CA2065738C - A silver halide photographic transfer element and a method for transferring an image from the transfer element to a receptor surface - Google Patents

A silver halide photographic transfer element and a method for transferring an image from the transfer element to a receptor surface Download PDF

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Publication number
CA2065738C
CA2065738C CA 2065738 CA2065738A CA2065738C CA 2065738 C CA2065738 C CA 2065738C CA 2065738 CA2065738 CA 2065738 CA 2065738 A CA2065738 A CA 2065738A CA 2065738 C CA2065738 C CA 2065738C
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Canada
Prior art keywords
silver halide
photographic
transfer
layer
image
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Expired - Fee Related
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CA 2065738
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French (fr)
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CA2065738A1 (en
Inventor
Donald S. Hare
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Foto Wear Inc
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Foto Wear Inc
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17Dry transfer
    • B44C1/1712Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B44C1/1716Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • 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
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/805Photosensitive materials characterised by the base or auxiliary layers characterised by stripping layers or stripping means
    • 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
    • G03C11/00Auxiliary processes in photography
    • G03C11/12Stripping or transferring intact photographic layers
    • 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
    • G03C8/42Structural details
    • G03C8/52Bases or auxiliary layers; Substances therefor
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/914Transfer or decalcomania
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24835Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24843Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] with heat sealable or heat releasable adhesive layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31844Of natural gum, rosin, natural oil or lac

Abstract

The present invention relates to a silver halide photographic transfer element (10, 50) which comprises a support (20) having a front and rear surface, a transfer coating (30) on the front of the support comprising a material capable of holding an image that can be transferred to a receptor surface upon the application of energy to the rear surface (52A) of the support, and at least one silver halide light sensitive emulsion layer (40) on said front surface of the support. The invention is also directed to a method for applying a photographic image to a receptor element (62) by the steps of exposing imagewise and then developing the above-described silver halide photographic transfer element (10, 50), positioning the developed photographic element (10, 50) against a receptor element (62), and applying energy to the rear surface (52A) of the silver halide photographic element (10, 50) to transfer a photographic image to the receptor element (62).

Description

A SILVER HALIDE PHOTOGRAPHIC TRANSFER ELEMENT AND A METHOD
FOR TRANSFERRING AN IMAGE FROM THE TRANSFER ELEMENT TO A
RECEPTOR SURFACE
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a silver halide photographic transfer element and to a method of applying a photographic image to a receptor element. More specifically, the present invention relates to photographic films or prints having images which are capable of being directly transferred to, for instance, a textile such as a shirt or the like without requiring the use of commercial equipment, such as video cameras, computers, color copiers, home and/or lithographic printers.
2. Description of the Prior Art Textiles such as shirts (e.g., tee shirts) having a variety of designs thereon have become very popular in recent years. Many shirts are sold with pre-printed designs to suit the tastes of consumers. In addition, many customized tee shirt stores are now in business which permit customers to select designs or decals of their choice. Processes have also been proposed which permit VtiO 91/03766 PCT/US90/050118 .,..."
20~~'~38 customers to create their own designs on transfer sheets for application to tee shirts by use of a conventional iron, such as described in U.S. Patent No. 4,244,358 issued September 23, 1980, to the present inventor. Furthermore, U.S. Patent No. 4,773,953 issued September 27, 1988, to the present inventor is directed to a method for utilizing a personal computer, a video camera or the like to create graphics, images, or creative designs on a fabric.
Therefore, in order to attract the interest of consumer groups which are already captivated by the tee shirt rage described above, the present inventor provides the capability of transferring photographic images directly to a receiver element using a material capable of holding and transferring an image. A unique advantage of the invention is to enable all consumers to wear and display on apparel their favorite moments captured on film and to do so in the single most cost and time efficient means.
SUMMARY OF THE INVENTION
Accordingly, the present invention is directed to a silver halide photographic transfer element which comprises a support having a front and rear surface, a ~O 91/03766 PCT/US90/05088 2~~~7~8 transfer coating layer on the front surface of the support comprising a material capable of holding an image that can be transferred to a receptor surface upon the application of energy to the rear surface of the support, and at least one silver halide light sensitive emulsion layer on the front surface of the support.
The silver halide photographic element of the invention is applicable to color paper (e.g., print and reversal), color negative film, color reversal film, color diffusion transfer film units (e. g., instant type prints), black and white film or paper, or the like.
The receptor surface for the image may be a textile such as a shirt (e. g., tee shirt) or the like.
Preferably, the transfer coating layer is located between the support and the at least one silver halide light sensitive emulsion layer.
The thickness of the transfer coating layer is preferably about ~ mil to 2 mil and more preferably about 1 mil.
The method for applying a photographic image to a receptor element comprises the steps of:
(a) exposing imagewise a silver halide photographic transfer element comprising a support having a front Vt~"O 91103766 PCT/US90/05088 206~7~
surface and a rear surface, a transfer coating layer on the front surface of the support comprising a material capable of holding an image that can be transferred to a receptor surface upon the application of energy to the rear surface of the support, and at least one silver halide light sensitive emulsion layer on the front surface of the support, (b) developing the imagewise exposed silver halide light sensitive photographic element to form a photographic image, (c) positioning the front surface of the silver halide photographic element against the receptor element, and (d) applying energy to the rear surface of the silver halide photographic element to transfer the photographic image to said receptor element.
The transfer coating layer of the silver halide photographic element preferably comprises a Singapore Dammar type resin.
The type of energy used for transferring the photographic image to the receptor element is preferably heat or pressure.

Vh0 91/03766 PCT/US90/05088 S
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow, and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIGURE 1 is a cross-sectional view of the preferred embodiment of the silver halide photographic transfer element of the present invention: and FIGURE 2 illustrates the step of ironing the silver halide photographic transfer element onto a tee shirt or the like.
DETAILED DESCRIPTION OF THE INVENTION
Referring to Figure 1, there is generally illustrated a cross-sectional view of the silver halide photographic transfer element 10 of the present invention.
The transfer element 10 comprises a suitable support or substrate 20 which may be any type of material ordinarily used as a support for photographic materials. Examples thereof include cellulose acetate films, cellulose acetate propionate films, cellulose nitrate films, cellulose Vt'O 91/03766 PCT/US90/05088 ~~ss~~~s acetate butyrate films, polyethylene terephthalate films, polystyrene films, polycarbonate films, and laminated sheets of these films and papers. Suitable papers include papers coated with a polymer of an alpha olefin and preferably an alpha olefin having 2 to l0 carbon atoms, such as polyethylene, polypropylene, etc., and baryta-coated papers, etc.
A transfer coating of a release material 30 capable of holding a developed image which can then be transferred to a receptor surface is coated on the support or substrate. The release material provides a colorfast image when transferred to the receptor surface. Suitable release materials include but are not limited to Singapore Dammar resin (m. p. 115°C), Batavia Dammar resin (m. p. 105°C), accroide (yucca) resin (m. p. 130°C), East India resins (m. p. 140-174°C), Kauri resins (m. p. 130-160°C), Manila resins (m.p. 120-130°C), pontianak (m.p. 135°C), and acrylics. A preferable release material which is coated on the support is Singapore Dammar resin.
The release material may be coated on the support in any desired thickness by any suitable conventional coating technique (e.g., spin coating, rollers such as graveuer or rubber, spray or knife application).

Preferably, the release material is in the range of about ~ mil to 2 mi=L in thickness when dry, and more preferably, the thickness of the release coating is about 1 mil.

The release coating may be optionally coated on known transfer papers such as transfer paper manufactured by Kimberly-Clarl{ Corporation under the trademark ~TRANS-EZE'~'1" . Alternatively, the silver halide light sensitive emulsion layers may be directly coated onto known types of transfer papers having suitable properties as the coated supports of the present invention. Thus, ~TR.ANS-EZE'~" per se may be suit: able as a support and transfer coating layer for the present invention.

The photographic support or substrate which is coated with the transfer coating (e.g., release coating) is subsequently coated with the desired photographic emulsions in a conventional manner by methods known to one of ordinary skill in the art.

One pre:Eerred application of this invention is directed to photographic transfer elements capable of producing multicolor dye images. Such a photographic transfer element comprises a support, a transfer coating (e. g., release coating layer such as Singapore Dammar resin) and a plurality of color forming layers coated ....
20~.5'~~8 thereon. The color forming layers include at least one blue recording yellow dye image forming layer, at least one green recording magenta dye image forming layer, and at least one red recording cyan dye image forming layer. Each image forming layer includes at least one silver halide emulsion layer. A dye image providing material can be located in the emulsion layer, in an adjacent layer, or introduced during development. The blue sensitive emulsion layers can rely on native sensitivity to blue light or contain a blue sensitizing dye adsorbed to the silver halide grains of the blue sensitive layers. Spectral sensitizing dyes capable of absorbing green and red light are adsorbed to silver halide grain surfaces in the emulsions of the green and red recording color forming layers, respectively.
To prevent color contamination of adjacent color layers, oxidized development product scavengers including an oxidized developing agent and oxidized electron transfer agents can be incorporated at any location in the color forming layers or in an interlayer separating adjacent color forming layers. Suitable scavengers include alkyl substituted aminophenols and hyroquinones as disclosed in U.S. Patent Nos. 2,336,327 and 2,937,086, sulfoalkyl Vn0 91/03766 PCT/US90/05088 2~6~'~~8 substituted hydroquinones as disclosed in U.S. Patent 2,701,197, and sulfonamido substituted phenols as disclosed in U.S. Patent 4,205,987.
The order of the photographic layers on the support is any order conventional in the art. For example, in color print paper, the order of layers starting from the support is a blue sensitive layer, an interlayer, a green sensitive layer, an U.V. layer, a red sensitive layer, an U.V. layer and a surface overcoat.
In the photographic materials of the present invention various conventionally known hydrophilic colloids are used. Examples of typical hydrophilic colloids used as the binders for photographic silver halide emulsions and other emulsions such as non-light sensitive emulsions (e.g., surface overcoat, interlayers, etc.) for the photographic layers include gelatin; sugar derivatives such as agar agar, sodium alginate, starch derivatives, etc.;
casein; cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose etc.: colloidal albumin:
synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, malefic anhydride copolymers, polyacrylamide, and the derivatives or partially hydrolyzed products thereof. A

Vt~O 91/03766 PCT/US90/05088 2os~~~.s ~o mixture of two or more of these colloids may be used when the combination is compatible with each other.
Gelatin is generally used in the hydrophilic colloid layers of the photographic materials. However, gelatin may be replaced partially or wholly with a synthetic polymer.
Examples of synthetic polymers include water-dispersed vinyl polymers in the form of a latex, including compounds capable of increasing dimensional stability of the photographic materials when used in place of or together with a hydrophilic water permeable colloid.
The silver halide photographic emulsion used in the present invention may be prepared by mixing an aqueous solution of a water-soluble silver salt such as silver nitrate with an aqueous solution of a water soluble halogen salt such as potassium bromide in the presence of a water soluble polymer solution such as an aqueous solution of gelatin. The silver halide may be silver chloride, silver bromide, etc., or mixed silver halides such as silver chlorobromide, silver chloriodide, etc. These silver halide grains may be prepared according to conventionally known processes. Examples of such known processes include the so-called single jet method, the so-called double jet method, or the controlled double jet method. In addition, 1~D0 91 /03766 PCT/US90/05088 2~~~~'~~~
m two or more different silver halide emulsions separately prepared may be used together.
The silver halide photographic emulsions may also contain compounds to prevent the formation of fog during production, processing or preserving the photographic material, and to prevent a reduction in sensitivity.
Suitable compounds for this purpose include 1-phenyl-5-mercaptotetrazole, 3-methylbenzothiazole, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and many metal salts, mercury-containing compounds, mercapto compounds and heterocyclic compounds, etc.
The silver halide emulsions may be chemically sensitized in a conventionally known manner. Suitable chemical sensitizers include gold compounds such as gold trichloride, salts of noble metals such iridium and rhodium: sulfur compounds capable of forming silver sulfide by causing reaction with a silver salt such as sodium thiosulfate; amines, stannous salts, and other reducing compounds.
Moreover, the silver halide photographic emulsions may be spectrally sensitized or super dye sensitized using cyamine dyes such as merocyanine, carbocyanine, or cyanine alone or in combinations thereof or using a combination of Vt'O 91/03766 PCT/US90/05088 cyanine dyes and styryl dyes. The selectio:- of such dyes depends upon the object and use of the photographic materials including the desired sensitivity and the wavelength regions.
The hydrophilic colloid layers may be hardened with cross-linking agents such as vinyl sulfate compounds, active halogen compounds, carboiimide compounds, etc.
The dye forming couplers suitably used in this invention include cyan, magenta and yellow dye forming couplers. These couplers may be 4-equivalent couplers or 2-equivalent couplers as described in U.S. Patent Nos.
3,458,315 and 3,277,155.
Examples of suitable yellow dye-forming couplers include those described in U.S. Patent Nos. 3,384,657, 3,277,155, 3,253,924, 3,227,550, 4,026,706, 2,428,054, 2,908,573, 2,778,658, 2,453,661 and 2,499,966.
Examples of suitable magenta dye forming couplers include those described in U.S. Patent Nos. 4,026,706, 2,725,292, 3,227,550, 2,600,788, 3,252,924, 3,062,653, 2,908,573, 3,152,896 and 3,311,476.
Examples of suitable cyan dye forming couplers which can be used in the invention include those described in U.S. Patent Nos. 3,043,892, 4,026,706, 2,275,292, Vn0 91 /03766 PCT/US90/05088 2~~~'~~8 13 ~ : Y
3,253,294, 2,474,293, 3,227,550, 2,423,730, 2,908,573 and 2,895,826.
A further general discussion of suitable couplers is described in Photographic Chemistry by Glafkides, volume 2, pages 596-615 and Encyclopedia of Chemical Technoloav, Vol. 5, p. 822-825.
Dyes may be formed by the reaction of the couplers with an oxidized aromatic primary amine silver halide developing agent during conventional processing. Typical processing steps for color negative films and color print papers are development, bleach, fix, washing, optionally stabilization and then drying. Two or more of these steps may be combined into a single step. For instance, the bleaching and fixing steps may be combined into a single bleach-fix step. Color development is usually carried out in an alkaline solution containing an aromatic primary amine developing agent such as aminophenol, phenylenediamine or a mixture thereof.
Where it is desired to reverse the sense of the color image, such as in color slide processing, reversal processing can be undertaken. A typical sequence for reversing color processing includes black and white development, stop, washing, fogging, washing, color Vd0 91/03766 PCT/US90/05088 development, washing, bleaching, fixing, washing, stabilizing and drying. An optional prehardening bath prior to black and white development may be employed. The washing step can be omitted or relocated in the sequence.
The fogging bath can be replaced by uniform light exposure or by the use of a fogging agent in the color development step to render the silver halide not developed in the black and white step developable.
When the color photographic material of the present invention is a color photographic diffusion transfer film unit the processing of the photographic material is carried out automatically in the photographic material. In these instant product type units, the color developer containing a color developing agent is contained in a rupturable container. Suitable developing agents include 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, N-methylamino-phenol, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 3-methoxy-N,N-diethyl-p-phenylene-diamine.
Accordingly, in order to form color images in photographic materials various known methods can be used, including the coupling reaction of the above-described dye-forming color couplers and the oxidation products of a p-Vn0 91/03766 PC1'/US90/05088 2~0~573$
phenylenediamine series color developing agent; the oxidation cleavage reaction of DRR compounds, the dye releasing reaction upon coupling of DDR couplers; the dye forming reaction upon the coupling reaction of DDR couplers 5 and a silver dye bleaching process.
Therefore, the present invention can be applied to various types of color photographic materials such as color positive films, color papers, color negative films, color reversal films, color diffusion transfer film units, silver 10 dye bleaching photographic materials, black and white films and papers, etc.
Methods for preparing silver halide photographic elements of the present invention are well known in the art. Representative methods thereof are set forth in U.S.
15 Patent Nos. 4,822,728, 4,743,533, 4,710,455, 4,705,747, 4,680,247, 4,659,647, 4,654,293, 4,636,457, 4,634,661, 4,619,884, 4,588,672, 4,565,778, 5,552,834, 4,529,690, 4,459,353, 4,499,174, 4,144,070, 4,379,837 and Reissue 32,149.
The following examples are provided for a further understanding of the invention, however, the invention is not to be construed as being limited thereto.

Vn0 91/03766 PCT/US90/05088 A silver halide photographic transfer element is prepared as follows. A 1 mil thick layer of Singapore Dammar resin is coated on a paper support coated with polyethylene on both surfaces thereof. A conventional package of color paper silver halide photographic light sensitive emulsions is coated thereon.
All quantities below are in terms of grams per square meter unless otherwise specified.
Layer 1 comprises 1.5g of gelatin, 0.32 g of a blue-sensitive silver chlorobromide emulsion, and 0.3 g of dioctyl phthalate (DOP) in which 1.2 x 10-3 mol of a-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)-a-pivalyl-2-chloro-5-[a-(dodecyloxycarbonyl)ethoxycarbonyl]
acetanilide as a yellow coupler and 0.015 g of 2,5-di-t-ocytl hydroquinone (HQ).
Layer 2 is an interlayer which comprises 0.9 g of gelatin and 0.6 g of DOP in which 0.09 of HQ is dissolved.
Layer 3 comprises 1.3 g of gelatin, 0.27 g of a green sensitive silver chlorobromide emulsion, and 0.2 g of DOP in which 0.59 x 103 mol of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimide-Vn0 91/03766 PCT/US90/05088 m anilino)-5-pyrazolone as a magenta coupler and 0.015 g of HQ are dissolved.
Layer 4 comprises 1.5 g of gelatin and 0.6 g of DOP
in which 0.8 g benzophenone as an ultraviolet absorbent and 0.04 g of HQ are dissolved.
Layer 5 comprises 1.6 g of gelatin, 0.3 g of a red sensitive silver chlorobromide emulsion and 0.2 g of DOP
in which 0.75 x 10-3 mol of 2,4-dichloro-3-methyl-6-[a-(2,4-di-t-amylphenoxy)- butylamide]phenol as a cyan coupler l0 and 0.005 g of HQ are dissolved.
Layer 6 is a surface overcoat (e. g., protective layer) and comprises 1.0 g of gelatin.
The color print paper thus produced is exposed to light through a standard negative.
The exposed color print paper sample is processed as follows. The sample is processed in a color developer having a temperature of 33°C for 3.5 minutes. The developed sample is placed in a solution of bleach-fix at a temperature of 33°C for 1.5 minutes. The sample is washed for 3 minutes with water maintained at 30°-34°C.
Finally, the sample is dried for 2 minutes at a temperature of 60°-80°C.

V~DO 91/03766 PCT/US90/05088 The composition of the above-mentioned color developer is listed below:
Pure water 800 ml Ethylene glycol 15 ml Benzyl alcohol 15 ml Hydroxylamine sulfate 2 g Potassium carbonate 32 g Potassium bromide 0.65 g Sodium chloride 1.0 g Potassium sulfite 2.0 g N-ethyl-N-beta-methanesulfonamide 4.5 g ethyl-3-methyl-4-aminoaniline sulfate Whitex BB (in 50% aqueous solution) 2 ml (Optical whitening agent, mfd. by Sumitomo Chemical Ind. Co. Ltd., Japan) 1-hydroxyethylidene-1,1 2 ml diphosphonic acid (in 60% aqueous solution) Pure water is added therein to make 1 liter and the pH value thereof is adjusted by the use of 10% potassium hydroxide or dilute sulfuric acid solution to pH = 10.1.

~O 91/03766 PCT/US90/05088 The composition of the bleach-fix solution is listed below:
Pure water 550 ml Color Developer 200 ml Iron (III) ammonium ethylenediamine 65g tetraacetic acid Ammonium thiosulfate 85 g Sodium hydrogensulfite 10 g Sodium metahydrogensulfite 2 g Di-ethylenediaminetetraacetate 12 g Sodium bromide 10 g Potassium chloride 1.0 g Pure water is added thereto to make 1 liter and the pH value is adjusted to pH = 7.0 with the use of dilute sulfuric acid or concentrated aqueous ammonia.

Referring to Figure 2, the method of applying a photographic image to a receptor element will be described.
More specifically, Figure 2 illustrates how the step of heat transfer from the silver halide photographic transfer element (50) to a tee shirt or fabric (62) is performed.
The silver halide photographic transfer element is prepared, exposed and developed to form a photographic image as in Example 1. A tee shirt (62) is laid flat, as ~'O 91/03766 PCT/US90/05088 20~~7~~ 20 illustrated, on an appropriate support surface, and the front surface of the silver halide photographic transfer element (50) is positioned onto the tee shirt. An iron (64) is run and pressed across the back (52A) of the silver halide photographic transfer element. The image is transferred to the tee shirt and the support is removed and discarded.

An integral imaging receiver (IIR) element is prepared by coating the following layers in the order recited on a transparent polyethylene terephthalate) film support. Quantities are parenthetically given in grams per square meter unless otherwise stated.
(1) Image receiving layer of polystyrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzyl-ammonium chloride-co-divinylbenzene) (molar ratio 49/49/2) (1.1) and gelatin (1.2) ;
(2) Image receiving layer of polystyrene-co-1-vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride) (50:40:10 mole ratio) (1.6) and gelatin (0.75):
(3) Reflecting layer of titanium dioxide (17) and gelatin (2.6);

Vn0 91/03766 PCT/US90/05088 20~i~~~~ i ( 4 ) Opaque layer of carbon black ( 0 . 95 ) and gelatin (0.65);
(5) Gelatin interlayer (0.54);
(6) Transfer coating of Singapore Dammar resin (1 mil);
(7) Gelatin interlayer (0.65);
(8) Cyan redox dye-release layer, (9) Gelatin interlayer (10) Red sensitive silver halide emulsion layer;
(11) Gelatin interlayer;
(12) Magenta-redox dye-releaser layer;
(13) Green-sensitive silver halide emulsion layer;
(14) Gelatin interlayer;
(15) Yellow redox dye-releaser layer;
(16) Blue-sensitive silver halide emulsion layer;
and (17) Gelatin overcoat layer.
Layers 8-17 are similar to those described in Example I of U.S. Patent No. 4,356,250.
A cover sheet and processing pod are prepared and assembled into film assemblages. (For example, see Example I of U.S. Patent No. 4,356,250).

VtfO 91/03766 PCT/US90/05088 2Ufi~'~'~8 The above film assemblages are exposed to a test object. The assemblages are processed in a conventional manner by spreading the contents of the processing pod between the cover sheet and the Integral Imaging Receiver by using a pair of juxtaposed rollers.

The method of Example 2 is repeated using the IIR
element of Example 3. A tee shirt is laid flat on a suitable support surface and the front surface of the IIR
element is positioned onto the tee shirt. An iron is run and pressed across the back of the IIR element and the image is transferred to the tee shirt.

A multilayer light sensitive color reversal element comprising layers having the following composition is coated on a cellulose triacetate film support.
(1) A transfer layer of Singapore Dammar resin having a thickness of about 1 mil.
(2) An antihalation layer comprising gelatin containing black colloidal silver at a silver coating weight of 0.2 g/mZ.

VtlO 91 /03766 PCT/US90/05088 ~~~Jr~ ~~

(3) A red sensitive low speed emulsion layer of gelatin comprising a silver bromo-iodide emulsion (silver iodide: 7% by mol; average grain size: 0.65 u) at a silver coating weight of 0.62 g/mZ and a silver/gelatin ratio of 0.30, sensitizing dye I in an amount of 0.000135 mol per mol of silver, sensitizing dye II in an amount of 0.000316 mol per mol of silver, Coupler A in an amount of 0.211 mol per mol of silver dispersed in tricresylphosphate and diethylauramide.
(4) A red sensitive high speed emulsion layer of gelatin comprising a silver bromo-iodide emulsion (silver iodide: 7% by mol; average grain size: 1.18 u) at a silver coating weight of 0.57 g/m2 and a silver/gelatin ratio of 0.30, sensitizing dye I in amount of 0.000123 mol per mol of silver, Coupler A in an amount of 0.221 mol per mol of silver dispersed in tricresylphosphate and diethyl-lauramide.
(5) An intermediate layer of gelatin comprising 2,5-ditert-octylhydroquinone dispersed in tricresylphosphate.
(6) A green sensitive high speed emulsion layer of gelatin comprising a silver bromo-iodide emulsion (silver iodide: 7% of mol, average grain size: 1.18 u) at a silver VlyO 91/03766 PCT/US90/05088 coating weight of 0.63 g/m2 and a silver/gelatin ratio of 0.46, sensitizing dye III in an amount of 0.000866 mol per mol of silver sensitizing dye IV in an amount of 0.000190 mol per mol of silver, Coupler B in an amount of 0.183 mol per mol of silver.
(7) A green sensitive low speed emulsion layer of gelatin comprising a blend of a silver bromo-iodide emulsion (silver iodide: 7% by mol: average grain size:
0.65 u) and a silver bromo-iodide emulsion (silver iodide:
5% by mol; average grain size: 0.29 u) at a total silver coating weight of 0.46 g/m2 and a total silver/gelatin ratio of 0.41, sensitizing dye III in an amount of 0.000935 mol per mol of silver, sensitizing dye IV in an amount of 0.00021 mol per mol of silver and Coupler B in an amount of 0.132 mol per mol of silver.
(8) An intermediate layer the same as layer (5).
(9) A yellow filter layer of gelatin comprising dispersed yellow colloidal silver.
(10) A blue sensitive high speed emulsion layer of gelatin comprising a blend of a silver bromo-iodide emulsion (silver iodide: 7% by mol, average grain size:
1.18 u) and a silver bromo-iodide emulsion (silver iodide:
14% by mol: average grain size: 1.4 u) at a total silver Vh0 91/03766 PCT/US90/05088 ~o~~~~$
coating weight of 0.85 g/m2 and a total silver/gelatin ratio of 0.52, sensitizing dye V in an amount of 0.00015 mol per mol of silver, Coupler C in an amount of 0.145 mol per mol of silver and Coupler D in an amount of 0.071 mol 5 per mol of silver both dispersed in tricresylphosphate and diethylalauramide.
(il) A blue sensitive low speed emulsion layer of gelatin comprising a silver bromo-iodide emulsion (silver iodide: 7~ by mol: average gram size: 0.65 u) at a silver 10 coating weight of 0.55 g/mZ and a silver/gelatin ratio of 0.46, sensitizing dye V in an amount of 0.000133 mol per mol of silver, Coupler C in an amount of 0.147 mol per mol of silver and Coupler D in an amount of 0.071 mol per mol of silver both dispersed in tricresylphosphate and 15 diethyllauramide.
(12) A protective layer of gelatin comprising polymethylmethacrylate particles of mean diameter 2 a and 2-(2'-hydroxy-3'S'-di-t-butylphenyl)-5-t-butyl benzotriazole W absorber dispersed in tricresylphosphate 20 and dibutylphthalate.
Gelatin hardeners, surface active agents, antifogging and stabilizing agents are also added to the layers.

Vn'O 91/03766 PCT/US90/05088 20~~'~ ~8 The element is exposed and processed through a reversal color process E6 described in "Using Process E6, Kodak Publication N2-119".
Compounds which may be used for preparing the above-described element are the following.
Sensiti:ink Dyt 1:
H ~C
1 I Hs I
C=CH-C=CH-C
H ~C ~ ~t,'I Br N
i I
CiHs (CH=)-COON I -Sensitizing Dye 11:
OCH ~
k C1H5 S
I I I
C=CH-C=CH-C
H~CO ~ ~ ' CHt N
C=Hy (CHI)-COON t-Coupler A:
OH
H~ iCs CsHi i NH-CO-C;F~
O- i H-CO-NH
CiHy C1 ~'O 91/03766 PCT/US90/05088 2~~~'~~8 Sensititin j Dyc Ill:
O l7Hs O
C=CH-C=CH-C
C1 N/ ~N
( I
(CHZ)sSO~' ( i N=y~
i H-CHI
SO~N~
Scnsiti:ink Dye !V:
CI ~iH~ ~iHs ~ C1 N N
I I
C=CH-CH=CH-C
C1 N/ ~N C1 i I
( i H=)Z ( i HI):
i H-CHI i H-CHI
SO~Na SO~' Coupler 8:
i=Hy CsHii i Hl NCH-NH-CO ~ NH-CO-CH-O
OC N
N
CsH~~

~O 91/03766 PCT/US90/05088 20b~ ~ ~~

Sensitizing Dye V:
S S

C-CH=C
C1 ' / \ C1 N N
( i Hi)~ t i H1)1 CH-CHy CH-CHI
SOy SOy (CiHy)~NH' Coupler C:
i Hy CHI- i -CO- ~ H-CO-NH NH-CO-tCH~)~-O
CHI
N
/ \
CsH~t pH CI
C N

Coupltr D:
CI
CO-CHI-CO-NH
'OC~tH)~ ~SOZ-NH

Vn0 91/03766 ~ ~ 7 ~ S PCT/US90/05088 The multilayer light sensitive color reversal element of Example 5 is applied to a tee shirt in the manner set forth in Example 2.
All cited patents and publications referred to in this application are herein incorporated by reference.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the present invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

Claims (15)

We Claim:
1. A silver halide photographic transfer material, which comprises a support having a front and rear surface, a heat activated transfer coating layer of at least 0.5 mil thick on said front surface of the support without an intervening release layer which is a material capable of transferring and adhering a photographic image containing developed image and non-image areas from said front surface of said support to a surface of a receptor element made of fabric upon the application of heat energy to the rear surface of the support, said transfer coating layer being capable of providing colorfast photographic images when transferred and, at least one silver halide light sensitive emulsion layer on said heat activated transfer coating layer, wherein adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said at least one silver halide light sensitive emulsion layer.
2. The silver halide photographic element of claim 1, wherein said transfer coating layer is located between the support and the at least one silver halide light sensitive emulsion layer.
3. The silver halide photographic element of claim 1, wherein the silver halide light sensitive emulsion layer is a color 1 fight sensitive photographic layer on color negative film, color reversal film, color reversal paper, color positive film or color print paper.
4. The silver halide photographic element of claim 1, wherein the silver halide light sensitive emulsion layer is a light sensitive photographic layer on color diffusion transfer film units.
5. The silver halide photographic element of claim 1, wherein the silver halide light sensitive emulsion layer is a light sensitive photographic layer on a black and while film or paper photosensitive material.
6. The silver halide photographic element of claim 1, wherein the transfer coating layer is selected from the group consisting of Singapore Dammar resin, Batavia Dammar resin and acrylic resin.
7. The silver halide photographic element of claim 1, wherein the thickness of the transfer coating layer is about 1/2 mil to 2 mil.
8. The silver halide photographic element of claim 8, wherein the fabric is a shirt.
9. The silver halide photographic element of claim 1, wherein said support and transfer coating layer are combined to form a heat transfer product known as a heat transfer sheet and said at least one silver halide sensitive emulsion layer is on said a heat transfer sheet.
10. A method of applying a photographic image to a receptor element, which comprises the steps of:

(a) exposing imagewise a silver halide photogenic transfer element comprising, a support having a front surface and a rear surface, a heat activated transfer coating layer of at least 0.5 mil thick on said front surface of said support without an intervening release layer which is a material capable of transferring and adhering a photographic image containing developed image and non-image areas from said front surface of said support to a surface of a receptor element made of fabric upon the application of heat energy to the rear surface of the support, said transfer coating layer being capable of providing a colorfast photographic image when transferred, and at least one silver halide light sensitive emulsion layer on said heat activated transfer coating layer, (b) developing the imagewise exposed silver halide light sensitive photographic transfer element to form a photographic image, (c) positioning the front surface of said silver halide photographic transfer element against said receptor element, and (d) applying heat energy alone or together with pressure to the rear surface of the silver halide photographic transfer element in order to release said photographic image, and transfer and adhere said photographic image to said receptor element, with the proviso that the adherence of said photographic image is a result of the heated transfer coating layer and said adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said at least one silver halide light sensitive emulsion layer.
11. A method of applying a photographic image to a receptor element, which comprises the steps of:
(a) exposing imagewise a silver halide photographic transfer element comprising, a support having a front surface and a rear surface, a heat activated transfer coating layer of Singapore Dammar resin at least 0.5 mil thick on said front surface of said support without an intervening release layer, and at least one silver halide light sensitive emulsion layer on said heat activated transfer coating layer, (b) developing the imagewise exposed silver halide light sensitive photographic transfer element to form a photographic image containing an image and non-image areas, (c) positioning the front surface of said silver halide photographic transfer element against said receptor element, and (d) applying heat energy alone or together with pressure to the rear surface of the silver halide photographic transfer element in order to release said photographic image and transfer said photographic image to said receptor element, with the proviso that the adherence of said photographic image is a result of the heated transfer coating layer and said adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said at least one silver halide light sensitive emulsion layer, thereby providing a colorfast photographic image when the transfer coating layer is transferred to said receptor element.
12. A method of applying a photographic image to a receptor element which comprises the steps of:

(a) exposing imagewise a silver halide photographic transfer element comprising, a support having a front surface and a rear surface, a heat activated transfer coating layer of at least 0.5 mil thick formed of one selected from the group consisting of Batavia Dammar resin and acrylic resin on said front surface of said support without an intervening release layer, and at least one silver halide light sensitive emulsion layer on the heat activated transfer coating layer (b) developing the imagewise exposed silver halide light sensitive photographic transfer element to form a photographic image containing an image and non-image areas, (c) positioning the front surface of said silver halide photographic transfer element against a receptor element made of fabric, and (d) applying heat energy alone or together with pressure to the rear surface of the silver halide photographic transfer element in order to release said photographic image, and transfer and adhere said photographic image to said receptor element, with the proviso that the adherence of said photographic image layer is a result of the heated transfer coating layer and said adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said at least one silver halide light sensitive emulsion layer, thereby providing a colorfast photographic image, when the transfer coating layer is transferred to said receptor element.
13. A method of applying a photographic image to a receptor element, which comprises the steps of:
(a) exposing imagewise a silver halide photographic transfer element comprising:

a heat transfer paper having a front and rear surface, and a heat activated transfer coating layer of at least 0.5 mil thick comprising a material capable of maintaining a photographic image containing developed image and non-image areas transferable to a surface of a receptor made of fabric upon the application of heat energy on the rear surface of the heat transfer sheet, the transfer coating layer being provided on the front surface of the heat transfer sheet without an intervening release layer, and at least one silver halide light sensitive emulsion layer on the heat activated transfer coating layer, (b) developing the imagewise exposed silver halide light sensitive photographic transfer element to form a photographic image, (c) positioning the front surface of said silver halide photographic transfer element against a receptor element made of fabric, and (d) applying heat energy alone or together with pressure to the rear surface of the silver halide photographic transfer element in order to transfer said photographic image to said receptor element, with the proviso that the adherence of said photographic image is a result of the heated transfer coating layer, said adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said at least one silver halide light sensitive emulsion layer, thereby providing a colorfast photographic image when the transfer coating layer is transferred to said receptor element.
14. The method of claim 13, wherein said transfer coating layer is selected from the group consisting of Singapore Dammar resin, Batavia Dammar resin and acrylic resin.
15. The method of claim 11 wherein said heat energy is manually applied by an iron.
CA 2065738 1989-09-11 1990-09-11 A silver halide photographic transfer element and a method for transferring an image from the transfer element to a receptor surface Expired - Fee Related CA2065738C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US40529889A 1989-09-11 1989-09-11
US405,298 1989-09-11
PCT/US1990/005088 WO1991003766A1 (en) 1989-09-11 1990-09-11 A silver halide photographic transfer element and a method for transferring an image from the transfer element to a receptor surface

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CA2065738C true CA2065738C (en) 2001-04-17

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EP0491807A1 (en) 1992-07-01
US5620548A (en) 1997-04-15
EP0491807A4 (en) 1992-09-09
JPH05503587A (en) 1993-06-10
JP3056246B2 (en) 2000-06-26
WO1991003766A1 (en) 1991-03-21
CA2065738A1 (en) 1991-03-12
US6258448B1 (en) 2001-07-10

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