JP2001330936A - Silver halide photographic element and recording material each provided with authenticity, and authenticating and identifying method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive easy authenticating and identifying method which does not use a special device in verification and does not impair the aesthetic aspect and artistry of image, a recording material, and also a silver halide photographic material each having a security pattern in authentication and a base for the recording material. SOLUTION: The objective silver halide photographic element has a security pattern formed with an oil-soluble fluorescent dye before exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material capable of demonstrating reliability and protected against intellectual property protection and counterfeiting of fair documents and the like, and more particularly to a recording material support. , Silver halide photographic elements.

[0002]

2. Description of the Related Art Materials that must be able to demonstrate reliability include identification materials (for example, passports, visas, identification cards, driver's licenses, bank cards, credit cards, admission cards), and valuable materials (for example, banknotes). , Stock certificates, borrowed letters, certificates, checks, lottery tickets), admission tickets (eg, airline tickets) and copyrighted works (eg, copyrighted images, photographs)
Etc. With the recent development of copying technology, the above materials can be easily copied. For this reason, intellectual property rights and copyrights are infringed, and materials including the above-mentioned public documents are often forged, which has become a serious problem. Various techniques are available to protect fraudulent alteration and duplication of these materials by photocopying, such as melt lamination or bonding with a preprinted plastic overcoat, coloring or metallizing the substrate of the material, introducing holograms, Fine line printing, watermark, light diffraction mark, liquid crystal mark, metal foil, pearl foil, interference pigment, fiber,
Application of protective fibers is used. However, in these methods, the artistic quality of the image of the material handling the image is impaired, or the cost burden is large, and the image,
In particular, it is not always satisfactory when emphasizing the artistic and aesthetic properties of photography.

In recent years, not only silver halide photographic materials, but also sublimation transfer printers, ink jet printers, and electrophotographs have been improved in the output of images, especially photographic images, and the output of these materials has been increased. In the photographic field as well, in order to protect the intellectual property and copyright of the photographer or to prevent forgery of certificates, US Pat. No. 5,822,436 applies in advance before exposure of the main image. Encoded auxiliary information signal for copy control, JP-A-9-226227, JP-A-11-8761
In Japanese Patent Application Laid-Open No. 11-15104, use microcopy dots for copy control (given as a latent image to a silver halide emulsion in a specific layer such as a blue-sensitive layer before exposure to a main image). However, these methods require analysis software using a special algorithm and special equipment for verification, and are not general-purpose.

On the other hand, as a method that does not require a special device as described above, it has been proposed to attach a specific mark to an attached photograph. In the image receiving sheet of diffusion transfer (DTR method), a light interference pigment is used in Japanese Patent Application Laid-Open No. Hei 9-510925, and in US Pat. It has been proposed to print a security pattern using a pigment and apply it to the security field such as an ID card. However, in the proposed method, a printing ink is prepared using a normal dye or pigment to print a security pattern, so that the security pattern is blurred when placed under alkaline conditions or high-temperature high-humidity conditions. There was a problem. Moreover, the robustness of security patterns formed from these dyes has not always been satisfactory.

[0005]

SUMMARY OF THE INVENTION The inventor of the present invention has studied an authentication and identification method which does not use a special device for verification and does not impair the aesthetics and artistic quality of an image. In particular, we studied the phenomenon of color bleeding when the printed security pattern was placed under alkaline conditions or high-temperature and high-humidity conditions. It has been found that the colorant printed under alkaline conditions or high-temperature and high-humidity conditions is diffused due to weak interaction between the agent and the binder. Therefore, a first object of the present invention is to use a special device for verification, and not to impair the aesthetics and artistic quality of an image, and not to affect the color balance of a photographic image, and to reduce the cost. To provide a recording material, a silver halide photographic material, and a recording material support having a security pattern in the authentication. A second object of the present invention is to enhance the interaction between the binder and the colorant so that a security pattern without bleeding can be obtained even under alkaline conditions or high temperature and high humidity conditions. Accordingly, it is an object of the present invention to establish a recording material, particularly a silver halide photographic element, and an authentication / identification method, which provide a highly reliable security. A third object of the present invention is to form a highly robust security pattern.

[0006]

As a result of diligent studies, the present inventor has found that the above object is achieved by the following. (1) a silver halide photographic element characterized in that a security pattern is formed beforehand by an oil-soluble fluorescent dye beforehand; (2) the oil-soluble fluorescent dye has at least one diffusion-resistant group (1) The silver halide photographic element as described in (1) above, wherein (3) the diffusion-resistant group in the oil-soluble fluorescent dye has at least 8 carbon atoms. (2)
(4) The silver halide photographic element according to (1), wherein the silver halide photographic element is a diffusion transfer type silver halide photographic element, and a security pattern is formed in the image receiving layer. (5) The recording material having a support, wherein a security pattern is formed beforehand by using an oil-soluble fluorescent dye having at least one diffusion-resistant group before recording. (6) a recording material support wherein a security pattern is formed by an oil-soluble fluorescent dye having at least one diffusion-resistant group; and (7) at least one resistance-resistant support. An identification method characterized by performing authentication identification based on the presence or absence of a security pattern composed of an oil-soluble fluorescent dye having a diffusible group.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
First, the oil-soluble fluorescent dye of the present invention will be described. The fluorescent dye used in the present invention is oil-soluble. In the present invention, any dye may be used as long as it does not dissolve in water, but preferably a dye having a solubility of preferably 1 g or less, more preferably 0.1 g or less at room temperature in 100 ml of water. . In the present invention, a dye capable of forming a transparent ink is preferable. Therefore, the dye itself is preferably a substantially colorless or white powder or liquid. However, even if it is slightly colored, when printed on a substrate as a transparent ink, it does not matter if the aesthetics of an image added later are not impaired.

The oil-soluble fluorescent dye of the present invention preferably emits fluorescence upon irradiation with ultraviolet rays. The fluorescent color may be any color as long as it can be visually detected, but is preferably blue to purple. And more preferably blue.

It is particularly preferred that the oil-soluble fluorescent dye of the present invention has at least one diffusion-resistant group. A diffusion-resistant group is a hydrophobic substituent for suppressing the diffusion of a substance, and any of an aliphatic group, an aromatic group, or a group substituted by these groups can be used. Preferably has 8 to 50 carbon atoms, more preferably 12 to 50 carbon atoms.
~ 30. A more preferred oil-soluble fluorescent dye of the present invention has a total of 16 to 100 carbon atoms in all the diffusion-resistant groups in the molecule, and more preferably 16 to 5 carbon atoms.
0.

The oil-soluble fluorescent dye of the present invention may be any dye having any structure as long as it satisfies the above-mentioned properties. , Naphthalimide, triazole, oxazole, oxazolidone, and benzoxazinone. More preferred are stilbene dyes, benzoxazinone dyes, coumarin dyes, pyrazoline dyes, and oxazole dyes. As for the benzoxazinone-based compounds, compounds described in European Patent No. 314350A1 are preferably used.

Among the oil-soluble fluorescent dyes of the present invention, particularly preferred ones can be represented by the following general formula (F).

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In the general formula (F), A is a divalent heteroaromatic ring group (preferably, a divalent heteroaromatic ring group having at least one sulfur atom, nitrogen atom or oxygen atom as a ring-constituting atom. And more preferably a divalent 5-membered heteroaromatic group, for example, 2,5-thiophenediyl, 2,5-furandiyl, 2,5-pyrrolediyl), arylene Group (which may have a substituent;
For example, it represents a divalent group consisting of p-phenylene, 1,4-naphthalenediyl), a vinylene group, or a combination of these groups. R ₁ , R ₂ and R ₃ are independently:
Represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group,
Aryloxy group, sulfonamide group, carbamoyl group, sulfamoyl group, acylamino group, alkylamino group, arylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, etc., and these groups are further substituted It may have a group. However, at least one of A, R ₁ , R ₂ and R ₃ is a diffusion-resistant group or a group substituted by a diffusion-resistant group. The oil-soluble fluorescent dyes that can be used in the present invention are described below, but the present invention is not limited to these.

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These compounds can be easily synthesized by known synthesis methods. Also, commercially available compounds can be easily obtained.

As a method of forming a specific security pattern using these compounds, any method can be used. For example, it is convenient and preferable to prepare and print an ink containing the oil-soluble fluorescent dye of the present invention and spray a solution or dispersion containing the oil-soluble fluorescent dye of the present invention with a spray or the like. Among them, in order to form a specific security pattern with good reproducibility, it is preferable to prepare and print the ink containing the oil-soluble fluorescent dye of the present invention.
As for printing, a printing plate such as a planographic plate, a relief plate, an intaglio plate may be prepared and printed, or printing may be performed by an inkjet method without using a plate. The oil-soluble fluorescent dye of the present invention may be in any amount as long as it can be detected by the detection means. It varies depending on the type of recording material, preferably, in the recording ^{material, 0.1mg / m 2 ~1g / m} 2, more preferably ^{1mg / m 2 ~100mg / m 2} .

Any security pattern can be used as long as it can be verified. For example, a character, a signature, a sign, a symbol, a line pattern, a graphic pattern, a logo mark, a coded pattern, a disordered pattern, and a combination thereof are included.

In the present invention, the security pattern is provided in advance before the main information such as images and characters is provided. In the case of a silver halide photographic element, the security pattern is applied before the main information is exposed. To form.

The recording material for recording main information may be any recording material having a support, but is preferably a silver halide photographic element, a sublimation type thermal transfer recording material,
Fused thermal transfer recording materials, ink jet recording materials, electrophotographic recording materials, graphic printing recording materials, heat-sensitive or pressure-sensitive recording materials, more preferably silver halide photographic elements.

The silver halide photographic element may be a black-and-white photographic element represented by a wet-processed X-ray or a photosensitive material for printing, or a color photographic element represented by a color paper, a color negative, a color reversal or the like. May be
The photosensitive element may be a conventional photosensitive element which is solution-developed, a black-and-white or color diffusion transfer photosensitive element, or a black-and-white or color heat-developable photosensitive element. Preferred are color photographic light-sensitive elements, especially color paper, and color diffusion transfer elements, most preferably color diffusion transfer elements.

The exposure for providing the main information of the silver halide photographic element may be normal surface exposure or laser scanning exposure.

The silver halide color photographic element is preferably a light-sensitive material described in JP-A-11-282108, and is particularly preferably a paragraph No. 00 in JP-A-11-282108.
The description of 21 to 0036 is incorporated as it is as a part of the specification of the present invention.

The support in the silver halide photographic element will be described. The support is a transmission type support or a reflection type support,
That is, any of a transparent support, a translucent support and an opaque support may be used. Examples of the transmissive support include transparent films such as cellulose acetate film and polyethylene terephthalate, polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and polyesters of NDCA, terephthalic acid and EG. Provided with an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. Further, the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent whitening agent, a benzoxazole type, a coumarin type or a pyrazoline type can be preferably used, and a benzoxazolyl naphthalene type and a benzoxazolyl stilbene type fluorescent whitening agent are more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, and more preferably 0.001 to 0.5% by mass, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface. The support of the silver halide photographic element in the present invention includes, in addition to the above-described support itself, when an undercoat layer is further provided thereon, the undercoat layer.

Next, the color diffusion transfer photosensitive material most preferably applied in the present invention will be described. In a typical form of the color diffusion transfer film unit, the image receiving element and the photosensitive element are laminated on one transparent support, and after the transfer image is completed, there is no need to peel the photosensitive element from the image receiving element. It is a form. More specifically, the image receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a blue-sensitive emulsion layer, a combination of a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer, A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer,
A yellow dye image forming compound, a magenta dye image forming compound and a cyan dye image forming compound are combined with each of the above emulsion layers (herein, the term “infrared-sensitive emulsion layer” means 700 nm or more, particularly 740 nm). An emulsion layer having a maximum spectral sensitivity to the above light). Then, between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer, so that the transfer image can be viewed through a transparent support,
A white reflective layer containing a solid pigment such as titanium oxide is provided.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example,
67840 and Canadian Patent 674,082.

As another embodiment of a laminate type, which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, on a white support described in JP-A-63-226649. (C) a release layer, (d) a photosensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming compound, an alkali treatment composition containing a light-shielding agent, and a transparent cover sheet, the emulsion layer comprising And a color diffusion transfer photographic film unit having a layer having a light-shielding function on the side opposite to the side on which the processing composition is spread.

In another embodiment which does not require peeling, the above-described photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,71.
No. 8 is described.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type, and the other is a peeling-free type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. Before the end of the exposure, the coated surface of the photosensitive layer and the coated surface of the mordant layer do not face each other, but after the end of the exposure (for example, during the developing process), the coated surface of the photosensitive layer is inverted in the image forming apparatus and comes into contact with the coated surface of the image receiving layer. It is devised as follows. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

In a preferred embodiment of the peeling-free film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. Thus, the photosensitive layer application surface and the mordant layer application surface face each other and are superimposed.

A pressure-rupturable container (processing element) further containing an alkaline processing liquid may be combined with the above-described embodiment. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains one or both of a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

Hereinafter, each component which can be used in the light-sensitive material of the present invention will be described in more detail.

I. Photosensitive Sheet A) Support The support of the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic photosensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. The thickness of the support is 5
It is 0 to 350 μm, preferably 70 to 210 μm, and more preferably 80 to 150 μm. If necessary, a layer for curl balance may be provided on the back side of the support.
An oxygen barrier layer described in JP-A-6-78833 can be provided.

B) Image Receiving Layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer containing a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Things. The coating amount of the mordant is generally 0.5
10 g / m ² , preferably 1.0 to 5.0 g / m ² , particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred. In the image receiving layer, JP-A-62-30620
And the discoloration inhibitors described in JP-A Nos. 62-30621 and 62-215272 can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. As white pigments for the white reflective layer, barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. These may be used alone or as a mixture as long as the desired reflectance is obtained. A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of the pigment, the mixing ratio of the pigment and the binder, and the amount of the applied pigment, but the light reflectance is desirably 70% or more. In general, as the amount of the pigment applied increases, the whiteness improves.However, when the image forming dye diffuses through this layer, the pigment becomes resistant to the diffusion of the dye. Is desirable. 5 to 40 g of titanium dioxide /
m ² , preferably 10 to 25 g / m ² , and a white reflective layer having a light reflectance of 78 to 85% with light having a wavelength of 540 nm is preferred. Titanium dioxide can be selected from various commercially available brands. Among them, it is particularly preferable to use rutile type titanium dioxide. Many commercial products are
Surface treatment is performed with alumina, silica, zinc oxide, or the like, and a surface treatment amount of 5% or more is desirable in order to obtain high reflectance. Examples of commercially available titanium dioxide include those described in Research Disclosure No. 15162, in addition to DuPont's Ti-pure R931.

As the binder for the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be used. A particularly desirable binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1/1 to 20
/ 1 (mass ratio), desirably 5/1 to 10/1 (mass ratio). In the white reflective layer, JP-B-62-3062
It is preferable to incorporate an anti-fading agent such as No. 0 or No. 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used. U.S. Pat.
Degradable dyes described in US Pat. No. 5,966 or the like may be used.
As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred. As a carbon black raw material, for example, Do
nnel Voet "Carbon Black" MarcelDekker, Inc. (19
Any method such as a channel method, a thermal method, and a furnace method described in 76) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 °. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shielded from light, but is preferably about 5 to 10 in optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming compound is provided above the light-shielding layer. The components will be described below.

(1) Dye image forming compound Specific examples of the dye image forming compound are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,453
No. 107, No. 3,544,545, No. 3,932,3
No. 80, No. 3,931,144, No. 3,932,30
No. 8, 3,954, 476, 4, 233, 237
Nos. 4,255,509 and 4,250,246
Nos. 4,142,891, 4,207,104
No. 4,287,292, JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36804,
No. 56-73057, No. 56-71060, No. 55
-134, JP-A-7-120901 and 8-286
No. 343, No. 8-286344, No. 8-292535
What is described in the issue.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827.
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17,630 (1978) and 16,475 (1977).

Dye image forming compounds which form a dye by coupling can also be used. For example, JP-A-8-28634
No. 0, No. 9-152705, Japanese Patent Application No. 8-357190
No., JP-A Nos. 10-186564 and 10-29338.
No. 8, etc. Also, a positive dye image forming compound can be used. In this case, a negative emulsion may be used as the silver halide emulsion. An example of this is disclosed in
No. 6542, No. 4-155332, No. 4-17234
No. 4, No. 4-172450, No. 4-318844,
4-356046, 5-45824, 5-4
No. 5825, No. 5-53279, No. 5-107710
No. 5,241,302, No. 5,107,708, No. 5,232,659 and U.S. Pat. No. 5,192,649.

These compounds are disclosed in JP-A-62-2152.
No. 72, pages 144 to 146. These dispersions are described in JP-A-62-2152.
No. 72, pages 137 to 144 may be included. Specific examples of these dye-forming compounds include the following compounds. Dye in the following compounds represents a dye group, a temporarily shortened dye group, or a dye precursor group.

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(2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion which mainly forms a latent image on the surface of silver halide grains,
An internal latent image type direct positive emulsion which forms a latent image inside silver halide grains may be used.

The internal latent image type direct positive emulsion may be, for example, a so-called “conversion type” emulsion which is prepared by utilizing the difference in solubility of silver halide, or may be doped with metal ions.
Or a "core / shell" emulsion in which at least the photosensitive sites of the silver halide inner nucleus (core) grains subjected to chemical sensitization or both are coated with an outer shell of silver halide. These are described in U.S. Pat. Nos. 2,592,250 and 3,206,313, British Patent 1,027,146, and U.S. Pat.
Nos. 6, 3,935,014 and 3,447,927
No. 2,297,875, No. 2,563,785
Nos. 3,551,662 and 4,395,478
No. 2,728,108, US Patent 4,43.
1,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to give a surface fog nucleus using light or a nucleating agent after image exposure. As a nucleating agent for that,
U.S. Pat. Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat. No. 3,227,5
No. 52, hydrazines and hydrazones described in British Patent No. 1,283,835, JP-A-52-69613.
No. 3,615,615 and 3,719,4
Nos. 94, 3,734, 738 and 4,094,68
Heterocycle 4 described in No. 3, No. 4, 115, 122, etc.
Grade salt compounds, sensitizing dyes having a nucleating substituent described in US Pat. No. 3,718,470 in dye molecules, US Pat. Nos. 4,030,925 and 4,031,1
No. 27, No. 4, 245, 037, No. 4, 255, 51
No. 1, 4,266,013, 4,276,364
Thiourea-linked acylhydrazine-based compounds described in US Pat. No. 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748, British Patent 2,011,391B and the like An acylhydrazine-based compound in which a heterocyclic group such as a thioamide ring or a triazole or a tetrazole described in (1) is bonded as an adsorptive group is used.

In the present invention, spectral sensitizing dyes can be used in combination with these negative emulsions and internal latent image type direct positive emulsions. For a specific example thereof, see JP-A-59-18.
Nos. 0550 and 60-140335, Research Disclosure (RD) 17029, U.S. Pat.
No. 46,300, No. 2,078,233, No. 2,08
9,129, 2,165,338, 2,23
No. 1,658, No. 2,917,516, No. 3,35
No. 2,857, No. 3,411,916, No. 2,29
5,276, 2,481,698, 2,68
8,545, 2,921,067, 3,28
2,933, 3,397,060, 3,66
No. 103, No. 3,335,010, No. 3,35
2,680, 3,384,486, 3,62
No. 3,881, No. 3,718,470, No. 4,02
5,349 and the like.

(3) Composition of the photosensitive layer In order to reproduce a natural color by the subtractive color method, the above-mentioned dye which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above-mentioned spectral sensitizing dye is used. A photosensitive layer comprising at least two of the combinations with the image forming compound is used. The emulsion and the dye image-forming compound may be coated as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred.
The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming compound layer. For example, JP-A-60-1735
No. 41, a layer containing a nucleation development accelerator,
The color image density can be increased by providing a partition layer described in JP-A No. 0-15267, or the sensitivity of a photosensitive element can be increased by providing a reflective layer.

The reflection layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.1 g / m ² .
It is a ^{2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354.

In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side. Arbitrary layers can be provided between the emulsion layer units as needed.
In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer, and the like are provided as needed.

F) Release Layer In the present invention, a release layer can be provided, if necessary, to peel off the photosensitive sheet in the unit at an arbitrary place after the treatment. Therefore, this release layer must be easily peelable after the treatment.

As a material for this, for example, Japanese Unexamined Patent Publication No.
Nos. 7-8237, 59-220727 and 59-2
No. 29555, No. 49-4653, U.S. Pat.
20,835 and 4,359,518,
No.-4334, No.56-65133, No.45-240
No. 75, U.S. Pat. Nos. 3,227,550 and 2,75
9,825, 4,401,746, 4,36
No. 6,227 or the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Other examples include various natural polymers such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Further, another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, polybutyl methacrylate, or a copolymer thereof, or the like. The release layer may be a single layer or, for example, disclosed in JP-A-59-220727 and JP-A-60-60642.
It may be composed of a plurality of layers as described in the number.

The color diffusion transfer photosensitive material of the present invention preferably has a neutralizing function between the support and the photosensitive layer, between the support and the image receiving layer, or on the cover sheet.

G) Support The support for the cover sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. ,
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of a dye to prevent light piping.

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali introduced from the treatment composition. Accordingly, a multilayer structure composed of layers such as a neutralization rate control layer (timing layer) and an adhesion strengthening layer may be used. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that provides such an acidic group by hydrolysis), and more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. Ester copolymers;
No. 4,139,383 and Research Disclosure No. 16102 (19
And latex-type acidic polymers as disclosed in (77). In addition, U.S. Pat.
8,493, JP-A-52-153739, and JP-A-53-153739.
No. 1023, No. 53-4540, No. 53-4541
And the acidic substances disclosed in JP-A-53-4542 and the like.

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiene phthalate and the like.

The above-mentioned polymer acid can be used by mixing with a hydrophilic polymer. Such polymers include:
Examples include polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer in the polymer acid,
For example, cellulose acetate or the like may be mixed.

The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The mass ratio of the hydrophilic polymer to the polymer acid is 0.1 to 10, preferably 0.3 to 10.
３3.0.

In the layer having a neutralizing function of the present invention, additives can be incorporated for various purposes. For example, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. Other, if necessary,
An antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof can also be added.

The timing layer used in combination with the neutralizing layer has low alkali permeability such as, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like. Polymer made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid monomer,
Latex polymers that increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

Among them, JP-A-54-136328, US Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849 and the like, a timing layer using cellulose acetate;
No. 335, No. 56-69629, No. 57-6843
No. 4,056,394 and 4,061,4
Nos. 96, 4,199,362, 4,250,24
No. 3, 4,256, 827, 4,268,604
A latex polymer prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; a polymer having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346 and 57-6842, European Patent (EP) 31,957A1, 37,72
The polymers disclosed in Nos. 4A1, 48,412 A1, and the like are particularly useful.

In addition, those described in the following documents can also be used. U.S. Pat. Nos. 3,421,893 and 3,455
686, 3,575,701, 3,778,2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, 4,088, 493, 4, 123, 275
No. 4,148,653, 4,201,587
No. 4,288,523 and 4,297,431
No., West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disclosure 1516
2, No. 151 (1976). The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

The timing layers composed of these materials are described, for example, in US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and 3,014,6.
No. 72, JP-A Nos. 54-155837 and 55-138.
No. 745, etc., and a development inhibitor and / or a precursor thereof, and US Pat.
It is also possible to incorporate the hydroquinone precursor disclosed in No. 8 and other useful photographic additives or precursors thereof. Further, as a layer having a neutralizing function, JP-A-63-168648 and JP-A-63-168648 describe the same.
Providing an auxiliary neutralizing layer as described in Japanese Patent No. 168649 is effective in reducing a change in transfer density with time after processing.

I) Others In addition to the layer having a neutralizing function, a layer having an auxiliary function may have a back layer, a protective layer, a filter dye layer and the like. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used for preventing adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are overlapped. The sensitivity of the photosensitive layer can be adjusted by adding a dye to the cover sheet. The filter dye may be added directly to the support of the cover sheet or to a layer having a neutralizing function, further to the back layer, the protective layer, the capture mordant layer, or a single layer may be provided. .

II. Alkali processing composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is disposed on the back of the support or on the side opposite to the processing solution of the photosensitive layer to form a pair with the light shielding layer. Thus, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the contained components. For this purpose, the composition contains an alkali, a thickener, a light-blocking agent, a developer, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developer. Etc. A light-shielding agent is always contained in the composition for light-shielding.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes a hydroxide of an alkali metal (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickener is used in order to spread the treatment liquid uniformly.
Also, it is necessary to maintain the close contact between the photosensitive layer and the cover sheet. For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used. As the light-shielding agent, any dye or pigment can be used as long as the light-shielding agent does not diffuse to the dye image-receiving layer to produce stain, or a combination thereof. A typical example is carbon black.

As the preferable developing agent, any one can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially generate stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and the like.

Either a photosensitive sheet, a cover sheet or an alkali treatment composition, a development accelerator described in JP-A-62-215272, pp. 72-91, a hardener described on pages 146-155, a hardener described in pages 201-210. Surfactant, 210
Fluorine-containing compounds described on pages 223 to 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 23
It may contain a polymer latex described on pages 0 to 239, a matting agent described on page 240, and the like. Also, Japanese Patent Laid-Open No. 6-2
73907, JP-A-7-134386, JP-A-7-134386
No. 175193 and JP-A-7-287372.
A graded amine latex can be included.

Further, these alkaline liquid compositions have a developed thickness (amount of the processing liquid per m ² after transferring the processing liquid) of 20 μm to ² μm.
It is desirable that the image is spread on the photosensitive element at a thickness of 00 μm. The processing temperature for processing a photosensitive material is preferably from 0 to 50 ° C, more preferably from 0 to 40 ° C.

The details of the heat-developable color light-sensitive material (dye-fixing element) in which the dye image forming compound of the present invention is used, and the exposure / heating method and apparatus to be used are described, for example, in JP-A-7-219180, [0128]. From [01
59].

Next, the unit of the color diffusion transfer photosensitive material is composed of a photosensitive element (specifically, a photosensitive sheet), an image receiving element (specifically, a sheet including an image receiving layer on a support) and an alkaline processing composition. The case of the configuration will be described. It is basically the same as the above, but will be schematically described below. I. Photosensitive Element A) Support The support for the photosensitive element used in the present invention may be any smooth support commonly used in photographic light-sensitive materials, such as paper, cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. Support thickness is 50
To 350 μm, preferably 70 to 210 μm, more preferably 80 to 150 μm. On the back side of the support, if necessary, a curl balance layer or JP-A No.
An oxygen barrier layer described in -78833 can be provided.

B) Light-shielding layer Same as described above. C) Photosensitive layer Same as described above. (1) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the dye image-forming substance which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye is used. And a photosensitive layer comprising at least two of the following combinations. The emulsion and the dye image forming substance may be coated as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-15
No. 267 can be provided to increase the color image density, or a reflective layer can be provided to increase the sensitivity of the photosensitive element. The reflective layer is a layer containing a white pigment and a hydrophilic binder, preferably the white pigment is titanium oxide,
The hydrophilic binder is gelatin. The coating amount of titanium oxide is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.2 g / m ² .
a m ² ~4g / m ^2. An example of the reflection layer is disclosed in
No. 91354. In a preferred layered configuration,
From the exposure side, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged. Arbitrary layers can be provided between the emulsion layer units as needed. In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units.

In the case of using a compound capable of releasing a diffusible dye by silver ions as described in JP-B-55-7576, it is preferable to include a compound that captures silver ions in the intermediate layer. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer, and the like are provided as needed.

II. Image receiving element A) Support In the present invention, a support capable of withstanding the processing temperature is used as the support of the image receiving element. In general,
Paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate,
Synthesis of polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetyl cellulose) or those containing pigments such as titanium oxide in their films, and film-processed synthetic paper made of polypropylene, etc., and synthesis of polyethylene, etc. Mixed paper made from resin pulp and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, a material obtained by kneading carbon black into polyethylene inside the paper may be contained in a form sandwiched between the papers to provide a light-shielding property. In addition, JP-A-62-253159 (29)-
The support described on page (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

B) Release Layer Same as described above. C) Layer having neutralizing function Same as above. D) Image receiving layer Same as described above. E) Others Same as above. III. Alkali treatment composition Same as above.

Next, recording materials other than the silver halide photographic element will be described. The recording material having the support of the present invention, in addition to a silver halide photographic element, an ink jet recording system, a sublimation type thermal transfer recording system, a fusion type thermal transfer recording system,
Recording materials such as an electrophotographic system, a thermal recording system, a pressure-sensitive recording system, and an ink dot recording system are included. this house,
In the present invention, a recording material of an ink jet recording system, a sublimation thermal transfer recording system, a fusion thermal transfer recording system, or an electrophotographic recording system is preferable. Each of these recording materials forms (receives) main information on an image receiving sheet by inkjet or transfer. Therefore, in the present invention, an image receiving sheet (recording sheet) of these recording materials is regarded as a recording material, and the image receiving sheet is regarded as a support.

Examples of the image receiving sheet of the recording material of the ink jet recording system, the sublimation type thermal transfer recording system, the fusion type thermal transfer recording system, and the electrophotographic system include an image receiving sheet made of a non-coated support such as a plain paper. Alternatively, at least a hydrophilic polymer, an inorganic porous material, or the like according to the characteristics of an image forming agent, as an image receiving layer (also referred to as a receiving layer, and in the case of ink, also referred to as an ink absorbing layer) of an ink, a toner, a sublimable dye, or the like. Alternatively, an image receiving sheet comprising a coating support containing a hydrophobic polymer may be used.

As the substrate, synthetic paper, woodfree paper, art paper, coated paper, cellulose fiber paper, or various plastic films or sheets such as polyolefin, polyethylene terephthalate, and polycarbonate can be used. A white opaque film formed by adding a white pigment or a filler to a plastic or a foamed foam sheet can also be used. In addition, a laminate of the above-mentioned substrate can also be used, and typical examples thereof include a laminate of cellulose fiber paper and synthetic paper, a laminate of cellulose fiber paper and plastic film, and a laminate of plastic film and synthetic paper. The thickness of the substrate may be arbitrarily determined, and for example, is generally about 10 to 300 μm. Further, the surface of the substrate is preferably subjected to a primer treatment or a corona discharge treatment as necessary for improving the adhesive strength with the image receiving layer.

The ink jet recording type image receiving sheet will be described. The ink receiving layer provided on the support contains a pigment and a hydrophilic polymer. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples include inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate, and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and in particular, synthetic amorphous silica having a large pore area is preferable.
As the synthetic amorphous silica, both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, and it is particularly preferable to use hydrous silicic acid.

The hydrophilic polymer contained in the ink receiving layer includes polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, polyvinylpyrrolidone, and poly (vinylpyrrolidone). Alkylene oxide, polyalkylene oxide derivative, alginic acid, polyvinyl acetal, sodium polyacrylate, cross-linked polyacrylic acid, polyvinyl methyl ether, polystyrene sulfonic acid, polyacrylamide, aqueous urethane resin, water-soluble acrylic resin, water-soluble epoxy compound, water-soluble Water-soluble polymers such as water-soluble polyesters,
Water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion are exemplified. These aqueous binders can be used alone or in combination of two or more. Among these, particularly polyvinyl alcohol, silanol-modified polyvinyl alcohol has adhesion to the pigment,
It is suitable in terms of the peel resistance of the ink receiving layer.

The ink receiving layer may contain a mordant, a water-proofing agent, a light fastness improving agent, a surfactant, and other additives in addition to the pigment and the aqueous binder. The mordant added to the ink receiving layer is preferably immobilized.
For this purpose, a polymer mordant is preferably used.
For the polymer mordant, see JP-A-48-28325.
No., 54-74430, 54-124726,
Nos. 55-22766, 55-142339, 6
0-23850, 60-23851, 60-2
No. 3852, No. 60-23853, No. 60-5783
No. 6, No. 60-60643, No. 60-118834
No. 60-122940, No. 60-122941
No. 60-122942, No. 60-235134
JP-A-1-161236, U.S. Pat.
484,430, 2,548,564, 3,1
No. 48,061, No. 3,309,690, No. 4,11
5,124, 4,124,386, 4,19
No. 3,800, No. 4,273,853, No. 4,28
No. 2,305, 4,450,224. JP-A-1-161236, 212-2
The image receiving material containing the polymer mordant described on page 15 is particularly preferred. Using the polymer mordant described in the publication,
An image with excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant,
As these waterproofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by mass, more preferably from 3 to 15% by mass, based on the total solid content of the ink receiving layer.
It is preferably 10% by mass. Examples of the light fastness improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

Surfactants include coating aids, release improvers,
It functions as a slipperiness improver or an antistatic agent. The surfactants are described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (eg, fluorinated oil) and a solid fluorinated compound resin (eg, an ethylene tetrafluoride resin).
About the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. (columns 8 to 17), JP-A No. 61-20994, 6
It is described in each gazette of 2-135826. Other additives added to the ink receiving layer include a pigment dispersant,
Examples include a thickener, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, a pH adjuster, a matting agent, and a hardening agent. The ink receiving layer may be a single layer or two layers.

The recording paper and the recording film may be provided with a back coat layer. Examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate,
White inorganic pigments such as magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, styrene plastic pigment, acrylic Organic pigments such as plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin. Examples of the hydrophilic polymer contained in the back coat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxy. Water-soluble polymers such as methylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone; and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

A polymer latex may be added to the constituent layers (including the back layer) of the ink jet recording paper and the recording film. Polymer latex is dimensionally stable,
It is used for the purpose of improving film physical properties such as curling prevention, adhesion prevention and film cracking prevention. Polymer latex is described in JP-A-62-245258 and JP-A-62-1366.
Nos. 48 and 62-11066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, even if a polymer latex having a high glass transition temperature is added to the back layer,
Curling can be prevented.

The image receiving material of the sublimation type thermal transfer recording system and the fusion type thermal transfer recording type will be described. The thermal transfer image-receiving material used in the present invention has a support provided with an image-receiving layer for receiving a dye transferred from a dye-providing material. This image receiving layer accepts a heat transfer dye which is transferred from the heat transfer dye providing material at the time of printing, and a substance which receives the heat transfer dye which has a function of dyeing the heat transfer dye alone. ,
Alternatively, it is preferable that the film is a film having a thickness of about 0.5 to 50 μm, which is contained together with another binder substance. Examples of the polymer which is a typical example of the substance capable of accepting the heat transferable dye include the following resins.

(A) Those having an ester bond: dicarboxylic acid components such as terephthalic acid, isophthalic acid and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group); Polyester resin obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: Polyacrylate resin or polymethacrylate resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
Nos. 63-7971, 63-7972, 63
-7973 and 60-294862. As commercially available products, Byron 290, Byron 200 and Byron 280 manufactured by Toyobo Co., Ltd.
Byron 300, Byron 103, Byron GK-14
0, Byron GK-130, Kao ATR-200
9, ATR-2010 etc. can be used.

(B) Those having a urethane bond Polyurethane resin and the like. (C) Those having an amide bond, such as polyamide resin. (D) Those having a urea bond, such as a urea resin. (E) Those having a sulfone bond, such as polysulfone resin. (F) Those having a saturated carbon bond, such as polystyrene resin.

(G) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers thereof can also be used. In addition, Japanese Patent Laid-Open No. 1-1
The basic compounds and / or mordants described in JP-A-88391 and JP-A-3-83885 can also be used.

The image receiving layer of the thermal transfer image receiving material may have a structure in which a substance capable of accepting a heat transferable dye is dispersed in a water-soluble binder and carried. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a cross-linking reaction with a hardener is preferable. The image receiving layer may be composed of two or more layers. In this case, use a synthetic resin with a low glass transition point for the layer closer to the support, or use a high-boiling organic solvent or a heat solvent to enhance the dyeing properties of the dye. Use a synthetic resin with a higher point, minimize the amount of high-boiling organic solvent or hot solvent used or minimize the amount of sticky surface, adhere to other substances,
It is desirable to adopt a configuration that prevents failures such as retransfer to another substance after transfer and blocking with a thermal transfer dye-providing material. The total thickness of the image receiving layer is 0.5 to 50 μm, particularly 3
A range of from 30 to 30 μm is preferred. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

The thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer depends on the constituent material,
Any one of a cushion layer, a porous layer, and a dye diffusion preventing layer, or a layer having two or more of these functions, and in some cases also serves as an adhesive. The dye diffusion preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but is preferably a water-soluble binder, and examples thereof include the water-soluble binder described above as the binder for the image receiving layer, particularly gelatin. The porous layer is a layer that serves to prevent the heat applied during thermal transfer from diffusing from the image receiving layer to the support, and to effectively use the applied heat.

For the image receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer, etc. constituting the thermal transfer image receiving material, silica,
Fine powders of clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina and the like may be contained. Whatever the support used for the thermal transfer image-receiving material can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, dent after transfer, etc. Anything can be used. For example, synthetic paper (polyolefin-based, polystyrene-based synthetic paper), high-quality paper, art paper, coated paper, cast-coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper backing, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), and various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, and polycarbonate. A film or sheet treated to give white reflectivity to the plastic or a laminate of any combination of the above can also be used.

The thermal transfer image-receiving material may use a fluorescent whitening agent. For example, K. Veenkataraman ed., “The Chem
istry of Synthetic Dyes ", Vol. V, Chapter 8, JP-A-61
Compounds described in -143752 and the like can be mentioned. More specifically, a stilbene compound,
Coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyril-based compounds, 2,5-dibenzoxazole-thiophene-based compounds, and the like can be given. The fluorescent whitening agent can be used in combination with the anti-fading agent. In the present invention, in order to improve the releasability between the thermal transfer dye-providing material and the thermal transfer image-receiving material, the outermost layer which contacts the surface of the dye-providing material and / or the image-receiving material, particularly preferably the surface where both materials are in contact with each other It is preferred that a release agent be contained in the resin. Solid or wax-like substances such as polyethylene wax, amide wax, Teflon (registered trademark) powder and the like: surfactants such as fluorine-based and phosphate-based agents: paraffin-based, silicone-based, and fluorine-based oils For example, any of conventionally known release agents can be used, and silicone oil is particularly preferable. As silicone oil, carboxy-modified other than unmodified,
A modified silicone oil such as amino-modified or epoxy-modified can be used. For example, see “Modified Silicone Oil” published by Shin-Etsu Silicone Co., Ltd.
Examples include various modified silicone oils described on page 18B. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with isocyanate) is emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, KF-100T, manufactured by Shin-Etsu Silicone Co., Ltd.)
Is valid.

The layer constituting the thermal transfer image-receiving material used in the present invention may be cured by a hardener. In the case of curing an organic solvent-based polymer, JP-A-61-1999
Hardening agents described in JP-A Nos. 97 and 58-215398 can be used. It is particularly preferable to use an isocyanate-based hardening agent for the polyester resin. US Pat. No. 4,678,739 No. 4 discloses curing of a water-soluble polymer.
Column 1, JP-A-59-116655, JP-A-62-2452
Hardening agents described in Nos. 61 and 61-18942 are suitable for use. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-62-23415).
No. 7, etc.).

An anti-fading agent may be used in the thermal transfer image-receiving material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Unexamined Patent Publication No.
The compound described in -159644 is also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681), and benzophenone-based compounds (Japanese Unexamined Patent Publication No. 2784) and JP-A Nos. 54-48535 and 62-136641.
And the compounds described in JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. As the metal complex, US Pat. Nos. 4,241,155 and 4,245,018, No. 3
Columns 36 to 36; columns 4 to 8 of JP-A-4,254,195; JP-A-62-174741 and JP-A-61-88256 (2).
7) to (29), JP-A-1-75568, JP-A-6
There are compounds described in 3-199248 and the like.
Examples of useful anti-fading agents are described in JP-A-62-215272, pages (125) to (137). The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

In the constituent layers of the thermal transfer image-receiving material, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, accelerating development and the like. For example,
Saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene) Non-ionic surfactants such as oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars: alkyl carboxylate, alkyl sulfone Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, NA Carboxy groups such as ru-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyethylenealkylphenyl ethers, and polyoxyethylene alkylphosphates, sulfo groups, phospho groups, sulfate groups, phosphate groups, etc. Anionic surfactant containing an acidic group: amino acids,
Amphoteric surfactants such as aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, alkylbetaines and amine oxides: alkylamine salts,
Use of aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and cationic surfactants such as aliphatic or heterocyclic-containing phosphonium or sulfonium salts. it can. Specific examples thereof are described in JP-A Nos. 62-173463 and 62-183457. Also, a substance that can accept a heat transfer dye,
When dispersing a releasing agent, an anti-fading agent, an ultraviolet absorber, a fluorescent whitening agent and other hydrophobic compounds in a water-soluble binder, it is preferable to use a surfactant as a dispersing aid.
For this purpose, in addition to the above surfactants, surfactants described in JP-A-59-157636, pp. 37-38, are particularly preferably used.

The constituent layers of the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving the slipperiness, preventing static charge, and improving the releasability. Representative examples of organic fluoro compounds are described in JP-B-57-9053, columns 8-17,
Hydrophobic surfactants such as fluorine-based surfactants described in JP-A Nos. 1-20944 and 62-135826, oily fluorine-containing compounds such as fluorine oil, and solid fluorine-containing compounds such as tetrafluoroethylene resin Compounds. A matting agent can be used for the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of the matting agent include compounds described in JP-A-61-88256 (page 29) such as silicon dioxide, polyolefin and polymethacrylate, and JP-A 63-2 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
Nos. 74944 and 63-274952.

The image receiving sheet for electrophotography will be described.
In the electrophotographic system, a toner image receiving layer made of a thermoplastic polymer may be provided in order to obtain an image having the same image quality as photographic printing paper. In addition to the image receiving layer, depending on the purpose, a surface protective layer, an intermediate layer, an undercoat layer, a cushion layer, a charge control (prevention) layer, a reflection layer, a color adjustment layer, a storage stability improving layer, an adhesion prevention layer, an anti-curl layer, and a smooth layer. A layer or the like can be provided. Each layer may be composed of two or more layers. Further, the electrophotographic image-receiving sheet may have a back layer on the side opposite to the image-receiving layer with the support interposed therebetween. In the case of a double-sided output image-receiving sheet that forms an image on the back surface, the back layer is also preferably white.

The image receiving layer receives at least a toner for forming an image from the developing drum or the intermediate transfer member by (static) electricity or pressure in the transfer step, and is fixed by heat, pressure or the like in the fixing step. Consisting of an image-receiving substance that can be converted to As the receptive substance, a thermoplastic resin, a water-soluble resin, a pigment having a small particle diameter, or the like is used. The thickness of the image receiving layer is preferably at least 1/2 of the particle diameter of the toner, and more preferably 1 to 3 times the particle diameter of the toner.

The physical properties of the image receiving layer preferably satisfy at least one of the following items, more preferably a plurality of items, and most preferably all of the following items. Tg (glass transition temperature) of the image receiving layer is 30 ° C. or more,
Tg of the toner is preferably + 20 ° C. or less. T1 of the image receiving layer
/ 2 (1/2 method softening point) is preferably 60 to 150 ° C.
More preferably, it is in the range of 80 to 120 ° C. The Tfb (outflow starting temperature) of the image receiving layer is preferably from 40 ° C. to 100 ° C. More preferably, the Tfb of the image receiving layer is equal to or less than the Tfb of the toner. The viscosity of the image receiving layer is 1 × 10 ⁵ mPa
It is preferable that the temperature at which s is 40 ° C. or higher and lower than that of the toner. As the image receiving layer, Japanese Patent No. 2788
No. 358, JP-A-7-248637, JP-A-8-3050
Those satisfying the physical properties and the like disclosed in JP-A Nos. 67 and 10-239889 and the like are preferable.

The above physical properties can be measured by a differential scanning calorimeter (DSC). Also,~
Physical properties of, for example, Shimadzu flow tester CFT-
500. The physical properties can be measured using a rotary rheometer (for example, a dynamic analyzer RADII manufactured by Rheometrics).

As the thermoplastic resin to be used, any resin can be used as long as it can be deformed at the fixing temperature and the temperature and can accept the toner. Preferably, a resin of the same system as the resin used as the binder of the toner is preferable. In many cases, a polyester resin is used for the toner. In this case, it is preferable to use the polyester resin also as the thermoplastic resin used for the electrophotographic image-receiving sheet of the present invention. Further, a styrene-acrylate copolymer,
Styrene-methacrylate copolymers and the like are preferably used. Hereinafter, a resin preferably used will be described.

(A) Those having an ester bond. Terephthalic acid, isophthalic acid, maleic acid, fumaric acid,
Dicarboxylic acid components such as phthalic acid, adipic acid, sebacic acid, azelaic acid, abietic acid, succinic acid, trimellitic acid, and pyromellitic acid (these dicarboxylic acid components are substituted with sulfonic acid groups, carboxyl groups, etc. And ethylene glycol, diethylene glycol,
Propylene glycol, bisphenol A, a diether derivative of bisphenol A (for example, bisphenol A
Alcohol components such as ethylene oxide 2 adducts and bisphenol A propylene oxide 2 adducts), bisphenol S, 2-ethylcyclohexyl dimethanol, neopentyl glycol, cyclohexyl dimethanol, glycerin, and other alcohol components (these alcohol components include hydroxyl groups and the like) May be substituted), a polyester resin obtained by condensation with polymethyl methacrylate,
Polybutyl methacrylate, polymethyl acrylate,
Polyacrylate resin or polymethacrylate resin such as polybutyl acrylate, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, styrene-methacrylate copolymer resin,
Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395, JP-A-63-7971, and JP-A-63-7971.
No. 7972, No. 63-7973, No. 60-29486
No. 2 can be mentioned. In addition, as commercial products, Toyobo Byron 290, Byron 200,
Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, Tufton U-5, Tufton NE382, ATR-200 manufactured by Kao
9, ATR-2010, Unitika ELIETEL UE3
500, UE3210, XA-8153, Nippon Synthetic Chemical's Polyester TP-220, R-188 and the like can be used.

(B) Polyurethane resin and the like. (C) Polyamide resin, urea resin and the like. (D) Polysulfone resin and the like. (E) polyvinyl chloride resin, polyvinylidene chloride resin,
Vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like. (F) Polyol resins such as polyvinyl butyral, and cellulose resins such as ethyl cellulose resin and cellulose acetate resin. (G) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like. (H) Polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene with other vinyl monomers, and acrylic resins. In addition to the above synthetic resins, mixtures or copolymers thereof can also be used.

As the thermoplastic resin used for the toner image receiving layer, those which can satisfy the above-described physical properties of the image receiving layer when the image receiving layer is formed are preferable. More preferably, a resin alone that satisfies the above-mentioned preferable physical properties for the image receiving layer is used. It is also preferable to use two or more resins having different physical properties as described above.

It is also preferable to use, as the thermoplastic resin used in the toner image receiving layer, a mixture of resins having the same composition and different average molecular weights. Further, the thermoplastic resin used for the toner image receiving layer includes Japanese Patent Publication No. 5-127.
Nos. 413, 8-194394, 8-334915
And those satisfying the physical properties disclosed in JP-A Nos. 8-334916, 9-171265, and 10-221877 are preferably used.

In these resins, if necessary, a modified or unmodified silicone oil, a releasing agent such as a fluorine-type additive,
Pigments such as titanium oxide, zinc oxide, calcium carbonate, and finely divided silica, ultraviolet absorbers, antioxidants, and the like may be added. The thickness of the image receiving layer is suitably from 1 to 50 μm,
μm is preferred.

In these image receiving layers, dye fixing agents, pigment dispersants, thickeners, flow improvers, defoamers,
Antifoaming agents, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, optical brighteners, ultraviolet absorbers, light stabilizers, antioxidants, antibacterial agents, waterproofing agents, and wet paper strength An agent, a dry paper strength enhancer and the like can also be appropriately compounded.

The method for coating the image-receiving layer on the substrate is such that various apparatuses such as a blade coater, a roll coater, an air knife coater, a bar coater, a rod blade coater, a short dwell coater and a size press are used on-machine or off-machine. be able to. Further, after coating or dipping, finishing may be performed using a calendar such as a machine calendar, a TG calendar, a super calendar, and a soft calendar.

In the present invention, the place where a specific security pattern is formed may be any place where visual judgment can be made on a recording material containing an obtained image. For example, the back surface of the support, the surface of the support on the recording layer side, and any layer provided on the support may be mentioned. The pattern may be formed on the entire surface of a specific layer or a specific surface, or may be formed partially. In the present invention,
In the production process, it is preferable that the security pattern is directly formed on the support, and more preferably, the surface of the support on the recording layer side. In the silver halide photographic element, it is preferable to coat or form a layer necessary for forming the silver halide photographic element on the support. In the diffusion transfer type silver halide photographic element which is the most preferred embodiment, the one in which a security pattern is formed in the image receiving layer is preferable, and the surface of the support in the image receiving layer on the recording layer side is particularly preferable. . By forming a security pattern on the recording layer side on the support, falsification becomes difficult.

Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited to these examples.

[0123]

Example 1 An ink containing the dyes shown in Table 1 was coated on the side on which an image receiving layer was provided on a 150 μm paper support coated with 20 μm polyethylene on both sides and coated with gelatin undercoat. As a security pattern, letters of "security pattern" (Mincho style of 14 points) were printed by letterpress printing. In addition, since all dyes are oil-soluble,
Oil-soluble inks (Macromelt JP119 (Henkel Hakusui Co., Ltd.), Ezrol R972 (Nippon Aerosil Co., Ltd.), and ink solvents (toluene, butanol, isopropanol, etc.) to which 1% by mass of a dye was added) were used. Using each of the above-mentioned supports, coating was carried out in a layer constitution as shown below to produce image receiving elements (101) to (110).

[0124] Back layer side: (a) the light-shielding layer containing carbon black 2.8 g / m ² and gelatin 4.8 g / m ^2. (B) 4.1 g / m ^{2 of} titanium dioxide and gelatin 1.
White layer containing 0 g / m ² . (C) A protective layer containing 0.5 g / m ² of gelatin. Image receiving layer side: (1) Acrylic acid / butyl acrylate copolymer (molar ratio 8: 2, average molecular weight 50,000) 4.0 g / m ² ,
Polyvinyl alcohol (polymerization degree 500, saponification rate 88%)
And a neutralizing layer containing 0.04 g / m ² of the following hardener (F).

[0125]

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(2) Diacetyl cellulose (degree of acetylation: 5
(1.3%) 3.5 g / m ² , styrene / maleic anhydride copolymer (molar ratio 1: 1, average molecular weight 10,000)
39 g / m ² , 0.07 g / m ^{2 of} the following compound (B), and 0.09 of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.)
Timing layer containing 8 g / m ² .

[0127]

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(3) Polymer latex (styrene / butyl acrylate / N-methylol acrylamide emulsion-polymerized at a mass ratio of 49.7 / 42.3 / 8)
1.32 g / m ² and polymer latex (emulsion polymerization of methyl methacrylate / acrylic acid / N-methylolacrylamide at a mass ratio of 93/3/4) 1.3
2 g / m ^2, the following compound (C) 0.162g / m ^2, and the following coating aids (D) timing layer containing 0.0148g / m ^2.

[0129]

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(4) The following mordant (E): 3.7 g / m ² ,
0.21 g / m ^{2 of} formaldehyde, 0.10 g / m ^{2 of} the hardener (F), 0.01 of the coating aid (D)
mordant layer containing g / m ² and gelatin 2.8 g / m ^2.

[0131]

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(5) Acrylic acid / butyl methacrylate copolymer (molar ratio: 85:15, average molecular weight: 100,00
0) 0.06 g / m ² and the following compound (H) 0.00
Release layer containing 3 g / m ² .

[0133]

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On the other hand, a photosensitive element was prepared as follows.
A photosensitive element (101) was prepared by coating on a 100 μm transparent polyethylene terephthalate film support in the following manner. Back layer side: (a) the light-shielding layer containing carbon black 6.0 g / m ² and gelatin 2.0 g / m ^2. (B) A protective layer containing 0.5 g / m ² of gelatin. Emulsion layer side: (1) Titanium dioxide 3.7 g / m ² and gelatin 0.
Layer containing 5 g / m ² . (2) The following cyan dye releasing redox compound 0.46
g / m ² , 0.07 g of tricyclohexyl phosphate
/ M ^2, dispersion aids following (A) 0.05g / m ^2, dispersion aids below (B) 0.06g / m ^2, and gelatin 0.
Color material layer containing 5 g / m ² .

[0135]

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(3) Gelatin 0.5 g / m^TwoContains
layer. (4) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size
0.65 μm, 0.11 g / m 2 in silver^Two), Gelatin
0.3g / m^Two, The following nucleating agent 0.003 g / m ^TwoAnd
And 2-sulfo-5-n-pentadecylhydroquinone.
Sodium salt 0.02 g / m^Two-Sensitive emulsion containing
layer.

[0137]

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(5) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.23 g /
m ² ), gelatin 0.4 g / m ² , 2-sulfo-5-n-
Pentadecyl hydroquinone sodium salt 0.04g
/ M ² and the same nucleating agent as layer (4) 0.005 mg /
a red-sensitive emulsion layer containing m ² . (6) 2,5-di-t-pentadecylhydroquinone 0.61 g / m ² , the following polymer dispersant 0.33 g /
an anti-color mixing layer containing m ² and gelatin 0.3 g / m ² .

[0139]

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(7) An intermediate layer containing 0.2 g / m ² of gelatin. (8) The following magenta dye-releasing redox compound is used in 0.1.
46 g / m ² , the same dispersing aid (A) as layer (2) 0.04
g / m ^2, a dispersion aid (B) 0.07g / m ^2, and the color material layer containing gelatin 0.7 g / m ^2.

[0141]

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(9) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, 0.11 g / silver amount)
m ² ), gelatin 0.2 g / m ² , the same nucleating agent as in layer (4) 0.005 mg / m ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.02 g / m 2
A green-sensitive emulsion layer containing ² . (10) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.26 g / m ² ), gelatin 0.6 g / m ² , same nucleation as layer (4) Agent 0.004
A green-sensitive emulsion layer containing mg / m ² and 0.04 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. (11) 2,5-di-t-pentadecylhydroquinone 0.91 g / m ² , the following polymer dispersant 0.29 g /
an anti-color mixing layer containing m ² and 0.4 g / m ² of gelatin.

[0143]

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(12) The same layer as in (7). (13) A yellow dye-releasing redox compound having the following structure
0.53g / m^Two, Tricyclohexyl phosphate
0.16 g / m^TwoAnd the same dispersing aid (A) as in layer (2).
05g / m^Two, Dispersing aid (B) 0.03 g / m^TwoAnd Ze
Latin 0.5g / m ^TwoA coloring material layer.

[0145]

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(14) Blue-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.15 g /
m ² ), gelatin 0.2 g / m ² , the same nucleating agent as layer (4) 0.006 mg / m ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.01 g / m 2
Blue-sensitive emulsion layer containing ² . (15) blue-sensitive in latent type direct positive silver bromide emulsion (average grain size 0.98 .mu.m, 0.23 g / m ² in an amount of silver), gelatin 0.3 g / m ^2, the same nucleating and the layer (4) Agent 0.005
A blue-sensitive emulsion layer containing mg / m ² and 0.01 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. (16) The following UV absorbers (A) and (B)
Ultraviolet absorbing layer containing 2 g / m ² and gelatin 0.5 g / m ^2.

[0147]

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(17) Matting agent (PMMA) 0.2 g /
m ^2, a hardener described below (A) 0.11g / m ^2, the following hardener (B) 0.03g / m ² and gelatin 0.4 g / m ²
A protective layer containing.

[0149]

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Further, an alkali treatment composition was prepared in which 1 g of a treatment solution having the following composition was filled in an aluminum foil pod laminated with vinyl chloride under a nitrogen atmosphere.

Hydroxyethyl cellulose 42 g Zinc nitrate / 6H ₂ O 0.9 g 5-methylbenzotriazole 5.4 g Benzyl alcohol 3.4 ml Titanium dioxide 1.2 g Aluminum nitrate / 9H ₂ O 15 g Potassium sulfite 1.0 g 1-phenyl-4 -Hydroxy-4-hydroxymethyl-3-pyrazolidone 13.0 g Potassium hydroxide 63 g Water 854 ml

Next, after the photosensitive element (101) was subjected to imagewise exposure, the image receiving element (101) was overlaid, and an alkali treatment composition was developed between the two elements to a thickness of 60 μm. The processing was performed at 25 ° C., and the photosensitive element and the image receiving element were separated 90 seconds after the processing.

The image-receiving elements (102) to (110) were also exposed to light and processed with an alkali treatment composition using the above-described photosensitive element (101).

After an image was formed on each image receiving element as described above, the bleeding and fastness of the security pattern were evaluated by the following compulsory test. 1) Stored at 60 ° C (without humidity control) for 14 days 2) Stored at 60 ° C and 80% RH for 14 days 3) Sunlight exposure for 7 days
The evaluation was performed by applying 4 nm ultraviolet light and visually observing the emission of fluorescence from the security pattern. The following three-level evaluation was performed for the evaluation level.

Evaluation level of bleeding and fastness ：: Same as before compulsory test △: Inferior to before compulsory test ×: Remarkably inferior to before compulsory test

Table 1 summarizes the obtained results. As a result, compared with other dyes, the oil-soluble dye of the present invention showed good results in both bleeding and fastness even under high temperature, high temperature and high humidity, and exposure to sunlight.

[0157]

[Table 1]

[0158]

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Example 2 In producing the photosensitive material (samples 401 to 405) described in Example 4 of JP-A-11-282108, the support (polyethylene resin laminated paper) used in Example 4 was prepared. On the emulsion layer coating surface side, the above-described oil-soluble fluorescent dyes 2, 18 and 2 were prepared in the same manner as in Example 1 of the present invention.
7, 30, 32, 33, and 37, respectively, except that letterpress printing was performed using ink containing 35, 37, 32, 33, and 37 inks.
Seed x photographic layer 5 same as samples 401 to 405 of Example 4
), A new sample was prepared.
After exposing and developing by the method described in Example 4 of the above item, bleeding and fastness were evaluated by the method described in Example 1 of the present invention. As a result, all samples obtained good results in both bleeding and fastness.

Example 3 A sheet provided with a colorant receiving layer for ink jet recording was produced by the following method. (1) The composition of the coating solution for forming the porous layer (colorant receiving layer before cross-linking) (the values in parts by weight [parts by weight] indicating the blending amounts of all the following coating solutions all represent solid contents or nonvolatile contents. Anhydrous silica fine particles (average primary particle diameter: 7 nm, surface silanol groups: 2-3 particles / nm ² , refractive index: 1.45, trade name: Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.))
10 parts by mass polyvinyl alcohol (degree of saponification: 81.8%, degree of polymerization: 4000, trade name: PVA440 (Kuraray Co., Ltd.)
3.3) parts by mass Deionized water 136.0 parts by mass

The silica fine particles were added to ion-exchanged water (73.3 parts by mass), and the mixture was mixed with a high-speed rotating wet-type colloid mill (CLEARMIX (M Technic Co., Ltd.)
)) And dispersed at 10,000 rpm for 20 minutes, and then an aqueous solution of polyvinyl alcohol (dissolved in the remaining 62.7 parts by mass of ion-exchanged water) was added.
Further, dispersion was performed under the same conditions as above to obtain a coating solution for forming a porous layer. The above coating solution is applied to the surface of the 210 μm-thick photographic printing paper laminated paper at an application amount of 200 ml / m ² using an extrusion die coater,
It was dried at 80 ° C. (wind speed 3 m / sec) for 3 minutes using a hot air dryer. The coating layer exhibited a constant rate of drying during this period. Immediately after the drying for 3 minutes, the coating layer was immersed for 1 second in a borax-containing solution of the following (2) to adhere 20 ml / m ^2, and then dried at 80 ° C. for 10 minutes. Thus, an ink receiving layer having a dry film thickness of 30 μm was formed.

(2) Borax-containing solution Borax 1 part by mass Surfactant 0.2 part by mass (trade name: F
-144D, manufactured by Dainippon Ink and Chemicals, Inc.) 1.4 parts by mass of diallyldimethylammonium chloride / sulfur dioxide copolymer 97.4 parts by mass of ion-exchanged water

In the same manner as in Example 1 of the present invention, the ink-jet recording sheet thus obtained contains the above-described oil-soluble fluorescent dyes 1, 3, 4, 7, 13, 15, and 25, respectively. Seven new samples were prepared in exactly the same manner, except that letterpress printing was performed using black ink. An image from a computer file was printed by an inkjet printer (trade name: PM-770C, manufactured by Seiko Epson Corporation). The recorded image was evaluated for bleeding and fastness by the method described in Example 1 of the present invention. As a result, all samples obtained good results in both bleeding and fastness.

Example 4 11.6 parts by mass of a polyester resin (manufactured by Kao Corporation, trade name: Tufton U-5) and titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.) were placed on the upper surface of a double-sided polyethylene laminated paper for photographic printing paper having a total thickness of 190 μm. , Product name: Taipaek A220) 1.5
An image receiving layer composition comprising 4 parts by mass and 30 parts by mass of a solvent (MEK) has a mass of about 13.2 g / m 2 after being dried with a Mayer bar.
^Then , an image receiving sheet was prepared. Then, in the same manner as in Example 1 of the present invention described above, except that letterpress printing was performed using inks containing the above-described exemplary oil-soluble fluorescent dyes 1, 3, 4, 7, 13, 15, and 25, respectively,
Seven new samples were made.

A color laser printer Color Laser Wi manufactured by Fuji Xerox Co., Ltd.
nd 3320PS and an image from a computer file was printed. The recorded image was evaluated for bleeding and fastness by the method described in Example 1 of the present invention. As a result, all samples obtained good results in both bleeding and fastness.

[0166]

The recording material, the silver halide photographic material and the recording material support using the oil-soluble fluorescent dye of the present invention do not require any special equipment for their verification, and have the esthetic and artistic quality of the image. And an inexpensive and simple authentication identification method and a security pattern in the authentication can be realized without impairing the image quality and without affecting the color balance of the photographic image. In addition, the security pattern in the present invention does not bleed even when placed under alkaline conditions or high-temperature and high-humidity conditions, thereby providing a highly reliable security ink jet recording image receiving paper, sublimation type thermal recording image receiving paper, Recording materials, including electrophotographic recording papers, especially silver halide photographic elements, and authentication and identification methods can be established. Further, the security pattern according to the present invention is excellent in robustness. That is, the present invention has an excellent operation and effect that authentication and identification can be reliably performed even after being subjected to severe conditions such as an alkaline processing solution for development processing and high heat and high humidity.

Claims (7)

[Claims] 1. A silver halide photographic element, wherein a security pattern is formed beforehand by an oil-soluble fluorescent dye before exposure. 2. A silver halide photographic element according to claim 1, wherein said oil-soluble fluorescent dye is a dye having at least one diffusion-resistant group. 3. The silver halide photographic element according to claim 2, wherein the number of carbon atoms contained in the diffusion-resistant group in the oil-soluble fluorescent dye is at least 8 or more. 4. The silver halide photographic element according to claim 1, wherein the silver halide photographic element is a diffusion transfer type silver halide photographic element, and the security pattern is formed in the image receiving layer. 5. A recording material having a support, wherein a security pattern is previously formed by an oil-soluble fluorescent dye having at least one diffusion-resistant group before recording is applied. 6. A recording material support, wherein a security pattern is formed by an oil-soluble fluorescent dye having at least one diffusion-resistant group. 7. An identification method characterized by performing authentication identification based on the presence or absence of a security pattern comprising an oil-soluble fluorescent dye having at least one diffusion-resistant group.