JP2006506673A - Deformable color photographic silver halide material - Google Patents

Abstract

On a deformable plastic support, at least one blue sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green sensitive silver halide emulsion layer containing at least one magenta coupler, and at least A deformable color photographic silver halide material comprising at least one red sensitive silver halide emulsion layer containing one cyan coupler can be deformed without damage in image quality and large format and automatic processing Suitable for.

Description

  The present invention relates to a deformable material for forming a deformed image without significant image degradation and suitable for large formats and automated processing.

  Deformable materials with color and / or black and white motifs, in particular those made of plastics, are used, for example, as protective and / or decorative foils, in particular in the furniture industry, where they are low-cost and / or lightweight support materials And / or used as a design element for coating support materials that are essential for their use conditions, the deformable material and the construction of the support material are much more expensive and / or heavier and It is / are replaced by materials that are easier to handle and / or less resistant, such as natural wood, stainless steel or marble.

  The manufacture of deformed plastic pieces with any kind of indication such as images, designs, patterns, letters etc. is generally by printing on the undeformed flat foil of thermoplastic polymer Proceed and then deform using heat and pressure.

  The results obtained are unsatisfactory because the printed strip shows damage in image quality after deformation, i.e. the deformation is visible in all parts that have led to an elongation of the deformed material. In particular, significant damage in the image quality at the bends and at the sharper edges is observed after deformation, which is a curve in the homogeneously colored dark area and / or a bright line following the edge and / or Particularly noticeable as increased grain size, which is unacceptable, especially in the case of decorative furniture. Furthermore, the printing process requires complex pre-printing steps and is therefore expensive and not suitable for forming individual designs for small scale production operations.

  The photographic layer laminated on the support is disclosed, for example, in Patent Document 1, Patent Document 2, Patent Document 3 and Patent Document 4 for manufacturing for identification and for a wider color gamut. The production of is disclosed in Patent Document 5. For example, the layers can be subsequently covered with a protective foil, as disclosed in US Pat.

  Since all of the disclosed identity cards are flat, no conditions were disclosed regarding deformability and their suitability or otherwise.

  In addition, while stackable photographic layers have been disclosed with special binders, none of these options produce optimal image quality. In particular, the particle size achieved using current stackable materials is unacceptably high. These TDR materials, also known as stackable, are not suitable for the furniture industry because the two sheet method has not been applied to the large scale automated processing required in this field.

  Indications such as top quality images, designs, patterns, letters, etc. are provided on at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler on the support, at least one kind. Color comprising at least one green-sensitive silver halide emulsion layer containing a magenta coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler It can be realized using photographic materials. As a support for the reflective material, a paper coated on both sides with polyethylene and a polyester stretched in the machine and transverse directions are generally used for the transparent material. Variations in accordance with the present invention of such color photographic materials are not possible.

  The deformability of special photographic materials consisting of a support, an optional adhesive layer, and a black and white silver halide emulsion photographic layer with a special binder was disclosed in US Pat. According to Patent Document 8, gelatin cannot be used as a binder because cracking occurred during bending.

  Known deformable photographic materials, such as those disclosed in US Pat. Nos. 6,057,069 and 5,099,9, did not meet the current quality situation with respect to photographic images and the bending performance was unsatisfactory.

  U.S. Pat. Nos. 6,057,049 and 3,049,086 disclose a moldable photographic material comprising a thermoplastic base sheet, a primer layer providing an important component for the photosensitive layer, and a thermoplastic protective foil, the foil being optical Bonded to the photosensitive layer using quality adhesive.

  Furthermore, for example, no deformable photographic material is known that meets both the long-term exposure and the digital exposure required in the furniture industry to enable large format exposure. Analog long-term exposure is desirable to allow the use of inexpensive exposure configurations, but digital exposure is increasingly required because it is much faster and the roll of film is much more easily continuously exposed . Furthermore, since no film is required as an intermediate step, different designs can be realized much more easily during manufacturing. In this section, new designs are generally made by computer and can be used directly in digital exposure to achieve optimal image quality.

  Digital exposure is short or very high per pixel, for example using high intensity, strongly focused bundles of luminous flux from lasers, light emitting diodes (LEDs), DMD (digital micromirror building blocks) devices, cathode ray tubes, etc. Proceed pixel-by-pixel, line-by-line or region-by-line using short exposure times. A pixel is the smallest image area on a copy material that can be addressed by an exposure device. Conventional silver halide emulsions exhibit too low sensitivity due to unsatisfactory reciprocity, which results in too low contrast and insufficient maximum density at such short exposure times.

Similar reciprocity failure is also observed with exposure times longer than the 10 seconds required for large format analog exposure (long exposure times).
European Patent Application No. 0250657 US Pat. No. 3,871,119 European Patent Application No. 0490416 European Patent Application No. 0276506 European Patent Application Publication No. 1898108 US Pat. No. 4,370,397 British Patent 2,121,812 French Patent No. 968638 British Patent 739,477 British Patent 2,321,977 International Publication No. 98/35269 Pamphlet

  Accordingly, the object of the present invention is to enable the realization of high quality displays such as images, designs, patterns, characters, etc. that undergo the desired deformations due to heat and / or pressure without significant visible damage in image quality. It is to provide a deformable color photographic material. Another advantage of the present invention, which is comparable to the printing process, is that a single piece as a proof or display example can be produced.

  Other features and advantages of the present invention will become apparent from the following description.

  It has been surprisingly found that the deformable color photographic recording material of the present invention is suitable for digital exposure and gives a high quality image, the color photographic silver halide material being deposited on a deformable plastic support. At least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, and at least one cyan coupler. It comprises one red sensitive silver halide emulsion layer.

  Surprisingly, it has been found that, unlike the disclosure in French Patent No. 968638, gelatin can be used successfully in the materials used in the process according to the invention. The reason why the unsuccessful use of gelatin according to French Patent No. 968638 has been so successful in the context of the present invention is that it contains essentially only silver halide crystals dispersed in a binder. The difference between a single layer black and white material such as that described in patent No. 968638 and a multilayer color photographic material according to the present invention which also comprises a softer material such as a coupler in those layers. sell.

  Aspects of the invention include at least one blue sensitive silver halide emulsion layer containing at least one yellow coupler on a deformable plastic support, at least one green sensitive halogenation containing at least one magenta coupler. It is realized with a deformable color photographic silver halide material comprising a silver emulsion layer and at least one red sensitive silver halide emulsion layer containing at least one cyan coupler.

Aspects of the invention are modified comprising exposing the color photographic silver halide material described above, processing the exposed color photographic material in a conventional manner to form an image, and deforming the color photographic material. This is also realized by a method for forming a continuous image.
DETAILED DESCRIPTION OF THE INVENTION Definitions A variation of the term used in disclosing the present invention (also known as molding) is to form a flat object, such as a plate or sheet, to which pressure and / or heat is applied. An instrument is used to deform into a three-dimensional shape, during which at least a portion of the initially flat object is stretched (stretched), which refers to the three-dimensional deformation that is maintained during cooling and / or pressure release. Out-of-plane generally has a measurement that is greater than the thickness of the initially flat object, which thickness is the surface to which the instrument is applied and the opposite surface of the initially flat object. Defined as the distance between. The term deformable, as used in qualifying color photographic silver halide materials, is the ability to undergo deformation as defined above.

  The term deforming means a deformation process.

  The term deformable plastic as used in disclosing the present invention includes all polymers that can be deformed without breaking, appearance of cracks or pyrolysis. The term deformable plastic includes all polymers that are available in foil form and are not stretched.

  The term conventional processing as used in disclosing the present invention is a chromogenic chemical color that is used for processing conventional photographic materials such as, for example, color paper, color film or display materials and is further specified in the following description. Means processing.

  The terms immediate and rapid curing agent mean that the curing agent can be cured to the extent that no further changes in syncytometry and swelling performance occur immediately after coating or within at least a few days after coating due to the presence of the curing agent. Swelling refers to the difference between the wet layer thickness and the dry layer thickness during aqueous processing of the material.

The term silver nitrate (corresponding to the AgX designation) used to identify silver halide emulsions in the examples is the constant amount that occurs when the amount of silver halide in the emulsion is converted to an equivalent weight of silver nitrate. The weight of silver nitrate in the silver halide emulsion.
Method of forming a deformed image An aspect of the present invention is to expose a color photographic silver halide material according to the present invention, process the exposed color photographic material in a conventional manner to form an image, and deform the color photographic material. In a method for forming a deformed image comprising the step of:

  Equipment that is available for exposure and conventional processing of photographic materials of the present invention capable of processing long and wide sheets and wide rolls of material, such as required in the furniture industry, is commonly used.

  The exposure is preferably done digitally and preferably proceeds from a surface remote from the support, but in the case of a transparent or slightly colored support, exposure should be done through the support if the loss in sharpness can be tolerated. You can also.

  In order to avoid light diffusion and the resulting loss in sharpness in the case of transparent or translucent supports, it is preferable to place a dark sheet in contact with the material surface remote from the light source when exposed. The same effect can also be achieved if the material comprises an antihalation layer, i.e. bleached during the chemical processing of the material. Absorbing materials suitable for the antihalation layer are described in Research Disclosure 38957, 1966, VIII. , Page 610. The antihalation layer must be placed on the side of the emulsion layer that is remote from the light source.

  In a preferred embodiment of the invention, the support is a silver halide layer and a layer that reflects white light on the layer surface, as described in US Pat. No. 4,224,402, which is incorporated herein by reference. And a support having a non-bleachable black antihalation layer on the opposite side.

  After image-wise exposure, the color photographic material is processed appropriately. Details of the processing and chemicals required for this are given together with exemplary color photographic materials, Research Disclosure 37254, part 10 (1995) page 294 and Research Disclosure 37038, part XVI to XXIII, which are incorporated herein by reference. 1995), part from page 95.

Conventional processing of color photographic materials comprises color development, bleaching and fixing as well as black and white development, and for color reversal materials, other stages of reversal and black and white development. The bleaching and fixing stages can be carried out in one bleach / fixing stage. Particularly suitable methods and compounds for the purposes of the present invention, the technology is generally known and for example, the contents of the present invention by reference ^{Ullmann's Encyclopedia of Industrial Chemistry, 5} th edition, Vol. A20, p68 to 98, especially for silver bromide chloride emulsions such as EP-2 (Eastman Kodak) and AP92 (Agfa), and for negative silver emulsions mainly RA -4 (Eastman Kodak) and AP94 (Agfa) methods.

In another preferred embodiment of the method according to the invention, the conventional processing of color photographic materials is carried out with a development time of between 15 and 130 seconds. For example, longer development times are required when processing silver-rich materials to obtain particularly high color densities.
Deformable plastic support Deformable plastics are those that can be deformed without breaking, the appearance of cracks or pyrolysis. All polymers that are available in foil form and that are not stretched fall within the term deformable plastic.

  A good reference point for the temperature required for deformation is the glass transition temperature (Tg). Deformation generally takes place between the glass transition temperature and the melting point of a deformable plastic. The pressure required for deformation can be easily tested, the higher the deformation temperature with respect to the glass transition temperature, the lower the required pressure. Just below the melting point, only very low pressure is required. The time required for deformation can also be easily tested and adjusted. Higher temperatures and / or higher pressures result in shorter times.

  Suitable support materials such as foils, films or sheets are preferably employed from the group of plastics known as thermoplastics and are poly (vinyl chloride) (PVC), polycarbonate (PC), unoriented polyester, acrylonitrile-butadiene -Includes styrene (ABS), polyolefins, copolymers and mixtures of the polymers. Suitable copolymers include vinyl chloride copolymers, particularly ABS copolymerized with vinyl chloride, and polyolefin copolymers.

  According to a preferred embodiment of the deformable color photographic silver halide material according to the invention, the deformable plastic support is polycarbonate, poly (vinyl chloride), a vinyl chloride copolymer or polyester, or a PET based copolyester. is there.

  Polycarbonates suitable for use in the color photographic materials of the present invention have the formula

[Wherein, X is _{-S -, - SO 2 -,} - C (R 5, R 6) - or _{-C [= C (R 7,} R 8)] - _represents, R _{1, R} 2, R ₃ , R ₄ , R ₇ and R ₈ independently represent a hydrogen atom or an alkyl- or aryl-group and R ₅ and R ₆ independently represent a hydrogen atom or an alkyl- or aryl-group or Together represent the atoms necessary to form an alicyclic ring, such as a cyclohexane ring]
The repeating unit represented by these is contained. The polycarbonate preferably has a weight average molecular weight between 10,000 and 500,000. Polycarbonate based on bisphenol A is particularly preferred.

  The poly (vinyl chloride) for use in the color photographic material of the present invention preferably contains at least 50% by weight of vinyl chloride units and optionally may contain other hydrophobic units. Preferred comonomers are vinylidene chloride, vinyl acetate, acrylonitrile, styrene, butadiene, chloroprene, dichlorobutadiene, vinyl fluoride, vinylidene fluoride and trifluoroethylene. The poly (vinyl chloride) preferably contains 60-65% by weight chlorine. The PVC supports used in the color photographic materials of the present invention can contain plasticizers, but preferably do not contain plasticizers for morphological reasons and for photographic material stability reasons. Furthermore, PVC can contain stabilizers and antioxidants along with inorganic heavy metal salts, metal soaps (especially those of Ba, Cd, Pb, Zn and Ca), dibutyl and dioctyl tin compounds and epoxidized soybean oil. Other optional PVC components include lubricants, impact modifiers, processing aids, filters, flame retardants, smoke suppressants, foaming agents, colorants, antistatic agents, viscosity modifiers, biostabilizers ( biostabilizers) and UV absorbers.

  Suitable polyesters include condensation products of aromatic, aliphatic or cycloaliphatic dicarboxylic acids with aliphatic or cycloaliphatic glycols, whereby the carbon number of the dicarboxylic acid is preferably 4-20 and the glycol Preferably carbon number is 2-24. Polyesters can also be modified by adding a small amount of another monomer. Preferred polyesters are poly (ethylene terephthalate) (PET) or PET-based copolyesters (CoPET) such as the preferred CoPET Eastar PETG copolyester 6763 supplied by Eastman. However, stretched (orientated) polyesters are inappropriate because they form fine cracks upon deformation.

  Suitable polyolefins include polypropylene, polyethylene and polymethylpentene, either individually or in a mixture. Preferred polyolefins include copolymers of propylene and / or ethylene with hexene and / or butene and / or octene.

  Preferred deformable plastics for the deformable color photographic material according to the present invention are PVC, vinyl chloride copolymer and PC, because they bend well and the photographic layer is not particularly affected. PC is particularly preferred due to its high tensile strength and ensures good storage stability.

  The support can be a single layer foil, but can also consist of a mixed arrangement of several plastic foils. All plastic foils must be deformable plastic. The thickness of the support is preferably between 0.05 and 0.75 mm.

  The support can be coated with one or several layers to give, for example, a color layer or an adhesive layer to the support.

  Depending on the desired effect, the support can be white, transparent, translucent or colored with dyes or pigments and has a structure or roughness on one or both sides You can also. The structure or roughness in the foil is preferably provided during its manufacture.

  The support can contain pigments or other colorants. An opaque white color can be realized by coextrusion of a white pigment such as titanium dioxide. Suitable colorants include dyes such as ultramarine blue.

  In order to improve the adhesion of the hydrophilic layer of the color photographic material on the hydrophobic support, the support is preferably pretreated by a hydrophilization method such as a corona (air ionization at about 10-20 kV) treatment. . Furthermore, an undercoat layer between the support and the layer constituting the layer of the color photographic material closest to the support is also preferred.

  In a preferred embodiment of the deformable color photographic silver halide material according to the present invention, the deformable color photographic material comprises 1.3-80% by weight protein colloid, 0-85% by weight colloidal silica and 0-30% by weight. And an undercoat layer containing a siloxane capable of forming a reaction product with the colloidal silica. In yet another preferred embodiment of the deformable color photographic silver halide material, the deformable color photographic material further comprises a subbing layer on the same support surface as the silver halide emulsion layer. Particularly preferred is a subbing layer further containing 1.0 to 70% by weight of an ionogenic polyester-polyurethane, which is coated from an aqueous dispersion, in which the isocyanate groups have reacted with ionomer compounds in their structure, Contains at least one active hydrogen atom and a carboxylate or sulfonate salt group, and the number of salt groups is sufficient to make the polyester-polyurethane dispersible in an aqueous medium. Preferred protein colloids are gelatin and casein, with gelatin being particularly preferred.

  Suitable anionic polyester-polyurethanes are described in US Pat. No. 3,397,989, US Pat. No. 4,338,403 and German Patent Application No. 3630045, which are incorporated herein by reference. Particularly preferred are those disclosed in the specification and having carboxylate and sulfonate groups, such as those disclosed in US Pat. No. 3,397,989. The polyester-polyurethane preferably contains a linear polyester having an OH-end and a molecular weight between 300 and 2,000. The polyester-polyurethane is preferably used as an aqueous dispersion, and a particularly preferred dispersion is based on the following components with respect to the final dispersion: 23% by weight polyester based on adipic acid and hexanediol having an average molecular weight of 840, 14% by weight Of 4,4'-diisocyanatodicyclohexylmethane, 2% by weight dimethylolpropionic acid and 1.5% by weight trimethylamine reaction product, the composition being 7.5% by weight N-methyl-pyrrolidone And 52% by weight of water. This particularly preferred dispersion is hereinafter referred to as dispersion (D-1).

Suitable polyester - polyurethane dispersion includes a disk page call ^{(Dispercoll) (R)} products from Bayer (Bayer).

Suitable colloidal silica, trade name Ludox ^{(LUDOX) (R)} (Du Pont (Du Pont)), Saiton ^{(SYTON) (R)} (DuPont) and Kieserusoru ^{(KIESELSOLE) (R)} products sold as (Bayer) Is included. Their average particle size is preferably between 5 and 100 nm.

  Suitable siloxanes are of the formula:

[Wherein R ¹ represents a polymerizable group or can react with a protein-containing colloid, such as an OH- and / or NH ₂ -group, in particular a reactive halogen, an epoxy group or an α, β-ethylenically unsaturated group. Having a group containing
Is represented by Examples of R ¹ are ClCH ₂ CONH-A-, BrCH ₂ CONH-A-, CH ₂ = CH (CH ₃ ) COO-A-, CH ₂ = CHSO ₂ CH ₂ OCH ₂ SO ₂ NH-A-, CH _{2 = CHCONH-A-, CH 2 =} C (CH 3) CONH-A-,

Where A is an alkylene group, or

Where Y represents a divalent hydrocarbon chain which can be interrupted by oxygen. R ¹ , R ² and R ³ independently represent an optionally substituted hydrocarbon group such as methyl or ethyl.

  Suitable siloxane compounds include the following:

  The adhesion of the subbing layer to the support can be improved by corona pretreatment of the support. A surfactant (wetting agent) can be added to the undercoat layer coating composition to improve the wettability of the undercoat layer.

Suitable wetting agents are, (supplied by Union Carbide Corp. (Union Carbide Corp.) and near the set Corp. (Niacet Corp.)) shall contain saponin and trade name Tergitol ^{(TERGITOL) (R)} or Manokisoru ( Manoxol® ^(R) (supplied by Rohm and Haas).

  With regard to the support material and the undercoat layer, the content of the present invention is incorporated by reference in EP-A-0276506 and EP-A-490416.

In another preferred embodiment of the deformable photographic color silver halide material according to the invention, the deformable plastic support is coated, for example, by coating the back side of the support with an adhesive layer suitable for pressure and / or thermal bonding methods. Laminate. Such a pressure sensitive adhesive layer is preferably coated with a protective foil. The adhesive layer with or without protective foil can be applied to the support at any point before lamination, and thus before coating the support with a photosensitive layer. It is preferred to apply the adhesive layer after processing the color photographic material.
Application of protective foil on the image side of the support In a preferred embodiment of the deformable color photographic silver halide material according to the invention, the protective foil is preferably on the outermost side on the image side of the deformable color photographic material, For example, it is provided via an adhesive layer that protects the image from scratching by oxygen, ultraviolet light and water and environmental effects. The protective foil provided on the image side of the support preferably comprises a homopolymer such as PVC, PC, polyalkylene or a polyester such as PET or CoPET, in particular PVC. The protective foil is also preferably a block copolymer having polymer subunits selected from the homopolymers described above, at least two monomers, in particular at least two vinyl monomers, such as vinyl chloride, A mixed copolymer obtained by a mixed polymerization of alkylene or styrene, or a blend of at least two polymers selected from the above homopolymers and / or block copolymers and / or mixed copolymers Can also be.

  In a preferred embodiment of the invention, the adhesive layer is a polyalkylene foil (adhesive foil), in particular a polyethylene foil, which can be laminated in direct contact with the protective foil or is glued to the protective foil using a glue layer. .

  Preferably, the protective foil and / or the adhesive layer and / or the glue layer, if present, contains a UV absorber, hydroxybenzophenone or hydroxybenzotriazole. Preferred UV absorbers are those known under the trade name Tinuvin and supplied by Ciba-Geigy. Suitable protective foils, adhesives and glues are disclosed in EP 0348310, US Pat. No. 4,456,667, US Pat. No. 4,455,359, which is incorporated herein by reference. U.S. Pat. No. 4,378,392, U.S. Pat. No. 4,370,397, U.S. Pat. No. 3,871,119 and British Patent Application No. 2,321,977. Including those disclosed in the specification. The protective foil can consist of a single polymer composition or can be a mixture or laminate of identical or different polymers employed from PV, PC, PET, CoPET or polyalkylene. It is preferred that at least one of the polymers used for the protective foil is the same plastic material as that used for the support.

In a preferred embodiment of the protective foil used for the material according to the invention, the protective foil has a T _g similar to the T _g of the deformable plastic support. A particularly preferred adhesive foil of polyethylene has a melting point of about 90-100 ° C.

  In another preferred embodiment of the protective foil used for the material according to the invention, the protective foil can be colored and / or printed with any design, image or text.

  The sandwich of protective foil, optional glue layer and adhesive layer is preferably laminated using a roller laminator on the image side of the photographic material.

According to a preferred embodiment of the method according to the invention, the color photographic material is provided with a protective foil before the deformable color photographic silver halide material is deformed with the product.
Deformation of the color photographic material The deformation of the color photographic material is generally performed after conventional processing of the exposed color photographic material, but can also be performed before processing and before exposure. However, it is preferred to perform the deformation after conventional processing of the exposed color photographic material.

  According to a preferred embodiment of the method according to the invention, the deformation step comprises the application of heat and pressure and at least a part of the deformable color photographic material is stretched during the process. The instrument used in the deformation stage can be, for example, a mold in which the heated plastic is sucked, blown or pressurized therein. In the furniture industry, for example, a piece of furniture to which a color photographic material is to be applied can itself be a molding tool. In this case, the molding tool is referred to as a “work piece”. The color photographic material is thereby pressed onto the piece of furniture (workpiece), for example using a membrane press, and thereby tightly bonded to the piece of furniture. In this method, the photographic material-covered work itself is either completely filled with hot water at about 95 ° C. or an elastic membrane (typically placed on top of a tank filled with hot oil). The process according to the invention can be carried out at higher temperatures.

  According to a preferred embodiment of the method according to the invention, the deformation step comprises the step of deforming the deformable color photographic material by vacuum deformation.

  The adhesion of the deformed color photographic material to the piece of furniture is preferably supplemented with an adhesive. In the case of very soft materials that can be deformed at room temperature (25 ° C.), a pressure adhesive (eg contact adhesive) is sufficient. Only furniture pieces, such as chipboard pieces, are taken as an example. By simply replacing the work piece and using an adhesive known to be used for the material from which the work piece is made, the deformable color photographic material according to the present invention can be easily used in other technical fields such as the automotive industry. Can be used.

  According to a preferred embodiment of the method according to the invention, the deformation step comprises deforming the deformable color photographic material in contact with the work piece, in which the photographic material is placed in a die mold and injected. The plastic material deforms the deformable color photographic material and forms a single object with the deformable color photographic material.

  In a preferred embodiment of the method according to the invention, the deformation step comprises deforming the deformable color photographic material in contact with the work piece. In general, a support surface of deformable color photographic material is applied to a work piece, for example a piece of furniture. In this case, a transparent protective foil as described above is applied immediately before to the image side of the processed color photographic material to prevent damage during the deformation stage.

  If the support is clear or at least transparent and not strongly colored, the silver halide emulsion surface of the deformable color photographic material can be applied to the work. In such cases, in addition to the usual cold and hot-melt adhesives, gelatin solutions containing gelatin-hardening agents can also be used as adhesives. Instead of adhering the silver halide emulsion surface directly to the work piece, preferably a reflective, eg white or opaque, protective foil is placed between the silver halide emulsion face of the color photographic material and the work piece You can also.

In a preferred embodiment of the invention, the adhesion of the deformed photographic material to the work is in particular at the corners and edges of the work and at the edges of the deformed material, for example the corners and edges on the back of the furniture piece. Further improved. This is particularly the case for pre-processing of a product using pre-deformation glue at the corners and edges, or processing of a product coated with deformable photographic material using a heat-knife after deformation and / or after deformation. And if necessary, by applying glue after cutting off excess photographic material to seal corners and edges and prevent delamination of the deformed material.
Color photographic material In a preferred embodiment of the deformable color photographic silver halide material according to the present invention, a color photographic silver halide material is provided that can be deformed without significant image degradation, the color photographic silver halide material being deformable. At least one blue sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green sensitive silver halide emulsion layer containing at least one magenta coupler and at least one cyan on a plastic support. It comprises at least one red sensitive silver halide emulsion layer containing a coupler.

  In another preferred embodiment of the deformable color photographic silver halide material according to the present invention, the silver halide emulsion has a total silver chloride content of at least 70 mol% to allow for short development times, and at least 98. A silver chloride content of mol% is particularly preferred. Silver halide emulsions substantially free of silver iodide are preferred, emulsions having less than 1 mole percent iodide and especially those having less than 0.1 mole percent iodide are particularly preferred.

  The at least one silver halide emulsion used in the material according to the invention preferably contains silver halide crystals doped with at least one dopant. In each case at least one blue-, at least one green- and at least one red-sensitive silver halide emulsion layer comprises at least one halogen in which the silver halide crystal is doped with at least one dopant. A silver halide emulsion. Suitable dopants and methods for their addition can be found in the section from Research Disclosure 37038, part XVI-B (1995), page 90, which is incorporated herein by reference. For silver halide crystals having a high silver chloride content, preferred dopants are Ir-, Rh- and Hg-salts.

  The silver halide emulsion used in the color photographic material of the present invention is preferably a double jet method or combination with a simple double jet method, separate preprecipitation (crystal nucleation) and subsequent precipitation. Manufactured by a double jet recrystallization method.

  The at least one silver halide emulsion preferably comprises a silver halide crystal (a crystal with a well-defined structure) having at least two different regions, the outermost region having a higher silver bromide content than the rest of the crystal. contains. Crystal nuclei with a well-defined structure are preferably produced by a double jet process using silver nitrate solution and halide, mainly chloride, solution, and a fine-grained odor with a silver bromide molar content of at least 5%. Precipitation is preferably caused by a silver chloride emulsion (Lippmann emulsion).

  According to another preferred embodiment of the deformable color photographic silver halide material according to the invention, in each case at least one blue-, at least one green- and at least one red-sensitive silver halide emulsion layer are It comprises at least one silver halide emulsion containing crystals with a well-defined structure.

  According to another preferred embodiment of the deformable color photographic silver halide material according to the invention, the green sensitive silver halide emulsion layer and / or the red sensitive silver halide emulsion layer has an average grain size (volume average, at least 0.40 μm). At least one silver halide emulsion having silver halide crystals having a diameter of a shape having equal capacity.

  According to another preferred embodiment of the deformable color photographic silver halide material according to the invention, the silver halide emulsion contains one or more binders, with binders that are at least 80% by weight of gelatin being particularly preferred. .

In a preferred embodiment of the color photographic material according to the invention, yellow couplers, purple couplers and blue-green couplers represented by the formulas (IV), (V), (VI), (XIV), (VII) and (VIII) are used. The
Yellow coupler:

[Where:
R ¹ represents an alkyl, alkoxy, aryl or hetero-aryl group;
R ² represents an alkoxy or aryloxy group or halogen,
R ³ is _{^{-CO 2 R 6, -CONR 6 R}} 7, -NHCO 2 R 6, -NHSO 2 -R 6, -SO 2 NR 6 R 7, -SO 2 NHCOR 6, -NHCOR 6 group represent Cl ,
R ⁴ represents hydrogen or a substituent,
R ⁵ represents hydrogen or a group decomposable during coupling;
R ⁶ , R ⁷ independently represent hydrogen or an alkyl or aryl group, and one of the R ² , R ³ and R ⁴ groups is a ballast group]
Magenta coupler:

[Where:
R ⁸ and R ⁹ independently represent hydrogen or an alkyl, aralkyl, aryl, aryloxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, alkylcarbamoyl or alkylsulfamoyl group, wherein The groups may optionally be further substituted and at least one of these groups contains a ballast group and R ¹⁰ represents hydrogen or a group decomposable during chromogenic coupling;
R ⁸ is preferably tert. -Butyl group and R ¹⁰ is preferably chlorine]

[Wherein, r is an integer of 1 to 5, q is 1, 2 or 3, R ^c represents a group decomposable during chromogenic coupling, and R ^a represents ^a halogen or an alkoxy or acylamino group] And R ^b represents halogen or a cyano, thiocyanato, alkoxy, alkyl, acylamino or alkoxycarbamyl group].

R ^c is preferably hydrogen or a group decomposable as an anion under basic conditions of chromogenic coupling.

Particularly preferably, R ^c represents —S-aryl or —N═N-aryl, where aryl is preferably a phenyl or naphthyl group, optionally halogen such as chlorine or bromine or C ₁ -C ₁₈ -Alkyl or C ₁ -C ₁₈ -alkoxy groups may be substituted.
Cyan coupler:

[Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represent hydrogen or a C ₁ -C ₆ -alkyl group].
R ¹¹ is preferably CH ₃ or C ₂ H ₅ , R ¹² is preferably a C ₂ -C ₆ -alkyl group, and R ¹³ and R ¹⁴ are preferably t-C ₄ H ₉ or t-C. ₅ is a H _11.

[Wherein R ¹⁵ represents an alkyl, alkenyl, aryl or hetero-aryl group, R ¹⁶ and R ¹⁷ independently represent a hydrogen, alkyl, alkenyl, aryl or hetero-aryl group, and R ¹⁸ represents hydrogen or color development. Represents a group decomposable during coupling, and R ¹⁹ represents —COR ²⁰ , —CO ₂ R ²⁰ , —CONR ²⁰ R ²¹ , —SO ₂ R ²⁰ , —SO ₂ NR ²⁰ R ²¹ , —CO—CO ₂ R ²⁰ , —COCONR ²⁰ R ²¹ or formula

Wherein R ²⁰ represents an alkyl, alkenyl, aryl or hetero-aryl group, R ²¹ represents hydrogen or R ²⁰ and R ²² represents —N═ or —C (R ²⁵ ) ═. , R ²³ , R ²⁴ and R ²⁵ independently represent —OR ²¹ , —SR ²¹ , —NR ²⁰ R ²¹ , —R ²¹ or Cl, and p is 1 or 2.

The following groups of couplers according to formula (VIII) are preferred:
(1) A coupler in which p = 1 and R ^{15 to} R ²⁵ have the above meanings.
(2) A coupler in which p = 2, R ¹⁹ represents —CO—R ²⁶ , R ²⁶ represents an alkenyl or hetero-aryl group, and R ^{15 to} R ¹⁸ have the above meanings.
(3) p = 2 and R ¹⁹ is —SO ₂ R ²⁷ , —SO ₂ N (R ²⁷ ) ₂ , —CO ₂ R ²⁷ , —COCO ₂ —R ²⁷ , or —COCO—N (R ²⁷ ). ₂ ^{represents, R 27} is alkyl, aryl, alkenyl or hetero - couplers represents an aryl group and ^{where R} 15 ^{to R 18} have the meanings given above.
(4) p = 2 and R ¹⁹ is the formula

And R ^{15 to} R ¹⁸ and R ^{22 to} R ²⁴ have the meanings given above.
(5) p = 2 and R ¹⁹ is the formula

A coupler in which R ²⁸ represents hydrogen, Cl, CN, Br, F, —COR ²⁹ , —CONHR ²⁹ or CO ₂ R ²⁹ and R ²⁹ represents an alkyl or aryl group.
(6) p = 2 and R ¹⁹ is the formula

Wherein R ^I represents a halogen, CN, —CF ₃ or alkoxycarbonyl group, R ^II represents hydrogen or has the same meaning as R ^I , and R ^{15 to} R ¹⁸ are A coupler having the meaning of
(7) A coupler in which p = 2 and R ¹⁹ is —COR ²² ; R ²² represents an alkyl, aryl or hetero-aryl group and R ^{15 to} R ¹⁸ have the above meanings.
(8) p = 2 and R ¹⁹ is the formula

Wherein R ^I represents —OR ^II or —NR ^III R ^IV , R ^II and R ^III represent an optionally substituted C ₁ -C ₆ -alkyl group, and R ^IV Represents a hydrogen or has the same meaning as R ^III , and R ^{15 to} R ¹⁸ have the meanings given above.

In formula (VIII) and compounds (1) to (8), the substituents have the following preferred meanings: R ¹⁵ represents an alkyl or aryl group, R ¹⁶ and R ¹⁷ are independently H or an alkyl or aryl group R ¹⁸ represents H, Cl, alkoxy, aryloxy, alkylthio or arylthio, R ²² represents —N═, and R ²³ and R ²⁴ independently represent —OR ²¹ , —NR ²⁰ R ²¹ or Represents -Cl.

In formula (VIII) and compounds (1) to (8), the substituents have the following particularly preferred meanings: R ¹⁵ represents formulas (15-1), (15-2) and (15-3):

[Wherein R ^I represents an alkyl group having at least 8 carbon atoms]

Wherein R ^I is alkyl, alkenyl, alkoxy, aryloxy, acyloxy, acylamino, sulfonyloxy, sulfamoylamino, sulfonamide, ureido, hydroxycarbonyl, hydroxy, carbonylamino, carbamoyl, alkylthio, arylthio, alkylamino, Represents an arylamino group or hydrogen, R ^II represents an alkyl or aryl group, X represents S, NH or NR ^III , and R ^III represents an alkyl or aryl group]

In which R ^I represents an optionally substituted alkyl group, R ¹⁶ represents an alkyl group, in particular a C ₁ -C ₄ -alkyl group, R ¹⁷ represents H, and R ²⁰ represents Represents an alkyl or aryl group]
Is a group according to one of

Particularly preferred couplers are couplers according to formula (VIII) in which group (6) R ¹⁵ is represented by formula (15-1), couplers according to formula (VIII) in which group (7) R ¹⁵ is represented by formula (15-2) A coupler according to formula (VIII) wherein group (8) R ¹⁵ is represented by formula (15-3), and a coupler according to group (8) formula (VIII) and wherein R ¹⁵ has 8 to 18 carbon atoms.

  Alkyl- and alkenyl-groups can be linear, branched, cyclic, and optionally substituted. The aryl- and hetero-aryl-groups may be optionally substituted and the aryl group is preferably a phenyl group. Possible substituents for alkyl, alkenyl, aryl and hetero-aryl groups are alkyl, alkenyl, aryl, hetero-aryl, alkoxy, aryloxy, alkenyloxy, hydroxy, alkylthio, arylthio, halogen, cyano, acyl, acyloxy Or an acylamino group, wherein the acyl group can be derived from an aliphatic, olefinic or aromatic carbonic acid, carboxylic acid, carboxylic amino acid, sulfonic acid, sulfonamidic acid, sulfinic acid, phosphoric acid, phosphonic acid or phosphorous acid.

Examples of cyan couplers according to formula (VII) are:
VII-1, wherein R ¹¹ = C ₂ H ₅ , R ¹² = n-C ₄ H ₉ , R ¹³ = R ¹⁴ = t-C ₄ H ₉
VII-2 where R ¹¹ = R ¹² = C ₂ H ₅ , R ¹³ = R ¹⁴ = t-C ₅ H ₁₁
VII-3 where R ¹¹ = C ₂ H ₅ , R ¹² = n-C ₃ H ₇ , R ¹³ = R ¹⁴ = t-C ₅ H ₁₁
VII-4 where R ¹¹ = CH ₃ , R ¹² = C ₂ H ₅ , R ¹³ = R ¹⁴ = t-C ₅ H ₁₁ .

  An example of a cyan coupler according to formula (VIII) where p = 2 is the following:

  p = 2 and

An example of a cyan coupler according to formula (VIII) is:

  An example of a cyan coupler according to formula (VIII) where p = 1 is:

  Examples of cyan couplers of group (6) according to formula (VIII) where p = 2 are:

  Examples of cyan couplers of group (7) according to formula (VIII) where p = 2 are:

  Examples of cyan couplers of group (8) according to formula (VIII) where p = 2 are:

  The production of cyan couplers according to formula (VIII) proceeds analogously to the synthesis disclosed in US Pat. No. 5,686,235, which is incorporated herein by reference.

  Examples of magenta couplers according to formula (V) are:

Examples of magenta couplers according to formula (VI) are:

  Examples of magenta couplers according to formula (XIV) are:

  Examples of yellow couplers according to formula (IV) are:

  According to a preferred embodiment of the deformable color photographic silver halide material according to the invention, the blue-sensitive silver halide emulsion layer is of the formula (IX):

Wherein X ¹ and X ² independently represent S or Se, and R ^{31 to} R ³⁶ independently represent hydrogen, halogen or alkyl-, alkoxy, aryl or hetero-aryl groups, or R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ together represent the atoms necessary to form a fused benzo-, naphtho- or heterocyclic ring; ³⁷ and R ³⁸ are independently alkyl-, sulfoalkyl-, carboxyalkyl, — (CH ₂ ) ₁ SO ₂ R ³⁹ SO ₂ -alkyl, — (CH ₂ ) ₁ SO ₂ R ³⁹ CO-alkyl, — (CH _{2) l} COR ³⁹ SO ₂ - alkyl or _{- (CH} 2) represents a ^{l COR} 39 CO- alkyl ^{group, R 39} is -N ^- - or -NH The expressed, l is an integer between 1 to 6, and M is a counterion present donor charge compensation optionally (counter-ion providing charge compensation)]
The blue sensitizer represented by these is contained.

R ^{31 to} R ³⁶ preferably independently represent hydrogen, F, Cl, Br or alkyl, CF ₃ , OCH ₃ or a phenyl group, or R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ^35. Or R ³⁵ and R ³⁶ together represent the atoms necessary to form a fused benzo- or naphtho-ring.

  Particularly suitable blue sensitizers include the following compounds, where “Et” represents ethyl:

In a preferred embodiment of the present invention, the color photographic material is of the formula (IX) [wherein X ¹ and X ² represent S, R ³⁵ represents a trifluoromethyl group or a halogen atom, in particular a chlorine atom, R ³² and R ³³ represents the atoms necessary to form a benzo-, naphtho- or heterocyclic ring fused together, in particular a fused benzo-ring, and R ³⁷ and R ³⁸ are independently Sulfoalkyl-, carboxyalkyl, — (CH ₂ ) ₁ SO ₂ R ³⁹ SO ₂ -alkyl, — (CH ₂ ) ₁ SO ₂ R ³⁹ CO-alkyl, — (CH ₂ ) ₁ COR ³⁹ SO ₂ -alkyl, — At least one blue-sensitive layer comprising a blue sensitizer according to (CH ₂ ) ₁ COR ³⁹ CO-alkyl group, especially a sulfoalkyl group.

  Suitable red sensitizers are formulas (X) and (XI):

[Wherein R ^{41 to} R ⁴⁶ independently represent hydrogen, halogen or alkyl-, alkoxy, aryl or hetero-aryl groups, or R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴⁴ and R ⁴⁵ , Or R ⁴⁵ and R ⁴⁶ together represent the atoms necessary to form a fused benzo-, naphtho- or heterocyclic ring; R ⁴⁷ and R ⁴⁸ are independently alkyl-, sulfoalkyl- , _{carboxyalkyl, - (CH 2) l SO} 2 YSO 2 - _{alkyl, - (CH 2) l SO} 2 YCO- _{alkyl, - (CH 2) l COYSO} 2 - alkyl or _{- (CH} 2) l COYCO- alkyl group the expressed, Y is -N ^- - or -NH- and ^{represents, R 49} and ^{R 50} are independently hydrogen atom or alkyl - also Ku represents an aryl group, R ⁵¹ represents a hydrogen atom, a halogen atom or an alkyl group, and M is a counter ion donating charge compensation optionally present]
Including the compounds according to

R ^{41 to} R ⁴⁶ preferably independently represent hydrogen, F, Cl, Br or alkyl, CF ₃ , OCH ₃ or a phenyl group, or R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴⁴ and R ^45. Or R ⁴⁵ and R ⁴⁶ together represent the atoms necessary to form a fused benzo- or naphtho-ring.

  Examples of red sensitizers are shown below, where “Et” represents ethyl:

  In a further preferred embodiment of the invention, the deformable color photographic silver halide material has the formula (XII)

[Wherein R ⁵² represents H, CH ₃ or OCH ₃ , and R ⁵³ represents H, OH, CH ₃ , OCH ₃ , NHCO—R ⁵⁴ , COOR ⁵⁴ , SO ₂ NH ₂ , NHCONH ₂ or NHCONH—CH ₃ And R ⁵⁴ represents C ₁ -C ₄ -alkyl]
A layer containing at least one compound represented by: The compound according to formula (XII) is preferably present in the photosensitive layer in an amount of 50 to 5000 mg per kg of Ag, particularly preferably in an amount of 200 to 20000 mg per kg of Ag.

  Preferred compounds according to formula (XII) are shown below:

  In a particularly preferred embodiment of the invention, the color photographic material contains a compound according to formula (XII) in a blue sensitive silver halide emulsion layer.

  In a preferred embodiment of the invention, the color photographic material has the formula (XIII):

[Wherein R ⁵⁵ represents a substituent and n is 1, 2 or 3]
Containing at least one layer containing a compound according to Preferably, R ⁵⁵ represents a polar group, in particular a sulfo group, a sulfonate group, or a substituted or unsubstituted sulfonamido group. The sulfonamide group can be attached via the S- or N- atom of the group.

  The compound according to formula (XIII) is preferably present in the red-sensitive silver halide emulsion layer in an amount of 100 to 5000 mg / kg of Ag, particularly preferably in an amount of 500 to 3000 mg / kg of Ag.

R ⁵⁵ is

Particular preference is given to stabilizers according to formula (XIII) in which R ⁵⁶ and R ⁵⁷ independently represent H, Cl or a C ₁ -C ₄ -alkyl, phenyl or chlorophenyl group.

  Particularly preferred compounds according to formula (XIII) are

Is included.

  In a particularly preferred embodiment of the invention, the red sensitive layer contains at least one compound according to formula (XII) and at least one compound according to formula (XIII).

  The main components of the photographic emulsion layer are a binder, silver halide crystals and a color coupler. Details regarding suitable binders can be found in Research Disclosure 37254, part 2 (1995) page 286, which is incorporated herein by reference.

  Mostly hydrophobic color couplers, as well as other hydrophobic components in the layer, are generally dissolved or dispersed in a high boiling organic solvent. These solutions or dispersions are then emulsified in an aqueous binder (generally gelatin) solution and they remain as fine droplets (0.05-0.8 μm in diameter) in the layer after drying.

  Suitable high boiling organic solvents, methods for introducing photographic materials into layers and other methods for introducing chemical compounds into photographic layers are disclosed in Research Disclosure 37254, part 6 (1995) page, which is incorporated herein by reference. See 292.

  A non-photosensitive layer that is typically coated between photosensitive layers having different spectral sensitivities prevents undesired diffusion of developer oxidation products from one photosensitive layer to another such layer having different spectral sensitivities. It may contain the component which does.

  Suitable compounds (white couplers, scavengers for developer oxidation products (also referred to as DOP scavengers, Dox scavengers, interlayer scavengers or just scavengers) are described in Research Disclosure 37254, part 7 (1995), which is incorporated herein by reference. ) Found on page 292 and Research Disclosure 37038, part III, page 84.

Color photographic materials improve UV-absorbing compounds, brighteners, spacing agents, filter dyes, formaldehyde scavengers, anti-fading agents, antioxidants, _Dmin -dyes; dyes, couplers and white image area stability Additives for reducing color cast; plasticizers (latexes), biocides and polyvinylpyrrolidone can also be included. Such additives and other additives may be included in the emulsion and interlayer, but in another layer between the support and the emulsion layer and / or without the support emulsion layer It can also be contained on the surface. Suitable compounds include Research Disclosure 37254, part 8 (1995) page 292 and Research Disclosure 37038, part IV, V, VI, VII, X, XI and XII (1995), page 84, which are incorporated herein by reference. Seen from the part.

  The layers of the color photographic material are generally hardened, i.e. the binder used, preferably gelatin, is cross-linked by a suitable chemical method. Immediate or rapid curing agents are preferably used. Suitable immediate and rapid curing agents are found in Research Disclosure 37254, part 9 (1995) page 294 and Research Disclosure 37038, part XII (1995) page 86, which are incorporated herein by reference.

The outermost layer of the photographic material and in particular the outermost layer on the image side can be embossed and / or colored and / or printed with any kind of design, image or text.
Industrial application The method of forming a deformed image according to the present invention is used to apply any kind of display such as images, designs, patterns, letters, etc. to a wide range of works including furniture pieces. Can do.

  In the following, the invention is illustrated by means of comparative examples and examples of the invention. The percentages and ratios indicated in these examples are by weight unless otherwise indicated.

  The following compounds were used in the examples:

Production of silver halide emulsion Lippmann emulsion (EMm1):
The following solutions were prepared:

In a precipitation vessel, solutions 02 and 03 at 40 ° C. were simultaneously added to solution 01 at a constant rate over a period of 30 minutes with vigorous stirring at a pAg of 7.7 and a pH of 5.3. During precipitation, the pAg-value was maintained by adding sodium chloride solution to the precipitation vessel and the pH was maintained by adding dilute sulfuric acid. A silver chloride emulsion having an average silver chloride grain size of 0.09 μm was obtained. The weight ratio of gelatin to silver nitrate was 0.14. The emulsion is then ultrafiltered at 50 ° C. and 200 g silver chloride per kg dispersion, a weight ratio of 0.3 gelatin to silver nitrate (corresponding to AgX present) and 0.13 μm average silver chloride grains Redispersed with enough gelatin and deionized water to produce a dispersion containing the dimensions.
Lippmann emulsion (EmM2):
Lippmann emulsion EmM2 was prepared as described for EmM1, except that solution 04 was used instead of solution 02.

The resulting emulsion contained 90 mol% silver chloride, 10 mol% silver bromide and 500 × 10 ⁻⁹ mol Ir ⁴⁺ per mol silver chloride.
Blue sensitive emulsion EmB1-EmB4:
EmB1:
The following solutions were prepared:

In a precipitation vessel, solutions 12 and 13 at 50 ° C. were simultaneously added to solution 11 at a pAg of 7.7 with vigorous stirring over a period of 150 minutes. During precipitation, the pAg-value was maintained by adding sodium chloride solution to the precipitation vessel and the pH of 5.3 was maintained by adding dilute sulfuric acid. The addition rate of the two solutions 12 and 13 is such that it increases linearly from 2 mL / min to 16 mL / min in the first 100 minutes and remains constant at 20 mL / min in the last 50 minutes. Adjusted. This gave a silver chloride emulsion having an average silver chloride grain size of 0.85 μm. The weight ratio of gelatin to silver nitrate (corresponding to AgX) was 0.14. The emulsion is then ultrafiltered at 50 ° C. to produce a dispersion containing a weight ratio of 200 g silver chloride and 0.56 gelatin to silver nitrate (corresponding to AgX present) per kg dispersion. Redispersed with sufficient gelatin and deionized water. The resulting emulsion contained 5 × 10 ⁻⁹ moles of Ir ⁴⁺ per mole of silver chloride.

The emulsion is then added over a period of 180 minutes using 0.13 × 10 ⁻⁶ moles of ammonium tetrachloroaurate and 5.4 × 10 ⁻⁶ moles of sodium thiosulfate per mole of silver chloride at a pH of 5.3 over 180 minutes. Chemical aging at a temperature of ° C. After chemical ripening, the following ingredients were added per mole of silver chloride at 40 ° C .: 0.32 mmol of spectral sensitizing compound (IX-21), 0.5 mmol of stabilizing compound EST-1, 0 .5 mmol of stabilizing compound EST-2 and finally 0.6 mmol of potassium bromide.
EmB2:
Precipitation, desalting and redispersion were performed as described for EmB1. The resulting emulsion contained 5 × 10 ⁻⁹ moles of Ir ⁴⁺ per mole of silver chloride.

At a temperature of 47 ° C. for 180 minutes with 0.13 × 10 ⁻⁶ mol of ammonium tetrachloroaurate and 5.4 × 10 ⁻⁶ mol of sodium thiosulfate per mol of silver chloride at a pH of 5.3 After chemical ripening, the following ingredients were added at 40 ° C. per mole of silver chloride: 0.32 mmol of spectral sensitizing compound (IX-11), 0.5 mmol of stabilizing compound (XII) -8) and finally 0.6 mmol of potassium bromide.
EmB3:
Precipitation, desalting and redispersion were performed as described for EmB1, except that 9.6 mg of mercury (II) chloride was added to solution 12. The resulting emulsion contained 5 × 10 ⁻⁹ moles of Ir ⁴⁺ and 6 × 10 ⁻⁶ moles of Hg ²⁺ per mole of silver chloride.

At a temperature of 60 ° C. for 180 minutes with 0.60 × 10 ⁻⁶ mol of ammonium tetrachloroaurate and 10.0 × 10 ⁻⁶ mol of sodium thiosulfate per mol of silver chloride at a pH of 5.5 After chemical ripening, the following ingredients were added at 40 ° C. per mole of silver chloride: 0.32 mmol of spectral sensitizing compound (IX-11), 0.5 mmol of stabilizing compound (XII) -8) and finally 0.6 mmol of potassium bromide.
EmB4:
Precipitation, desalting and redispersion were performed as described for EmB1, except that solution 12 did not contain K ₂ IrCl ₆ . Within 20 minutes before chemical sensitization, the emulsion was mixed with 50 g of Lippmann emulsion EmM2 at 40 ° C. The emulsion produced thereby contains 10 mmoles silver bromide and 5 × 10 ⁻⁹ mol Ir ⁴⁺ per mol of silver chloride, which is localized in the outermost region (shell) of the emulsion crystals. It was converted.

Chemical at a temperature of 45 ° C. for 180 minutes with 0.01 × 10 ⁻⁶ mol of ammonium tetrachloroaurate and 5.0 × 10 ⁻⁶ mol of thiourea per mol of silver chloride at a pH of 5.5 The following ingredients were added at 40 ° C. per mole of silver chloride after ripening to 0.32 mmol of spectral sensitizing compound (IX-11) and 0.5 mmol of stabilizing compound (XII-14): ).
Green sensitive emulsion EmG1-EmG4:
EmG1:
The following solutions were prepared:

In a precipitation vessel, solutions 22 and 23 at 48 ° C. were simultaneously added to solution 21 at a pAg of 7.7 with vigorous stirring over a period of 75 minutes. During precipitation, the pAg-value was maintained by adding sodium chloride solution to the precipitation vessel and the pH of 5.3 was maintained by adding dilute sulfuric acid. The rate of addition of the two solutions 22 and 23 is such that it increases linearly from 4 mL / min to 36 mL / min in the first 50 minutes and remains constant at 40 mL / min in the last 25 minutes. Adjusted. This gave a silver chloride emulsion having an average silver chloride grain size of 0.37 μm. The weight ratio of gelatin to silver nitrate (corresponding to AgX) was 0.14. The emulsion is then ultrafiltered at 50 ° C., washed and 200 g of silver chloride per kg of dispersion, 5 × 10 ⁻⁹ mol Ir ⁴⁺ and 2.5 × 10 ⁻⁹ mol Rh ³⁺ , and. Redispersed with enough gelatin and deionized water to produce a dispersion containing a weight ratio of 56 gelatin to silver nitrate (corresponding to AgX present).

The emulsion is then mixed for 45 minutes over 240 minutes with 0.82 × 10 ⁻⁶ moles of ammonium tetrachloroaurate and 2.74 × 10 ⁻⁶ moles of sodium thiosulfate per mole of silver chloride at a pH of 5.3. Chemical aging at a temperature of ° C. After chemical aging, the following ingredients were added per mole of AgCl at 40 ° C .: 1.2 mmol of green sensitive compound (GS-1), 2.4 mmol of stabilizing compound EST-3, 1.2 Molar stabilizing compound (XII-1) and finally 10 mM potassium bromide.
EmG2:
Precipitation, desalting and redispersion were performed as described for EmG1, except that the amount of EmM1 in solution 21 was reduced from 480 g to 195 g. After desalting and redispersion, the silver chloride crystals had an average diameter of 0.50 μm.

Chemical at 45 ° C. for 220 minutes with 0.45 × 10 ⁻⁶ mol ammonium tetrachloroaurate and 1.52 × 10 ⁻⁶ mol sodium thiosulfate per mol silver chloride at a pH of 5.3 The following ingredients were added per mole of AgCl at 40 ° C .: 0.6 mmol of green sensitive compound (GS-1), 1.2 mmol of stabilizing compound (EST-1), 0.6 mmol of stabilizing compound (XII-1) and finally 10 mmol of potassium bromide.
EmG3:
Precipitation, desalting and redispersion were performed as described for EmG2. At a temperature of 50 ° C. for 220 minutes with 0.95 × 10 ⁻⁶ mol of ammonium tetrachloroaurate and 2.35 × 10 ⁻⁶ mol of sodium thiosulfate per mol of silver chloride at a pH of 5.5 After chemical aging, the following ingredients were added at 40 ° C. per mole of AgCl: 0.6 mmol of green sensitive compound (GS-2), 1.2 mmol of stabilizing compound (XII-8) ) And finally 10 mmol of potassium bromide.
EmG4:
Precipitation, desalting and redispersion were performed as described for EmG2, except that solution 22 did not contain K ₂ IrCl ₆ .

Within 20 minutes before chemical sensitization, the emulsion was mixed with 50 g of Lippmann emulsion EmM2 at 40 ° C. The emulsion produced thereby contained 10 millimole of silver bromide and 5 × 10 ⁻⁹ moles of Ir ⁴⁺ per mole of silver chloride, which was localized in the outermost region of the emulsion crystals.

Chemical at a temperature of 50 ° C. for 220 minutes with 0.02 × 10 ⁻⁶ moles of ammonium tetrachloroaurate and 1.4 × 10 ⁻⁶ moles of thiourea per mole of silver chloride at a pH of 5.3 After aging, the following ingredients were added at 40 ° C. per mole of AgCl: 0.6 mmol of green sensitizing compound (GS-3) and 1.2 mmol of stabilizing compound (XII-14) .
Red sensitive emulsion EmR1-EmR4:
EmR1:
Precipitation, desalting and redispersion were performed as described for EmG1. The emulsion was heated at 55 ° C. for 280 minutes with 2.2 × 10 ⁻⁶ mol of ammonium tetrachloroaurate and 9.0 × 10 ⁻⁶ mol of sodium thiosulfate per mol of silver chloride at a pH of 5.3. Chemical aging at temperature. After chemical aging, the following ingredients were added at 40 ° C. per mole of AgCl: 150 μmol of spectral sensitizing compound (X-1), 5.0 mmol of stabilizing compound EST-4 and finally 10 mmol Of potassium bromide.
EmR2:
Precipitation, desalting and redispersion were performed as described for EmG2. The emulsion was heated at 55 ° C. for 256 minutes with 1.2 × 10 ⁻⁶ moles of ammonium tetrachloroaurate and 5.0 × 10 ⁻⁶ moles of sodium thiosulfate per mole of silver chloride at a pH of 5.3. Chemical aging at temperature. After chemical aging, the following ingredients were added per mole of AgCl at 40 ° C .: 75 μmol of spectral sensitizing compound (X-1), 2.5 mmol of stabilizing compound EST-4 and finally 10 mmol Of potassium bromide.
EmR3:
Precipitation, desalting and redispersion were performed as described for EmR2. Emulsions were made at 50 ° C. for 330 minutes with 1.8 × 10 ⁻⁶ moles of ammonium tetrachloroaurate and 7.5 × 10 ⁻⁶ moles of sodium thiosulfate per mole of silver chloride at a pH of 5.5. Chemical aging at temperature. After chemical ripening, the following ingredients were added at 40 ° C. per mole of AgCl: 75 μmoles of spectral sensitizing compound (X-2), 1.2 mmoles of stabilizing compound (XII-8), 0. 4 mmol of stabilizing compound (EST-5) and finally 10 mmol of potassium bromide.
EmR4:
Precipitation, desalting and redispersion were performed as described for EmG4.

Within 20 minutes before chemical sensitization, the emulsion was mixed with 50 g of Lippmann emulsion EmM2 at 40 ° C. The emulsion produced thereby contained 10 millimole of silver bromide and 5 × 10 ⁻⁹ moles of Ir ⁴⁺ per mole of silver chloride, which was concentrated in the outermost region of the emulsion crystals.

The emulsion is used at a temperature of 50 ° C. for 300 minutes with 0.10 × 10 ⁻⁶ mol of ammonium tetrachloroaurate and 6.3 × 10 ⁻⁶ mol of thiourea per mol of silver chloride at a pH of 5.3. Chemically aged. After chemical aging, the following ingredients were added at 50 ° C. per mole of AgCl: 75 μmol of spectral sensitizing compound (X-2) and 1.2 mmol of stabilizing compound (XII-14).
Example 1
A color photographic material suitable for photographic processing was prepared by coating the following layers on a PVC plastic foil in the following order: Silver halide coverage is given as the equivalent of silver nitrate.
Layer assembly 101:
Support: PVC toned white with 220 μm thick TiO ₂ (without plasticizer)-corona pretreated primer layer:
0.4 g / m ² gelatin 1.5 ml / m ² dispersant D-1 40% aqueous dispersion 6.0 ml / m ² colloidal silica 30% aqueous dispersion (average particle size 0.025 μm, 8 ph)
0.1 ml / ^{m 2} of wetting agent Tergitol ^{(Tergitol) (R)} 4 silane 5% aqueous solution 0.1 g / ^{m 2} of (near Set Corporation (Niacet Corporation) is the supplied by) SL-1
26.0 g / m ² deionized water layer 2: (blue sensitive layer)
Blue sensitized silver halide emulsion EmB1 corresponding to 0.48 g / m ² AgNO ₃ (99.94 mol% chloride, 0.06 mol% bromide, average grain size 0.85 μm)
1.00 g / m ² gelatin 0.20 g / m ² yellow coupler GB-1
0.40 g / m ² yellow coupler GB-3
0.30 g / m ² tricresyl phosphate (TKP)
0.10 g / m ² of stabilizer ST-1
Layer 3: (intermediate layer)
1.00 g / m ² gelatin 0.06 g / m ² Dox-scavenger SC-1
0.06 g / m ² Dox-scavenger SC-2
TKP of 0.12 g / m ²
Layer 4: (green sensitive layer)
Green-sensitized silver halide emulsion EmG1 corresponding to 0.35 g / m ² AgNO ₃ (99 mol% chloride, 1 mol% bromide, average grain size 0.37 μm)
0.76 g / ^{m 2} of magenta coupler XIV-43 gelatin 0.44 g / ^{m 2}
0.07 g / m ² of stabilizer ST-2
0.14 g / m ² stabilizer SC-2
TKP of 0.18 g / m ²
Layer 5: (UV protective layer)
1.05 g / m ² gelatin 0.35 g / m ² UV absorber UV-1
0.20 g / m ² UV absorber UV-2
0.13 g / m ² UV absorber UV-3
0.06 g / m ² Dox-scavenger SC-1
0.06 g / m ² Dox-scavenger SC-2
TKP of 0.33 g / m ²
Layer 6: (Red sensitive layer)
Red-sensitized silver halide emulsion EmR1 corresponding to 0.33 g / m ² AgNO ₃ (99.0 mol% chloride, 1 mol% bromide, average grain size 0.37 μm)
0.81 g / ^{m 2} gelatin 0.42 g / ^{m 2} of cyan coupler VII-2
TKP of 0.20 g / m ²
0.20 g / m ² dibutyl phthalate layer 7: (UV protective layer)
0.54 g / m ² gelatin 0.35 g / m ² UV absorber UV-1
0.10 g / m ² UV absorber UV-2
0.05 g / m ² UV absorber UV-3
TKP of 0.15 g / m ²
Layer 8: (Protective layer)
0.90 g / ^{m 2} gelatin 0.05 g / ^{m 2} lightening agent W-1
0.07 g / m ² polyvinylpyrrolidone 1.20 ml / m ² silicone oil 2.50 mg / m ² poly (methyl methacrylate) spacing agent, average particle size 0.8 μm
0.30 g / m ² immediate curing agent H-1
Examples 2-4
Layer assemblies of color photographic materials of Examples 2-4 having layer assemblies 102, 103 and 104, respectively, were prepared as in Example 1. The layer assembly is summarized in Table 1:

Table 2 shows the grain size M ^* , the type and amount of dopant, and the stabilizers and sensitizers used in the silver halide emulsion layers shown in Table 1. Hg-, Ir- and Rh- amounts are molar ratios relative to silver halide.

Chemical Processing of the Photographic Materials of Examples 1-4 All examples were processed as follows:
a) The following composition at 35 ° C. for 45 seconds:
9.0 g triethanolamine 4.0 g N, N-diethylhydroxylamine 0.05 g diethylene glycol 5.0 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline 2 g potassium sulfite 0.05 g triethylene glycol 22 g potassium carbonate 0.4 g potassium hydroxide 2.2 g ethylenediamine-tetraacetic acid disodium salt 2.5 g potassium chloride 0.3 g 1,2-dihydroxybenzol Development using a color developer with pH = 10.0 with water to make 1000 mL of 3,4,6-trisulfonic acid trisodium salt b) The following composition at 35 ° C. for 45 seconds:
75 g ammonium thiosulfate 13.5 g sodium bisulfite 2.0 g ammonium acetate 57 g ethylene-diamine-tetraammonium iron tetraacetate 9.5 g 25% aqueous ammonia with acetic acid to make 1000 ml pH = 5.5 Bleaching / fixing using a bleach / fixer bath c) Washing with deionized water at 33 ° C. for 2 minutes d) Drying.
Evaluation of Sensitometric Properties of Color Photographic Materials of Examples 1-4 Sensitometric evaluation results are displayed in Table 3 in the form of the following parameters:
D _min : minimum exposure density of material according to X-Rite Status A E: sensitivity at density of D _min + 0.6 × 1000; exposure required to achieve the required density The quantity logIxt depends on the color filter placed between the exposure device and the material, so the sensitivity is a gamma-value G1 expressed as a relative value G1: threshold slope × 100, ie D _min +0.10. concentration and _D min 100 times gamma gradient of the sensitometric curve between concentration of Tasu0.85 - value G2: intermediate slope × 100, _i.e., the density of the density and _D min _+1.60 of D min Tasu0.85 100 times analog exposure of the slope of the sensitometric curve between:
The sensitometric properties of a color photographic material during analog exposure are measured by using a halogen lamp with a constant exposure (light intensity x time) through a grade gray wedge with a density change every 0.1 density steps. Measured by exposing for exposure times of seconds, 0.82 seconds, 4.91 seconds and 76 seconds.
Digital exposure:
The following technical specifications describe the sensitometric properties of color photographic materials during digital exposure:
Red laser: wavelength of 683 nm Green laser: wavelength of 543 nm Blue laser: wavelength of 458 nm Optical resolution: 400 dpi
Exposure time: Approximately 131ns per pixel (pixel exposure time)
Number of color steps obtained: 256 per channel
Measured by exposure using a digital printer with

First, a portion of the sample was exposed with intensity I at a pixel exposure time of 131 ns so that the processed density D (according to X-light statistics A) was about 0.6. The light intensity was then reduced or increased so that log (Ixt) was 0.1 lower or 0.1 higher than the previous exposure step. This process was continued until a total of 29 steps were exposed. The lowest stage corresponds to 0 light intensity (D _min ).

  With digital exposure, high sensitivity is not required because commercial laser devices have extra power. For analog exposure, reduction in heat development is desirable, and consequently the use of lower intensity lamps is desirable, which means that high sensitivity is important. Furthermore, high sensitivity is required for large format exposures in order to reduce the exposure time and thereby increase productivity.

  The results in Table 3 showed that all of the color photographic materials tested showed acceptable performance for digital (131 ns) or long exposure (76 s).

  However, layer assemblies 102 and 103 had higher sensitivity than layer configuration 101 with respect to long exposure, and layer configuration 104 exhibited the highest sensitivity.

  Higher G1- and G2- values result in images with higher contrast and consequently better images. For analog exposure, G1-values between 1.7 and 1.9 and G2-values between 250 and 400 are preferred. For digital exposure, the shoulder gradient G2 should be as high as possible to enhance image quality. However, even when the G1- and G2-values are outside these ranges for analog exposure, as in layer structure 101, color photographic materials are still usable but have slightly lower image brightness.

  On the other hand, the layer arrangements 102-104 can be used without damage in image quality within the entire exposure range and are very suitable for both digital and long exposure.

It has been surprisingly found that the deformable color photographic recording material of the present invention is suitable for digital exposure and gives high quality images. Particularly good results have been obtained with color photographic materials containing stabilizers according to formula (XII). Furthermore, it is advantageous to use a blue sensitizer according to formula (IX) and a red sensitizer according to formula (X), and in particular to use a silver halide emulsion having a larger silver halide grain size. Was found.
Examples 5-7
The photographic material layer assemblies of Examples 5-7, each having layer assemblies 105, 106 and 107, as in Example 4 (layer assemblies), except that the PVC support was replaced by the following support: 104):
Example 5: Polyethylene coated paper (photographic support supplied by Scheller; weight 258 g / m ² ; 35 g / m ² polyethylene containing about 11% by weight TiO ₂ pigment on the front (photo layer applied) The back side is coated with 28 g / m ² of polyethylene and an antistatic layer is applied to the back side of the coated paper.
Example 6: PC foil (175 μm thick; supplied by General Electric)
Example 7: PET foil (175 μm thick; stretched in the machine and transverse directions); such a foil is commonly used as a support for display materials.
Example 8
The layer assembly 108 consisted only of 220 μm thick PVC, tinted white with TiO ₂ (without plasticizer)-corona pretreated.
Image Quality and Deformation Tests Layer assemblies 104-107 were digitally exposed as described above with images comprising black characters of varying dimensions (3 mm to 10 mm in height) and as described for Examples 1-4. And chemically processed.

  On the layer assembly 108, an image including black characters with variable dimensions (height 3 mm to 10 mm) was formed by conventional offset printing.

  An 80 μm transparent PVC sheet pre-coated with a 75 μm thick polyethylene sheet on one side is placed on the image thus formed and brought into contact with the top coat of the image layer of the layer assembly 104-108. And laminated. A roller laminator was used to press the stacked materials together at a temperature of 104 ° C. measured in the sandwich.

After lamination, the following deformation tests were applied to the layer assemblies 104-108. A membrane press was used to press the photographic material onto the work pre-treated with wood glue and the test was conducted at a temperature of 95 ° C. A product in the form of a drawer-front is produced from a piece of wood, which has a groove in the form of a semi-tube with a diameter of 0.8 cm on its front. Upon deformation, the photographic material lying on the half tube is pressed into the half tube and thereby stretched. The material is also stretched at the front edge and corners of the work. The overhanging material is cut off on the back of the product. The specimens were qualitatively evaluated and the following results were obtained:
Deformation results The layer assembly (104) could be easily deformed and showed no cracks or microcracks.
The layer assembly (105) could not be deformed (showing cracks and fine cracks).
The layer assembly (106) could be deformed, but required more time than the layer assembly 104, which showed no cracks or microcracks.
The layer assembly (107) could not be deformed (showed fine cracks).
The layer assembly (108) was easily deformable and showed no cracks or microcracks.

Since the layer assemblies (105) and (107) failed the deformation test, they were not suitable for the present invention and were therefore not evaluated further.
Image Quality Results Image quality was evaluated by viewing the black text in the deformed part of the specimen with the naked eye.
The layer assembly (104) showed no damage in image quality at the deformed part.
The layer assembly (106) showed small damage in image quality seen with the naked eye as a low density damage (dark gray instead of black) in the deformed part.
The layer assembly (108) showed significant damage in image quality in the form of clearly visible brightness of the characters in the deformation. Gray and white lines appear in the text along the edges and corners.

  From the test results it is clear that PVC and PC are preferred supports for the photographic materials of the present invention. The advantage of PVC is its ease of deformation. XXX material (108) gives poor image quality when deformed and cannot be used according to the present invention.

  The present invention may encompass any feature or combination of features or their generality explicitly or implicitly disclosed herein, whether or not it relates to the claimed invention. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.

Claims (19)

  On a deformable plastic support, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green sensitivity containing at least one magenta coupler. -A deformable color photographic silver halide material comprising a silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler.   The material of claim 1 wherein the silver halide emulsion has a total silver chloride content of at least 70 mol%.   A material according to claim 2 wherein the silver halide emulsion has a total silver chloride content of at least 98 mol%.   Clearly the silver halide crystals of at least one silver halide emulsion have at least two different regions with a silver chloride content of at least 70 mol% and an outermost region having a higher silver bromide molar content than the rest of the crystal The material according to claim 1, wherein the material contains structured crystals.   The support comprises 1.3-80 wt% protein colloid, 0-85 wt% colloidal silica and 0-30 wt% siloxane capable of forming a reaction product with the colloidal silica. The material according to claim 1, wherein an undercoat layer is provided.   6. A material according to claim 5, wherein the undercoat layer is provided on the same side of the support as the silver halide emulsion layer.   The green sensitive silver halide emulsion layer and / or the red sensitive silver halide emulsion layer contains at least one silver halide emulsion having silver halide crystals having an average grain size of at least 0.4 μm. 1. The material according to 1.   The material of claim 1 wherein the silver halide emulsion layer contains one or more binders.   9. A material according to claim 8, wherein the binder in the silver halide emulsion layer is at least 80% by weight gelatin. The color photographic material has the formula (XII):

[Wherein R ⁵² represents H, CH ₃ or OCH ₃ , and R ⁵³ represents H, OH, CH ₃ , OCH ₃ , NHCO—R ⁵⁴ , COOR ⁵⁴ , SO ₂ NH ₂ , NHCONH ₂ or NHCONH—CH ₃ And R ⁵⁴ represents C ₁ -C ₄ -alkyl]
The material according to claim 1, comprising at least one photosensitive layer containing a compound represented by: The blue-sensitive silver halide emulsion layer has the formula (IX):

Wherein X ¹ and X ² independently represent S or Se, and R ^{31 to} R ³⁶ independently represent hydrogen, halogen or alkyl-, alkoxy, aryl or hetero-aryl groups, or R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ together represent the atoms necessary to form a fused benzo-, naphtho- or heterocyclic ring; ³⁷ and R ³⁸ are independently alkyl-, sulfoalkyl-, carboxyalkyl-, — (CH ₂ ) ₁ SO ₂ R ³⁹ SO ₂ -alkyl, — (CH ₂ ) ₁ SO ₂ R ³⁹ CO-alkyl, — ( _{^{CH 2) l COR 39 SO 2}} - alkyl or _{- (CH} 2) represents a ^{l COR} 39 CO- alkyl ^{group, R 39} is -N ^- - or -N - represents, l is an integer between 1 and 6, and M is the case there the counterion donor charge compensation (counter-ion providing charge compensation)]
The material according to claim 1, comprising a blue sensitizer represented by:   2. A material according to claim 1, wherein the deformable plastic support is a polycarbonate, poly (vinyl chloride), vinyl chloride copolymer or polyester, or a copolyester based on PET.   2. A material according to claim 1, wherein a protective foil is provided on the outermost layer on the image side of the color photographic material.   A modified process comprising the steps of: exposing the color photographic silver halide material of claim 1; processing the exposed color photographic material in a conventional manner to form an image; and deforming the color photographic material. Image forming method.   15. The method of claim 14, wherein the deformation step comprises application of heat and pressure and at least a portion of the material is stretched.   15. The method of claim 14, wherein the deforming step comprises deforming the deformable color photographic material in contact with a work piece.   15. The method of claim 14, wherein the color photographic material is provided with a protective foil prior to transforming the deformable color photographic silver halide material with the work piece.   15. A method according to claim 14, wherein the deforming step comprises the step of deforming the color photographic material by vacuum deformation.   15. A method according to claim 14, wherein the deforming step comprises the step of deforming the color photographic material by injection molding.