JPH03144447A - Dye fixing material - Google Patents

Abstract

PURPOSE:To obtain a dye fixing material good in light fastness and unchanged in performance, such as surface gloss, by incorporating an oil-soluble fluorescent whitening agent in a layer on the side of a dye fixing layer and an anionic surfactant in the layer on the side of the dye fixing layer in the total amount of 20 - 200mg/m<2>. CONSTITUTION:The layer on the side of the dye fixing layer contains the oil- soluble fluorescent whitening agent and the anionic surfactant in the total amount of 20 - 200mg/m<2>, and this surfactant is high in diffusibility into a hydrophilic binder and diffuses to the surface even during storage to deteriorate the surface gloss, and it has an effect of promoting diffusion of the oil-soluble materials which causes deterioration of the surface gloss due to their migration to the surface, and accordingly, it is necessary to control the content of said surfactant in an amount of <= 200mg/m<2>, thus the obtained dye fixing layer to be good in lightfastness and stabilized at the time of storage.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for forming an image by heat development.
This invention relates to a dye fixing element.

(Background of the Invention) Photography using silver halide has been the most widely used method since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as electrophotography and diazo photography. It is used.

For information on how to obtain color images through heat development,
Many methods have been proposed. A method for forming a color image by combining an oxidized developer and a coupler is described in U.S. Patent No. 3. Yo 3/, 2! r6, US Special Liver No. 3,76
7.270, Belgian Percent No. 102, J/5' and Research Disclosure Magazine/Re7 February 3, 2013
It has been proposed in page 1, 32 negative, U.S. Tokuken No.←, 02/, 2←O, etc.

In this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, so that the color image becomes cloudy.

In order to overcome all these drawbacks, a method is proposed in which a mobile (diffusible) dye is formed or released in an imagewise manner by heating and the mobile dye is transferred to a dye-fixing element having a mordant by means of a solvent such as water; A method of transferring to a dye fixing element using a high boiling point organic solvent, a method of transferring to a dye fixing element using a hydrophilic heat solvent built into the dye fixing element, a method in which a mobile dye is transferred to a dye fixing element in a heat diffusive case or a sublimable case, and a support is applied. A method of transferring to a dye-receiving element such as a body has been proposed (U.S. Pat. No. 1I
, No. 1163,07, No. 41.1I711-. 16
No. 7, same No. ←, 4t7f,? , No. 27, No. 1I, 60
7゜310, same number! ,! No. 00.626, same No. ≠.

1tr3,'? /4 issue; Japanese Patent Publication Showa RR-ITTYO
ttt issue, same rl-/1AP0117 issue, same tatar/!
21tltO issue, the same Tatar! φ4t≠! Same issue! Tar/6! O! ←No., same jter/10j17r, same jF-
/A11139, same Tatar/7'tr! No. 2, same Tatar/No. 711133, same! 9-/7FJ'J4', Tatar 77φr3p, etc.).

Color images obtained using such a thermal development image forming method generally have a high density in fogged areas, are susceptible to staining in white areas, and are prone to unevenness during development processing.

Furthermore, when the obtained image is stored for a long period of time, contamination increases in the white background area where the image density has changed.

In order to deal with the above problem, JP-A-6/-14'j7
J, No. 2 proposes that the dye fixing element contain a fluorescent brightener. However, although this method improves the contamination of the white background immediately after image formation, stable effects such as large unevenness of the image cannot be obtained. for example,
When an image is exposed to fc and stored for a long time, there is a noticeable increase in the density of the white background part, and on the other hand, there is a problem that the degree of a of the image decreases significantly.

Further, Japanese Patent Application Laid-open No. 77-1/Tade No. 6φ1 proposes the use of no-hydroquinone derivatives as a dye-fixing material for the purpose of improving the light fastness of images. In this case, the light fastness of the formed image is certainly improved. However, there is a problem in that when stored in a dark place for a long time, the II degree of the white background area increases significantly.

On the other hand, Tokukai Hei/-/Tata 6! ! has proposed the use of a fluorescent whitening agent for an image forming method that does not cause unevenness during development processing, and also does not cause changes in image density or unevenness even after long storage. Among these, water-soluble fluorescent brighteners are said to be preferable from a manufacturing standpoint. However, in our research, from the perspective of image light fastness,
It has been found preferable to use oil-soluble fluorescent brighteners.

However, it has been found that when an oil-soluble fluorescent brightener is used as a dye fixing material, there is a problem in that the surface gloss deteriorates during storage.

Therefore, dye-fixing materials were piled up that gave the images good light fastness and did not change the performance (table if) glossiness during storage.

(Problems to be Solved by the Present Invention) An object of the present invention is to provide a dye fixation that provides good light fastness of images and does not change the performance (surface gloss) during storage in the case.

(Means for Solving the Problems) The above object is to provide a dye fixing material having a dye fixing layer capable of receiving a diffusible dye formed in a heat-developable photosensitive material by heat development. The side containing the oil-soluble fluorescent brightener is contained, and the total amount of anionic surfactant on the side containing the dye fixing layer is 4097 m2 to 00η/m2.
It is distantly related to dye-fixing materials characterized by

Anionic surfactants are originally used to stabilize emulsions, improve coating properties, and improve transportability and peelability of materials. However, in our research, we found that anionic surfactants have high diffusivity in hydrophilic binders and diffuse to the surface even during storage, causing a decrease in surface gloss.

Furthermore, it has been found that the anionic surfactant has the effect of promoting the diffusion of oil-soluble substances in the hydrophilic binder, and is also responsible for the reduction in surface gloss due to the movement of these oil-soluble substances to the surface.

Therefore, when using an oil-soluble substance such as an oil-soluble fluorescent brightener as in the present invention, the amount of anionic surfactant used must be 200 m97 m or less from the viewpoint of surface gloss. It turns out that it is. However, as stated in JP-A-62-/73ψ63, an anionic surfactant of 20 μ/m is required for the peelability between the dye fixing element and the light-sensitive material.

The anionic surfactant used in the present invention refers to a surfactant having an anionic group, excluding betaine type surfactants. The anionic groups mentioned here include carphokyfur group, sulfone group, sulfi7 group, phosphoric acid group, boric acid group,
These are groups that can form anions such as hydroxyl groups and their salts.

Anionic surfactants may be used in any layer in the dye-fixing material. The anionic surfactant may be added directly as an aqueous solution, or may be added by using it as a dispersant for high-boiling organic solvents, oil-soluble compounds, polymers, and the like.

Although only seven types of anionic surfactants may be used alone, it is common to use two or more types in combination depending on various purposes.

In the present invention, the anionic surfactants preferably used are those represented by the following formulas [I] to [■], but the present invention is not limited thereto.

General formula ("1,1 2 R' CON + CH2sn803M However, R is a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms and a fluorine substituted product thereof, 1 For example, a propyl group, a heptyl group, an octyl group, Nonyl group, decyl group, kundecyl group, dodecyl group
l/ group, tridecyl group, octadecyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, heptacosafluorotridecyl group, tritriacontafluoroheptadecyl group, and the like. R2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group,
n-propyl group, 1so-propyl group, etc. n
is an integer of /-20, particularly preferably /~t. Ma
It is a monovalent alkali metal, and Na and K are particularly preferred.

- Numerical formula (It) General formula (In) In general formula (n) and CIII), R', M, and n have the same meanings as in general formula [1]. a is 0, l or
Represents 2. m is an integer between / and especially 2. −φ
is preferred.

General formula [IV] CH2COORI M-o3S-CHC00RI' General formula (V) R-0-8O3M General formula [■] General formula (IV), CV] Oyo O: CVL 3 Nitte, R1, Ml”r, - has the same meaning as in formula [I].

However, R2 and M have the same meanings as in the general formula CI"JVC, and m has the same meaning as in the general formula [n).

- Numerical formula [■] General formula [IX] R' In the general formulas [■] and [■], R3U is a saturated or unsaturated hydrocarbon in which the hydrogen moiety having 3 to 2 carbon atoms is fluorinated, Preferably, it has 7 to 1 carbon atoms (for example, a pentadecanefluoroheptyl group, a heptadecafluorooctyl group, a heptacosafluorotrizoyl group, a tritriacontafluoroheptadecyl group, etc.). R2 and M have the same meanings as in general formula [1], and m has the same meaning as in general formula Cn).

Specific examples of anionic surfactants that are particularly preferably used are as follows. However, the present invention is not limited to these specific examples.

l −/ C11H23CONHCH25O3Nal −,2 C7F15CONH(CH2)2803Na-3 CH3 CsH17CON(CH2)2SO3 1−/ −x −3 Ill−/ 1−2 ■−/ CH2−Coo−C)−12CH(C2H5)C4H9
NaOaS-CH-COO-CH2CH(C2H5)C
4H9V-/ C7H1s-0-8O3 ■-2 CI 2H250-8O3Na ■-l ■-/ ■-7 C8F17-802NH(CH2)3cOONa■-2 C17F33SO2NH(CH2)4COONaIX-
/ CI 3F27S02NH(CH2)30PO(OH)
2. The fluorescent whitening agent used in the dye-fixing material of the invention is K, edited by Veen Rataraman, “The
Chemistry of 5yntheti
Compounds described in Chapter 1 of Volume 1 of C Dyes can be used. More specific examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, biglin compounds, and carbostyril compounds.

The fluorescent brightener of the present invention is an oil-soluble fluorescent brightener.

The term "oil-soluble" as used herein refers to something that is substantially water-insoluble, and specifically, the amount that can be dissolved in water 1009 with a Vcd of 200c is 1.
00■ or less.

Examples of fluorescent brighteners used in the present invention are listed below.
The present invention is not limited to these.

1-11 The above fluorescent brighteners can be used alone even if /ff is used alone.
These types or more may be used in combination.

The layer to which the fluorescent brightener is added is a protective layer in the dye fixing material,
It may be a dye fixing layer, an undercoat layer, etc., but a dye fixing layer is preferable. When the dye fixing layer contains a mordant, it may be mordanted with the mordant.

The fluorescent whitening agent used is preferably added so that it is finally present in the dye-fixing material in the range of o,i to 2θomg7m2, and most preferably used in the range of 1 to 70097m2. .

In order to introduce an oil-soluble fluorescent whitening agent into the layer of the dye fixing material, a dispersion method using a polymer or a method of dispersing it as fine particles in a binder can be used, but the oil protection method The preferred method is to introduce it inside.

Specifically, for example, the method described in US Pat. No. 2,322.027 is used. For this method, high boiling point organic solvents such as phthalic esters (digityl phthalate, dioctyl 7-talate, etc.), phosphoric acid esters A/(
tricredisfuos-7ate, dioctylbutyl phosphate, etc.), citric acid esters (acetyl tributyl citrate, etc.), benzoic acid esters (octyl benzoate, etc.), alkylamides (diethyl laurylamide, etc.), fatty acid esters (dibutoxyethyl succinate, etc.) nates, trimesic acid esters (tributyl trimesate, etc.),
Chlorinated paraffin (trade name: Empara≠θ, manufactured by Ajinomoto ■, etc.) is combined with a low-boiling organic solvent with a boiling point of about 300C to irooC, such as lower alkyl acetate (ethyl acetate,
After dissolution using ethyl propionate, secondary butyl alcohol, methyl imbutyl ketone, cyclohexanone, methyl cellosolve acetate, etc. as necessary, it is dispersed in a hydrophilic colloid and used as an emulsion.

In the present invention, a high boiling point organic solvent such as phthalic ester yarn or hachlorinated paraffin is used, or a combination of two or more of these or other high boiling point organic solvents as mentioned above is used to disperse the fluorescent whitening agent. It is preferable to provide

In the present invention, the use of a high boiling point organic solvent of 28i or higher means the use of two or more types of high boiling point organic solvents as described above (including cases where there are two or more types of isomers). , when two or more types are used, they have completely different structures. Two types may be used; for example, alkyl phosphoric esters with different alkyl chain lengths, phthalic esters, carboxylic esters, oxalic esters, aryl phosphoric esters with different substituent positions, and halogen substitution positions. It is effective to use a mixture of different halogenated paraffins.

Examples of isomers include those having a double bond in the alkyl chain length (cis-trans structural isomers), substituted cyclohexyl phosphates (structural isomers), and the like.

Examples of these include mixtures of the above-mentioned high-boiling organic solvents and those containing isomers.

Our research has shown that the use of phthalate esters, chlorinated paraffins, and two or more types of high-boiling point organic solvents as one dispersion medium in the present invention results in superior surface gloss, but the reason for this is not clear. I don't like it. However, these dispersion media often have better solubility of oil-soluble fluorescent brighteners than others, and are thought to have the effect of completely suppressing the diffusion of the fluorescent brightener. Therefore, it is thought that the reduction in surface gloss caused by the diffusion of the fluorescent brightener onto the surface is suppressed.

The dye fixing material of the present invention may be coated on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer are described in US Pat.

200, No. 26! The relationship described in column 7 is also applicable to the present application. In the present invention, the dye-fixing material is preferably coated on a support separate from the light-sensitive material. The dye fixing material has a dye fixing material on a support, and if necessary, a retaining w1 layer and a peeling layer 1-.

Auxiliary layers such as an anti-curl layer and a back layer can be provided. In particular, it is useful to provide a protective layer and a back layer.

One or more of the above layers may contain, in addition to a fluorescent whitening agent, a hydrophilic heat solvent, an ffi agent, an anti-fading agent, a UV absorber, a slip agent, a matting agent, an antioxidant, and a sizing agent. A dispersed vinyl compound or the like may also be added to increase the stability.

In the present invention, the dye fixing layer contains a polymer mordant capable of fixing the mobile dye released by development. Here, the polymer mordant refers to a polymer containing a tertiary amine 7 group, a nitrogen-containing heterocyclic moiety, etc. 'kW and polymers containing these primary cation groups, preferably t[, l
:C, used by mixing with other hydrophilic polymers (gelatin, etc.).

Regarding polymers containing vinyl monomer units having a tertiary amino group, JP-A No. 4T No. 3, JP-A No. 6
0-! 7134, etc., and specific examples of vinyl monomer unit Kanakura polymers having tertiary imidazole groups include JP-A-60-//r&'! No. 1I, Mukai 60-
/229'l/ issue, Tokuyo Sho 7/-47710, same 4/
-47/I/, U.S. Patent No. 'A, 2r2.30j-, U.S. Patent No. 41. //r, /2'A No. 3. /4tr,
It is described in No. 061, etc.

Preferred specific examples of polymers containing vinyl monomer units with quaternary imidazolium salts include
0rls, /0/ issue, 2,05+13゜OV
No. t, No. 1. Hari, Ri No. 61, American Special Liver MLT, /2
No. 11,1rlz, No. 'I, //j, /2←, No. 'A, No. 273, 113, No. +, +rO, No. 22'A, No. 11, 22 of the same year It is described in etc.

Other suitable examples of polymers containing vinyl monomer units containing quaternary ammonium salts include U.S. Patent No. 3,709. l, No. 90, same No. 3゜rye, orr
No. J, 9j1.9! P! No., Japanese Patent Publication No. 40-17
No. 136, No. 4O-AO4!3, No. 40-/22 ψ
θ, 6θ-722Pψλ and JO-Jjj/
It is written in J← issue etc.

The molecular weight of the polymer mordant used in the present invention is preferably /, 000 to /, 000.000. Especially / 0.0
00-200.000.

Such a polymer mordant is used in combination with a hydrophilic colloid as a binder, which will be described later, in the mordant layer of the dye fixing element.

The mixing ratio of the polymer mordant and hydrophilic colloid and the application rate of the polymer mordant can be determined easily by those skilled in the art, depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming method to be applied. It can be determined, but
Mordant/hydrophilic colloid ratio is 20/10-10/20
(by weight), the amount of mordant applied is about O11 to about /jg/m
is suitable, and it is particularly preferable to use it at O1/m2 to Ill/m2.

A polymer mordant can increase the dye transfer density by being used in combination with a metal ion in a dye fixing agent. This metal ion is present in the mordant layer containing the mordant, or in its vicinity/I (even in the vicinity of the support supporting the mordant layer, etc.).
Or it can be added to the far side). The metal ions used here are colorless and stable against heat and light. That is, Cu, Zn, Nl
Polyvalent ions of reduction metals such as Pt", )'d", and Co3+ ions are preferred, and Zn is particularly preferred. This metal ion is usually added in the form of a water-soluble compound, such as ZnSO4, Zn(CH3CO2)2, and the amount added is about 0.0/- to approx. g/m2 is appropriate, preferably o, t~/,! y/rn 2.

A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, the five hydrophilic colloids specifically listed above with respect to the mordant layer are useful.

The mordant layer containing a polymer mordant may contain various surfactants to improve coating properties.

The dye fixing material of the present invention may contain a base and/or a base precursor.

Examples of the base in the present invention include hydroxides, carbonates, bicarbonates, borates, λ and tertiary phosphates of alkali metals and l-class alkylammonium.

Inorganic bases such as metaborates; organic bases such as aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and their carbonates monobicarbonate boron acid salts, secondary and tertiary
Examples include phosphates.

Further, examples of the base precursor in the present invention include precursors of the organic bases described above. The base precursor mentioned here is one that releases basic gold by thermal decomposition or electrolysis. For example, salts of thermally decomposable organic acids such as triacetic acid, cyanoacetic acid, acetoacetic acid, α-sulfonylacetic acid, and the above organic bases,
, and salts with 2-carboxycarboxamide described in <ty+ issue. Other UK% allowance yyr, y←
Evening issue, US t\jFF No. 3. It is not possible to use the base precursors described in Kokoo, rψ6, JP-A-10-12127, and the like.

Further, the following compounds can be mentioned as compounds that generate a base by electrolysis. For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation. Through this reaction, carbonates of alkali metals and organic bases such as guanidines and azines can be obtained extremely efficiently.

In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitrone compounds, the production of amines by reduction of nitriles; the production of p-aminophenols and p-aminophenols by reduction of nitro compounds, azo compounds, azoxy compounds, etc. -7 Failures of 22 diamines, hydrazines, etc. can be mentioned. p-aminophenols, p-
In addition to being used as bases, 722 diamines and diamines can also be used directly as color image-forming acid substances. Of course, it is also possible to generate argali-class metal by electrolysis of water in the coexistence of various inorganic salts. Preferred specific examples are shown below, but the invention is not limited to these.

Lithium hydroxide, sodium hydroxide, sodium carbonate,
Cesium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium quinolate, dibasic potassium phosphate, dibasic potassium phosphate, tertiary sodium phosphate,
Tertiary potassium phosphate, potassium birophosphate, sodium metaborate, borax, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, (
CH3)2NH1(C2Hs)2NH,C5H7NH
2, HOC2H4NH2, (HOC2H4)2NH.

(HOC2H4)3N, H2NC2H4NH2, H2N
C4H3NH2, CH3N HC2H4N HCH3,
(CH3)2NC3H6N(CH3)2°CH3 1-13 H3 H H Guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloro6! , p-to, idine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine carbonate, piperidine carbonate, morpholine carbonate, tetramethylammonium trichloroacrate, etc.

Furthermore, a compound (for example, picolinate, etc.) that can undergo a complex reaction with a metal ion constituting the poorly soluble metal salt compound (for example, zinc oxide, basic zinc carbonate, calcium carbonate, etc.) in water as a medium, and the poorly soluble metal salt. A method of generating a water-soluble base by reaction with a compound can also be used. In this method, a light-sensitive material contains a dispersion of a sparingly soluble metal salt compound, and a dye-fixing material contains a water-soluble compound that can form a complex with the metal ion as a base precursor, and both are mixed in the presence of water. Since a base can be generated during heat treatment in close contact, it is particularly effective in improving the storage stability of light-sensitive materials and dye-fixing materials over time.

Hydrochloric acid and/or base precursors can be used alone or in combination of two or more.

Amount of base and/or base precursor used Id! ×
70'-6x10-'mol/m2, preferably 2.
j

The heat-developable photosensitive material used in combination with the dye-fixing material of the present invention basically consists of a support containing photosensitive silver halide, a dye-providing compound that can release or generate a diffusible dye by heat development (described below) (in some cases, a reducing agent also serves as a reducing agent) and a pineapple. Furthermore, if necessary, an organic metal salt oxidizing agent, a reducing agent, etc. can be contained. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination.

For example, there may be a combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, or a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials.

In addition, each of these photosensitive layers may be divided into two or more layers if necessary. Various auxiliary layers can be provided.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion.The internal latent image type emulsion is directly combined with a nucleating agent and a photofog. Used as a reversal emulsion. It may also be a so-called Faschel emulsion in which the inside of the grain and the surface layer of the grain have different phases.

The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. Particle size is 0.1-2
μ, particularly preferably 0.2 to 1.5 μ. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high 7-vecto ratio, or any other form.

Specifically, U.S. Patent No. 4,500,626, column 50, U.S. Pat.
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halidene emulsion may be used unripe, it is usually used after being chemically sensitized. 'i! A sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method, etc. for emulsions for J-type conventional photosensitive materials can be used alone or in combination. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 111 g to 10 g/l112 in terms of silver.

In the present invention, in addition to photosensitive silver halide, organic*
A metal salt can also be used in combination as an oxidizing agent.

Among such m*s salts, [4 salts are particularly preferably used.

Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Also useful are silver salts of carboxylic acids having a furkynyl group, such as silver phenylpropiolate described in JP-A-60-113235, and acetylene silver as described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. Photosensitive 1175/silver oxide and 8N! The total coating amount of I salt is suitably 50 tags to 10 g/m2 in terms of silver.

Various Kabuso fat fixing agents or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978 124-25ffl = 7zoles and 7zaindenes described, nitrogen-containing carboxylates I! 2 and phosphoric acids described in JP-A-59-168442, or J-Kokai IIi ¥59-111636) Mercapto compounds and their gold R salts, acetylene compounds described in JP-A-32-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxol dyes.

Specifically, U.S. Pat.
17029 (1978), pages 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is particularly suitable for the purpose of supersensitization. l-r! Along with the muka-sensitizing dye used, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, in the United States). Patent No. Pt53,615.641, JP 63-23145
(as stated in the item, etc.)

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
, 756, No. 4,225,666, it may be carried out before or after nucleation of silver halide grains.

The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

h'lt f! of photosensitive materials and dye fixing materials. A hydrophilic binder is preferably used as the binder for j and M. An example of this is from page (2G) of JP-A-62-253159.
Examples include those described on page (28). Specifically, transparent or translucent hydrophilic baingu is preferred, such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, gum arabic, dextran,
Examples include natural compounds such as poly[+1] such as pullulan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. In addition, super absorbent polymers described in JP-A No. 62-245260, i.e., homopolymers of vinyl monomers having -COOM or -3O,M (M is a hydrogen atom or an alkali metal), these vinyl monomers together, or other copolymers with vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5) 1 manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders are 2F! It is also possible to use one or more in combination.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. Further, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to another material after transfer.

In the present invention, the amount of binder applied is 2 per 1 m'.
It is preferably 0 g or less, particularly IOE or less, and more preferably 7 g or less.

Constituent layers (including back layers) of photosensitive materials or dye-fixing materials contain various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It is possible to contain latex. Specifically, JP-A-62-245258 and JP-A-62-136
Any of the polymer latexes described in No. 648, No. 62-110066, etc. can be used. In particular, if a polymer latex with a low glass transition point (40°C or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used for the back layer, curling can be prevented. is obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. It also includes a dye-donating compound that has reducing properties, which will be described later (in this case, other reducing agents can also be used in combination). Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in the present invention include U.S. Pat.
, No. 500.626, columns 49-50, same No. 4,483
, No. 914 fjS30~314! ! II, same No. 4゜3
30.617 dimensions, No. 4,590,152, Japanese Patent Application Publication No. 1983
No. 0-140335, pages m (17) to (18), 57
-40245, 56-138736, 59-1
No. 78458, No. 59-53831, No. 59-182
449chi., No. 59-182450, No. 60-119
No. 555, No. 60-128436 to No. 60-128
Up to No. 439, No. 60198540, No. 60-181
No. 742, No. 61-259253, No. 62-2440
445-1 (+2-131253 to 62-13)
There are reducing agents and reducing agent precursors described in pages 78 to 96 of European Patent No. f5220.746A2 up to No. 1256.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

When using a #-resistant, aged reducing agent, an electron transfer agent and a V/V are added as necessary to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Or Denden i! Combinations of drug precursors can be used.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. The electron transfer agent or its precursor has a mobility that is useful for a diffusion-resistant reducing agent (electron (J (donor)) is preferably larger than ↑), such as 1 phenyl-3-pyrazolidones or 7 Mi/phenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

Examples of dye-donating compounds that can be used in the present invention include two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through a coupling reaction with an oxidized color developing agent. It will be done.

This diffusion-resistant group may form a polymer chain.

Specific examples of color developers and couplers are given by Noames et al.
The Theory on the 7-year-old Tographic Process" 4th edition (T, H, J an+es "T be T l
+eoryor the PI+otogral〕l+
ic Process'') pages 291-334, and 3
pp. 54-361, JP-A-58-123533, JP-A No. 58
-149046, 58-149047, 59-
No. 111148, No. 59-124399, No. 59-1
No. 74835, No. 59-231539, “No. 59-
231540, No. 60-2950, No. 60-295
1, GO-60-14242, GO-23.174, GO-60-60249, etc.

Further, as another example of the dye-providing compound, there can be mentioned a compound having a function of releasing or diffusing a diffusible dye in an imagewise manner. Compounds of this type can be represented by the canine general formula (LI).

(Dye-Y)n Z (Ll) Dye represents a dye group, -temporally shortened dye group or dye precursor group, Y is a small bond or J1! It represents a group, and Z is ii! ii Correspondingly or inversely to the photosensitive silver salt having a latent image, (1) ye −Y ) n −Z″C causes a difference in the diffusivity of the compound, or releases Dye. , represents a group having the property of causing a difference in diffusivity between the released Dye and (Dye-Y) n-Z, where n represents 1 or 2, and when n is 2, two Dye Y may be the same or different.

- Examples of the dye-donating compound represented by formula [Lr] include the following compounds 6 to 6.
In addition, ■ to ■ below are those that form a diffusive dye image (positive dye image) in inverse correspondence to the development of silver lodenide, and ■ and ■ correspond to the development of silver halide. It forms a diffusive dye image (negative dye image).

■U.S. Patent Nos. 3,134,764 and 3,362.
No. 819, m3,597,200, m3.544
．． 545, PpJ3,482,972, etc., a dye developer in which a hydroquinone developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

(2) As described in US Pat. No. 4,503,137, non-diffusible compounds can be used that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide. Examples include U.S. Patent No. 3,980
．． Compound that releases a diffusible dye through an intramolecular nucleophilic substitution reaction described in No. 479, etc., US Pat. No. 54,199
．． Examples include compounds that release diffusible dyes through an intramolecular rewinding reaction of the inoxacilone ring described in No. 354 and the like.

■US Patent No. 4,559,290, European Patent No. 220
．． No. 746A2, U.S. Pat. Chemical compounds can also be used.

Examples of such methods are as described in U.S. Patent No. 4,139,389, U.S. Pat. Compound that releases diffusible dye by nuclear substitution reaction, U.S. Pat.
4025 (1984), etc., which releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. 3,008,588A, JP-A-56
-142530, U.S. Patent Section 4,343.893;
No. 4,619,884, etc., after reduction, the double bond is cleaved to release a diffusible dye, and the electrons described in U.S. Patent Section 4,450,223η, etc. Bone'f: Examples include nitro compounds that later release a diffusible dye, and compounds that release a diffusible dye after accepting electrons as described in US Pat. No. 4,609,610 and the like.

Also, more preferably, European Patent No. 220.7
No. 46A2, Published Technical Report 87-6199, U.S. Patent Section 4,
783,396';j, N-
Compound having an X bond (Xl represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Patent Application No. 10688, No. 1988
Compound having 5Q2-X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 5, JP-A-63-271
344, a compound having a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule, JP-A-63
Examples include compounds having a C-X (the double bond Xl has the same meaning as X or -5O2-) and an electron-withdrawing group in one molecule as described in No. 271341. Also, special application 1986-
Compounds described in No. 319989 and No. 62-320771 that release a diffusible dye by cleavage of a single bond after reduction by an X bond conjugated with an electron-accepting group can also be used.

Among these, compounds having an N-X bond and an electron-withdrawing group in the -molecule are particularly preferred. A specific example is European patent Pt5
220,746A2 or U.S. Patent Section 4.783,39
Compounds (1) to (3), (7) to (1) described in No. 6
o), (12), (13), (15), (23) to (2
6), (31), (32), (35), (36), (
40), (41), (44), (53) to (59), (
64), (70), the compound of Kokai Technical Report 87-6199 (
11) to (23), etc.

■A compound that has a diffusible dye as a leaving group and releases a diffusible dye upon reaction with an oxidized form of a reducing agent (
DDR coupler). For shellfish, British Patent Department 1,33
No. 0.524, Japanese Patent Publication No. 48-39゜165rf1 U.S. Patent ff13,443. ') 409・, In4.474
．． 8 G No. 7, FF No. 14, 483, 914, etc.

■Reducing to silver halide or growth silver salt,
A compound that releases a diffusible dye upon reduction of its partner (DR
R compound). Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent. Sonodai i example +, t, US patent f5
3,928,312vf, same PIS4,053,312
No. 4,055,428, ff14,336,
No. 322, JP-A-59-65839, JP-A No. 59-698
No. 39, No. 53-3819, No. 51-104.343
No. RD174G5, U.S. Patent Section 3,725.062
No. 53.728.113, No. 3,443,9
No. 39, JP-A-58-116,537, JP-A No. 57-17
98409, U.S. Patent Section 4,500. It is described in No. f326 etc. Specific examples of DRR compounds include the above-mentioned US Pat.
Among them, compounds (1) to (3), (10) to
(13L (16) to (19), (28) to (30),
(33) ~ (35), (38) ~ (40), (42) ~
(64) is preferred. Also, U.S. Patent Section 4.639. '4
Compounds described in No. 08, columns 37 to 39 are also useful.

In addition, dye silver compounds in which an organic silver salt and a dye are combined (Research Disk A-Noyer Magazine 19
May 1978, pp. 9.54-58), Azo dye used in heat-developable silver dye bleaching method (U.S. Pat. No. 4,235,957)
No., Research Disclosure Magazine, April 1976 issue, pages 30-32, etc.), leuco dyes (U.S. Patent Nos. 3 and 9),
No. 85,565, No. 4,022.617, etc.) can also be used.

(Left below) Hydrophobic additives such as dye-providing compounds and diffusion-resistant reducing agents can be incorporated into the layers of the photosensitive material by known methods such as the method described in U.S. Pat. No. 2,322,027. It's a monkey. In this case, Japanese Unexamined Patent Application Publication Nos. 59-83154 and 59-83154,
178451, No. 59-178452, No. 59-
No. 178453, No. 59-1.78454, No. 59-
178455, 59-178457, etc., if necessary, with a boiling point of 50°C or more.
It can be used in combination with a low boiling point organic solvent of 160°C.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. In addition, less than ice per 1g of binder, and even 0.5c
cc or less, particularly 0.3 cc or less is suitable.

The fractional method using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. In addition to the above-mentioned anionic surfactants, examples of surfactants include JP-A-59
The surfactants listed on pages m(37) to (38) of No.-157636 can be used.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see US 1. y permission 4th,
500.626, columns 51-52.

In the constituent layers of the light-sensitive material and the dye-fixing material, high-boiling, α-based solvents can be used as plasticizers, slipping agents, or peelability improvers between the light-sensitive material and the dye-fixing material. Some of these are described in 1982-253159, page (25), and 62-245253.

Oils (all silicone oils from trimethylsilicone oil to modified silicone oils with various organic groups added to trimethylsiloxane) can be used. Examples include various modified silicone oils, especially carboxy-modified silicone (product name:
-22-3710) etc. are effective.

Also, JP-A No. 62-215953Ii:T, No. 63-46
The silicone oil described in 449 Me. is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include taloman compounds, coumaran compounds, phenolic compounds (e.g. hindered phenols), hydroquinone 1 conductors, hingoamine derivatives, spiroingene I and Δlbl? 42 +
1+ prayer Qffff7JI': 1-111: Of
': j The compound described in item A is also effective.

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352GB1, etc.),
Benzo 7/N-based compounds (Japanese Patent Publication No. 4G-2784), Sono et al.
2-136 (341'';
The ultraviolet absorbing polymer described in No. 2 is also effective.

Examples of metal complexes include U.S. Patent No. i, 241,155, U.S. Patent No. 14,245,018, columns 3 to 36, U.S. Patent No. 4,
No. 254.195, columns 3 to 8, JP-A-62-17474
No. 1, No. 31882543 (27) to (29) L No. 63-199248, Japanese Patent Application No. 62-234103,
There are compounds described in No. 62-230595 and the like.

An example of a useful anti-fading agent is JP-A-62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material is preliminarily applied to the color '7. It may be contained in the fixing material, or it may be supplied to the dye fixing material from outside of the photosensitive material or the like.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Teli is used as a hardening agent for constituent layers of photosensitive materials and dye-fixing materials, as described in U.S. Pat. Mention may be made of the hardening agents described. More specifically, aldehyde hardeners (such as formaldehyde), anolinone hardeners, epoxy hardeners, vinyl sulfone hardeners (N,N'-ethylene-bis(vinylsulfonylacetamide)), ethane, etc.), N-
Examples include methylol-based hardeners (such as tumethylol urea) and polymer hardeners (compounds described in JP-A No. 62-234157, etc.).

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of photosensitive materials and dye-fixing materials may have slippery defects,
An organic fluoro compound may be included for the purpose of preventing banding and improving releasability. Typical examples of organic fluoro compounds include 1.) fluorine-based surfactants described in Publications No. 57 9053'7, columns 8 to 17, JP-A No. 61-2 (1944, No. 62-135826, etc.); Alternatively, hydrophobic fluorine compounds such as oily fluorine-based compounds such as 77% oil, solid fluorine compounds such as l!!177)-treated ethylene resins, and 0I fats may be mentioned.

A mantle agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc. JP-A-6L-8825 can be used.
In the pond of compounds described in No. G, page 29, benzoguanamine U (fat beads, Polycar No. 62-110064, No. 6) was added.
There is a compound described in No. 2-110065.

In addition, heat solvents, antifoaming agents, antibacterial agents, Froeglsilicity, etc. are added to the constituent layers of the photosensitive materials and dye fixing materials.
- You may let it. Specific examples of these additives are given in JP-A-61
No. 88256 (26) to (32) rc.

In the present invention, both image formation accelerators can be used in the light-sensitive material and/or the dye-fixing material. Both image formation accelerators promote the oxidation-reduction reaction between the silver salt oxidizing agent and the reducing agent, the generation of dye from a dye-donating substance, the decomposition of the dye, the release of diffusible dye, etc. It has functions such as promoting the movement of dye from the layer to the dye fixed layer, and from a physicochemical function, it has a base or base precursor, a nucleophilic compound, a high boiling point organic solvent (oil), a thermal solvent, a surfactant, It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions, and the above-mentioned promoting effects are described in U.S. Patent No. 4,
No. 678,739, columns 38-40.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that interacts with silver and i-salt to inhibit development. It is a compound that

In terms of structure, acid precursor releases acid upon heating;
By heating, electrophilic compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors, etc., which undergo a substitution reaction with the base that undergoes TI (hC) are depleted.

Further details L < 1. tvI-f7u? Y62-2531
No. 59, pages (31) and (32).

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. - Paper, synthetic polymers (films) can be used inside the shell. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimides, celluloses (e.g. triacetylcellulose), or films containing pigments such as titanium oxide, film-formed paper made from polypropylene, synthetic resin pulp such as polyethylene, and natural pulp. Mixed paper, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, glass, etc. are used.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-253159 (2) to (3)
The supports described on page 1) can be used.

A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods of exposing and recording images on photosensitive materials include, for example, using a camera to directly photograph wind and people, etc., exposing through reversal film or negative film using a printer or enlarger, and reducing the cost of copying. Exposure i
A method in which the original image is scanned and exposed through a slit etc. using a device such as a slit, a method in which image information is exposed by emitting light from a light emitting diode, various lasers, etc. via an electronic signal, a method in which image information is transmitted to a CRT, liquid crystal display, electroluminescence display, etc. There are methods of outputting the image to an image display device such as a spray or plasma display and exposing it directly or through an optical system.

Light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc. as mentioned above, such as U.S. Pat. No. 4,500.6.
2G Bow - The light source described in Title 56 can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. These are materials that can exhibit nonlinearity between the polarization and the 71 field that appear when considering nonlinear optics, such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and Dal120. Kuroiso compounds such as urea 1? nitroaniline derivatives, e.g. 3
-Methyl-4-nitrobilinone-N-Oquindo (POM
), compounds described in JP-A No. 61-53462 and JP-A No. 32-2104325 are preferably used. Examples of the form of the wavelength conversion element include a single crystal optical waveguide type, 7-fiper type and the like are known, and all of them are useful.

In addition, the above-mentioned RIJ image information is an image signal obtained from a video camera, an electronic still camera, etc., or a telepinotan signal standard v! (NTSC), an image signal obtained by dividing the original image into many pixels using a scanner, etc.
It uses image signals created using computers, such as CG and CAD.

Alternatively, it may have a conductive heating layer as a heating means for diffusion transfer of the dye.

In this case, the transparent or opaque heat generating element is
/-/111! You can use the one described in the 'l≠ specification, etc. Note that these four layers also function as an antistatic layer.

The heating temperature in the heat development process is about ro0c to about ltoc
It can be developed at a temperature of about tO°C to about /r00c, but is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but it is especially preferable to use a temperature range of rO"c or higher and about 100C lower than the temperature in the heat development process. It's cool.

Dye migration can also be caused by heat alone, but solvent sound may also be used to promote dye migration.

A preferable image forming method in the present invention is the image vl, 5
After 1e or at the same time as image g light, heating is performed in the presence of a trace amount of water and a base and/or base precursor, and at the same time as development, the diffusible dye generated in the area corresponding to or inversely corresponding to the silver image is transferred to the dye fixing layer. It is something to be transferred. According to this method, the production and release reaction of the diffusible dye proceeds extremely quickly, and the transfer of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.7 times, preferably 0.7 times or more, the weight of the entire coated film of the light-sensitive material and dye-fixing material, and corresponds to the maximum swelling volume of the entire coated film. The amount may be as small as the weight of the solvent (in particular, the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

The state of the film when it swells is unstable, and depending on one condition, it may cause local bleeding noise. To avoid this, add water equivalent to the maximum swelling volume of the total coating film thickness of the photosensitive material and dye fixing material. It is preferable that the amount is less than or equal to . Specifically, the total area of light-sensitive material and dye-fixing material per square meter/fl
-! 01/, particularly preferably in the range of 2g to 3g, more preferably 3g to 2jp.

The base and/or base precursor used in this embodiment can be incorporated into the dye-fixing material as well as the dye-fixing material.

It can also be supplied dissolved in water.

In the above embodiment, the image forming reaction system contains a basic metal compound that is sparingly soluble in water as a base precursor and a compound gold that can undergo a complex reaction as a water-metal medium with a metal ion constituting the sparingly soluble metal compound. It is preferable to raise the pH of the system by reaction of these two compounds during heating. Here, the image reaction system means a region where an image forming reaction occurs. Specifically, layers belonging to elements of both a photosensitive material and a dye fixing material can be mentioned. If two or more layers are present, any of the layers may be used.

The poorly soluble metal compound and the complex-forming compound need to be added at least in separate layers in order to prevent them from reacting in the development processing chamber. For example, in a so-called monont material in which a light-sensitive material and a dye-fixing material are provided on the same support, it is preferable that the above-mentioned two additive layers are separate layers, and a layer with an intervening IC/C or higher is interposed. Moreover, a more preferable form is
A poorly soluble metal compound and a complex-forming compound are contained in layers provided on separate supports, respectively. For example, it is preferable that the poorly soluble metal compound be contained in a light-sensitive material and the complex-forming compound be contained in a dye-fixing element having a support separate from the light-sensitive material. The complex-forming compound may be supplied after being dissolved in water to be coexisting. Hardly soluble metal compounds are covered by Tokukai Sho! t-774
It is preferable to contain it as a fine particle dispersion prepared by the method described in No. t130, Mukai J3-102733, etc., and the average particle size thereof is preferably to microns or less, particularly tamicrons or less. The sparingly soluble metal compound may be added to any layer of the photosensitive material, such as the photosensitive layer, intermediate layer, or protective layer, or may be added after being divided into two or more layers.

The amount of addition i in the case of containing a poorly soluble metal compound or a complex-forming compound in the layer on the support depends on the compounding process, the particle size of the poorly soluble metal compound, the complexing acid reaction rate, etc. It is appropriate to use it at 0% by weight or less when converted to weight, and more preferably 0.0/'! ILi
k percent to ttt.

A range of percent M amounts are useful. In addition, when supplying the complex acid compound dissolved in water, from 0.00 jmol/liter! rno I *Especially O,
A concentration of Ojmol to 2 mol is preferred. Furthermore, in the present invention, the content of the complex acid compound in the reaction system is 77,100 times to 100 times the molar ratio of the content of the poorly soluble compound.
A ratio of 1,710 times to 20 times is preferred.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, JP-A-47-/447.2! There is a method described in issue ←.

As a heating means in the development and/or case or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a means described in No. 72ψ1.

Alternatively, a layer of conductive material such as graphite, carbon black, metal, etc. is applied to the photosensitive element and/or the dye fixing element, and the conductive layer is heated directly by passing a t-stream through it. Good too.

The pressure conditions and method of applying pressure when layering a photosensitive material and a dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 4/1979/lt7.
The method described in ←ψ can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, Tokukai Akira! 2-7!2 Gua,
From the same, 1777ta No. 41-7, same! ? -/I/33;3
No. tO-/IYr1, Jitsugan 40-//bu 731
The apparatus described in No. 1 etc. is preferably used.

Example 1 A dye fixing material (5) having the composition shown in Table 1 was prepared.

Corn oil (1) Surfactant (1) Surfactant (2) C8FI 7SO2NCH2COOKJin3H7 Surfactant (3) CH3 CH2COOCH2(,:HC4)19(:2H5 Surfactant (5) 3H7 ?17SO2N(- CH2CH20sudcH2su4 S
O3N a addition agent (1), 2. ! Bis(!-ter7yabutylbenzoxazole (2)) Thiophene polymer (1) Kagel Lj-H (manufactured by Sumitomo Chemical ■) Water-soluble polymer (2) Dextran (molecular weight 70,000) Mordant (1) High in +CH3O3 Boiling point solvent (1) Surfactant (6) Hardener (1) Matting agent (1) "Nrica matting agent (2)" Benzoguanamine resin (XF-average particle size l!μ) Fluorescent brightener is as follows. It was used in the form of a so-called seratin dispersion.

Fluorescent brightener (1) g is mixed with high boiling point organic solvent (2) lφO
g and ethyl acetate ROCC, and heated and dissolved to form a homogeneous solution. This solution, an aqueous solution of lime-treated gelatin 300/i, and surfactants (1) to and og were stirred and mixed, and then dispersed using an ultrasonic disperser. This dispersion is called gelatin dispersion of fluorescent brightener (1).

Next, in the gelatin dispersion of fluorescent brightener (1), the fluorescent brightener and high boiling organic solvent shown in Table 2 were used instead of the fluorescent brightener (1) and the high boiling point organic solvent (2). Sara V using melt charge? c Second layer surfactant (1) in the amount shown in Table 2
, (4), or (6) in the same manner to prepare a gelatin dispersion of a fluorescent brightener and add the dye fixing material (1) as shown in Table 3.
) to (4) and (6) to (37) were made.

A photosensitive material (1) having a multilayer structure, which will be described later, was exposed to light for 1,710 seconds at 0,000 lux using a tungsten light bulb through a gray filter with a continuously changing density.

While feeding this exposed photosensitive material at a gold wire speed of 20 mm/sec, the emulsion surface is coated with /! ml/m of water was supplied with a wire bar, and the membrane was immediately superimposed so that the membrane surface was in contact with the dye fixing material.

Using a heat roller whose temperature is adjusted so that the temperature of the water-absorbed membrane is ro 0c, l! Heated for seconds. When it was then peeled off from the image-receiving material, a gray image corresponding to the gray filter was obtained on the dye-fixing material.

Regarding the dye fixing materials (11 to (37)), use a gloss meter manufactured by Nippon Densoku Kogyo @ to measure the surface of the dye fixing material at
The specular gloss was measured at an angle of .

Thereafter, after leaving it for UO time under the condition of ro'c-to%RH, the specular gloss was measured again in the same manner.

The respective values are shown in Table 2.

For dye fixing materials (1) to (37) treated in the same manner, the maximum density was measured using a Fuji Photo Film m degree measuring device (FCD).
-3), and then a fluorescent lamp (l!.

000Lux), the maximum concentration was measured again after the sample was left for ψ weeks. The ratios are shown in Table 2.

In addition, we evaluate the peelability by determining how much force is required to peel it off, and by observing the surface of the dye-fixing material after peeling to see if the film has peeled off or if the sensitive material film has not adhered to it. It was judged.

High boiling point organic solvent (2) High boiling point organic solvent (3) High boiling point organic solvent (4) High boiling point organic solvent (5) 'CI 1H23CON(-C2H5)2 High boiling point organic solvent (6) 2H5 2H5 High boiling point organic solvent ( 7) High boiling point organic solvent (8) High boiling point organic solvent 0ω High boiling point organic solvent Oυ (Cn H2 (1+ lO + P = 0 Ratio of alkyl chain length = O1ψ E: /7:7J' Ratio of alkyl chain length n = A.

n-♂, n=P =2 //: ♂7 High boiling point organic solvent α諌C3H7(i) High boiling point organic solvent 04) C26H43,5C16,5 Chlorine content approx.←lMultiple high boiling point organic solvent α9 C14Hzs, 9C14 , x Chlorine content approximately ←3% As is clear from Table 2, the anionic surfactant t of the present invention has no problem in peelability and has excellent surface gloss.

On the other hand, when the amount of surfactant is less than the range of the present invention (l, 24), the initial surface gloss is good, but there is a problem with the peelability.

Furthermore, it can be seen that the surface glossiness decreases over time.

Although it is not clear what causes this, it is thought that the stability of the fluorescent brightener emulsion is reduced and the precipitation of oil-soluble acids is promoted.

Furthermore, it can be seen that when the amount of surfactant is greater than the amount of the present invention, the surface gloss is low and the decrease is large.

Furthermore, the fastness of the color image is slightly reduced. Although this is not clear, the anionic surfactant interacts with the cationic mordant to reduce fastness, so it seems to be V'X. Furthermore, when the high boiling point organic solvent used in combination for dispersing the fluorescent brightener is a 7-tar acid ester (10 to 14) and when two or more types are used in combination (17
~20.23.24.25.26) It can be seen that the surface gloss is good and there is little change during storage. There are no particular problems with the fastness of color images of the dye (4) constant material group of the present invention.

From the above, the effects of the present invention are clear.

The structure of the photosensitive material (1) used in this example will be explained below.

This section describes how to prepare a photosensitive silver halide emulsion for each layer.

/) How to make photosensitive silver halide emulsion (I) A well-stirred seratin water bath solution (2 gelatin in water roocc)
0g. 3 g of potassium bromide, and 28 g of HO(CH2) (
CH2) 28 (CH2) 20H o, ip gold added! !
The following solutions (1) and (2) were simultaneously added to the container kept warm at 0C for 30 minutes.

Thereafter, the following solutions (3) and (4) were added simultaneously over a period of 20 minutes. Also, (3) after starting the addition of the liquid! The following dye solution was added over 11 minutes.

After washing with water and desalting, 20 g of lime-treated ossein seratin was added to adjust the pH to 2.2, pAg gold r, r, and thiosulfur (R sodium and ←-hydroxy-6-methyl-/,
．． 3a,7-chitrazaindene and chloroauric acid were added to perform optimal chemical amplification. In this way, the average particle size, O0
A monodisperse lψ-hedral silver iodobromide emulsion toog of ψOμ was obtained.

dye solution Et3 (CH2)a 5Oa- xg (CH2)45Q3- (CH2)4SO3H-NEt3 ag is dissolved in methanol/AOca.

j) How to make a photosensitive silver halide emulsion (■) A well-stirred aqueous solution (ceratin 2017, potassium bromide o, zog, sodium chloride 4 in 7 JOml of water)
g and the following chemicals ho, oirg2 plus to, o'C
The mixture was added to the following solution CI) and solution (II) at the same time over 60 minutes at the same flow rate. (1) After the addition of the solution, a memenol solution (III) of the following sensitizing dye was added. In this way, the average particle size O0←! A monodisperse cubic emulsion adsorbed with μ dye was prepared.

After washing with water and desalting, add 20fif of gelatin and adjust the pH to +.
p, pAg' to 7-IrKv! 4'RiL,, Tanochi, to.

Chemical sensitization was performed at oQc. The chemicals used at this time were 100 m9 of triethylthiourea/, 6■ Tobi-hydroxy-6-methyl-/, 3.3a, 7-chitrasaindene, and the aging time was ! ! It was a minute. The yield of this emulsion is 6
3! It was θ.

CH3 (sensitizing dye C) 3) How to make photosensitive silver halide emulsion (III) Seratin water bath solution (100 rtti of water) with good stirring.

Gelatin inside 209. Potassium bromide 19, and 0H (
CH2) 25 (CH2) 20H・0 ,j,! 1iIf
In addition, roocVc was kept warm), the following solution (I) and (
11) Solution and <■) solution were simultaneously added at equal flow rates over VCJθ minutes. In this way, the average particle size is 0.11
A monodispersed silver bromide emulsion vI4 to which a μ dye was adsorbed was prepared.

After washing with water and desalting, add lime-treated ossein seratin, 2 (7 g, p) ('64.
Chloroauric acid 0.07% aqueous solution Arn1. goohydroxy-2-methyl-'='r3a+7-chitrazaindene/
Add YO1'9, 4t! Chemical sensitization was performed for minutes. The yield of emulsion is A! It was r9.

(CH2)+5OaNa Next, how to make a gelatin dispersion of a dye-providing compound will be described.

Yellow, magenta, and cyan were each dissolved in ethyl acetate (QCK 7JD) by heating to a uniform solution according to the following recipe. This solution and 100 ml of a 10% aqueous solution of lime-treated gelatin, 0 ml of sodium dodecylbenzenesulfonate, 4 ml of water! OCe 'i
i After stirring and mixing, mix in a homojibuiner for io minutes, / 0
000 rpm. This dispersion is called a gelatin dispersion of a dye-providing compound.

Dye-donating compound (1) CONHC16H33 Electron donor ■ 0H High boiling point solvent ■ Precursor before electron transfer ■ Next, the preparation of a gelatin dispersion of the electron donor for the intermediate layer (■) will be described.

The following electron donor ■23. t9 and the above high boiling point solvent ■r
, rII were added to 30 CC of ethyl acetate to make a homogeneous solution. i of this solution and lime-treated gelatin.

Polyaqueous solution 10017, sodium bisulfite 0.2! g
1 After stirring and mixing 0.3 g of dobufulbencensulfonate and 30 QCf of water, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of electron donor (1).

Electron donor■ Next, a method for preparing a dispersion of zinc hydroxide will be described.

Zinc hydroxide/co with an average particle size of O0Xμ.

91 Carboxymethylcellulose/g as a dispersant,
Polyacrylic acid powder 0. /9f←Gelachi/aqueous solution 1
0OCC, and was ground for 30 minutes in a mill using glass beads with an average particle size of 0.7 mm.

The glass peas were separated to obtain a dispersion of zinc hydroxide.

Next, a method for preparing an activated carbon dispersion will be described.

Activated carbon powder (reagent, special grade) manufactured by Wako Tsumugi ■! g, Demol h/g manufactured by Kao Soap ■ as a dispersant, polyethylene glycol nonylphenyl ether O, co! Add g to 1 ooca of 1% aqueous seratin solution.

Using glass beads with an average particle size of 0.71 mm in a mill,
Milled for 120 minutes. The glass beads were separated to obtain a dispersion of activated carbon with average particle diameters of o and rμ.

Next, a method for preparing a dispersion of electron transfer agent (1) will be described.

The following electron transfer agent ■/ Ofl, polyethylene glycol nonylphenyl ether O6 as a dispersant! g, the following anionic surfactant ■0, j9f! % Seratin aqueous solution and a mill to reduce the average particle size to 0°7! It was ground for 60 minutes using mm glass beads. Separate the glass peas,
A dispersion of an electron transfer agent with an average particle size of 0.3 μm was obtained.

Electron transfer agent■ Anionic surfactant■ CH2C00CH2CH(C2H5)C4H9Na03
8-CHCOOCH2CH(C2H5)C4H9 Using these, heat-developable color photosensitive materials shown in the following table were prepared.

Note 1) Surfactant■ Note 2) Surfactant■ CH2C00CH2CH(C2H5)C4H9Na03
S-CHCOOCH2CH (C2H5)C4H9 Note 3) Water-soluble polymer SO3 Note 4) Antifoggant ■ Note 5) Surfactant ■ Note 6) Surfactant ■ Note 7) Electron transfer agent ■ Note 8) Electron transfer agent ■ Note 9) Hardener 0 / Corbis (vinylsulfonylacetamide) Ethane Note 1 O) Antifoggant■ Example 2 The photosensitive material of Example 1 was used in JP-A-63-! When the photosensitive material of Example 1 described in 1r41-r was substituted and the same test as in Example 1 was conducted, almost the same results as in Example 1 were obtained.

Claims (3)

[Claims] (1) In a dye-fixing material having a dye-fixing layer capable of receiving a diffusible dye formed in a heat-developable photosensitive material by heat development, an oil-soluble fluorescent brightener is added to the side having the dye-fixing layer. and the total amount of anionic surfactant on the side having the dye fixing layer is 20 mg/m^2 to 200 mg/m^2
A dye fixing material characterized by: (2) The dye fixing material according to claim 1, wherein the oil-soluble fluorescent whitening agent is contained as a dispersion using a phthalate ester or chlorinated paraffin type high-boiling organic solvent. (3) The dye fixing material according to claim 1, characterized in that the oil-soluble fluorescent whitening agent is contained as a dispersion using two or more types of high-boiling organic solvents.