US2717832A - Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol - Google Patents

Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol Download PDF

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Publication number
US2717832A
US2717832A US454837A US45483754A US2717832A US 2717832 A US2717832 A US 2717832A US 454837 A US454837 A US 454837A US 45483754 A US45483754 A US 45483754A US 2717832 A US2717832 A US 2717832A
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United States
Prior art keywords
diresorcyl
sulfoxide
resorcinol
sulfide
subsitiute
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US454837A
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Jr John Sulich
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GAF Chemicals Corp
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GAF Chemicals Corp
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Priority to US454837A priority Critical patent/US2717832A/en
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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

Description

John Sulich, Jr., Endicott, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application September 8, 1954, Serial No. 454,837

5 Claims. (Cl. 956) of different colors, red, sepia and the like. The desirability which may be processed to produce images simulating black in color is self-evident. However, the production of such materials is not a simple matter for the simple compound under alkaline conditions to yield a black image.

There are available on the market diazotype materials which are capable of being processed to black images. However, all such materials contain at least three coupling components, i. e., one which yields a yellow-green image, another whlch yields a blue image, and a third, normally considered a shading component, which yields a yellow-brown image.

In the past it has been customary to employ resorcinol s the shading component, yellow-green image and 2,3-dihydroxy naphthalene-6- sulfonic acid to yield the blue image. The mixture of the dyes obtained with these coupling components, when in admixture on paper, results in a reasonably black color in the maximum densities and a desirable greenishgray in the lower tones.

It is recognized that the storage of diazotype materials, particularly under warm humid conditions, results in a differential migration of the chemicals into the larly true with respect to resorcinol which, because of its relatively low molecular bility, is very susceptible to migration into the fibrous base and away from the light sensitive diazonium compound. It has been my experience that black line diazotype materials formulated in whole or in part by either diresorcyl sulfide or diresorcyl sulfoxide. It was ascertained that neither of these compounds showed any appreciable tendency to diffuse into the fibrous base. As a matter of fact, whereas previously humidity-aged prints (to simulate natural shelf storage of several months) showed a color shift to the weight and high water solublue due to the diffusion of resorcinol, similarly aged prints containing diresorcyl sulfide or diresorcyl sulfoxide with or without resorcinol remained a neutral black.

as the brown shader constitute the purposes and objects of the present invention.

Diresorcyl sulfide and diresorcyl sulfoxide have the following respective formulae:

Diresorcyl Sulfide Diresorcyl Sulfoxz'de OH OH OH OH OH OH carbonate, stripping the ether from the organic layer and crystallizing the sulfide from water.

In the event that the sulfoxide is to be employed, it may be prepared from the water-wet sulfide by suspending the same in water at C., and oxidizing the suifide with an excess of hydrogen peroxide at 65-75 C.

' It is a typical feature of black line diazotype materials that the mixture of the coupling components used must each have a low coupling speed. If this were otherwise the material would have poor shelf life due to produced by, using such high speed couplers as 2,3-di-hydroxy naphthalene, phloroglucinol and the like. For practical purposes I have found it to be essential to use with the diresorcyl sulfide or sulfoxide, as the case may be, acetoacetanilide to give the yellow-green image and 2,3-dihydroxy naphthalene-G-sulfonic acid to give the blue image. These components have the low coupling speed Resorcinol to complement the shading action of the diresorcyl comsitive diazonium compounds are those from N-diethyl-pphenylenediamine; N-dimethyl-p-phenylenediamine; N- dipropyl-p-phenylenediamine; N-ethyl-N-B-hydroxyethylp-phenylenediamine; N-methyl-fi-hydroxyethyl-p-phenylenediamine and the like. According to customary practice it is preferred to use these diazonium compounds in the form of their stabilized double salts with a metal halide, such as zinc chloride, aluminum chloride, tin tetrachloride and the like.

The coating solution, in addition to the coupling components and the light sensitive diazonium compound, may also contain the various adjuncts usual in the manufacture of light sensitive diazotype materials. These include metal salts for intensification of the dyestuff image, such as ammonium sulfate, nickel sulfate,. zinc chloride and the like; stabilizing. agents such asthiourea, thiosinamine, naphthalene trisulfonic acid and the like; acids acting to retard precoupling such. as acetic acid, boric acid, tartaric acid and the like; hygroscopic agents such as glycol, glycerin and the like; and wetting agents such as saponin, lauryl sulfonate, keryl benzene sulfonate, the oleic acid amide of N-methyl taurine and the like.

The base to which the coatingv solution is applied may be any fibrous base which has been previously suggested for employment in the diazotype field. Examples of such bases are high grade all-sulfite bond paper, rayon or cotton cloth, starch filled cloth and the like.

It is believed to be evident from the formulae of the diresorcyl derivatives contemplated herein that neither has a structure which is high in molecular weight. Furthermore, each possesses a plurality of hydroxyl groups which would tend to. render the two compounds soluble in water. The non-diffusibility of these derivatives, therefore, cannot be predicated either on high molecular weight or water insolubility of the products.

It is my opinion that the non-diffusibility of the diresorcyl compounds is attributable to the formation of a complex with the diazonium compound employed. Thus, it could be envisaged that one molecule of the diresorcyl sulfide would form the following complex with two molecules of the zinc chloride double salt of the diazo from N-diethyl-p-phenylenediamine HOQIOQOH EN ow gznoh HOQ L OH It is to be emphasize that no positive-proof has been. developed. to support. this theory. However,.it is a. fact that related compounds, such as.2,2',4t,4f-tetrahydroxybi* phenyl; 2,4,4-trihydroxybiphenyl and various condensation products of resorcinol with formaldehyde, on the one hand, and phosgene, on the other hand, were much closer to resorcinol in their tendency to diffuse than the diresorcyl compounds contemplated herein.

This leads me to believe that my theory is correct although it is to be understood that the possibility of the formation of a complex is only a theory and one which is offered merely for the sake of explaining the otherwise inexplicable results which I have attained.

The following examples will serve to further illustrate the invention, but it is to be understood that the examples are illustrative only.

Example I An all sulfite bond paper was coated with the following solution and dried:

The above paper, even when stored for a period of several months in a humid atmosphere, gave, upon printing and development with ammonia gas, prints which were of a neutral black shade.

Example II The procedure is the same as in Example I, excepting that the diresorcyl sulfoxide is replaced by an equimolecular quantity of diresorcyl sulfide. The results, obtained upon storage, printing and developing the resulting paper, were substantially the same as in Example I.

Example III The procedure is the same as in Example I, excepting that the light sensitive diazonium compound is the zinc chloride double salt of the diazonium compound from N-ethyl-N-B-hydroxyethyl-p-phenylenediamine which is employed in an amount equivalent to the sensitizer in Example I.

The product obtained is comparable in properties to the product of the preceding examples.

Example IV The procedure is the same as in Example I, excepting that there is used one gram of diresorcyl sulfide and 0.8 gram of resorcinol.

The paper compounded in this fashion yielded prints of a neutral black even after storage for a considerable period in a humid atmosphere.

Example V 75 minus the figures given in the examples, particularlywhen the absorbency of the paper coated is taken into consideration.

The present application is In part a continuation of my application Serial No. 383,406, filed September 30, 1953, now abandoned, entitled Diazotype Materials for Black Line Images Containing Diresorcyl Sulfide or Sulfoxide as a Substitute for Resorcinol.

Various modifications of the invention Will be apparent to operators in this field, and I, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.

I claim:

1. A storage stable light sensitive diazotype material capable of producing black azo dye images upon printing and development comprising a fibrous base coated With a light sensitive diazonium compound of the pphenylenediamine class and a mixture of coupling components comprising acetoacetanilide, 2,3-dihydroxy naphthalene-6-sulfonic acid and a diresorcyl derivative selected from the class of diresorcyl sulfide and diresorcyl sulfoxide.

2. The product as defined in claim 1, wherein the diresorcyl derivative is diresorcyl sulfide.

3. The product as defined in claim 1, wherein the diresorcyl derivative is diresorcyl sulfoxide.

4. The product as defined in claim 1, wherein the light sensitive diazonium compound is derived from N- diethyl-p-phenylenediamine.

5. The product as defined in claim 1, in which the mixture of coupling components includes resorcinol.

No references cited.

Claims (1)

1. A STORAGE STABLE LIGHT SENSITIVE DIAZOTYPE MATERIAL CAPABLE OF PRODUCING BLACK AZO DYE IMAGES UPON PRINTING AND DEVELOPMENT COMPRISING A FIBROUS BASE COATED WITH A LIGHT SENSITIVE DIAZONIUM COMPOUND OF THE PPHYLENEDIAMINE CLASS AND A MIXTURE OF COUPLING COMPONENTS COMPRISING ACETOCETANILIDE, 2,3-DIHYDROXY NAPHTHALENE-6-SULFONIC ACID AND A DIRESORCYL DERIVATIVE SELECTED FROM THE CLASS OF DIRESORCYL SULFIDE AND DIRESORCYL SULFOXIDE.
US454837A 1954-09-08 1954-09-08 Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol Expired - Lifetime US2717832A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US454837A US2717832A (en) 1954-09-08 1954-09-08 Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
BE539176D BE539176A (en) 1954-09-08
US454837A US2717832A (en) 1954-09-08 1954-09-08 Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol
DEG17507A DE1004919B (en) 1954-09-08 1955-07-02 Black developable diazotype
FR1129578D FR1129578A (en) 1954-09-08 1955-07-08 diazotype photosensitive material for pictures black lines
CH338091D CH338091A (en) 1954-09-08 1955-07-27 Black Drawing diazotype

Publications (1)

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US2717832A true US2717832A (en) 1955-09-13

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US (1) US2717832A (en)
BE (1) BE539176A (en)
CH (1) CH338091A (en)
DE (1) DE1004919B (en)
FR (1) FR1129578A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3184310A (en) * 1959-01-21 1965-05-18 Azoplate Corp Reproduction layers for printing plates
US3200135A (en) * 1959-07-29 1965-08-10 Sterling Drug Inc Copper, cadmium, and zinc salts of halo-2, 2'-dihydroxydiphenyl sulfides and sulfoxides
US3429814A (en) * 1966-04-05 1969-02-25 Mobil Oil Corp Grease compositions
US3499763A (en) * 1967-05-01 1970-03-10 Ibm Bis phenols as high opacity diazotype couplers
US3619191A (en) * 1967-09-13 1971-11-09 Tecnifax Corp The Diazo-type materials
US3836369A (en) * 1972-09-05 1974-09-17 Du Pont Diazo photosensitive composition
US3857896A (en) * 1967-09-13 1974-12-31 R Desjarlais Substituted diresorcyl sulfide and sulfoxide compounds
US3867147A (en) * 1969-05-20 1975-02-18 Hoechst Co American Light-sensitive diazo compounds and reproduction material employing the same
US3881931A (en) * 1972-05-22 1975-05-06 Fuji Photo Film Co Ltd Method for developing black diazotype photographic light-sensitive materials
US4207110A (en) * 1977-10-17 1980-06-10 Hoechst Aktiengesellschaft Diazotype material
US4304831A (en) * 1978-08-08 1981-12-08 Ricoh Co., Ltd. Black-color forming two-component type diazo copying material
US4642383A (en) * 1982-09-30 1987-02-10 James River Graphics, Inc. Fast coupling lemon-yellow phenolic couplers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3184310A (en) * 1959-01-21 1965-05-18 Azoplate Corp Reproduction layers for printing plates
US3200135A (en) * 1959-07-29 1965-08-10 Sterling Drug Inc Copper, cadmium, and zinc salts of halo-2, 2'-dihydroxydiphenyl sulfides and sulfoxides
US3429814A (en) * 1966-04-05 1969-02-25 Mobil Oil Corp Grease compositions
US3499763A (en) * 1967-05-01 1970-03-10 Ibm Bis phenols as high opacity diazotype couplers
US3619191A (en) * 1967-09-13 1971-11-09 Tecnifax Corp The Diazo-type materials
US3857896A (en) * 1967-09-13 1974-12-31 R Desjarlais Substituted diresorcyl sulfide and sulfoxide compounds
US3867147A (en) * 1969-05-20 1975-02-18 Hoechst Co American Light-sensitive diazo compounds and reproduction material employing the same
US3881931A (en) * 1972-05-22 1975-05-06 Fuji Photo Film Co Ltd Method for developing black diazotype photographic light-sensitive materials
US3836369A (en) * 1972-09-05 1974-09-17 Du Pont Diazo photosensitive composition
US4207110A (en) * 1977-10-17 1980-06-10 Hoechst Aktiengesellschaft Diazotype material
US4304831A (en) * 1978-08-08 1981-12-08 Ricoh Co., Ltd. Black-color forming two-component type diazo copying material
US4642383A (en) * 1982-09-30 1987-02-10 James River Graphics, Inc. Fast coupling lemon-yellow phenolic couplers

Also Published As

Publication number Publication date
DE1004919B (en) 1957-03-21
CH338091A (en) 1959-04-30
BE539176A (en)
FR1129578A (en) 1957-01-23

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