior shelf life as compared with the composition lacking said ingredient.
  • sodium trichloroacetate can be replaced by the corresponding potassium salts, or by nitrogen base salts, e.g., trichloroacetates of diethanolamine or triethanolamine.
  • nitrogen base salts e.g., trichloroacetates of diethanolamine or triethanolamine.
  • monoalkali metal salts of heat decomposable organic acids such as the monoalkali metal salts of oxalic, maleic or malonic acid, as well as other heat-decomposable reagents of neutral to acid reaction mentioned in the discussion preceding the examples.
  • naphthalene-1,3, 6-trisodium sulfonate instead of naphthalene-1,3, 6-trisodium sulfonate, other alkali metal or ammonium salts of naphthalene-1,3,6- trisulfo acid can be used, as well as corresponding amounts of alkali metal or ammonium salts of other naphthalene diand tri-sulfonic acids.
  • the heat developable two-component diazotype photoprint materials of the invention are characterized in each case by superior shelf life as compared with similar materials lacking the naphthalene dior tri-sulfonic acid salts.
  • Two-component diazotype photoprinting material susceptible to development on heating having on a surface of a supporting sheet, a light-sensitive layer containing an azo coupling component, a light-sensitive diazonium compound, an acid stabilizer against premature coupling, a neutral to acid monoalkali metal salt of a strong acid which is decomposed to yield an alkaline reacting compound on heating to a temperature between 100 and 200 C. and a neutral salt of a naphthalene sulfonic acid having the formula:
  • n is an integer from 2 to 3, amounting to at least 5% by weight of the components of the light-sensitive layer.
  • Diazotype photoprinting material as defined in claim 1 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-1,3,6-trisulfonic acid.
  • Diazotype photoprinting materials as defined in claim 1 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-2,7-disulfonic acid.
  • Diazotype photoprinting material as defined in claim 1, wherein the amount of said naphthalene sulfonic acid salt is from 5 to 25% of the remaining components of the light-sensitive layer.
  • a sensitizing composition for two-component diazotype photoprinting material susceptible to development on heating containing in an aqueous medium, an azo coupling component, a light-sensitive diazonium compound, an acid stabilizer against premature coupling, a neutral to acid monoalkali metal salt of a strong acid which is decomposed to yield an alkaline reacting compound on heating to a temperature between 100 and 200 C. and at least 1% of a neutral salt of a naphthalenesulfonic acid having the formula:
  • n is an integer from 2 to 3.
  • a sensitizing composition as defined in claim 5 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-2,7-disu1fonic acid- S.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Description

United States Patent 3,298,834 DIAZO'IYPE PHOTOPRINTING MATERIAL SUS- CEPTIBLE T0 THERMAL DEVELOPMENT Robert I. Eldred, Jr., Endicott, and John Joseph McKinney, Binghamton, N.Y., assignors to General Aniline & Film Corporation, New York, N .Y., a corporation of Delaware No Drawing. Filed July 1, 1963, Ser. No. 292,098 8 Claims. (Cl. 96-91) This invention relates to an improvement in two-component light-sensitive diazotype photoprinting material susceptible to development by heating.
Two-component diazotype material comprises a supporting sheet, such as paper or film, having in a surface coating or layer, an azo coupling component and a stabilized light-sensitive diazonium compound, stablized against premature coupling by inclusion of an acid stabilizer. On exposure of such coating to actinic light under an opaque pattern on a translucent background, the light-sensitive diazonium compound is destroyed in the light-struck areas, and upon subsequent exposure to an alkaline developing medium such as gaseous ammonia, the acid stabilizer is neutralized and the residual diazonium compound couples with the azo coupling component to form an azo dye image corresponding to the opaque pattern of the original.
It has been proposed to include in two-component light-sensitive diazotype photoprinting material, one or more reagents having an acid to neutral reaction which, on heating, are decomposed or converted to yield an alkaline reacting compound. Diazotype photoprinting material containing such reagents can be developed after exposure to light under an opaque pattern by heating at a temperature causing the aforesaid conversion or decomposition. The alkaline reaction product formed thereby neutralizes the acid stabilizer and causes imagewise coupling of the residual diazonium compound with the azo coupling component.
Incorporation in diazotype materials of various reagents or combination which provide an alkaline environment on heating have been disclosed in the prior art. Thus, United States Patents 2,228,562, 2,681,277, 2,732,- 299 and 2,774,669 disclose two-component diazotype photoprinting material containing nitrogen compounds (eg urea derivatives) which on heating, decompose to form ammonia or nitrogen bases which cause coupling in the two-component diazotype system. U.S.P. 2,653,- 091 discloses inclusion in a two-component diazotype photoprinting layer of trichloroacetic acid as a stabilizer and an alkali metal, ammonium or nitrogen base salt of said acid as a heat sensitive alkali generating compound, said salt being decomposed on heating to yield an alkaline carbonate which promotes coupling.
Acid stabilizers included in two-component diazotype material are usually organic acids such as citric acid, tartaric acid or the like. The stability of the photoprinting material aiforded by such stabilizers tends, how ever, to be reduced by the presence of the neutral to acid reagents which form an alkaline compound upon heating and this causes a critical reduction of the shelf life of the heat developable photoprinting material. While this effect can be reduced by increasing the amount of acid stabilizer, this has the disadvantage of impairing the development properties or requiring increased amounts of the heat-sensitive alkali generating reagents.
We have found that greatly improved shelf life can be obtained in heat developable diazotype photoprinting material of the nature described above, by incorporating ice in the sensitizing solution and consequently in the resultant light-sensitive layer a salt of a naphthalene sulfonic acid having two to three sulfonic acid groups e.g., the
sodium, potassium or ammonium salts of naphthalene-2, 7-disulfonic acid, naphthalene-1,6-disulfonic acid or naphthalene-1,3,6-trisulfonic acid.
The quantity of naphthalene sulfonic acid salt employed is preferably at least 5% of the other non-volatile ingredients of the sensitizing composition. Suitable proportions range up to about 25% of the other non-volatile ingredients of the sensitizing composition. The concentration of the naphthalene sulfonic acid salt in the sensitizing solution generally ranges from 1 to 10% by weight.
The sensitizing compositions of this invention may contain as light-sensitive stable diazonium compounds, those listed in U.S.P. 2,501,874 and in the article by Van der Grinten in the Photographic Journal, volume 92-3 (1952), page 46. They are especially diazonium compounds derived from N-monoand N-disubstituted pphenylenediamines, e.g., the diazotization products of:
N,N-diethyl-p-phenylenediamine N-benzyl-N-ethyl-p-phenylenediamine N-ethyl-p-phenylenediamine N,N-diethyl-2-ethoxy-p-phenylenediamine N-ethyl-2-methyl-p-phenylenediamine N,N-bis-hydroxyethyl-p-phenylenedia-mine N-beta-hydroxyethyl-N-methyl-p-phenylenediamine These compounds are preferably stabilized in the form of their double salts with zinc chloride, tin chloride, cadmium chloride and the like.
Azo coupling components which can be incorporated in the photoprinting materials of the invention are:
2,3-dihydroxynaphthalene 1,8-dihydroxynaphthalene 2-methy1 resorcinol 4,4'-diresorcyl sulfide Resorcinol Octylresorcinol Alpha-resorcylamide 3-methyl-1-phenyl-5 -pyrazolone H-acid 2,3 -dihydroxynaphthalene-6-sulfonic acid 2,5 -xylenol Acid stabilizers against premature coupling of the diazoni-um salt and azo coupling component include citric acid, tartaric acid, and similar acidic reagents.
Heat responsive reagents having an acid to neutral reaction at room temperatures, but which are adapted on heating to temperatures between and 200 C. to yield an alkaline reacting component for neutralization of the acid stabilizer in the light-sensitive photoprinting material of the invention, include the monoalkali metal salts of strong organic acids which are decomposed on heating to form basic compounds, such as the monoalkali metal salts of malonic, maleic or oxalic acids; alkali metal salts of aliphatic mono-carboxylic acids and especially the alkali metal (Na, K) and nitrogen base sats of trichloroacetic acid.
In addition to the foregoing materials, there can also be included reagents commonly employed in diazotype photoprinting materials, for example hygroscopic agent such as glycerin; and wetting agents such as saponin, lauryl sulfate, keryl benzene sulfonate or oleyl-N-methyltaurine.
Moreover, there can be included finely divided or colloidal silica or alumina, aqueous dispersions or colloidal solutions of organic film-forming binders, such as colloidally water-soluble polyvinyl alcohol, methyl cellulose, hydroxy ethyl cellulose, gelatin or the like or latex-like dispersions or resins such as polyvinyl acetate, polyvinyl chloride, polyvinyl chlorideacetate, polyvinylidene chloride, apolyacryl-onitrile or polymethylmethacrylate.
The components of the sensitizing composition are preferably incorporated in a single solution or suspension, and applied in a single coating step to the base. The latter may be paper or film, such as polyethylene-terephthalate (Mylar) and similar plastic materials which are capable of withstanding the elevated development temperatures. However, if desired, the various components of the sensitizing compositions can be applied in successive coatings, one containing for example, the diazonium salt and another, the alkali generating heat-sensitive acid to neutral reagent, the azo coupling component being incorporated in either of the two layers.
Materials coated in accordance with the invention are developed after exposure to actinic light under an opaque pattern by heating at temperatures between 100 and 200 C. or preferably between 120 and 160 C. at which decomposition or conversion of the acid to neutral heat sensitive reagent to an alkaline reacting material occurs, causing coupling of the residual diazonium compound With the azo coupling component in the areas corresponding to the opaque pattern to form an azo dye image thereof.
Diazotype photoprinting materials containing naphthalene sulfonic acid salts in accordance with the present invention are characterized by superior shelf life and stability to decomposition in storage, without impairment of the rate and effectiveness of the heat development.
The invention will be illustrated by the following examples, wherein parts and percentages are by weight, unless otherwise indicated.
Example I The following composition was coated on a paper base sheet and dried:
Citric acid 0.5 Sucrose 5.0 N-ethyl-N-2-hydroxyethyl p aminobenzene diazonium chlorozincate 0.7 2,3-dihydroxynaphthalene-o-sodium sulfonate 3.0
For purposes of comparison, a similar composition from which the naphthalene-1,3,6-trisulfonic acid salt was omitted was also coated on a paper sheet and dried. The dried materials were exposed under an opaque pattern to actinic light, and developed by passing the sheet over a cylinder heated at from 150 to 175 C. Similar development of an azo dye image was obtained with both materials. The two materials were then subjected to forced aging, and again tested as indicated above for making a photoprint of an opaque pattern. The results demonstrated that the material containing the naphthalene-trisulfonic acid salt was characterized by superior shelf life as compared with the material lacking said salt.
Example II The procedures of Example I were repeated, except that for naphthalene-1,3,6-trisodium sulfonate, there was substituted an equal amount of naphthalene-2,7-disodium sulfonate. The results obtained were substantially the same as in the preceding example.
4 Example 111 Paper was coated with the following sensitizing composition:
Finely-divided silica (average particle size; 3-6
microns) gr 4.0 Zinc chloride gr 0.5 Magnesium chloride .gr 0.1 Naphthalene-1,3,6-trisodium sulfonate gr 3.0
The foregoing composition, as well as one in which naphthalene-1,3,6-trisodiurn sulfonate is omitted were tested for photoprinting, and found to give substantially equal results on heat development. After forced aging, it was found that the material containing naphthalenetrisodium sulfonate was characterized by greatly superior shelf life as compared with the composition lacking said ingredient.
Inthe foregoing examples, sodium trichloroacetate can be replaced by the corresponding potassium salts, or by nitrogen base salts, e.g., trichloroacetates of diethanolamine or triethanolamine. Moreover, instead of these compounds, there can be used the monoalkali metal salts of heat decomposable organic acids such as the monoalkali metal salts of oxalic, maleic or malonic acid, as well as other heat-decomposable reagents of neutral to acid reaction mentioned in the discussion preceding the examples.
Instead of naphthalene-1,3, 6-trisodium sulfonate, other alkali metal or ammonium salts of naphthalene-1,3,6- trisulfo acid can be used, as well as corresponding amounts of alkali metal or ammonium salts of other naphthalene diand tri-sulfonic acids. The heat developable two-component diazotype photoprint materials of the invention are characterized in each case by superior shelf life as compared with similar materials lacking the naphthalene dior tri-sulfonic acid salts.
Variations and modifications which will be obvious to those skilled in the art can be made in the foregoing procedures and materials without departing from the scope and spirit of the invention.
We claim:
1. Two-component diazotype photoprinting material susceptible to development on heating, having on a surface of a supporting sheet, a light-sensitive layer containing an azo coupling component, a light-sensitive diazonium compound, an acid stabilizer against premature coupling, a neutral to acid monoalkali metal salt of a strong acid which is decomposed to yield an alkaline reacting compound on heating to a temperature between 100 and 200 C. and a neutral salt of a naphthalene sulfonic acid having the formula:
wherein n is an integer from 2 to 3, amounting to at least 5% by weight of the components of the light-sensitive layer.
2. Diazotype photoprinting material as defined in claim 1 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-1,3,6-trisulfonic acid.
3. Diazotype photoprinting materials as defined in claim 1 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-2,7-disulfonic acid.
4. Diazotype photoprinting material as defined in claim 1, wherein the amount of said naphthalene sulfonic acid salt is from 5 to 25% of the remaining components of the light-sensitive layer.
5. A sensitizing composition for two-component diazotype photoprinting material susceptible to development on heating, containing in an aqueous medium, an azo coupling component, a light-sensitive diazonium compound, an acid stabilizer against premature coupling, a neutral to acid monoalkali metal salt of a strong acid which is decomposed to yield an alkaline reacting compound on heating to a temperature between 100 and 200 C. and at least 1% of a neutral salt of a naphthalenesulfonic acid having the formula:
wherein n is an integer from 2 to 3.
6. A sensitizing composition as defined in claim 5 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-1,3,6-trisulfonic acid.
7. A sensitizing composition as defined in claim 5 wherein said naphthalene sulfonic acid salt is a member of the group consisting of the sodium, potassium and ammonium salts of naphthalene-2,7-disu1fonic acid- S. A sensitizing composition as defined in claim 5 wherein the concentration of said naphthalene sulfonic acid salt is from 1 to 10% by weight.
References Cited by the Examiner UNITED STATES PATENTS 2,65 3,091 9/ 1953 Grieg 9649 2,694.009 1 1/ 1954 Sus 9649 X 2,727,820 12/ 1955' Botkin 964-9 2,732,299 1/ 1956 Morrison 9649 3,102,812 9/ 1963 Welch 9 6- 49 X FOREIGN PATENTS 609,912 3/ 1962 Belgium.
750,080 5/ 1 933 France. 1,249,913 11/ 1962 France.
816,601 7/ 1959 Great Britain.
OTHER REFERENCES Kosar, Photographic Science and Engineering, vol. 5, No. 4, July-August, 196-1, pages 239-243.
I. TRAVIS BROWN, Primary Examiner.
NORMAN G. TORCH'IN, Examiner.
R. L. STONE, Assistant Examiner.

Claims (1)

1. TWO-COMPONENT DIAZOTYPE PHOTOPRINTING MATERIAL SUSCEPTIBLE TO DEVELOPMENT ON HEATING, HAVING ON A SURFACE OF A SUPPORTING SHEET, A LIGHT-SENSITIVE LAYER CONTAINING AN AZO COUPLING COMPONENT, A LIGHT-SENSITIVE DIAZONIUM COMPOUND, AN ACID STABILIZER AGAINST PREMATURE COUPLING, A NEUTRAL TO ACID MONOALKALI METAL SALT OF A STRONG ACID WHICH IS DECOMPOSED TO YIELD AN ALKALINE REACTING COMPOUND ON HEATING TO A TEMPERATURE BETWEEN 100 AND 200*V. AND A NEUTRAL SALT OF A NAPHTHALENE SULFONIC ACID HAVING THE FORMULA:
US292098A 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development Expired - Lifetime US3298834A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US284364A US3326686A (en) 1963-05-31 1963-05-31 Light-sensitive two-component diazotype materials adapted for heat development
US292097A US3301679A (en) 1963-05-31 1963-07-01 Two-component diazotype light-sensitive photoprinting material susceptible to thermal development
US292115A US3255011A (en) 1963-05-31 1963-07-01 Two-component diazotype photoprinting material susceptible to thermal development
US292066A US3294534A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development
US292098A US3298834A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development
US292114A US3166422A (en) 1963-05-31 1963-07-01 Diazotype heat development photographic paper comprising a sugar brightening agent
GB21014/64A GB1063132A (en) 1963-05-31 1964-05-21 Improvements in or relating to light-sensitive two-component diazotype materials adapted for heat development
NL6406013A NL6406013A (en) 1963-05-31 1964-05-28
BE648593D BE648593A (en) 1963-05-31 1964-05-29
FR976481A FR1405427A (en) 1963-05-31 1964-05-29 Two-component diazo-type materials, photosensitive for thermal development

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US284364A US3326686A (en) 1963-05-31 1963-05-31 Light-sensitive two-component diazotype materials adapted for heat development
US292097A US3301679A (en) 1963-05-31 1963-07-01 Two-component diazotype light-sensitive photoprinting material susceptible to thermal development
US292115A US3255011A (en) 1963-05-31 1963-07-01 Two-component diazotype photoprinting material susceptible to thermal development
US292066A US3294534A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development
US292098A US3298834A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development
US292114A US3166422A (en) 1963-05-31 1963-07-01 Diazotype heat development photographic paper comprising a sugar brightening agent

Publications (1)

Publication Number Publication Date
US3298834A true US3298834A (en) 1967-01-17

Family

ID=27559573

Family Applications (6)

Application Number Title Priority Date Filing Date
US284364A Expired - Lifetime US3326686A (en) 1963-05-31 1963-05-31 Light-sensitive two-component diazotype materials adapted for heat development
US292097A Expired - Lifetime US3301679A (en) 1963-05-31 1963-07-01 Two-component diazotype light-sensitive photoprinting material susceptible to thermal development
US292066A Expired - Lifetime US3294534A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development
US292114A Expired - Lifetime US3166422A (en) 1963-05-31 1963-07-01 Diazotype heat development photographic paper comprising a sugar brightening agent
US292115A Expired - Lifetime US3255011A (en) 1963-05-31 1963-07-01 Two-component diazotype photoprinting material susceptible to thermal development
US292098A Expired - Lifetime US3298834A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development

Family Applications Before (5)

Application Number Title Priority Date Filing Date
US284364A Expired - Lifetime US3326686A (en) 1963-05-31 1963-05-31 Light-sensitive two-component diazotype materials adapted for heat development
US292097A Expired - Lifetime US3301679A (en) 1963-05-31 1963-07-01 Two-component diazotype light-sensitive photoprinting material susceptible to thermal development
US292066A Expired - Lifetime US3294534A (en) 1963-05-31 1963-07-01 Diazotype photoprinting material susceptible to thermal development
US292114A Expired - Lifetime US3166422A (en) 1963-05-31 1963-07-01 Diazotype heat development photographic paper comprising a sugar brightening agent
US292115A Expired - Lifetime US3255011A (en) 1963-05-31 1963-07-01 Two-component diazotype photoprinting material susceptible to thermal development

Country Status (4)

Country Link
US (6) US3326686A (en)
BE (1) BE648593A (en)
GB (1) GB1063132A (en)
NL (1) NL6406013A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379531A (en) * 1965-03-30 1968-04-23 Gen Aniline & Film Corp Two-component heat developing diazotypes
US3389996A (en) * 1964-10-15 1968-06-25 Gen Aniline & Film Corp Two-component heat developable diazotypes
US3408192A (en) * 1964-06-10 1968-10-29 Ibm Light-sensitive diazotype compositions and elements
US3420666A (en) * 1964-10-15 1969-01-07 Gaf Corp Two-component heat developing diazotypes
US3529964A (en) * 1966-01-14 1970-09-22 L L Ridgway Enterprises Inc Heat developable diazo compositions and diazotype reproduction media
US3650750A (en) * 1968-12-28 1972-03-21 Ricoh Kk Heat-developable diazo-type light-sensitive material
US3793030A (en) * 1971-09-02 1974-02-19 Ricoh Kk Process for producing diazotype light-sensitive material
US3900324A (en) * 1972-06-25 1975-08-19 Ozalid Co Ltd Treatment of synthetic polyester film products
US4478926A (en) * 1981-12-28 1984-10-23 Andrews Paper & Chemical Co., Inc. Zinc sulfonates and their use in diazotypy

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1377476A (en) * 1963-09-24 1964-11-06 Bauchet & Cie Ets Process for manufacturing heliographic sheets and similar articles for the reproduction of documents by diazotyping and photosensitive sheets produced by the implementation of this process
US3300471A (en) * 1964-01-02 1967-01-24 Universal Oil Prod Co p-(nu-cyanoalkyl-nu-hydrocarbylamino)-benzenediazonium chlorides
US3536490A (en) * 1964-04-28 1970-10-27 Pitney Bowes Inc Novel diazotype copying process
US3389995A (en) * 1964-09-15 1968-06-25 Gen Aniline & Film Corp Two-component heat developable diazotypes containing amidine compounds
US3431109A (en) * 1964-10-16 1969-03-04 Addressograph Multigraph Heat sensitive diazotype materials
US3525618A (en) * 1964-12-04 1970-08-25 Geigy Ag J R Diazotype film materials
USB417241I5 (en) * 1964-12-09
US3406072A (en) * 1964-12-21 1968-10-15 Gaf Corp One-component diazotypes
US3409455A (en) * 1965-01-04 1968-11-05 Gaf Corp Process of reproduction on benzene diazonium fluoborate sheet by heat exposure
DE1572155A1 (en) * 1965-08-10 1970-01-02 Dr Eduard Roell Light or radiation sensitive material and process for its production
US3522048A (en) * 1965-12-09 1970-07-28 Gaf Corp Two-component heat developing diazotypes
NL136527C (en) * 1966-11-07
US3539345A (en) * 1967-02-01 1970-11-10 Gaf Corp Thermal diazotype papers
NL6800539A (en) * 1968-01-12 1969-07-15
US3779758A (en) * 1969-03-25 1973-12-18 Photocircuits Corp Photosensitive process for producing printed circuits employing electroless deposition
JPS4832722B1 (en) * 1969-09-01 1973-10-08
GB1488005A (en) * 1974-01-25 1977-10-05 Ici Ltd Diazotype materials
US4168171A (en) * 1977-08-05 1979-09-18 Minnesota Mining And Manufacturing Company Light-sensitive thermal developable diazotype sheets with imidazoles
US4230789A (en) * 1978-03-13 1980-10-28 Minnesota Mining And Manufacturing Company Thermal diazotype sheets
FR2455303A1 (en) * 1979-04-24 1980-11-21 Rhone Poulenc Syst PROCESS FOR THE MANUFACTURE OF A INVIOLABLE IDENTIFICATION CARD COMPRISING PHOTOGRAPHS AND CARD OBTAINED ACCORDING TO THIS PROCESS
FR2470984B1 (en) * 1979-11-28 1986-06-13 Schaeffer Andre DIAZOTYPE MATERIAL DEVELOPABLE BY VAPOR, WATER OR HEAT
BR8107605A (en) * 1981-11-23 1983-07-05 Oce Nederland Bv DIAZOTYPE MATERIAL
JPS5898729A (en) * 1981-12-08 1983-06-11 Ricoh Co Ltd Production of heat developing type diazo copying material
JPS58143336A (en) * 1982-02-19 1983-08-25 Ricoh Co Ltd Heat-developable diazo copying material
US4508808A (en) * 1982-11-12 1985-04-02 Xidex Corporation Method of using diazotype photographic materials with preexposure treatment to form uniform sites of refractive index change

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE609912A (en) * 1961-11-02
FR750080A (en) * 1932-04-27 1933-08-03 Process for preparing light-sensitive layers
US2653091A (en) * 1950-01-31 1953-09-22 Rca Corp Photographic diazotype composition and heat development thereof
US2694009A (en) * 1948-10-01 1954-11-09 Keuffel & Esser Co Diazo-n-sulfonate light-sensitive material
US2727820A (en) * 1952-04-29 1955-12-20 Gen Aniline & Film Corp Light-sensitive diazotype layers containing carboxamides
US2732299A (en) * 1952-07-22 1956-01-24 Light sensitive
GB816601A (en) * 1954-07-09 1959-07-15 Arnold Tanenbaum Improvements in or relating to diazotype processes
FR1249913A (en) * 1959-11-23 1961-01-06 Bauchet & Cie Ets Heat-developable diazotype product
US3102812A (en) * 1960-11-16 1963-09-03 Gen Aniline & Film Corp Stabilizers for one-component diazotype materials

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807545A (en) * 1952-07-18 1957-09-24 Dick Co Ab Process of applying a diazotype photoprinting material to a base and the resultant article
GB815005A (en) * 1957-07-03 1959-06-17 Ilford Ltd Improvements in or relating to radiation-sensitive diazotype materials
GB861601A (en) * 1957-07-26 1961-02-22 Napier & Son Ltd Control mechanism for aircraft power plants comprising a gas turbine engine driving a propeller
NL279582A (en) * 1958-07-03
FR1255950A (en) * 1959-11-23 1961-03-17 Bauchet Et Cie Ets New heat-developable diazotype product
US3220846A (en) * 1960-06-27 1965-11-30 Eastman Kodak Co Use of salts of readily decarboxylated acids in thermography, photography, photothermography and thermophotography
US3157503A (en) * 1963-03-19 1964-11-17 Keuffel & Esser Co Diazotype reproduction materials

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR750080A (en) * 1932-04-27 1933-08-03 Process for preparing light-sensitive layers
US2694009A (en) * 1948-10-01 1954-11-09 Keuffel & Esser Co Diazo-n-sulfonate light-sensitive material
US2653091A (en) * 1950-01-31 1953-09-22 Rca Corp Photographic diazotype composition and heat development thereof
US2727820A (en) * 1952-04-29 1955-12-20 Gen Aniline & Film Corp Light-sensitive diazotype layers containing carboxamides
US2732299A (en) * 1952-07-22 1956-01-24 Light sensitive
GB816601A (en) * 1954-07-09 1959-07-15 Arnold Tanenbaum Improvements in or relating to diazotype processes
FR1249913A (en) * 1959-11-23 1961-01-06 Bauchet & Cie Ets Heat-developable diazotype product
US3102812A (en) * 1960-11-16 1963-09-03 Gen Aniline & Film Corp Stabilizers for one-component diazotype materials
BE609912A (en) * 1961-11-02

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408192A (en) * 1964-06-10 1968-10-29 Ibm Light-sensitive diazotype compositions and elements
US3389996A (en) * 1964-10-15 1968-06-25 Gen Aniline & Film Corp Two-component heat developable diazotypes
US3420666A (en) * 1964-10-15 1969-01-07 Gaf Corp Two-component heat developing diazotypes
US3379531A (en) * 1965-03-30 1968-04-23 Gen Aniline & Film Corp Two-component heat developing diazotypes
US3529964A (en) * 1966-01-14 1970-09-22 L L Ridgway Enterprises Inc Heat developable diazo compositions and diazotype reproduction media
US3650750A (en) * 1968-12-28 1972-03-21 Ricoh Kk Heat-developable diazo-type light-sensitive material
US3793030A (en) * 1971-09-02 1974-02-19 Ricoh Kk Process for producing diazotype light-sensitive material
US3900324A (en) * 1972-06-25 1975-08-19 Ozalid Co Ltd Treatment of synthetic polyester film products
US4478926A (en) * 1981-12-28 1984-10-23 Andrews Paper & Chemical Co., Inc. Zinc sulfonates and their use in diazotypy

Also Published As

Publication number Publication date
US3294534A (en) 1966-12-27
BE648593A (en) 1964-09-16
NL6406013A (en) 1964-12-01
GB1063132A (en) 1967-03-30
US3326686A (en) 1967-06-20
US3301679A (en) 1967-01-31
US3166422A (en) 1965-01-19
US3255011A (en) 1966-06-07

Similar Documents

Publication Publication Date Title
US3298834A (en) Diazotype photoprinting material susceptible to thermal development
US3224878A (en) Thermographic diazotype reproduction material, method of making and method of using
US3408192A (en) Light-sensitive diazotype compositions and elements
US3520692A (en) Diazonium compounds and diazotype materials containing them
US3307952A (en) Formation of diazo couplers in situ
US3338713A (en) Diazotype material
US2429249A (en) Stabilized aryl diazo-n-sulfonate light-sensitive material
US3379531A (en) Two-component heat developing diazotypes
US3389996A (en) Two-component heat developable diazotypes
US2500099A (en) Diazo sulfonate light-sensitive element containing a diketone azo component
US3410688A (en) Black-line diazotype materials containing plural coupling components for thermal development
US3389995A (en) Two-component heat developable diazotypes containing amidine compounds
US3154417A (en) Heat developable light sensitive diazo compositions containing dicyandiamide
GB948661A (en) Diazotype photoprinting process
US3169067A (en) Heat developable diazotype material comprising an unsymmetrical urea as the base release agent
US3271155A (en) Thermo-developable diazo coatings employing dicyandiamide compositions
US3420666A (en) Two-component heat developing diazotypes
US3539345A (en) Thermal diazotype papers
US3694247A (en) Heat-sensitive copying material
US3740229A (en) Diazotype photographic copying material for heat development
US3272627A (en) Photothermographic diazo material and its method of use for photocopying
US3360369A (en) Diazotype reproduction material
US3331690A (en) Development of diazotype papers without a coupler
US3625693A (en) Thermally developable diazotype copying materials
US3191030A (en) Process of making and using thermographic reproduction paper

Legal Events

Date Code Title Description
AS Assignment

Owner name: R Q O HOLDING COMPANY INC 111 WEST 2ND ST JAMESTOW

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GAF CORPORATION;REEL/FRAME:004006/0585

Effective date: 19820526

Owner name: R Q O HOLDING COMPANY INC, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GAF CORPORATION;REEL/FRAME:004006/0585

Effective date: 19820526