US3820999A - Image-receiving element for use in photographic silver halide diffusion transfer process - Google Patents

Image-receiving element for use in photographic silver halide diffusion transfer process Download PDF

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Publication number
US3820999A
US3820999A US00193183A US19318371A US3820999A US 3820999 A US3820999 A US 3820999A US 00193183 A US00193183 A US 00193183A US 19318371 A US19318371 A US 19318371A US 3820999 A US3820999 A US 3820999A
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US
United States
Prior art keywords
image
receiving element
bisacrylamide
silver
poly
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
US00193183A
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English (en)
Inventor
N Tsuji
K Kato
T Miyazako
K Ohkubo
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.)
Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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.)
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3820999A publication Critical patent/US3820999A/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
    • G03C8/00Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/24Photosensitive materials characterised by the image-receiving section
    • G03C8/26Image-receiving layers
    • G03C8/28Image-receiving layers containing development nuclei or compounds forming such nuclei
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52Amides or imides
    • C08F20/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen

Definitions

  • An image-receiving element for use in silver halide diffusion transfer processes which element comprises a support having coated thereon a diffusion transfer image-receiving layer comprising a colloidal silicon dioxide containing silver-precipitating nuclei dispersed therein, said image receiving layer being overcoated with a layer containing therein poly-addition products derived from a bisacrylamide and a diamine compound, which bisacrylamide is represented by the following general formula wherein R is a divalent hydrocarbon group having not more than 10 carbon atoms.
  • the overcoating layer serves as a stripping layer of improved properties.
  • light-sensitive photographic materials comprising a support having coated thereon a dispersion of fine particles .of a light-sensitive silver salt, such as a silver halide in a hydrophilic binder such as gelatin.
  • a light-sensitive silver salt such as a silver halide in a hydrophilic binder such as gelatin.
  • the light-sensitive layer thereof was exposed to light image-wisely and then contacted with a processing composition containing therein a developing agent to affect development of the exposed layer. At this point, the exposed silver halide in the lightsensitive layer is reduced (developed) to metallic silver.
  • the light-sensitive element is processed with a silvercomplex forming agent, whereby a water-soluble silver complex is formed by reaction of the unexposed silver halide with the silver-complex forming agent.
  • a silvercomplex forming agent which substance serves as a catalyst for reduction of the abovedescribed water-soluble silver complex (said substance therefore comprising silver-precipitating nuclei or development nuclei)
  • an image-receiving element having an image receiving layer containing therein a substance dispersed in a hydrophilic binder, which substance serves as a catalyst for reduction of the abovedescribed water-soluble silver complex (said substance therefore comprising silver-precipitating nuclei or development nuclei)
  • the silver complex formed in the lightsensitive layer is, at least in part, transported to the image-receiving layer by diffusion. It is then reduced to silver by the effect of the development nuclei contained therein, thereby forming a positive image having a pattern corresponding to the original.
  • the imagereceiving element In order to obtain the desired print, the imagereceiving element must be dissociated or stripped from the light-sensitive element.
  • a coating film usually called a stripping layer, is usually provided on the image-receiving layer to facilitate the dissociation or stripping and to prevent a film of the diffusion transfer processing composition from attaching itself to and remaining on the surface of the processed imagereceiving layer.
  • the dissociation or stripping is unsatisfactory and/or the processing composition re mains thereon, the image-surface of the imagereceiving element is tainted and the quality of the image is remarkably lowered.
  • the silver images formed on the imagereceiving element frequently undergo deterioration upon storage and/or the highlight areas thereof yellow.
  • the above-mentioned materials are effective to stop processing composition remaining on the surface of the positive print, and to protect the surface of the image-receiving sheet from. being scratched during handling, they often present disadvantages in that the transferred image assumes a metallic luster and/or the maximum density of the positive image is lowered.
  • An object of the present invention is to provide the aforementioned image-receiving material which yields a positive print free from deteriorated silver images or yellowed areas even in its highlight areas.
  • Another object of the present invention is to provide the aforementioned image-receiving material which has a surface protected from being scratched on handling.
  • condensation products which characterize the present invention may be prepared by the poly-addition of bisacrylamide to diamine compound.
  • the representative polycondensation condition is provided in Polymer vo. ll, page 88 (1970).
  • One of the starting materials, bisacrylamide, may be represented by the following general formula wherein R stands for a divalent hydrocarbon group such as n being a number from 1 to 10,
  • the diamine compound may be, for example, ethylene diamine, 1,3- propanediamine, hexamethylene diamine, piperadine, xylylene diamine, phenylene diamine.
  • the condensation products wherein, above all, ethylene diamine, 1,3-propane diamine or piperidine are used have been found to be most suitable for accomplishing the afore-mentioned objects of the present invention.
  • the lower the number of carbon atoms in the R group in the bisacrylamide the better the results which are obtained.
  • the intrinsic viscosity [n] of the addition-polymerization products which reflects the polymerization degree thereof, preferably ranges from 0.005 to 0.5, particularly from 0.01 to 0.1. In this specification, intrinsic viscosity is measured in water at 30 C.
  • poly-addition products are all soluble in water or alcohols, so that they can be applied, in the form of a solution in water, alcohol or a mixture of water and alcohol, to the surface of an image-receiving element.
  • the coating weight of the products is in the range of from about 0.1 to about 2.0 g/m preferably from 0.3 to 1.0 g/m 1f the coverage is much less than the recited range, the effect of preventing attachment of the processing composition tends to be lessened while if the coverage exceeds the range, diffusion transfer tends to be inhibited.
  • any suitable material used as such supports by the prior art for exarnple, films or sheets of filmforming resins such as polyethylene terephthalate, cellulose triacetate, polycarbonate, polyvinyl chloride or polyethylene, baryta-coated paper, resin-coated papers, glass plates, metal plates, plates made of earthen ware or like materials.
  • filmforming resins such as polyethylene terephthalate, cellulose triacetate, polycarbonate, polyvinyl chloride or polyethylene, baryta-coated paper, resin-coated papers, glass plates, metal plates, plates made of earthen ware or like materials.
  • silver precipitating nuclei useful in the present invention, there may be preferably employed the normally water-insoluble sulfides, or selenides of Cd, Pt,
  • 2,698,237 describes a method for preparing such highly active silver precipitating nuclei, wherein a water-soluble metal salt and water-soluble sulfide are admixed in particulate silicon dioxide, thereby forming a precipitate of the resulting water-insoluble metal sulfide. Any other hitherto known techniques for forming such silver precipitating nuceli can be applied to the present invention.
  • the operable ratio of the silver precipitating nuclei: colloidal silicon dioxide in the layer is within 1:5 to 1:1,000 by weight, preferably 1:50 to 1:200.
  • the colloidal silicon dioxide which has incorporated therein the silver-precipitating nuclei and also serves as a binder is also known as anhydrous silicic acid, and per se is an acidic substance. When it is dispersed in water, it is in part hydrated to form silicic acid.
  • the pKa and pKa of silicic acid are 9.8 and 12.16 at 30 C, respectively, It is desirable that the silicon dioxide used in the present invention be in the form of particles which are as fine as possible such as less than 1 micron. Examples of silicon dioxides suitable for use in the present invention and commerically available are listed in the follows @1219.
  • ivalues of aqueous dispersions of the respective silicon followed by drying and providing on the resulting layer the stripping layer containing the aforementioned polyaddition products, the effective and preferred combined thickness of their layers being within 0.1 to microns, more preferably 0.5 to 5 microns.
  • surface active agents such as saponin
  • silicon dioxide layer may be incorporated such a surface active agent, a toning agent such as triphenyl-S-mercapto tetrazole or benzimidazole, a reducing agent such as phenidone, polyethanolamine, ethanol amine, glycerine, hydroquinone etc.
  • the thus obtained image-receiving element can accomplish the aforementioned objects and is very useful as a diffusion transfer photographic material.
  • the image-receiving element was separated from the negative element and it was found that the processing composition film adhered only to the negative element, but not to the image-receiving element.
  • the maximum density of the resulting positive images was 0.80 in terms of reflection density.
  • the transferred images in the areas of high density assumed a metallic luster.
  • the maximum density of the transferred positive image was 1.50 in terms of reflection density, and no metallic luster was observed even in the areas of high density.
  • the image-receiving element thus obtained was then diffusion transfer processed in the same manner as Comparison Example 1, thereby obtaining a positive print without any processing composition film remaining thereon.
  • the maximum density of the transferred positive image was 1.00 in terms of reflection density, and no metallic luster was observed, even in the areas of high density.
  • the image-receiving element coated with the compounds of 'the present invention are remarkedly superior to the hitherto known elements coated with other compounds, in that developing composition films are neither attached nor left on the positive element of the invention, and the maximum density of the transferred images is high.
  • any scratching during handling is avoided, and no processing composition film remains on the positive surface, so that any deterioration of the resulting silver images or brown-tainting by oxidation products contained in the processing composition will not occur.
  • an image-receiving element for use in silver halide diffusion transfer photographic processes which comprises a support having coated thereon a diffusion image-receiving layer comprising a colloidal silicon dioxide containing silver-precipitating nuclei dispersed therein, the improvement which comprises said imagereceiving layer being overcoated with a layer containing poly-addition products derived from 21 bisacrylamide represented by the following general formula:
  • a diamine compound selected from the group consisting of ethylene diamine, 1,3-propane diamine, hexamethylene diamine, piperazine, xylene diamine and phenylene diamine, said silver precipitating nuclei being a member selected from the group consisting of water-insoluble metal sulfides, metal selenides, colloidal heavy metals and colloidal noble metals.
  • colloidal silicon dioxide has a particle size of less than 1 micron.
  • heavy and noble metals selected from the group consisting of gold, silver, platinum, palladium and mercury, said silver precipitating nuclei having an average particle size of less than 10 microns.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
US00193183A 1970-10-27 1971-10-27 Image-receiving element for use in photographic silver halide diffusion transfer process Expired - Lifetime US3820999A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45094880A JPS494653B1 (de) 1970-10-27 1970-10-27

Publications (1)

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US3820999A true US3820999A (en) 1974-06-28

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US00193183A Expired - Lifetime US3820999A (en) 1970-10-27 1971-10-27 Image-receiving element for use in photographic silver halide diffusion transfer process

Country Status (5)

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US (1) US3820999A (de)
JP (1) JPS494653B1 (de)
DE (1) DE2153569A1 (de)
FR (1) FR2113244A5 (de)
GB (1) GB1360655A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4459346A (en) * 1983-03-25 1984-07-10 Eastman Kodak Company Perfluorinated stripping agents for diffusion transfer assemblages
US4629677A (en) * 1984-06-14 1986-12-16 Fuji Photo Film Co., Ltd. Element for diffusion transfer with stripping layer of crosslinked polymer from ethenically unsaturated carboxylic acid or salt thereof
US4871648A (en) * 1988-08-05 1989-10-03 Eastman Kodak Company Stripping layers for imaging elements
US20050164117A1 (en) * 2004-01-26 2005-07-28 Fuji Photo Film Co., Ltd. Diffusion transfer film unit for seal print
US20130037753A1 (en) * 2010-04-22 2013-02-14 Hitachi Chemical Company, Ltd Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device
WO2014072885A2 (en) 2012-11-09 2014-05-15 Basf Se Composition for metal electroplating comprising leveling agent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101385280B1 (ko) * 2012-05-23 2014-04-16 한국과학기술원 역상 현탁중합과 전구체를 이용한 가교된 하이퍼브랜치 폴리아미도아민 입자의 제조 방법

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4459346A (en) * 1983-03-25 1984-07-10 Eastman Kodak Company Perfluorinated stripping agents for diffusion transfer assemblages
US4629677A (en) * 1984-06-14 1986-12-16 Fuji Photo Film Co., Ltd. Element for diffusion transfer with stripping layer of crosslinked polymer from ethenically unsaturated carboxylic acid or salt thereof
US4871648A (en) * 1988-08-05 1989-10-03 Eastman Kodak Company Stripping layers for imaging elements
US20050164117A1 (en) * 2004-01-26 2005-07-28 Fuji Photo Film Co., Ltd. Diffusion transfer film unit for seal print
US20130037753A1 (en) * 2010-04-22 2013-02-14 Hitachi Chemical Company, Ltd Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device
US10566105B2 (en) * 2010-04-22 2020-02-18 Hitachi Chemical Company, Ltd. Method for producing charge transport film
WO2014072885A3 (en) * 2012-11-09 2014-07-03 Basf Se Composition for metal electroplating comprising leveling agent
KR20150082541A (ko) * 2012-11-09 2015-07-15 바스프 에스이 레벨링제를 포함하는 금속 전기도금용 조성물
CN104797633A (zh) * 2012-11-09 2015-07-22 巴斯夫欧洲公司 用于金属电镀的包含调平剂的组合物
EP2917265A4 (de) * 2012-11-09 2016-06-29 Basf Se Zusammensetzung zur metallgalvanisierung mit verlaufmittel
US9758885B2 (en) 2012-11-09 2017-09-12 Basf Se Composition for metal electroplating comprising leveling agent
WO2014072885A2 (en) 2012-11-09 2014-05-15 Basf Se Composition for metal electroplating comprising leveling agent
KR102140431B1 (ko) 2012-11-09 2020-08-03 바스프 에스이 레벨링제를 포함하는 금속 전기도금용 조성물

Also Published As

Publication number Publication date
JPS494653B1 (de) 1974-02-02
DE2153569A1 (de) 1972-05-04
FR2113244A5 (de) 1972-06-23
GB1360655A (en) 1974-07-17

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