US3811891A - Silver halide photographic element containing a vinylsulfonyl compound hardener and an acrylic urea as formaldehyde scavenger - Google Patents

Silver halide photographic element containing a vinylsulfonyl compound hardener and an acrylic urea as formaldehyde scavenger Download PDF

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Publication number
US3811891A
US3811891A US00266767A US26676772A US3811891A US 3811891 A US3811891 A US 3811891A US 00266767 A US00266767 A US 00266767A US 26676772 A US26676772 A US 26676772A US 3811891 A US3811891 A US 3811891A
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United States
Prior art keywords
photographic element
scavenger
element according
further improvement
urea
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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
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US00266767A
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English (en)
Inventor
R Darlak
C Wright
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US00266767A priority Critical patent/US3811891A/en
Priority to CA170,538A priority patent/CA1001472A/en
Priority to FR7322610A priority patent/FR2191150B1/fr
Priority to JP48069962A priority patent/JPS4953434A/ja
Priority to AU57283/73A priority patent/AU5728373A/en
Priority to DE2332426A priority patent/DE2332426A1/de
Priority to BE132816A priority patent/BE801553A/xx
Application granted granted Critical
Publication of US3811891A publication Critical patent/US3811891A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen

Definitions

  • ln multi-layer photographic elements used in color photography there are at least three selectively sensitive color forming units each made up of one or more emulsion layers'coated on one side of a photographic support, such as film or paper.
  • the color forming units are typically rendered variously responsive to the red, green and blue'regions of the spectrum.
  • the blue-sensitive color forming unit typically contains a yellow coupler, the green-sensitive color forming unit amagenta coupler and the red-sensitive color forming unit a c'yan coupler.
  • color couplers are not initially present in the photographic element, but are introduced during processing after an imageforming exposure. l-lydrophilic colloid subbing layers, interlayers and over-layers are also typically present.
  • the blue-sensitive color forming unit forms the outermost unit, and a Carey Lea silver filter layer various cyclic and acyclic ureas as aldehyde scavengers.
  • Aldehydes such as formaldehyde, glyoxal, succinaldehyde,glutaraldehyde, etc. have been proposed for this purpose.
  • certain disadvantages have been observed by those skilled in the art to result from associating aldehydes with photographic elements, even, in some instances, in the trace amounts found in the atmosph ere.
  • Aldehydes in some cases, can produce excessive hardening of the hydrophilic colloid containing'layers, direct interaction with color couplers, and emulsion fogging.
  • ethylene urea acetamide, N,N-diacetylethylene diamine, monomethylamine or dimethylamine as scavengers for formaldehyde gas contained in the atmosphere.
  • the art has recognized distinct advantages to the utilization of vinylsulfonyl compounds in place of aldehydes as hardeners for the hydrophilic colloid layers of photographic elements.
  • Such compounds are characterized by the inclusion of a plurality of vinylsulfonyl groups.
  • divinylsulfone a single sulfonyl group joins two vinyl groups.
  • Bis(- vinylsulfonyl) ethers such as bis(vinylsulfonylmethyl) and bis(vinylsulfonylethyl) ethers have been found particularly suitable for use as hardeners.
  • Representative vinylsulfonyl hardeners as well as procedures for their synthesis and use are disclosed in Bumess et'al.
  • the present invention is directed to a process wherein a vinylsulfonyl hardener and an acyclic urea aldehyde scavenger are concurrently associated within a hydrophilic colloid forming a portion of a photographic element.
  • this invention is directed to a photographic element having a hydrophilic colloid layer containing a vinylsulfonyl harde'ner and an acyclic urea scavenger.
  • an acyclic urea refers to those compounds in which none of the urea moieties HN E NH present form a portion of a ring structure, as is the case, for example, in compounds such as barbituric acid and urazole. It is contemplated that these acyclic ureas can include one or more cyclic nitrogen substituents, as is hereinafter more fully illustrated.
  • layers containing one of these heterocyclic ureas are reactive with the heterocyclicurea in preference to the hydrophilic colloid, to the detriment of both the hardening and aldehyde scavenging properties desired to be imparted by these addenda.
  • the vinylsulfonyl hardener and acyclic urea aldehyde scavenger can be concurrently associated with a hydrophilic colloid layer of a photographic element. This means simply that the colloid, the acyclic urea aldehyde scavenger and the vinylsulfonyl hardener (as opposed to the scavenger and the reaction product of the vinylsulfonyl hardener with the colloid) can be brought together.
  • the acyclic urea scavenger when non-ballasted can also wander from its situs of introduction in the photographic element.
  • Utilizing an aldehyde scavenger which is incompatible with the vinylsulfonyl hardener in this circumstance requires a subsequent preparation step to associate this addenda with a hydrophilic colloid layer.
  • hydrophilic colloids employed in the formation of photographic elements frequently contain water as one ingredient at the time they are deposited as layers on a support, it is preferred to utilize water soluble acrylic urea aldehyde scavengers.
  • Preferred acyclic ureas contemplated for use in the practice of this invention are aldehyde scavengers having the formula:
  • H 8 11 X is a HN-(OHz)mN or HN- group
  • n is 0 or 1; and R and R are independently selected from the class consisting of hydrogen, lower alkyl, hydroxyalkyl and aryl, such as a phenyl substituent.
  • lower alkyl refers to those alkyl groups having six or fewer carbon atoms.
  • Exemplary water soluble acyclic ureas within the contemplation of this invention include urea, methyl urea, ethyl urea, butyl urea, hexyl urea, N,N'-dimethyl urea, N,N'-diethyl urea, hydroxymethyl urea, N,N-di(2-hydroxyethyl) urea, N,N'-di(2- hydroxyhexyl) urea, phenyl urea, biuret, hydroxyethyl biuret, l,5-di(hydroxyethyl) biuret, methylene diurea, l,l-ethylene diurea, and- 3,3'-dihydroxyethyl-l ,1- ethylene diurea.
  • the acyclic urea scavenger can be incorporated within the vinylsulfonyl hardener containing hydrophilic colloid layer of the photographic element to be protected from aldehyde attack.
  • a photographic element according to this invention can comprise a support having thereon a single silver halide photographic emulsion layer containing a hydrophilic colloid, an acyclic urea aldehyde scavenger and a vinylsulfonyl hardener.
  • the aldehyde scavenger may be located beneath the layer to be protected or may be located both under and over the layer to be protected, as in a colloid subbing layer, interlayer, overcoat layer, or a combination of such layers.
  • the scavenger is preferably located in the outer hydrophilic colloid layer or the Carey Lea silver filter layer, but can be advantageously incorporated in any overlying layer or interlayer, including a blue-sensitive emulsion layer.
  • aldehyde scavenger need not be blended into a vinylsulfonyl hardener hydrophilic colloid layer to be associated therewith as contemplated by this invention, but can simply contiguously overlie the hardener containing hydrophilic colloid layer.
  • the concentration of acyclic ureaaldehyde scavengerassociated with a photographic element according to this invention can vary widely, depending upon such factors as the degree of protection from aldehyde attack desired, the concentrations of aldehyde expected to be encountered, the sensitivity of the ingredients within the photographic element sought to be protected, the water solubilityof the acyclic ureachosen and the like.
  • the acyclic urea be present in a concentration of at least 0.1 milligrams per square decimeter.
  • acyclic urea concentrations of from 0.1 to 40 milligrams per square decimeter are preferred with concentrations of from 1 to. 30 milligrams per square .decimeter being particularly useful.
  • the vinylsulfonyl hardener associated with the acyclic urea aldehyde scavenger can be incorporated in any conventional useful concentration and will typically be employed in a concentration of from 0.1 to 10 percent and, most commonly 0.5 to 6.0 percent, by weight, based on the weight of the hardenable material present.
  • gelatin constitutes the hardenable material present within the hydrophilic colloid layers of photographic elements.
  • Other materials known to be hardenable by vinylsulfonyl hardeners which may be present in one or more hydrophilic colloid layers of a photographic element-are colloidal albumin, acid or water-soluble vinyl polymers, cellulose derivatives, proteins, various polyacrylarnides, dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials exemplified by amine-containing polymers of alkyl acrylates,
  • acyclic urea aldehyde scavengers of this invention can be to protect such hardenable materials from further hardening by aldehydes after the desired degree of hardening has been imparted by the vinylsulfonyl hardener.
  • the acyclic urea aldehyde scavenger can be used to protect one or more other ingredients of a photographic element.
  • the acyclic urea-aldehyde scavenger can be used to protect fixed color couplers, such as those which are reactive with aryl amines,which can be present in one or more of the color forming units of a photographic element.
  • couplers are quite sensitive to the presence of aldehydes and, if left unprotected, during storage between preparation and processing, will readily react with formaldehyde present in the atmospheres to produce a compound visibly distinguishable from the compound desired to be formed by reaction of the coupler with the aryl amine developer.
  • magenta couplers such as S-pyrazolone couplers as described in Loria et al. U.S. Pat. No. 2,600,788, issued June 17, 1952, are known to suffer marked color loss when associated with relatively small quantities of aldehydes.
  • Photographic elements utilizing non-ballasted couplers such as those added during development are protected from color loss by protecting the colloid layers from undesirable hardeningthat can retard or impede introduction of these couplers. Accordingly, it is apparent that this invention is applicable to color photographic elements generally and is specifically noted to be useful in protecting photographic elements for producing both positive and reversal color images.
  • Exemplary color photographic elements capable of being benefited by the practice of this invention are set forth in Graham et al. U.S. Pat. No. 2,725,292, Salminen et al. U.S. Pat. No. 2,895,826, Bush et al. U.S. Pat. No. 2,920,961, Beavers U.S. Pat. No. 2,983,608, Loria et al. U.S.
  • EXAMPLE 1 containing a magenta-dye-forming coupler, which was in this case a S-pyrazolone coupler'as disclosed by Loria et a1, cited above; a yellow Carey-Lea silver gelatin filter layer; a blue-sensitive silver halide emulsion layer containing a yellow-dye-forming coupler; and a gelatin outerlayer containing the scavenging compound and bis(vinyl-sulfonylmethyl) ether hardener.
  • the hardener was incorporated in the outerlayer to diffuse through and harden each of the gelatin layers present at a concentration of 1.5 percent by weight based on the gelatin present.
  • One of the photographic elements served as a control and contained no aldehyde scavenger; the second element contained 3 mg/dm of barbituric acid; and the third element 5 mg/dm of 1,1- ethylene diurea.
  • the scavengers were prepared as an aqueous solution for blending with the gelatin prior to forming the layers.
  • Each of the photographic elements was given a sensitometric exposure and then exposed to an aldehyde by suspension for 16 hours in a stream of room temperature air having a relative humidity of from 50 to 60 percent and containing from 0.4 to 0.8 mg of gaseous formaldehyde'per liter of air.
  • the elements were immersed at 38C. for 3 minutes in Kodak F-6 developer, for 6 minutes in bleach-fix solution comprised of a ferric ethylene diamine te'tracetic acid and ammonium thiosulfate, for minutes in water and finally for 10 seconds in a stabilizer bath comprised of 6 ml of 35 percent formalin and 8 to 9 ml of an ethylene oxide wetting agent per liter.
  • the 1,1 '-ethylene diurea protected element exhibited only a 30 percent dye loss under the stringent conditions of comparison.
  • Percentage dye loss attributable to aldehyde attack wasin each instance determined by comparison with an identical photographic element identically exposed and processed, but not subjected to aldehyde exposure.
  • Example 2-7 The procedures of Example 1 were repeated using l,l-ethylene diurea and varying the concentration and location of the scavenger. The results are set forth in Table I.
  • Example 1 mg/dm gelatin and 9.5 mg/dm of the magenta dyeforming coupler of Example 1; and an overlayer comprised of 8.0 mg/dm of gelatin having dispersed therein 7.0 mg/dm of aldehyde scavenger and sufficient bis(vinylsulfonylmethyl) ether to adequately harden each of the gelatin layers present.
  • the image exposure, aldehyde exposure and processing were carried out as described in Example 1.
  • the specific aldehyde scavengers incorporated and the percentage of magenta dye loss are set forth in Table ll.
  • a silver halide emulsion containing photographic element in which a vinylsulfonyl hardener is associated with a hydrophilic colloid layer
  • said hydrophilic colloid layer contains in addition to said vinylsulfonyl hardener an acyclic urea aldehyde scavenger in an amount of at least 0.1 milligrams per square decimeter, said scavenger having the formula:
  • m is l or 2;
  • n 0 or 1
  • R and R are independently selected from the class consisting of hydrogen, alkyl containing one to six carbon atoms, hydroxyalkyl and aryl.
  • a vinylsulfonyl hardener is associated with a plurality of superimposed hydrophilic colloid layers on a support which is substantially impenetrable by formaldehyde and in which at least one of said layers contains a coupler capable of reacting with an aryl amine to produce a first compound having a visible color and, alternatively, capable of reacting with formaldehyde to produce a second compound visibly distinguishable from the first compound
  • the improvement comprising at least one of said hydrophilic colloid layers overlying said formaldehyde reactive coupler containing layer including an acyclic urea formaldehyde scavthe further improvement in which 9 enger in an amount of at least 0.] milligrams per square decimeter, said scavenger having the following structural formula:
  • Rand R are independently selected from the class consisting of hydrogen, alkyl containing one to six carbon atoms, hydroxyalkyl and a phenyl substituent.
  • said scavenger is a dialkyl urea.
  • said hardener is a bis(vinylsulfonyl) ether.
  • a silver halide emulsion containing photographic element comprising a plurality of bis(vinylsulfonyl) hardener containing gelatin layers located in superimposed relationship on a support which is substantially impenetrable to formaldehyde and in which said layers form at least three color forming units each sensitive to a different region of the visible spectrum, one of which units contains a S-pyrazolone coupler, the improvement comprising at least one of said gelatin layers overlying said 5- pyrazolone coupler containing layer comprising a concentration of ethylene diurea of at least 0.1 milligrams per square decimeter.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Detergent Compositions (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00266767A 1972-06-27 1972-06-27 Silver halide photographic element containing a vinylsulfonyl compound hardener and an acrylic urea as formaldehyde scavenger Expired - Lifetime US3811891A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00266767A US3811891A (en) 1972-06-27 1972-06-27 Silver halide photographic element containing a vinylsulfonyl compound hardener and an acrylic urea as formaldehyde scavenger
CA170,538A CA1001472A (en) 1972-06-27 1973-05-07 Acyclic urea scavenger containing photographic elements and processes for their preparation
FR7322610A FR2191150B1 (enrdf_load_stackoverflow) 1972-06-27 1973-06-21
JP48069962A JPS4953434A (enrdf_load_stackoverflow) 1972-06-27 1973-06-22
AU57283/73A AU5728373A (en) 1972-06-27 1973-06-25 Photographic materials and processes
DE2332426A DE2332426A1 (de) 1972-06-27 1973-06-26 Einen acyclischen harnstoff als aldehydentferner enthaltendes photographisches aufzeichnungsmaterial und verfahren zu seiner herstellung
BE132816A BE801553A (fr) 1972-06-27 1973-06-27 Nouveau produit photographique tanne et procede pour le preparer

Applications Claiming Priority (1)

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US00266767A US3811891A (en) 1972-06-27 1972-06-27 Silver halide photographic element containing a vinylsulfonyl compound hardener and an acrylic urea as formaldehyde scavenger

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US3811891A true US3811891A (en) 1974-05-21

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US (1) US3811891A (enrdf_load_stackoverflow)
JP (1) JPS4953434A (enrdf_load_stackoverflow)
AU (1) AU5728373A (enrdf_load_stackoverflow)
BE (1) BE801553A (enrdf_load_stackoverflow)
CA (1) CA1001472A (enrdf_load_stackoverflow)
DE (1) DE2332426A1 (enrdf_load_stackoverflow)
FR (1) FR2191150B1 (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4355100A (en) * 1980-01-16 1982-10-19 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
DE3241087A1 (de) * 1981-11-06 1983-05-19 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbphotographisches, lichtempfindliches silberhalogenid-material
US4414309A (en) * 1981-12-04 1983-11-08 Agfa-Gavaert Aktiengesellschaft Photographic recording material containing an aldehyde remover
US4418142A (en) * 1980-10-08 1983-11-29 Agfa Gevaert Aktiengesellschaft Light-sensitive photographic silver halide recording material
US4490460A (en) * 1982-03-03 1984-12-25 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59137946A (ja) * 1983-01-28 1984-08-08 Fuji Photo Film Co Ltd ハロゲン化銀感光材料

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4355100A (en) * 1980-01-16 1982-10-19 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
USRE31893E (en) * 1980-01-16 1985-05-21 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
US4418142A (en) * 1980-10-08 1983-11-29 Agfa Gevaert Aktiengesellschaft Light-sensitive photographic silver halide recording material
DE3241087A1 (de) * 1981-11-06 1983-05-19 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbphotographisches, lichtempfindliches silberhalogenid-material
US4411987A (en) * 1981-11-06 1983-10-25 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4414309A (en) * 1981-12-04 1983-11-08 Agfa-Gavaert Aktiengesellschaft Photographic recording material containing an aldehyde remover
US4490460A (en) * 1982-03-03 1984-12-25 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic materials

Also Published As

Publication number Publication date
BE801553A (fr) 1973-12-27
DE2332426A1 (de) 1974-01-17
FR2191150A1 (enrdf_load_stackoverflow) 1974-02-01
FR2191150B1 (enrdf_load_stackoverflow) 1983-03-18
JPS4953434A (enrdf_load_stackoverflow) 1974-05-24
CA1001472A (en) 1976-12-14
AU5728373A (en) 1975-01-09

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