US3785826A - Diazotype materials for blackline images - Google Patents

Diazotype materials for blackline images Download PDF

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Publication number
US3785826A
US3785826A US00247903A US3785826DA US3785826A US 3785826 A US3785826 A US 3785826A US 00247903 A US00247903 A US 00247903A US 3785826D A US3785826D A US 3785826DA US 3785826 A US3785826 A US 3785826A
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United States
Prior art keywords
diresorcyl
diazotype
images
blackline
diazo
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Expired - Lifetime
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US00247903A
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English (en)
Inventor
C Slimowicz
W Welch
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R Q O HOLDING CO Inc
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GAF Corp
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Assigned to R Q O HOLDING COMPANY INC reassignment R Q O HOLDING COMPANY INC ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GAF CORPORATION
Assigned to CONGRESS FINANCIAL CORPORATION, A CA CORP. reassignment CONGRESS FINANCIAL CORPORATION, A CA CORP. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: R.Q.O. HOLDING COMPANY, INC.
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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

  • ABSTRACT Sensitizing agents for ammonia vapor developable black -line two-component diazotype sensitizing formulations comprising diazotized derivatives of 4-N- pyrrolidinyl-3-alkyl-paraphenylenediamine are employed with a mixture of coupling components which include an acetoacetamide, a naphthol, a diresorcyl compound alone or also with resorcinol.
  • the present invention relates in general to diamotype materials capable of yielding blackline images upon color development and more particularly to the utilization of specific light-sensitive diazo-coupler systems for such purposes.
  • diazotype materials currently available commercially and specifically adapted to the production of colored images, e.g., blue, red sepia, are legion.
  • diazotype systems capable of yielding blue, red, green, i.e., non-black images, are in many instances advantageous, it is of critical importance in connection with the production of diazotype images contemplated for use as intermediates, i.e., for further exposures, that the image obtained possess optimum dye covering power and reprint capacity.
  • the importance of these desiderata in such photographic applications' is at once apparent.
  • the intermediate diazotype material provide an image which is totally opaque to the actinic radiation contemplated for employment in connection with requiring operations utilizing such materials.
  • coupler mixtures for the production of blackline images.
  • one of the coupler systems heretofore promulgated in this regard involves the use of at least three coupling components, i.e., capable of yielding a yellow green image, and a blue image respectively and a third or shading component capable of yielding a yellow brown image.
  • the several absorption spectra of the dye images yielded by the coupling compounds in question combine to yield a uniform and maximum absorption density across the entire visible spectrum.
  • black image formation results since all incident visible radiation is absorbed uniformly by the image in question.
  • the resorcinol component of the coupler system due to its relatively low molecular weight and high water solubility, exhibits a distinct susceptibility to migrate or otherwise diffuse into porous, e.g., fibrous materials. This correspondingly reduces the amount of coupling component available for image formation upon the alkaline-induced developing operation. This situation gives rise to very serious problems since there results an imbalance in the color aspect of the final image thereby vitiating substantially any attempt to achieve the desired black coloration. In the vast majority of instances, photographic reproductions produced with such diazotype materials are quite difficult if not impossible to distinguish from the conventional blueline diazotype prints.
  • remedial techniques envisage the use of specific structural arrangements, i.e., the positioning of diffusion barriers intermediate the sensitized layers and base. Although such techniques have provided some margin of improvement, it has nevertheless been ascertained in practice that the results are far from optimum. Moreover, such procedures have proved to be objectionable from an economic standpoint as well since the fabrication of specific and predetermined dizaotype materials or alternatively, the use of compounds which tend to promote diffusion resistance, can prove to be quite costly.
  • blackline diazotype materials fabricated with coupling systems of the foregoing type i.e., wherein diresorcyl sulfide or diresorcyl sulfoxide is employed in lieu of resorcinol with the remaining coupling components comprising, usually, acetacetanilide and 2,3-dihydroxynaphthalene-6-sulfonic acid, have nevertheless been ascertained to provide somewhat sub-optimum results in particular applications and especially in connection with fast printing processes specifically adapted for the production of blackline diazotype intermediates.
  • High speed processing has, of course, assumed a position of premier commercial importance in view of the manifold demands being imposed upon photographic reproduction processing.
  • a primary object of the present invention resides in the provision of blackline diazotype materials wherein the foregoing disadvantages are eliminated or at least mitigated to a substantial extent.
  • Another object of the present invention resides in the provision of diazotype materials capable of yielding blackline images utilizing high speed processing said images being characterized by exceptional reproduction quality, i.e., contrast, density, etc.
  • a further object of the present invention resides in the provision of high speed blackline diazotype materials particularly and beneficially adapted for use in the production of intermediates, the images obtainable therewith exhibiting exceptional dye covering power and reprint opacity.
  • a still further object of the present invention resides in the provision of blackline diazotype materials wherein problems associated with the loss of coupler due to migration, diffusion, etc. of such materials into adjacent layers, and in particular to porous base materials are completely eliminated despite the utilization of such materials in high speed reproduction techniques,
  • blackline diazotype materials containing a coupling mixture comprising an acetoacetamide, a hydroxynaphthalene coupler selected from 2,3- dihydroxynaphthalene-6-sulfonic acid and a 2- hydroxy-3-(N-B-diloweralkylaminoethyl) naphthamide and a diresorcyl derivative selected from the class consisting of diresorcyl derivative selected from the class consisting of diresorcyl sulfide and diresorcyl sulfoxide and wherein the diazo component comprises a diazo derivative of a 4-N-pyrrolidinyl-3-alkylparaphenylenediamine of the following structural formula:
  • R represents lower alkyl of one to four carbon atoms, i.e., methyl, ethyl, propyl, isobutyl, etc.
  • R in the above formula represents methyl, i.e., 3-methyl-4-pyrrolidinylbenzendiazonium.
  • the diamo and coupler materials described herein are known compounds with methods for their preparation being described in numerous publications both patent and otherwise.
  • diresorcyl sulfide can be readily prepared by reacting sulfur dichloride in ether, with resorcinol in ether at a temperature not higher than 12 C., neutralizing the reaction solution with sodium carbonate, stripping the ether from the organic layer and crystallizing the sulfide from water.
  • the diresorcyl sulfoxide component may be compared from the sulfide by suspending it in water at 65 C. and oxidizing the sulfide with an excess of hydrogen peroxide at 6575 C.
  • resorcinol may be employed for purposes of complementing the shading action of the diresorcyl compound and to insure against any possibility of a shift in the image color to red.
  • acetoacetamide couplers contemplated for use herein encompass the parent compound, i.e., acetoacetamide, as well as the N-substituted derivative thereof.
  • acetoacetamide as used herein to be accorded the corresponding significance.
  • Particularly beneficial results are obtained with the fast yellow" acetoacetamide derivatives, i.e., those containing N- alkyl or N-aryl bonded substituents.
  • Coupler compounds of this type are well known in the art being extensively described in the literature both patent and otherwise. Although such definition encompasses a relatively wide variety of materials, investigation nevertheless indicates that optimum results invariably attend their use.
  • Acetoacetanilide V N,N-ethylene-bis-acetoacetamide Acetoacet-a-naphthylamide mhydroxyacetoacetanilide o-methylacetoacetanilide o-methoxyacetoacetanilide p-methoxyacetoacetanilide 2-methoxy-5-methylacetoacetanilide N-(p-methoxybenzyl)acetoacetamide N-piperonylacetoacetamide N- l -indonylacetoacetamide N-(p-methoxyphenethyl)-acetoacetamide N-benzylacetoacetamide diacetoacet-dianisidide ....etc.
  • the diazo coating composition in addition to the above enumerated coupling and diazo components may contain any of the usual adjuncts conventionally employed in the manufacture of light sensitive diazotype materials.
  • Such materials include, for example, metal salt for intensification of the dyestuff image, e.g., ammonium sulfate, methyl sulfate, zinc chloride and the like: stabilizing agents such as thiourea, thiosinamine, naphthalene, trisulfonic acid and the like; acid stabilizers to retard precoupling such as acetic acid, boric acid, tarteric acid and the like; wetting agents such as saponin, lauryl sulfonate, keryl benzene sulfonate, the oleic acid amide of N-methyl taurine, and the like.
  • stabilizing agents such as thiourea, thiosinamine, naphthalene, trisulfonic acid and the like
  • the 3-alkyl-4-pyrrolidinylbenzenediazonium salt is preferably employed in the form of the stabilized salt, e.g., chlorozincate, borofluoride, etc.
  • the provision of benzene diazonium compounds in the form of stabilized salts is, of course, well established technology being extensively described in the prior art and requires nothing in the way of detailed comment here. Suffice to any that any of the conventional stabilized salt forms are admirably suited for use herein.
  • the base to which the diazo coating solution is applied may be of any of those conventionally employed for such purposes in the art.
  • the base in a particular instance may be comprised of a film-forming material, e.g., plastic, cellulose acetate, cellulose acetate buty rate, polyester, polycarbonate and the like; alternatively such base may be of fibrous structure, e.g., highgrade all-sulfide bond paper, cotton, cloth, starch filled cloth, etc.
  • the base may be provided with a suitable protective pre-coating composition for purposes of promoting adhesion of the sensitized layer to the base material.
  • Such embodiments are particularly preferred in those instances wherein difficulty is encountered in achieving the requisite degree of adhesion between the sensitized layer and base material; moreover, such procedures are uniquely advantageous since the pre-coating can serve as a diffusion barrier, thereby further insuring against any possibility of spurious migration of coupling compound, sensitizer or other ingredients of a hydrophilic nature.
  • Suitable pre-coating compositions in this regard include, for example, aqueous dispersion, of polyvinyl acetate, silica, etc. In any event, compositions for such purposes are well known in the art.
  • Example 1 An all sulfite bond paper was precoated with the following precoating solution and dried:
  • Example 2 The procedure described in Example 1 is repeated except that the diresorcyl sulfoxide is replaced by an equimolecular quantity of diresorcyl sulfide.
  • the coupling material 2-hydroxy-3-(N-propylmorpholino)- naphthamide was used in place of the 2,3- dihydroxynaphthalene-6-sulfonic acid.
  • the results obtained are similar to those desxribed above, i.e., superior image reproduction is obtained.
  • Example 3 Example 1 was repeated with the exception that the 2,3-dihydroxynaphthalene-6-sulfonic acid was replaced by the same weight of 2-hydroxy-3-(N-B- diethylaminoethyl)naphthamide.
  • Example 4 Example 1 is repeated except that following coating of the sensitized solution upon the sulfide bond paper base, the sensitized element is stored for a period of several months, being subjected throughout such storage to a humid atmosphere.
  • the image reproduction obtained exhibited each of the improved characteristics, i.e., contrast, density, etc., noted with the above example; it was also noted that spurious diffusion of any of the sensitizing composition ingredients did not occur. If such had been the case, the image obtained would quite obviously exhibit a lack of density and thus covering power, reprint opacity, etc.
  • Example 5 Example 5
  • Example 5 Example 5
  • Example 5 Example 5
  • Example 5 Example 5
  • the coupler mixture includes, additionally, resorcinol.
  • the coupler mixture includes, additionally, resorcinol.
  • Upon exposure and development there was obtained an image having excellent contrast and density indicating clearly that the usual tendency of the resorcinol coupled to diffusion into the fibrous base material had been counteracted; apparently, the use of resorcinol in the particular relationship specified herein, i.e., the nature of the coupling components included therewith, influences greatly this property.
  • diazo sensitizers described herein may be employed in admixtures comprising two or more, depending solely upon the requirements of the processor and of course whether variations in dye shading are desired. In any event, optimum mixtures may be readily ascertained in particular instances by rather routine laboratory investigation. Similar improvement is likewise obtained when the base material employed is non-fibrous in nature, e.g., cellulose acetate, cellulose acetate butyrate, synthetic film-forming polymeric materials, e.g., polyesters such as polyethylene terephthalate, polycarbonates and the like.
  • the pyrrolidene moiety of the diazo sensitizer compounds of the present invention may contain additional substituents of an innocuous nature, e.g., alkyl, alkoxy, etc. Accordingly, such substituent derivatives are to be considered equivalents to the compounds specifically enumerated herein.
  • the salient requirement with respect to the nature of such substituents is that they be totally devoid of any tendency to deleteriously effect the spectral response of the diazonium compound or such other vital properties as stability, compatability, and the like.
  • An ammonia vapor developable diazo sensitizing composition for the production of blackline images consisting essentially of, a mixture of coupling components consisting of an acetoacetamide selected from the group consisting of acetoacetamide, acetoacetanilide, N,N-ethylene-bis-acetoacetamide, acetoacetanaphthylamide, m-hydroxyacetoacetanilide, 0- methylacetoacetanilide, o-methoxyacetoacetanilide, p-methoxyacetoacetanilide, 2-methoxy-5- methylacetoacetanilide, N-(p-methoxybenzyl)- acetoacetamide, N-piperonylacetoacetamide, N-lindonylacetoacetamide, N-(p-methoxyphenethyl)- acetoacetamide, N-benzylacetoacetamide and diacetoacet-dianisidide, a compound selected
  • composition according to claim 1 wherein said diazo sensitizing compound is 3-methyl-4-pyrrolidinyl benzene-diazonium chlorozincate.
  • a composition according to claim 1 wherein said diresorcyl is diresorcyl sulfide.
  • a light sensitive diazotype element for the production of blackline images comprising a base coated with the composition of claim 1.
  • a diazotype element according to claim 5 provided with a pre-coated layer intermediate the base and light sensitive diazo layer.
  • a diazotype element according to claim 5 wherein said pre-coat comprises an aqueous emulsion of polyvinyl acetate and silica.

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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)
US00247903A 1967-03-22 1972-04-26 Diazotype materials for blackline images Expired - Lifetime US3785826A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62499967A 1967-03-22 1967-03-22
US24790372A 1972-04-26 1972-04-26

Publications (1)

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US3785826A true US3785826A (en) 1974-01-15

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US (1) US3785826A (de)
CH (1) CH509607A (de)
DE (1) DE1772017A1 (de)
FR (1) FR1558142A (de)
GB (1) GB1213719A (de)
NL (1) NL6804041A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225662A (en) * 1978-04-14 1980-09-30 Ricoh Company, Ltd. Diazo copying material
US4446218A (en) * 1982-03-18 1984-05-01 American Hoechst Corporation Sulfur and/or amide-containing exposure accelerators for light-sensitive coatings with diazonium compounds
US4448873A (en) * 1982-03-18 1984-05-15 American Hoechst Corporation Negative working diazo contact film
US4642383A (en) * 1982-09-30 1987-02-10 James River Graphics, Inc. Fast coupling lemon-yellow phenolic couplers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836369A (en) * 1972-09-05 1974-09-17 Du Pont Diazo photosensitive composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225662A (en) * 1978-04-14 1980-09-30 Ricoh Company, Ltd. Diazo copying material
US4446218A (en) * 1982-03-18 1984-05-01 American Hoechst Corporation Sulfur and/or amide-containing exposure accelerators for light-sensitive coatings with diazonium compounds
US4448873A (en) * 1982-03-18 1984-05-15 American Hoechst Corporation Negative working diazo contact film
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
CH509607A (de) 1971-06-30
DE1772017A1 (de) 1972-01-13
FR1558142A (de) 1969-02-21
GB1213719A (en) 1970-11-25
NL6804041A (de) 1968-09-23

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

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Effective date: 19820526

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

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Owner name: CONGRESS FINANCIAL CORPORATION, A CA CORP., NEW YO

Free format text: SECURITY INTEREST;ASSIGNOR:R.Q.O. HOLDING COMPANY, INC.;REEL/FRAME:005328/0029

Effective date: 19900406