JPH049054A - Laminating material, image receiving element, and image forming method - Google Patents

Abstract

PURPOSE:To obtain an infrared image high in density and low in fogging by transferring a dye image on the surface of an image receiving material and laminating the laminating material containing a specified metal source. CONSTITUTION:The laminating material to be laminated on the image receiving layer formed on a support and having the dye image transferred contains at least one of the compounds represented by formula I or II in which M is a transition metal ion; each of X1 - X3 is a ligand coordinated by the metal ion and forming a complex; R1 is alkyl or aryl; (l) is 1, 2, or 3; (m) is 0, 1, or 2; (n) is 0 or 1; p is 1 or 2; and each of R2 - R5 is alkyl, cyano, or the like, thus permitting the laminating material to be used in combination of photographic elements capable of forming an image high in density in a short time and low in fogging and reading by using wavelengths longer than 750nm.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a laminate material, an image receiving element using the laminate material, and an image forming method, and more particularly, to a photograph suitable for recording information readable with light with a wavelength longer than 750 nm. The present invention relates to an image receiving element, a laminate material, and an image forming method in combination with the element. [Background of the Invention] In recent years, in information recording materials such as various rD cards,
Developments are underway to provide character information, signal information such as a bar code, etc. to the same recording material along with color image information. Recording materials on which character information or signal information is recorded are often read mechanically using light with a wavelength longer than 750 nm, such as from semiconductor lasers or light emitting diodes, in order to speed up information determination and prevent misidentification. be. Therefore, in order to obtain a dye image using a recording material, an image forming method using dry heat treatment is known in which the dye is transferred using heat to form an image. There are roughly two types of these methods; one is a technique that uses a diffusion transfer type heat-developable photosensitive material, and the other is a technique that uses a heat-sensitive transfer material. Diffusion transfer heat-developable light-sensitive materials basically consist of a light-sensitive element and an image-receiving element. ) and various additives are added. The image-receiving element forms a dye image on the image-receiving layer by transferring a transferable dye that is released or formed as a function of thermal development from the dye-providing substance contained in the photosensitive element, and forms a dye image on the image-receiving layer. Accordingly, this image-receiving element has a support. On the other hand, a heat-sensitive transfer material basically consists of a heat-sensitive element and an image-receiving element. An image-receiving layer capable of forming a dye image by thermal transfer of the heat-transferable dye is coated on a support. The relationship between the thermal transfer element and the image receiving element in the thermal transfer material by these thermal diffusion transfer methods is at least a stacking relationship at the time of thermal transfer, and there are cases where they are configured in advance as an integral type and a stacking relationship at the time of thermal transfer. There are cases where the configuration is
Furthermore, there are two types: one in which both element forces are separated by <ff111 after thermal transfer, and one in integrated type, which can be used depending on the purpose. The present inventors have developed a technology that enables mechanical reading using light with a wavelength longer than 750 nm from semiconductor lasers, light emitting diodes, etc. in the technology for obtaining color images on image receiving elements using thermal diffusion as described above. proposed a heat-developable color photosensitive material containing a dye-donating substance that forms or releases an infrared dye (Japanese Patent Application No. 118,476/1982).
There was a need to improve the stability of the infrared dye that is formed against heat and light. In addition, the coupler represented by the formula (I) represents a group of atoms forming a nitrogen-containing heterocycle. R1 represents a hydrogen atom, a halogen atom, or a monovalent organic group. n represents an integer of 1 to 4, and when n is an integer of 2 to 4, two or more R1s may be the same or different. Y represents a hydrogen atom or a group capable of being eliminated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] After imagewise exposure or at the same time, heat-developable color photosensitive material containing a heat-developable color photosensitive material is heat-developed in close contact with an image-receiving member, and all or part of the dye formed from the coupler is transferred, and at the same time during or after transfer. has proposed an image forming method characterized by metal-chelating a part or all of the dye to form a metal-chelated dye image in an image-receiving member (Japanese Patent Application No. 1-189668, 1). -25607
9-No., 1-217'106). In this method, a metal source is added to the light-sensitive material or image receiving member as a source of metal ions in order to generate a metal chito/-1- dye, so it is possible to develop under high temperature, short time development and processing conditions. , it was found that the fog increased by 1]. Therefore, in view of the fact that in photographic elements such as those described above, adding a metal source to the photosensitive material or image receiving member increases fog, the inventors of the present invention have proposed that infrared dyes be added to the dye image formed on the image receiving member. 1. Fog does not increase in response to heat, etc. (As a result of various studies to obtain clear images, we found that 2. After forming a dye image on the image receiving member, by contacting it with a metal source) It was found that the increase in fog was unexpectedly suppressed in the obtained dye images.The present invention was made based on this knowledge. A first object of the present invention is to provide an image-receiving element, a laminate material, and an image-forming method that can be used in combination with a photographic element suitable for recording information readable with light with a wavelength longer than 750 nm. can obtain high concentration in a short time,
It is an object of the present invention to provide an image receiving element, a laminate material, and an image forming method that can be used in combination with a photographic element that can be read with light having a wavelength longer than 750 nm and has low fog. [Structure of the Invention] The notation purpose of the present invention is as follows: (1) In an image-receiving material having an image-receiving layer on which a dye image is transferred onto a support, the laminate material laminated on the surface of the image-receiving layer has the general formula C1) or - A laminate material characterized by containing at least one compound represented by the format [■]. 2) A laminate containing at least one compound represented by -format CI) or -format [■] on the surface of the image-receiving layer of an image-receiving material having an image-receiving layer on which a dye image has been transferred onto a support. Image receiving element consisting of laminated materials. 3) In an image-receiving material having an image-receiving layer with a dye image transferred to a support, a laminate material Δ material containing a compound that causes a complex formation reaction with some or all of the dyes contained in the image-receiving layer is laminated on the surface of the image-receiving layer. This is achieved by an image forming method characterized by: -Format (1) %Formula%) [In the formula, M represents a transition metal ion, Xl, X2X3 represent a coordination compound that can coordinately bond to a transition metal ion to form a complex, and R4 represents an alkyl or aryl group. ρ represents 1, 2 or 3, m represents 1, 2 or 0
, n represents 1 or 0, and p does not represent 1 or 2. ] General format 11) % formula %) [In the formula, M, X+, X2, X3. I! , m, n, p are the same general formula (R2R:l R4R, 5 is each alkyl group, cyano group, heterocyclic residue, or hydrogen atom (each is the same) The present invention will be described in more detail below. As used herein, the term "laminated" refers to laminating a laminate material with an image-receiving material, Preferably, the method includes adhering a laminate material having an adhesive layer to an image-receiving material. More preferably, the method includes adhering or welding a laminate material having a hot-melt layer and a heat-welding layer to an image-receiving material. The image forming method of the present invention includes laminating a support on the image receiving surface of an image receiving material having an image receiving layer to which a dye image has been transferred from a photographic element, and the laminating material to be laminated is generally In an image format method containing at least one of the compounds of formula [T) or -format (II), in particular a small amount (both photosensitive silver halide, reducing agent, binder and -format ()) is present on the support. After imagewise exposure of a heat-developable color photosensitive material having a photosensitive layer containing a coupler represented by The laminate material is laminated on the image-receiving layer surface of an image-receiving member having a layer.General formula (III) [-In formula (I), represents a group. R1 represents a hydrogen atom, a halogen atom, or a monovalent organic group. n represents an integer of 1 to 4, but when n is an integer of 2 to 4, 2
The above R1s may be the same or different. Y represents a hydrogen atom or a group capable of being eliminated by reaction with an oxidized product of an aromatic primary amine color developing agent (active site leaving group). ] General formula [T) or -ritual CI [) used in the present invention
In the compound represented by, M represents a transition metal ion, preferably a divalent transition metal ion, such as cobalt (■), nickel (ff), copper (■), zinc (■).
, iron(II), etc. Particularly preferably, nickel (I
I) and copper (U). X1, X2. Each of X3 represents a coordination compound (which may be the same or different) that can coordinate with a transition metal ion to form a complex. (5) It can be selected from the coordination compounds described in Nankodo. p represents 1, 2 or 3, m represents 1, 2 or 0, X
3 represents 1 or 0, but these are -ritual CI) and (I
Depending on whether the complex represented by I) is tetradentate or hexadentate,
and/or X1, X2. It is determined by the number of ligands of X3. p represents 1 or 2, preferably 2. Moreover, when p is 2, X1, X2 . The coordination group of the coordination compound represented by X3 is never anionized. In general formula (I), RI each represents an alkyl group or an aryl group, but they may further have a substituent, and preferably have 8 or more carbon atoms, more preferably 12 or more carbon atoms, including the carbon atoms of the substituents. is an alkyl group or an aryl group. Particularly preferred is a substituted phenyl group having 12 or more carbon atoms. -Ritual CI) A specific example of R1-303- is shown below. (1) C9)+2Q+lSO3-(q=8~24
(integer) (2) CJzQ++0CHzCHzSO3
-(q = 8 ~ 24) (81CqH2Q-1-CH2
CH2SO! (q-8 to 24) The .\zene ring substituted with a 5O1l- group or a CH2Cl□-803- group may further have a substituent. Next, specific examples of the ligands represented by X+, Xz, and N3 are shown below. (1,) NH3 (21N1 (2GHz (NHCHHzCHz)1, NH3
(n = 0 or 1) 13) N) 12 (C)
12), IN) + 2 (n = 2 or 3) (4, l
CJsNH(lIzcHzNHczHs(1■ (n-1 or 2) (+7) In the general formula (II), R2 and is preferably an alkyl group or an aryl group having 4 to 12 carbon atoms, which may be substituted.Particularly preferable R2, R3R4, and RS are phenyl groups or alkyl-substituted phenyl groups. A specific example of R2~B''-R5 is shown below. ■ 4° (CtH9) tB C2H5NCH2CH2NH2 Next, the specific side of the ligand represented by X is shown below. 1) Nl (3 NLC) Iz (NHCHzGHz)ゎH2 (n 0 or 1) Nllz (CHz) -NHz (n-2 or 3) CZH5NHCH2CH2NHC2H5 (n=1 or 2
) ■ Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. Although specific examples of compounds represented by -ritual [■] are shown above, the present invention is not limited thereto. II 1 1:Cu(NHzCHzCHzNl(z)
zl”[(C6Hs)4B-]zII-2(Ni(NH
□CH2CH□Nt+2)zl”f(c614B-lz
H3[Co(NlhCHzC)lzNHz)il''[(
CJs) J-12II 4 (Zn(NHHzCHzC
HzNHz:):+]”[(CJs)J-]lzH5(
Ni (Czll, NHCHzCH2NHz) il
2" [(c6ns) aB-] 26 (Ni (Cz
llsNtlCtlz(jl□NlIC2H5) 3]
” [(C6115) 4B-127(Ni (NH
zCH□CHzNI(CHzCH2NH□)2]2+'
f(C6Hs)J]2 [(C6H5)4.8 [(CJ5)4B [(cbHs)aB ■-14 ■ [Ni (CzHsNHCHzCHzNHCzHs)
z■-15 ((C6H5) 4B-] z ■-19 ■Ri6 [(c1, Hs) 4B-12 ■■-17 [(C6H5) tB-] 2 [(C61(5) 4.8-12 [(C6Hs) J-CNI z [(c614.8-] ■-22 [Ni (NHzCHzCHzCHzNHz) 3]
”[(n-C4H7)tB-)z [Ni (CJsNHCH□CHzNHz) z (N
H2CH2CH2NH2) ] ”[(C6H5) t
B-]z ■-24 ■ ■ ■ Laminating the compound represented by the general formula (1) or (II) of the present invention on the image-receiving layer surface of an image-receiving material having an image-receiving layer on which a dye image has been transferred onto a support. The method of adding it to the laminate material to be treated is arbitrary, and the amount used is not limited and varies depending on the type of compound and the form of use, but it is usually 0.05 g to 10 g per support In.
Preferably it is 0.1 g to 3.0 g. Although the compound used in the present invention can be contained in any layer of the laminate material, preferably at least a portion of the compound is contained in the adhesive layer. In particular, it is preferably contained in a hot melt layer or a heat welding layer. In addition to the adhesive layer, the compound used in the present invention can be added to the support itself of the laminate material, and in addition to being added to the laminate material, it can also be added to the image-receiving layer of the image-receiving material. Furthermore, at least one compound selected from the compounds represented by formulas CI) and [Ir) may be added, but two or more compounds may be added in combination. The laminate material of the present invention may be any material as long as it can physically protect the dye image on the image-receiving layer surface, but preferably has at least one adhesive layer on the support. It may have a single layer structure. The support of the laminate material A may be transparent or light-reflective, but if the support of the image-receiving material is a reflective support, it must be a transparent support. There is. Reflective support used in the laminate material of the present invention 7
Examples of the support include paper, baryta paper, art paper, resin coated paper such as cast 1-coated paper and polyethylene coated paper, and plastic supports such as polyester and polystyrene containing white pigment. Further, as the transparent support, various synthetic polymer films such as polyester, polycarbonate-1-, polyvinyl chloride, polyethylene, etc. can be used. For the adhesive layer preferably used in the laminate material of the present invention for adhesion to the image-receiving layer surface, known adhesives can be appropriately selected and used. The adhesive used in the present invention is, for example, Chemical Handbook Applied Edition.
Revised 3rd edition (Marukubi Publishing 1980) No. 897-903
Pages and Technical Series [Adhesion-11, ij Chapter 11, Part 3 Supervised (Asakura Shoten, 1981), pages 20 to 38. Adhesives preferably used in the present invention include 1. Fosol-Mel-1-type adhesives (e.g. ethylene-
(vinyl acetate copolymer, polyethylene, polyamide, polyester resin, etc.), thermoplastic resin adhesives (e.g. vinyl acetate, chloroprene, acrylic emulsion, etc.), rubber adhesives (chloroprene rubber, etc.), heat Curable resin adhesives (urea resin, melamine resin, phenol resin, epoxy resin, polyurethane resin, etc.),
Examples include photocurable resin adhesives and natural adhesives (gelatin, starch, glue, etc.). The laminate material of the present invention is preferably one in which an adhesive layer is provided on the (support) layer as described above, but more preferably one in which an adhesive layer is provided on the (support) layer, which is bonded under heat, or one in which a heat-welded layer is provided. It has layers.In particular,
A laminate material having a heat-welding layer on the support is preferred from the viewpoint of preventing forgery and alteration. The heat-welding layer referred to here refers to a layer that, when bonded to the image-receiving layer under heat and pressure, is at least partially heat-melted and bonded to the binder of the image-receiving layer without using a special adhesive. To tell. Further, the support itself can also be a heat-fusible layer. The binder used in the heat-adhesive layer is preferably a thermoplastic resin, as long as it can be melted and mixed with the binder of the image-receiving layer under heating. Preferably, the binder and laminate material of the image-receiving layer are the same! It is preferable that both of the heat-welding layers of No. 4 are made of thermoplastic resin, and that at least some of the repeating units constituting each resin are chemically the same. In the present invention, polycarbonates, polyacrylates, polyesters, polyvinyl chlorides, and the like are preferably used as the thermoplastic resins used in the binder of the image-receiving layer and the heat-adhesive layer, and polyvinyl chlorides are particularly preferred. Lamination carried out under heat is carried out by internal heating or external heating. For internal heating, there are methods that use ultrasound, high frequency, microwave, etc. In particular, ultrasound,
Alternatively, high frequency waves are preferable because they can more easily melt the contact area between the image recording body and the laminate material to form a bonded one-piece color. Further, as external heating, a heat roller, infrared rays, heat seal, laser, etc. can be used. In addition, the temperature, pressure, and time during lamination can vary widely depending on the laminating method, but in general, the laminating temperature is 80 to 180°C, and the lamination temperature is 0.1 to 1 ml per 1 cl.
．． OOkg, preferably in the range of 0.2 to 30 kg, and the lamination time is
It is carried out for 0.01 to 30 seconds, preferably 0.1 to 10 seconds. The lamination l1 portion may be all or part of the contact area between the image recording body and the laminate material. For example, in the case of an ID card, it may be the entire peripheral area or a part of the peripheral area (or it may be the entire area of the image recording area or a part of it, but preferably the area where the image recording area and the laminate material come into contact). A method for recording a dye image on the image-receiving layer is, for example, a thermal transfer printer as described in Non-Impact Printing - Technology and Materials (edited by Makoto Ohno), published by CMC (1986). and inkjet printer, Journal of the Photographic Society of Japan, Vol. 50, No. 5, p. 397-407
(1987) using a heat-developable silver salt color recording material, or an instant photography method. Particularly preferably, a method using the heat-developable silver halide salt color recording material and a method using a thermal transfer printer are preferably used in the present invention. In these methods, the image-receiving layer is composed of a hydrophobic binder, and in the case of a laminate material that has a heat-adhesive layer on the support, it can be bonded by welding, so for example, in the case of an ID card, it is difficult to create a fake image. Not only is the tamper-proofing effect high, but the dye image stabilizer added to the laminate material also has a particularly great stabilizing effect against heat and humidity. The image-receiving layer formed on the image-receiving material to be laminated with the laminate material of the present invention may be hydrophobic, hydrophilic,
Any material may be used as long as it has the function of receiving the dye, etc. in the photosensitive layer of the heat-developable photosensitive material released or formed by heat development. For example, polymers containing tertiary amines or quaternary ammonium salts, US Pat.
Those described in No. 709.690 are preferably used. For example, a polymer containing a quaternary ammonium salt is one in which the ratio of polystyrene to N,N,N-tri-nhexyl-N-vinyl-benzylammonium chloride is 1=4 to 4:1, preferably 1:l. . Examples of polymers containing tertiary amines include polyvinylpyridine. The image-receiving layer may be obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. The image-receiving layer particularly preferably used in the present invention is preferably a heat-resistant organic polymer material having a glass transition temperature of 40 DEG C. or higher and 250 DEG C. or lower, as described in, for example, JP-A No. 57-207250. These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support. Examples of the heat-resistant polymer substances include polystyrene, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral. polyacetals such as
Polyvinyl chloride, chlorinated polyethylene, polytrichlorinated fluorinated ethylene, polyacrylonitrile, polyN,N dimethylallylamide, polyacrylates and polyacrylics containing p-cyanophenyl, pentachlorophenyl and 2,4-dichlorophenyl groups chloroacrylate,
Polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly t
Polyesters such as ert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polycarbonates such as polysulfone, bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. can be mentioned. In addition, [Polymer Handbook, Second Edition] (Joy)
Brand Wrap, Edited by E.H. Inmargat) John Willian & Sands Publishing (Polymer Ha
ndbook2 nd ed, (, J, Bran
drup, E, H, I mmergutlit)
Also useful are synthetic polymers with glass transition temperatures of about 40° C. or higher, such as those described by John Wiley & Co., Ltd. - For boat fishing, the molecular weight of the polymer substance is 2.000.
~200,000 is useful. These polymeric substances may be used alone or in a blend of two or more thereof, or may be used in combination of two or more as a copolymer. Useful polymers include cellulose acetates such as triacetate and diacetate, heptamethylene diamine and terephthalic acid, fluorene diamine and adipic acid, hexamethylenecyamine and diphenic acid, and hexamethylenecyamine and isophthalic acid. Polyamides made from combinations such as diethylene glycol and diphenylcarboxylic acid, polyesters made from combinations such as p-carboxyphenoloxyphenyl and diethylene glycol, polyethylene terephthalate, and polycarbonate are the worst. It will be done. These polymers may be modified. For example, polyethylene terephthalate I. using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy4hensensulfonic acid, etc. as a modifier is also effective. Particularly preferred image-receiving layers include layers made of polyisophthalic acid esters, polyethers, polyvinyl chloride, polyvinyl chloride-vinyl acetate, or polycarbonate. Furthermore, as the support for the image-receiving material, any material such as a transparent support or an opaque support may be used, but for example, polyethylene 1/1
Nterephthalate, polycarbonate, polystyrene,
Films such as polyvinyl chloride, polyethylene, and polypropylene; supports containing pigments such as titanium oxide, barium sulfate 1, calcium carbonate, and talc; pure Halique paper; pigments on paper; Heat containing +1
RC (resin coat) paper laminated with J plastic resin,
Metals such as alumina 1, etc., and - of these supports
Examples include a support on which an electron beam curable resin composition containing a pigment is coated and cured, and a support on which a coating layer containing a pigment is provided. Furthermore, a special request was made in 1986.
．． Kist coated paper described in No. 126972 is also useful as a support. The photographic element in the present invention refers to an element obtained by laminating a laminate material onto an image-receiving material having an image-receiving layer to which a dye image has been transferred, as described above.
Examples include cards, stickers, decorative photographs, and various cards, but the present invention is particularly preferably applied to ID cards. Although any photosensitive material may be used to form such a photographic element, it is preferable that the support be coated with photosensitive silver halide, a reducing agent, a binder, and if necessary. A heat-developable photosensitive material having at least one photographic constituent layer containing a dye-providing substance is used. After imagewise exposure, an image is formed in the heat-developable photosensitive material by simply subjecting it to heat treatment. By overlapping the heat-developable photosensitive material and the image-receiving material at the same time or after heating, a transferable compound such as a dye image is transferred into the image-receiving layer of the image-receiving material. The heat-developable photosensitive material of the present invention can be embodied as a black-and-white photosensitive material or as a color photosensitive material. In the case of producing a color photosensitive material, a dye donor 5-substance is used. Dyes that can be used when the present invention is applied to color photosensitive materials (for example, JP-A No. 62 -
No. 44737, No. 62-129852, No. 62 = 1
．． 69158, e.g. the L phyco dyes described in U.S. Pat. No. 475.441, or e.g. U.S. Pat.
Azo dyes used in the heat-developable dye bleaching method described in , No. 957, etc. can also be used as the dye-donating substance, but
More preferably, a diffusible dye-providing substance that forms or releases a diffusible dye is used, and it is particularly preferable to use a compound that forms a diffusible dye by Cambrinck reaction. Diffusible dye-providing substances that can be used in the present invention will be explained below. Diffusible dye-donor substances may be those capable of forming or releasing a diffusible dye as a function of the reduction reaction of the photosensitive silver halide and/or the organic silver salt used if necessary. Depending on their reaction form, they can be classified into negative-working dye-donating substances and positive-working dye-donating substances. As a negative dye-donating substance, for example, U.S. Pat.
No. 63,079, 4. , No. 439, 513, Japanese Patent Publication No. 5
No. 9-60434, No. 59-65839, No. 59-7
No. 1046, No. 51-87, 150, No. 59-887
No. 30, No. 59-123837, No. 59-12432
No. 9, No. 59-165054, No. 59-164055
Examples include reducible dye-releasing compounds described in specifications such as No. Other negative dye-providing substances include, for example, U.S. Pat.
, 4.74,867, JP-A-59-12431, 5'! -48765, 59-174834, 5
No. 9-77664'2, No. 59-159159, No. 5
! Examples thereof include coupled dye-releasing compounds described in specifications such as No. 11-231040. Another particularly preferred negative-tone dye-providing substance of the coupled dye-forming compound is one represented by the following general formula (a). General formula (A) Cp-+J←-B) In the formula, Cp represents an organic group (coupler residue) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusible dye. , J represents a divalent bonding group bonded to an active position that reacts with the oxidized form of the reducing agent, and B represents a ballast group. Here, the ballast group is a group that substantially prevents the dye-providing substance from diffusing during heat development processing, and includes groups that exhibit this effect depending on the nature of the molecule (such as a sulfo group),
Refers to groups that exhibit their effects depending on their size (groups with a large number of carbon atoms, etc.). The coupler residue represented by cp preferably has a molecular weight of 700 or less, more preferably 500 or less, in order to improve the diffusibility of the dye formed. The ballast group preferably has 8 or more carbon atoms, more preferably 12 or more carbon atoms, and even more preferably a group that is a polymer chain. The cambling dye-forming compound having a group that is a polymer chain is preferably one having a polymer chain having a repeating unit derived from a monomer represented by formula (b) as the above-mentioned group. General formula (b) Cp −+ J−++Y juice−←Z←→L) In the formula, Cp,
J has the same meaning as defined in general formula (a), Y represents an alkylene group, arylene group or aralkylene group, β represents 0 or 1, Z represents a divalent organic group,
L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group. Specific examples of coupling dye-forming compounds represented by general formulas (a) and (b) include JP-A No. 591, 24339;
No. 59-181345, No. 60-2950, No. 61-57943, No. 61-59336, etc., U.S. Patent Nos. 4,63L251 and 4,650.748.
No. 4,655,124, particularly U.S. Pat. No. 4,656,124,
U.S. Patent Nos. 4,631,251 and 4,650,74
The polymer type dye-providing substances described in each specification of No. 8 are preferred. As a positive dye-donating substance, for example, JP-A-59-
No. 55430, No. 59-165054, No. 5!115
No. 4445, No. 59-766954, No. 5!11-1
No. 16655, No. 59-124327, No. 51-15
Examples include compounds described in publications such as No. 2440. These dye-providing substances may be used alone or in combination of two or more kinds. The amount used is not limited and depends on the type of dye-providing substance, whether it is used for cars or a combination of two or more types, and whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more. For example, the amount used is 0.005 to 50 g per 1 d, preferably 0.00 g to 50 g per d.
It can be used at 1g to iog. The method of incorporating the dye-providing substance used in the present invention into the photographic constituent layer of the heat-developable light-sensitive material is arbitrary. , tricresyl phosphate, etc.).
Either by emulsifying and dispersing it, or by dissolving it in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.) and then neutralizing it with an acid (e.g., citric acid or nitric acid, etc.),
or an aqueous solution of a suitable polymer (e.g. gelatin,
It can be used after being solidly dispersed in polyvinyl butyral, polyvinyl pyrrolidone, etc.). Next, the photosensitive silver halide used in the present invention will be described. Any silver halide can be used, and examples thereof include silver chloride, finished silver, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and the like. The photosensitive silver halide can be made of steel by any method commonly used in the photographic art. Furthermore, it is possible to use an emulsion containing grains having a multilayer structure in which the halogen composition of the grains differs on the surface and inside. For example, core/shell type silver halide grains in which the halogen composition changes stepwise.1. Alternatively, silver halide emulsions with continuously varying grains can be used. In addition, the shape of photosensitive silver halide is cubic, spherical, 8
It is possible to use materials that have a clear crystal habit, such as a hedron, dodecahedron, and tetradecahedron, or those that do not. This type of silver halide is described in Japanese Patent Laid-Open No. 60-215948. Also, for example, JP-A-Sho, No. 58-111933, No. 58-111933;
No. 111934, No. 58-108526, Research
As described in Disclosure No. 22534, etc., the particle has two parallel crystal planes, and each of these crystal planes has a larger area than other single crystals of this particle, and its aspect ratio That is, a silver halide emulsion containing tabular silver halide grains with a grain diameter to thickness ratio of 5:1 or more can also be used. Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces are not coupled in advance can be used. For internal latent image type silver halide whose surface is not previously coupled, for example, U.S. Pat.
．． No. 592,250, No. 3.206,313, No. 3,
No. 31.7,322, No. 3.511,622, No. 3,
No. 447,927, No. 3.761.266, No. 3,7
It is described in various specifications such as No. 03,584 and No. 3.736, No. 14.0. Internal latent image type silver halide grains whose surfaces are not coupled in advance are silver halide grains in which the sensitivity inside the grain is higher than the sensitivity on the surface of the silver halide grain, as described in the above specifications. be. Also, U.S. Patent No. 3.27L L
No. 57, No. 3,447,927 and No. 3,531
, 291, or dopants as described in U.S. Pat. No. 3,761,276]. Silver halide emulsion in which the grain surface of silver halide grains is weakly chemically sensitized, or JP-A-5085
Silver halide emulsions comprising grains having a laminated structure described in publications such as No. 24 and No. 50-38525;
Others published in 1986, 1983, 1986, and 1972
Silver halide emulsions such as those described in No. 549 can be used. The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is about 0.005 μm to about 1.571 μm, more preferably about 0.0101 μm. ~0.5 μm. In the present invention, another method for preparing photosensitive silver halide (7) is to coexist a photosensitive silver salt-forming component with an organic silver salt described below, and form photosensitive silver halide in a part of the organic silver salt. You can also do it. These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various embodiments, and the amount used is -1.25 to 1.25 cm per layer per support. The amount of light-sensitive silver halide emulsion is preferably 0.001 g to 50 g, more preferably 0.1 to Log. The photosensitive silver halide emulsion used can be spectral sensitized using a known spectral sensitizing dye to impart sensitivity to blue, green, red, and near-infrared light. Typical spectral sensitizing dyes that can be used include, for example, cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holobola-cyanine,
Examples include sudaryl, hemicyanine, oxonol, and the like. The preferred amount of these sensitizing dyes added is 1 x 10 - per mole of photosensitive silver halide or silver halide forming component.
The amount is 6 mol to 1 mol. More preferably lXl0-5
~1×10 mol. The sensitizing dye may be added at any stage of the preparation of the silver halide emulsion. That is, it may be carried out at any time, such as when silver halide grains are formed, when soluble salts are removed, before the start of chemical sensitization, during chemical sensitization, or after the end of chemical sensitization. In the heat-developable photosensitive material of the present invention, it is preferable to use various organic silver salts, if necessary, for the purpose of increasing sensitivity and improving developability. Examples of organic silver salts that can be used in the heat-developable photosensitive material of the present invention include JP-A Nos. 53-4921 and 41-5262.
No. 6, No. 51-141222, No. 53-36224 and No. 51-37626, No. 52-141222,
Publications such as No. 53-36224 and No. 53-37610, as well as U.S. Patent No. 3,330,633, No. 3,
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having heterocycles, such as behenic acid, as described in the specifications of No. 794,496 and No. 4,105,451, etc. Silver, α-(1-phenyltetrazolethio)silver acetate, etc., Japanese Patent Publication No. 4126582, No. 45-1270
No. 0, No. 45-18416, No. 4522185, JP-A-52-137321, No. 58-118638,
No. 58-118639, U.S. Patent No. 4,123,27
There are silver salts of imino groups described in each publication of No. 4. Among the above organic silver salts, imino group silver salts are preferred;
In particular, silver salts of benzotriazole derivatives, more preferably benzotriazole and its derivatives 5-methylbenzotriazole and its B'A 4 form, sulfobenzotriazole and its FJr''!, N-alkylsulfamoylbenzotriazole and its derivatives It is preferable that the silver salts used in the present invention may be used alone or in combination of two or more.Alternatively, the silver salts may be prepared in a suitable binder and used as they are without isolation. Good and
The isolated product may be used after being dispersed in a binder by an appropriate means. Dispersion methods include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like. The amount of the organic silver salt used is generally preferably 0.01 to 500 moles, more preferably 0.1 to 100 moles per mole of photosensitive silver halide. More preferably 0.
It is 3 to 30 moles. Reducing agent used in the photothermographic material of the present invention (reducing agent precursor is also included in the reducing agent herein)
Those commonly used in the field of heat-developable photosensitive materials can be used. Examples of reducing agents that can be used in the present invention include U.S. Pat. Nos. 3,531,286 and 3,761,27
No. 0, No. 3.764, 328 specifications, and RD (
Research Disclosure) Patient 12146, same No.
15108, same floor 15127 and JP-A-56-271
No. 32, U.S. Pat.
p- described in each publication such as No. 28 and No. 57-79035.
Phenylene diamine and p-aminophenol developing agents, phosphoramidophenol and sulfonamide aniline developing agents, hydrazone color developing agents and their brecassers, or phenols, sulfonamide phenols, or polyhydroxybenzenes. , naphthols, hydroxybinaphthyls and methylene bisnaphthols, methylene bisphenols, ascorbic acid, 3-pyrazolidones, and pyrazolones can be used. Further, the dye-donating substance may also serve as a reducing agent. As a particularly preferable reducing agent, JP-A-56-146133
N(p-
N,N-dialkylamino) phenylsulfamate is mentioned. Two or more types of reducing agents may be used simultaneously. The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide used, the type of organic silver salt, the type of other additives, etc., and is not necessarily constant. The amount is generally preferably from 0.01 to 1,500 mol, more preferably from 0.1 to 200 mol, per mol of photosensitive silver halide. Binders that can be used in the heat-developable photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate,
Ethyl cellulose, polymethyl methacrylate-1, cellulose acetate, polyvinyl alcohol,
Gelatin such as polyvinylpyrrolidone, seratin, phthalated gelatin = i-form, cell 1 course derivative, protein,
Synthetic components such as starch and arahiacom include natural polymeric substances, and these

[Can be used alone or in combination of two or more.] In particular, gelatin or its derivatives and polyvinylpyrrolidone, polyvinylpyrrolidone,
It is preferable to use a hydrophilic polymer such as J1-L in combination, and more preferably to use a binder of gelatin and polyvinylpyrrolidone described in JP-A-59-229556. The preferred amount of binder used is usually 0.05 g to 50 g per m' of support, more preferably 0.2 g.
g to 20 g. In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use ~lOg, more preferably 0.2
~5g. The heat-developable photosensitive material of the present invention can be obtained by forming a photographic constituent layer on a support, and examples of the support that can be used here include polyethylene film, cellulose acetate film, polyethylene terephthalate film, and polyethylene terephthalate film. Synthetic plastic films such as vinyl chloride, paper supports such as photographic base paper, printing paper, art paper, cast coat paper, baryta paper, and resin coated paper, and electron beam curable resin compositions on these supports. Examples include supports coated with and cured. When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, various heat solvents are preferably added to the photothermographic material and/or the image receiving member. The thermal solvent is a compound that is liquid during thermal development and promotes thermal development and/or thermal transfer. These compounds include, for example, U.S. Pat.
, No. 667.9591, (in RD Research Disclosure) Nl117643 (XI) JP-A-59-22
No. 9556, No. 59-68730, No. 51-8423
No. 6, No. 60-191251, No. 60-232547
No. 60-14.241, No. 6152643, No. 62-78554, No. 62-42153, No. 62-
4.4737 publications, etc., U.S. Patent No. 3.438,77
No. 6, No. 3,666.477, No. 3.667.959
Specifications of each issue, JP-A-5L1.9525, JP-A-53-24
No. 829, No. 53-60223, No. 58-11864
Examples of organic compounds having polarity such as those described in No. 0, No. 58-198038, and those particularly useful in carrying out the present invention include urea derivatives (e.g., dimethylurea, dimethylurea , phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, p-1-ruamide, etc.), sulfonamide j
Ai forms (e.g. benzenesulfonamide, α1-luenesulfonamide, etc.), polyhydric alcohols (e.g. 1,
6-hexanediol, 2-cyclohexanediol, pentaerythritol, etc.), or polyethylene glycols. Among the above thermal solvents, water-insoluble solid thermal solvents are particularly preferably used. Specific examples of the water-insoluble heat solvent include, for example, JP-A No. 6
No. 2-136645, No. 62-139549, No. 63
-53548 Specification Publication, Japanese Patent Application No. 63-205228,
There is one described in No. 61-54113. Examples of the layer to which the thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving surface of an image receiving member, etc., and the heat solvent is added to each layer so as to obtain an effect depending on each layer. The preferred amount of the heat solvent added is usually 10% to 500% by weight, more preferably 30% to 200% by weight of the binder amount.
Weight%. The organic silver salt and the thermal solvent may be dispersed in the same dispersion. The same binder, dispersion medium, and dispersion device as used for producing each dispersion can be used. In addition to the above-mentioned components, the photothermographic material of the present invention may contain various additives, such as a development accelerator, an antifoggant, and a base precursor, as required. As development accelerators, compounds described in JP-A-59-177550, JP-A-59-111636, and JP-A-51-124333 are used, as well as compounds described in JP-A-61-159642 and JP-A-62-203908. The development accelerator-releasing compounds described above or the metal ions having an electronegativity of 4 or more as described in Japanese Patent Application No. 1046/1988 can also be used. As an antifoggant, for example, U.S. Patent No. 3.645,
Higher fatty acids described in specification No. 739, Japanese Patent Publication No. 4
．． Second mercury salt described in Publication No. 7-11113, JP-A-Sho 5
N-halogen compounds described in Publication No. 1-47419, U.S. Patent No. 3,700,457, and JP-A-5150
Mercapto compound releasing compound described in Publication No. 725,
49-125016, carboxylic acid lithium salts described in 51-47419, British Patent No. 1.455,271, JP-A-101-019-1986 Oxidizing agent described in Publication No. 53
Sulfinic acids or thiosulfonic acids described in Japanese Patent Publication No. 19825, 2-thiouracils described in Japanese Publication No. 51-3223, simple sulfur described in Japanese Publication No. 51-26019, No. 51-42529, No. 51-81124, 5
Disulfide and polysulfide compounds described in Publication No. 5-93149, rosins or diterpenes described in Publication No. 51-57435, polymer acids having free carboxyl groups or sulfonic acid groups described in Publication No. 51-104338, US Pat. Thiazolinthione described in Patent No. 4.138.265, JP-A-54-5182
1.2.4 described in Publication No. 1 and US Pat. No. 4,137,079. -) Riazole or 5-mercapto-1,2,4-1-riazole, JP-A-55-1.
Thiosulfinate esters described in No. 40883, 1,2,3,4-thiatriazoles described in No. 55-142331, No. 59-46641, No. 59-5
Dihalogen compounds or trihalogen compounds described in No. 7233, No. 5!157234, and No. 59
Thiol compound described in Publication No. 111636, 60-
Examples include the hydroquinone derivatives described in Japanese Patent No. 198540, and the combined use of hydroquinone derivatives and benzotriazole derivatives described in Japanese Patent No. 60-227255. Still another particularly preferred antifoggant is disclosed in JP-A No. 6
Examples include an inhibitor having a hydrophilic group as described in JP-A No. 2-78554, a polymer inhibitor as described in JP-A-61-121452, and an inhibitor having a ballast group as described in JP-A-62123-456. . Further, the colorless coupler described in Japanese Patent Application No. 61-320599 is also preferably used. Examples of base precursors include compounds that release basic substances by decarboxylation upon heating (e.g., guanidinium trichloroacetate), compounds that decompose through reactions such as intramolecular nucleophilic substitution reactions, and release amines, etc. For example, Japanese Patent Application Publication No. 56-130745, Japanese Patent Application Publication No. 56-132332, British Patent No. 2,079,480, US Patent No. 4,0
Specification No. 60,420, JP-A-59-157637,
No. 59-166943, No. 59-180537, No. 51-1741130, No. 59-19'5237,
Examples include base releasing agents described in JP-A No. 62-108249 and JP-A No. 62-174745. In addition, various additives used in heat-developable photosensitive materials as necessary, such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, spreading agents, capping agents, surfactants, It can contain anti-fading agents, etc., and these are specifically described in RD (Research Disclosure) Magazine Vol. 1.170.1978, 1702.
No. 9, JP-A-62-13' 5825, etc. These various additives may be added not only to the photosensitive layer but also to non-photosensitive layers such as an intermediate layer, a protective layer or a backing layer. The heat-developable light-sensitive material of the present invention contains (al-sensitive silver halide, ('b) a reducing agent, and (Cl binder), and when used as a color light-sensitive material, contains (d) a dye-providing substance. It is preferable to contain te+organic depending on the te+organic content.Basically, these may be contained in one heat-developable photosensitive layer, but they do not necessarily need to be contained in a single photographic constituent layer.For example, The heat-developable photosensitive layer is divided into two layers, and the components (a), (bl, (C), and (e+) are -.
The dye-providing substance (d) may be contained in one heat-developable photosensitive layer, and the dye-providing substance (d) may be contained in the other layer adjacent to this photosensitive layer. It may be contained separately in the constituent layers. Alternatively, the heat-developable photosensitive layer may be divided into two or more layers, a low-sensitivity layer and a high-sensitivity layer, a high-density layer and a low-density layer, or more. The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers. In the case of full-color photosensitive materials,
Generally, it has three heat-developable photosensitive layers with different color sensitivities, and in each photosensitive layer, dyes with different hues are formed or released by heat development. Typically, a yellow dye is used in the blue-sensitive layer, a macenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer. The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, or a blue-sensitive layer is sequentially formed on the support. , a green-sensitive layer, and a red-sensitive layer, or a structure in which a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer are sequentially formed on the support. 1. In addition to the heat-developable photosensitive layer, the heat-developable photosensitive material of the present invention may optionally include non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer. can. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, the same methods as those used for coating and preparing general silver halide photosensitive materials can be applied. The heat-developable photosensitive material of the present invention usually preferably has a
0°C to 200°C1, more preferably 100°C to 17
at a temperature range of 0°C, preferably for 1 second to 180 seconds,
More preferably, development can be carried out by simply heating for 1.5 seconds to 120 seconds. Transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development, or by bringing the image-receiving member into close contact with the image-receiving member after heat development. Alternatively, the transfer may be carried out by supplying water and then applying heat if necessary. Also, before exposure, 70°C to 180°C.
Preheating may be performed within the temperature range of . Also, Japanese Patent Application Publication No. 1143338, No. 6116204
As described in Publication No. 1, in order to improve mutual adhesion, the photosensitive material and the image receiving member are heated to 80° C. immediately before thermal development transfer.
The heat-developable photosensitive material of the present invention may be preheated at a temperature of ˜250"C. Various heating means can be used for the heat-developable photosensitive material of the present invention. The heating means can be applied to ordinary photothermographic materials. Any method of obtaining the product can be used, for example by contacting a heated block or plate, by contacting a heated roller or drum, by passing through a hot atmosphere, or by using radio frequency heating, and also by the method of the present invention. It is also possible to provide a conductive layer containing a conductive substance such as a carbon blank on the back side of the photosensitive material or the back side of the image receiving member for thermal transfer, and utilize the Joule heat generated by energization.There are no particular restrictions on the heating pattern. There are several methods, including preheating (breheating) and then reheating, at high temperatures for a short period of time.
Alternatively, heating may be performed at a low temperature for a long period of time, or the temperature may be continuously raised and lowered, or these may be repeated. Discontinuous heating is also possible, but a simple slam method is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used. Various exposure light sources include tungsten lamps, halogen lamps, xenon lamps, mercury lamps, cathode ray tube flying spots, light emitting diodes, lasers (e.g. gas lasers, YAG lasers, dye lasers, semiconductor lasers, etc.), CRT light sources, and FOT. These can be used alone or in combination. A semiconductor laser and a second harmonic generating element (SHG element) can also be used. In addition, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Exposure time is usually i
/1000 seconds to 1 second exposure time as well as 1/
Exposures shorter than 1000 seconds can also be used, such as 1/10 to 1/108 second exposures using xenon flash lamps or cathode ray tubes. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. The photosensitive material of the present invention can be used for scanner exposure using a laser or the like. It is preferable to provide a protective layer on the photothermographic material and image receiving member of the present invention. Various additives used in the photographic field can be used in the protective layer. The additives include various capping agents, colloidal silica, slipping agents, organic fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers,
High boiling point organic solvent, antioxidant, hydroquinone t'r'
L-form, polymer latex, surfactant (including polymeric surfactant), hardener (including polymeric hardener), organic silver salt particles, non-photosensitive silver halide particles, antifoggant, developer Examples include accelerators. Regarding these additives, see RD (Research Disclosure Magazine) Vol. 170. June 1978 No.
No. 17029 and JP-A-62-135825. [Example] Specific examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below. Example-1 ■ Preparation of silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em-1) was prepared using the five types of solutions shown below.
-1) was adjusted. The seed emulsion has a silver iodide content of 2 mol%.
A silver iodobromide emulsion (SE-1) having an average grain size (the length of one side of a cube having the same volume; the same applies in the following description) of 0.09 μm was used. (Solution A-1) Ossein gelatin 0.4.5 g Polyisopropylene-polyethylene oxydisuccinate sodium salt 10% methanol solution 28% ammonia water seed emulsion (SE-1) Ion exchange water (Solution B-1 ) Ossein gelatin Br [ With ion-exchanged water (solution C-1) C-1) A+ 246
．． 3 g28% ammonia water 200.9
m7! With ion exchange water 414 n+j
! (solution D-1) 50% KBr aqueous solution (solution E-1) 56% acetic acid aqueous solution Pu adjustment required amount 5.0 g 200.0 g 5.8 g ml pAg adjustment required amount 5.0 m1 9 m4 0 .071 mol equivalent amount 1750 ml At 40°C, JP-A No. 57-92523, No. 57
Using the mixing agitator shown in the specification of -92524,
(Solution B-1) and solution C-1) were added to (solution A-1) at equal flow rates by a simultaneous mixing method. The pH during simultaneous mixing was kept constant at 8.0 using a roller tube pump with variable flow rate (solution E-1).
was controlled by changing the flow rate. flAg was adjusted to 8.8 at the time of starting the addition of (solution B-1) and (solution C-1), and then (solution B-1)
Continuously change in proportion to the amount added, (solution B-1)
At the end of the addition of (solution C-1), the temperature was controlled to be 9.3. p/Ig was controlled by changing the flow rate of (solution D1) using a variable flow rate roller tube pump. (Solution B-1) and (Solution C-1) were added at the maximum allowable speed (critical speed) without generating small particles.
) 296ml was added, 4;5X10-7
moles of potassium hexachloroiridate(IV) (K
zIr Cβ6) was also added as an aqueous solution. Continue to add Shijinji (solution 13-1) and solution C-1,), and when all of (solution C-1) has been added, hq -
r I did. material i te ('/ yo; night I] - river use (n yo fi)
, E-1>, the pAglO,4 and pH were adjusted to 6.0, and demineralized water washing was carried out using the usual method. Thereafter, after dispersing in an aqueous solution containing 45.65 g of ossein-seratin, the total volume was adjusted to ]1,200 m6 with distilled water, and further using (Solution I)-1) (Solution I-1), 40' In C, p/ig was 8.5 and pl+ was 5.8 (this was adjusted accordingly. As you can see, the emulsion obtained in C7 (Em-1) had a silver iodobromide content of 2 mol%. It was a silver iodobromide emulsion, and as a result of electron microscopy observation, it was found that it was a JR dispersion emulsion with an average grain size of 0.25 μm.The shape of the obtained silver iodobromide grains was approximately hexagonal. ,
It had slightly rounded corners and sides. ■ Preparation of photosensitive silver halide emulsion fa+ Preparation of red-sensitive emulsion (R-1) Silver iodobromide emulsion E
rn-1300m6 was kept warm at 52°C and stirred, and the following sensitizing dye (a) 50■ and the following sensitizing dye (bl 100
1% methanol solution and C2 were added respectively, and 10 minutes later, 15μmo/? of thiosulfate I~lium 0
．． Added as a 1% aqueous solution 5, and after another 60 minutes added chloroauric acid (0.05% aqueous solution and C7) 10, +rmo7! and ammonium thiocyanate (0.1% aqueous solution) 20μmo
ff was added. After further aging at 52°C and stirring for the optimum time (30 to 80 minutes),
The temperature was lowered to °C, and the 4-hydroxy-6-methyl-1,3,
The emulsion was stabilized by adding 5 mg of 3a,7-titraazaindene 250■,■-phenyl-5-mercapI-teI-razol and the following antifoggant 5T-IQ) as a 5% methanol solution, followed by ion exchange. Add the entire amount to 54 ml with water.
0+np. In this way, the red-sensitive emulsion R-
I got 1. Sensitizing dye (a) Sensitizing dye (b) (CH□) asO30 (CHz) 3SO311-N (C2)151h T, 4-hydroxy-6-methyl-C3,3a, 7-chitraazaindene 250■, 5 mg of 1-phenyl-5-mer putotetrazole and the antifoggant S T-1
The emulsion was stabilized by adding 25 nv of 5% methanol solution, and the total volume was adjusted to 540 m6 with ion-exchanged water. In this way, green-sensitive emulsion G-1 was obtained. Sensitizing dye (C) (bl Preparation of green-sensitive emulsion (G-1) Silver iodobromide emulsion E
300 m6 of m-2 was kept warm at 52 °C and stirred, the above-mentioned sensitizing dye tel 150 was added as a 1% methanol solution, and 10 minutes later, sodium thiosulfate of 1511 moA was added as a 0.1% aqueous solution. 7. After another 60 minutes, add 5μ of chloroauric acid (as a 0.05% aqueous solution).
mol and ammonium thiocyanate (0.1% aqueous solution)
lOumo7! was added. Keep the temperature as it is at 52℃ and continue aging with stirring for 75 minutes + another 40 minutes.
"Preparation of C1 infrared-sensitive emulsion (IR-1) 300m6 of silver iodobromide emulsion Em-2 was kept at 52°C and stirred, and the following sensitizing dye (dl 10■) was added to 0.05 % methanol solution, and the following sensitizing dye (e) 25.
Added as a 1% methanol solution 1 and 10 minutes later 1
5 μm Oβ of sodium thiosulfate J was added as an O01% aqueous solution, and after another 60 minutes, 5 μm of chloroauric acid (as a 0.05% aqueous solution) and ammonium thiocyanate (
0.1% aqueous solution) 10 μmol was added. 5 as is
After keeping the temperature at 2°C and continuing aging with stirring for 55 minutes, the temperature was lowered to 40°C, and 250 mg of 4-hydroxy-6-methyl-L3,3a,7-titraazaindene, 1
The emulsion was stabilized by adding 5 ml of phenyl-5 mercaptotetrazole and 25 ml of the above antifoggant ST-1 as a 5% methanol solution, and the total amount was adjusted to 54 ml with ion-exchanged water.
It was adjusted to 0mj2. In this way, infrared-sensitive emulsion IR-1 was obtained using L7. Sensitizing dye (d+ Sensitizing dye (e) ■ Preparation of organic silver salt emulsion At 50°C, JP-A No. 5'l-92523, No. 57
Using the mixing agitator shown in the specification of -92524,
500 g of modified gelatin in which 90% or more of the amino groups of gelatin are substituted with phenylcarbamoyl groups, 4000 n+j2 of ion exchange water, 15.3 g of benzotriazole
g, 28% ammonia water 84ml! The aqueous solution (A) containing 416 g of benzotriazole and 282 ml of 28% aqueous ammonia is 2360 mjl! (B) and 2360 nl of an aqueous solution (C) containing 10 mol of silver nitrate and 560 me of 28% aqueous ammonia.
were added at equal flow rates by simultaneous mixing method. The pH during mixing was controlled at 9.3, and the p/Ig during mixing was controlled at 11. After the addition was completed, 100 g of modified gelatin in which 90% or more of the amino groups of gelatin were substituted with phenylcarbamoyl groups was added as a 20% aqueous solution, and then
The pi was adjusted to 5.5 with % acetic acid, and excess soluble salts were removed by precipitation. In addition, ion exchange water 8000
nl and adjust the pH to 6.0 with a 10% aqueous potassium hydroxide solution.
0 and dispersed for 5 minutes, the above-mentioned modified gelatin 50
g was added as a 20% aqueous solution, and then the pH was adjusted to 4.5 with 3.5N sulfuric acid to precipitate the solution to remove excess soluble salts. After that, adjust the pH to 6.0 and add ion-exchanged water to a total volume of 4200m7! Finished at 300℃ at 50℃
An organic silver salt emulsion was prepared by dispersing for minutes. ■ Preparation of hot solvent dispersion-1 125 g of the following hot solvent and 0.04 g of surfactant.
0 containing 1 (Alkanol XC, manufactured by DuPont),
It was dispersed in 100me of a 5% polyvinylpyrrolidone aqueous solution using an alumina ball mill to give 120rr11. Thermal Solvent-1 Surfactant-1 ■-1 Preparation of Dye-Providing Substance Dispersion-1 35.5 g of the following polymeric dye-providing substance (1) and 2.4 g of the following color stain preventive agent W-1 were dissolved in acetic acid. Ethyl 200mI
! 1, di(2-ethylhexyl) phthalate io,
o g, and 124 mjl of a 5% by weight aqueous solution of surfactant-1 dissolved in 10.0 g of tricresyl phosphate.
! , mixed with 720 m# of 6% gelatin aqueous solution, emulsified and dispersed with an ultrasonic homogenizer, and after distilling off ethyl acetate,
The total volume was adjusted to 795 ml with ion-exchanged water to obtain dye-providing substance dispersion-1. Anti-staining agent W-1 CH3 10CH, ~CH→-7 Polymer dye-providing substance (1) x=60% by weight y-40% by weight ■=(2) Dye-providing substance dispersion-2 Dye-providing substance This is the same dye-providing substance dispersion as Dye-providing substance dispersion-1 except that the following polymeric dye-providing substance (2) was used. Polymer dye-providing substance (2) x - 40% by weight y - 60% by weight - (3) Dye-providing substance dispersion - 3 This is the process in which the dye-providing substance is replaced with the following polymeric dye. This was obtained in the same manner as above except that the donor substance (3) was used instead. Polymer dye-providing substance (3) x-70% by weight y-30% by weight ■-(4) Dye-providing substance dispersion-4 In the dye-providing substance dispersion-1, the dye-providing substance was replaced with the following polymeric dye-providing substance. This was obtained in the same manner as above except that (4) was changed. Polymer dye donor - Dissolve 0.50 g of substance (4) in water, adjust the pH to 7.0, and add 250 m
A reducing agent solution of p was obtained. Reducing agent CR-1) Reducing agent (R-2) ■ Preparation of reducing agent solution The following reducing agent (R-1>20.0g, the following reducing agent (R-2
) 13.3g, Surfactant-2 Surfactant-2 NaO,,S CHC00CH2(CF2CFZ)-
HCIIZ C00CR2 (CFZCF2)l, H(
m, n = 2 or 3) ■ Preparation of heat-developable color photosensitive material Using the above-prepared dispersion of organic silver salt and thermal solvent, silver halide emulsion, dispersion l containing the coupler of the present invention, and reducing agent solution. 180μm thick with latex undercoat
Each composition was coated on a transparent polyethylene terephthalate film in the following amounts per one support to prepare a photosensitive material 1. Silver benztriazole 1.5g Green-sensitive silver halide 0.45g Reducing agent
1. Og polymeric dye-donor substance of the present invention (4,10,8g tricresyl phosphate
0.2g gelatin 3
．． 0 g Polyvinylpyrrolidone 0.5 g Hot solvent 5.0 g Antifoggant (ST-1) 0.015 g ■ Preparation of image receiving member On a transparent polyethylene terephthalate support with a thickness of 100 μm, a Latinx subbing layer was provided on it. Furthermore, an image receiving layer having the following composition was coated to prepare an image receiving member-1. The amount added is expressed per 1% unless otherwise specified. Polyvinyl chloride (degree of polymerization 500) 10
g-(2-ethylhexyl) phthalate (DOP)
0.2g Compound A (below) Compound B (below) Compound A HOCH2CH2SCH2CH2SCH2CH20H Compound B 0.2g 0.8g Shi! Furthermore, the metal sources shown in Image Receiving Member 2 to Compound-1 were added and applied in the same manner as Image Receiving Member 1. Table 1 Table 2 (1) Preparation of laminate material A barium sulfate-containing gelatin layer was provided on a 70 g/m paper support, and a 10 μm thick polyvinyl chloride layer was further provided thereon as a heat-welding layer. In this case, the metal sources shown in Table 2 were added to the polyvinyl chloride layer to produce laminate material levels 1 to 4. (Image Transfer) The obtained heat-developable photosensitive material is subjected to imagewise exposure, and the image-receiving materials 1 to 7 are superimposed so that the image-receiving layer overlaps the protective layer of the photosensitive material, and then heated at 155° C. for 45 seconds. A developing process was performed. (At this time, 10 kg/cnj 15 seconds after the start of development.
It was pressed using a pressure roller. ) As shown in Table 2, when the photosensitive material is peeled off after development, on the image-receiving layer of the image-receiving material,
A dye image was obtained in which an unchelated infrared dye, ie, a cyan dye, a chelated infrared dye, ie, a dye having infrared absorption, and a mixture of the above two types of dyes were obtained. (Lamination) The laminate material was laminated on the image-receiving layer surface of the image-receiving material to which the dye had been transferred, and laminated by heating and pressing with a heated roller kept at 130°C. The reflection density of the images of the obtained samples 1-1 to 1-24 was measured using red light and infrared light (850 nm). Maximum density (D1, X) and minimum temperature (-fog;
Dmin) is shown in Table 3. As shown in Table 3, the image forming method of laminating using the laminating material of the present invention is particularly effective when using image receiving member No. 1 and laminating materials Nos. A dye image can be obtained. Further, image receiving member N112 containing a small amount of metal source. 4. 6
It is also possible to obtain an infrared dye image with high density and low fog when laminating material levels 2 to 4 are used. On the other hand, it can be seen that in the comparison image receiving member m3, 5.7, fog (D, i1,) is higher than that of the present invention in which a metal source is added to the laminate material. Margin Table Example-2 The same laminate material floors 5 to 21 as the laminate material floors 2 to 4 were prepared except that the metal source of the laminate material and the amount of metal sauce added were changed to the amounts shown in Table 4. Using the same photosensitive material as in Example 1 and using the same image-receiving material as in Example 1, the same exposure and development as in Example 1 was carried out, and the resulting dye transfer image was laminated with laminate materials 5 to 21 under the same conditions as in Example 1. I did it. Image density was measured using infrared light. The results obtained are shown in Table-4. As shown in Margin Table 4 below, an infrared dye image with high density and low fog could be obtained. Example 3 A multilayer photosensitive material 2 having the structure shown in Table 5 was produced. Color photosensitive material 2 having a multilayer structure as shown in Table 5 was prepared using the organic silver salt dispersion, silver halide emulsion, and dye-providing substance dispersion prepared above. Coating is done by applying a backing layer on a support coated with a subbing layer on both sides.
After coating and drying two layers of Banking Layer 1 and Banking Layer-2 at the same time, on the opposite side, coating and drying three layers of Layers 1 to 3 at the same time, and then layer 4 on top of that. Layer ~ 7th
Four layers were applied simultaneously. The 1st to 7th layers and backing layers 1 and 2 each contain the following surfactant 3 as a coating aid, and each layer contains tetrakis(vinylsulfonylmethyl)methane as a hardening agent. Reactants with taurine potassium salt (reaction ratio 1:0.75 (molar ratio)) were each added at a rate of 0.04 g per 1 g of gelatin. Surfactant-3 Table zHs CH2COOCH2C1 (CH2)3CH3 [NaO+S CHCOOCH2GH (CHz)3c)
13zHs The first to seventh layers were coated after adjusting the coating solution to pH 5.8. Below is the blank space (V A Anti-irradiation dye ■ DOP Nizi-(2-ethylhexyl) phthalate TC1
):l, licresyl phosphene-1, and other compounds listed in the above table are shown below. The amount of each sweat pile 11 represents the amount of application per 1 d. (However, 5, halogen 4U skin peeling, nzotriazole n4
) B is the value converted to silver. ) Anti-irradiation dye-2 Anti-irradiation dye-3 When laminating material 4 in the same manner as in Example 1,
Yellow, magenta, and cyan color images were provided depending on the exposure, and an infrared image was also provided in the infrared light exposed area. The reflection density of each image was measured using a densitometer (PDA65).
．． (manufactured by Konica Corp.). Table of results obtained.
6. As is clear from Table 6, by using the laminating material of the present invention, not only images with high density were obtained, but also good images with low guffling in unexposed areas were obtained. Table 6: For the obtained photosensitive material 2, a tungsten lamp was used as the light source, and light was passed through a wavelength filter (IIOYA KIRL-78-131 and Toshiba color glass filter R-68) having a maximum wavelength of 780 nm, and the light was green. After being exposed to light and red light, image receiving member 1 was subjected to the same heat development treatment as in Example 1, followed by lamination Example 4 In the production of image receiving member 1 in Example 1, polyvinyl chloride was replaced with polyester. Except for changing to
Image receiving material-8 was produced in the same manner. On the other hand, in the preparation of Laminate Material-4 in Example 1, the same polyester as used in the preparation of the image-receiving material was provided as a heat-welding layer on a 120 g/rrf coated paper to prepare Laminate Material-20. After exposing the photosensitive material 2 produced in Example 3 to blue light, green light, and red light, heat development was performed in the same manner as in Example 1 using image receiving member 8 to form laminate material 20. When the same lamination as in Example 1 was carried out using the same, an image similar to that in Example 3 was obtained. The results obtained are shown in Table-7. As is clear from Table 7, images with high density and low fog were obtained. Table 7 [Effects of the Invention] As illustrated from the above examples, by laminating the laminate material containing the metal source of the present invention on the image-receiving layer surface of the image-receiving layer material to which the dye image has been transferred, a high density It is possible to obtain infrared images that are large and have low fog.

Claims (1)

[Claims] 1) In an image-receiving material having an image-receiving layer with a dye image transferred onto a support, the laminate material laminated on the surface of the image-receiving layer is represented by general formula [I] or general formula [II] A laminate material containing at least one compound. 2) A laminate material containing at least one compound represented by general formula [I] or general formula [II] on the surface of the image-receiving layer in an image-receiving material having an image-receiving layer on which a dye image is transferred onto a support. An image receiving element made by laminating. 3) In an image-receiving material having an image-receiving layer in which a dye image is transferred onto a support, a laminate material containing a compound that reacts with a complex formation reaction with some or all of the dyes contained in the image-receiving layer is laminated on the surface of the image-receiving layer. Characteristic image forming method. General formula (I) [M(X_1)_l(X_2)_m(X_3)_n]^
p^+(R_1-SO_3^-)_p [In the formula, M represents a transition metal ion, and X_1, X_2, and X_3 represent coordination compounds that can coordinately bond to the transition metal ion to form a complex, R_1 represents an alkyl group or an aryl group. l represents 1, 2 or 3, m represents 1, 2 or 0, n represents 1 or 0, p represents 1 or 2. ] General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, M, X_1,
represents each alkyl group, aryl group, cyano group, heterocyclic residue, or hydrogen atom (which may be the same or different). ]