JPH04172347A - Thermally developed color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain thermally developed color photosensitive material, which is excellent in forming high quality images, and preservability, and improved curling property by using a paper supporting body whose one side has photosensitive silver halide coloring matter donor property compound, and amino group inert gelatin derivative and whose other side has not hydrophilic binder. CONSTITUTION:One side of a paper supporting body of 200 micron or less in thickness has at least photosensitive silver halide coloring matter donor property compound and amino group inert gelatin derivative, and the other side of the paper supporting body has not hydrophilic binder. Paper, generally, or blended paper of synthetic resin pulp such as polyethylene and natural pulp can be used for the paper supporting body. By this constitution, thermally developed color photosensitive material which is excellent in forming high quality images, preservability and curling property can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-developable photosensitive material, and in particular to a heat-developable color photosensitive material with high image quality and excellent storage stability. (Prior art and its problems) Heat-developable photosensitive materials using silver halide as a photosensitive component are well known in this technical field, such as "Fundamentals of Photographic Engineering" Non-Silver Salt Photography! (Published by Corona Publishing, 1982) No. 24
Pages 2 to 255, video information published in April 1978, page 40,
Nebletts Handbook Op Photography and Reprography
book of Photography and Re
prography) 7th Edition (7th Ed,) Van Nostrand Reinhold Company (Van
Nostrand Re1nhold Company
), pages 32-33, U.S. Patent No. 3,152,904, U.S. Patent No. 3,301.678, U.S. Patent No. 3,392,020
No. 3,457,075, British Patent Box 1,131
No. 108, No. 1.167.777, and Research Disclosure Magazine (hereinafter abbreviated as RD) 197
It is described on pages 9-15 of the June 1988 issue.

Many methods have been proposed for obtaining a color image by heat development.

For example, a method of forming a color image by combining a coupler with an oxidized developer produced by reduction of silver halide is disclosed in U.S. Pat.
61,270, Belgian Patent No. 4,021.240, Belgian Patent No. 802,519, RD-13142, etc.

In addition, US Pat. No. 4,235 discloses a method of forming a dye image on a ribbon by thermal development using a silver dye bleaching method using silver halide.
, No. 957, RD-14433, RD-15227, etc.

Further, a method in which a diffusible dye is formed or released in an image form from a dye-providing compound by thermal development of silver halide, and this diffusible dye is transferred to a dye fixing element having a mordant using 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 the mobile dye is heat diffusible or sublimable, and a support is used. A method of transferring the dye to a dye-receiving element has been proposed. In this method, by changing the type of dye-providing compound used or the type of silver halide emulsion used, both negative and positive dye images can be obtained with respect to the original (U.S. Pat. No. 463,079, same 4,
No. 474.867, No. 4,478,927, No. 4,5
No. 07.380, No. 4,500,626, No. 4,48
3゜914, JP-A-58-149046, JP-A-58-149046
No. 149047, No. 59-152440, No. 59-1
No. 54445, No. 5'1k165054, No. 59-1
No. 80548, No. 59-168439, No. 59-17
No. 4832, No. 59-174833, No. 59-174
No. 834, No. 59-174835, No. 62-6503
No. 8, No. 61-23245, European Patent Publication No. 210.6
60A2, 220,746A2, etc.).

(Problem B to be solved by the invention) Paper is often used as a support for photosensitive materials such as those described above because it is inexpensive and easy to dispose of. A thin paper support is preferably used. In this case, paper with a size of 200 microns or less has a weak stiffness, and if a hydrophilic binder coating is applied to one side, the amount of curling changes when the environmental conditions, especially humidity, change, and the passage through the processing device is particularly poor. There was a problem with that.

Therefore, a conventional method has been known in which a hydrophilic binder is applied as a bank layer on the opposite side of the paper support to balance the curling against fluctuations in environmental humidity. It takes more time and costs more.

In addition, when stored in a rolled form, there is a problem that adhesion failure occurs between hydrophilic binders when stored at high temperatures.

(Objective of the Invention) An object of the present invention is to provide a heat-developable color photosensitive material that has high image quality, excellent storage stability, and excellent curling properties.

(Structure of the Invention) The object of the present invention is to (1) have at least a photosensitive silver halide, a dye-donating compound, and an amino group-deactivated gelatin derivative on one side of a paper support having a thickness of 200 microns or less; and (2) a heat-developable color photosensitive material characterized in that it does not have a hydrophilic binder on the other side of the support; or (2) on one side of the paper support with a width of 200 microns or less;
A heat-developable color photosensitive material comprising at least a photosensitive silver halide, a dye-providing compound, a hydrophilic binder, and a polymer latex, and having no hydrophilic binder on the other side of the support. achieved by;

The paper support used in the photosensitive material of the present invention is one that can withstand processing temperatures, and for -a, paper or a mixed paper of synthetic resin pulp such as polyethylene and natural pulp can also be used. The thickness is less than 200 microns, especially less than 180 microns.

The paper used as the support may be any paper such as photographic base paper, plain paper, high quality paper, Yankee paper, etc.

Particularly preferred supports have improved smoothness, and the following are preferred.

In other words, the smoothness of the support conforms to JIS standard B○.
Cutoff value 0 from the cross-sectional curve measured according to 610
．． When the maximum filtering swell is measured with a reference length of 2.5m for the filtering swell curve derived under the 8m condition, the maximum swell of 4μm among the 100 arbitrary measurement points.
It has a surface characteristic in which the number of points with a maximum waviness of 2 μm or more is within 10, particularly preferably within 5, and more preferably, the number of points with a maximum waviness of 2 μm or more is within 10.
It is preferable to have a surface property of 5 or less, especially 5 or less.

Here, the cross-sectional curve is the curve that appears when the surface to be measured is cut by a plane perpendicular to the average surface of the surface to be measured, and the filtered waviness curve is the curve that appears when the surface to be measured is cut by a plane perpendicular to the average surface of the surface to be measured. This is a curve obtained by removing short surface roughness components. In addition, the cutoff value is the wavelength corresponding to the frequency at which the gain is 70% when a reduction filter with an attenuation rate of -12dB 10ct is used to obtain the filtering waviness curve, and the maximum filtering waviness is the wavelength corresponding to the frequency at which the gain is 70%. Maximum wavelength (W) within a certain length (reference length) (L)
CN) expressed in μm.

As mentioned above, the filtered waviness curve using a high cutoff value was used as a method to represent the unevenness of the support surface.
This is because density unevenness is hardly affected by unevenness shorter than the wavelength.

The reference length is set to 2.5 mm because density unevenness is less affected by surface irregularities with long wavelengths. This tendency is particularly remarkable when the length of the support is 100 μm or less.

The surface smoothness of the support is obtained as a cross-sectional curve when measured by a stylus method according to the JISBO610 standard.

From this, a filter waviness curve is obtained using a low-pass filter with a cutoff value of 0.8''. Then, set the standard length to L
Determine the value of the maximum filtering undulation when That is, a portion of length L is arbitrarily extracted from the Uranami swell curve to obtain an average line. The average line is determined by setting the line so that the sum of squares of the deviations from that line to the filtering waviness curve is minimized.

Then, the sum of the deviations from the average line of the wave heights of the waves with the maximum wave height and the wave with the minimum wave height is the filtered maximum swell W2.
It becomes N.

In this way, in the present invention, 10
When 0 WCMs are obtained, W with a value of 4 μm or more
The feature is that o is 10 or less.

In the present invention, the support having the above-mentioned characteristics includes, for example, coachite paper. Coachite paper is a coating made of a mixture of a mineral filler such as white clay and an adhesive side (e.g. casein, starch, latex, polyvinyl alcohol, or a combination thereof) on one side or one side of a base paper (e.g., wood-free paper, medium-quality paper, etc.). Refers to paper coated on both sides, and depending on the amount of paint applied, art paper (applied amount 1
(approximately 20g per rrr), coated paper (approximately 1
(approximately 0g), lightweight coated paper (approximately 5g per rrr coated amount), and after applying the paint, while the plasticity still remains, it is pressed to a dryer with a mirror finish and dried.
Including cast coat G, which does not have strong luster (For details, see "Paper and Pulp Technology Handbook J19" edited and published by the Gion Pulp Technology Association)
(See 1982 edition, pages 415, 535-536, etc.).

Since this coachite paper has a high surface smoothness even if the base paper is thin (especially cast coat paper has an extremely high surface smoothness), the surface of the coating film of the photosensitive layer applied thereon also becomes smooth. Therefore, when the photosensitive material and the dye-fixing material are superimposed, the adhesion is extremely high, and density unevenness can be prevented from occurring.

The thickness of the coachite paper used in the present invention is preferably relatively thin (light) with a weight of 20 g/rd to 200 g/rrt, particularly 50 g/rr to 100 g/rrt.

The above supports 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 this case, the polyethylene used ranges from low density to high density.

Furthermore, it can also be used as a support by coating and curing an electron beam curable resin composition containing a pigment.

These methods are used to improve the smoothness of paper, mixed paper,
Alternatively, it is particularly effective for coated paper.

In the present invention, a support whose surface is coated with a conductive metal oxide such as alumina sol or SnO can also be used in order to provide antistatic properties and/or smoothness.

The surface condition of the support may be glossy or matte.
Further, the back surface side may be glossy or matte, and preferably, the back layer side is a matte surface to prevent adhesion.

Further, a support whose surface has been treated by vapor deposition with metal such as aluminum can also be used.

In the present invention, for the purpose of improving the curl balance of the photosensitive material, a coated paper in which both sides of the paper support are coated is used. Specifically, it is effective to use double-sided coated paper, single-sided coated/single-sided cast paper, or double-sided cast paper support.

Further, it is preferable to use a paper support laminated on both sides with a polymer such as polyethylene, and it may be effective to use a paper support having different polyethylene densities on each side.

The amino group-inactivated gelatin derivative used in the present invention refers to one that is acylated, deaminated, or added with an incyanate or isothiocyanate compound.

Among the "amino group-deactivated gelatin derivatives" used in the present invention, acylation can be adjusted by treating gelatin with an acylation agent such as an organic acid, an acid anhydride ketene, or an acid chloride. is U.S. Patent No. 261429, 2
No. 768079, JP-A-46-5182 or H
, S., 0Icott, H.

Frankel Conrat: Chemical
It is described in Revs Do Do, 151 (1947), etc.

Gelatin derivatives with added isocyanate (RNCO) or inthiocyanate (RNC3) (where R
is an aliphatic group or an aromatic group) is S, J, Hopkins
+AJormall:Bioche+s, J,, Q,
1706 (1933).

The "amino group-deactivated gelatin derivative" of the present invention is preferably used when 50% or more, preferably 80% or more, etc., 90% or more of the amino groups in gelatin are inactivated.

As the method of "amino group inactivation" used in the present invention, a method using acylation is preferable.

Examples of amino group-deactivated gelatin derivatives used in the present invention include acetylated gelatin, phthalated gelatin, maleinoylated gelatin, benzoylated gelatin,
Examples include succinoylated gelatin, methylurea gelatin, and the like.

The amino group-deactivated gelatin derivative of the present invention may be used alone, but is often used in combination with other hydrophilic binders.

The preferred coating amount of the amino-deactivated gelatin derivative of the present invention is between 0.01 g and 3 g, more preferably between 0.1 g and 1 g per rrf.

Examples of monomers constituting the polymer latex used in the present invention include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacryl esters, etc. Amides, vinyl ethers, styrenes, etc. are included.

More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2- Ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2-
Examples include (2-methoxyethoxy)ethyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-
Examples include hydroxyethyl methacrylate and 2-ethoxyethyl methacrylate. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Vinyl esters include vinyl acetate,
Examples include vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2
-Methoxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide, phenyl acrylamide, and the like.

Examples of methacrylamide include methylmethacrylamide,
Examples include ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2-methoxymethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, and the like. Vinyl ethers include methyl vinyl ether, butyl vinyl ether,
Examples include hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene,
Dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene,
Acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoic acid methyl ester,
Examples include 2-methylstyrene.

These monomers may be homopolymers or copolymers, depending on the purpose of the invention. Preferred are acrylic esters, copolymers of acrylic esters and methacrylic esters, and copolymers of acrylic esters and acrylic acid or methacrylic acid.

Free radical polymerization of ethylenically unsaturated solid monomers can be carried out by thermal decomposition of chemical initiators or by the action of reducing agents on oxidizing compounds (redox initiators) or by physical action such as ultraviolet light or other high-energy radiation, radiofrequency, etc. It is initiated by the addition of free radicals to monomer molecules that are formed.

The main chemical initiators are persulfates (ammonium and potassium persulfate), hydrogen peroxide,
4.4'-Azobis(4-cyanovaleric acid) etc. (which are water soluble), azoisobutyronitrile, benzoyl peroxide, chlorohensyl peroxide and other compounds (which are water insoluble). There is).

Common redox initiators include hydrogen peroxide-iron(II) salts, potassium persulfate-potassium bisulfate, cerium salt alcohols, and the like.

Examples of initiators and their effects are given by F. Bovey.
Esulsion Polymerization
J IntersciencePublishes
Inc., New Work Published 1955 No. 59-
It is described on page 93.

As the emulsifier, a surface-active compound is used, and preferred examples include soaps, sulfonates and sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects are Be1
g1sche ChesischeIndustrie
It is described in Vol. 28, pp. 16-20 (1963).

In the present invention, among the above-mentioned polymer latexes, those having a low glass transition point, particularly those below 40°C, are preferred.

Specific examples of the polymer latex used in the present invention are described below, but the present invention is not limited thereto.

P-1 co2-(:H+-.

C00CHZCH:+ P-2-4cuz-co+-.

C00CHzCHzCHs P-3 I cow-co+-.

C00CHzCHzOCHzCHs The glass transition point (Tg) of the above polymers P-1 to P-5 is 4
The temperature was below 0°C.

The amount of polymer latex added is defined as the ratio of the total volume of the polymer in the latex added to the core layer to the total volume of the hydrophilic binder in the addition layer, and is preferably 5 to 20.
0νo1%, more preferably 10 to 100vof
%. If it is less than 5 voI%, the curling property will be insufficient, and if it is more than 200voI%, the film strength will become weak and the maximum concentration will tend to decrease. Expressed in coating amount, the weight of the polymer in the latex is preferably 1 mg/
Bo~5g/n (and more preferably 10■/bo~2
g/rr? It is.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a binder, and a dye-providing compound (which may also serve as a reducing agent as described later) on a support. An organic metal salt oxidizing agent, etc. can be included depending on the situation. These components are often added to the same layer, but if they are in a reactable state, they can be added separately to separate layers.1For example, a colored dye-providing compound may be added to the lower layer of the silver halide emulsion. If present in , 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 wide aS colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to different spectral regions are used in combination.

For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and 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.

Further, each of these photosensitive layers may be divided into two or more layers as necessary.

The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate #ft color filter layer, antihalation dust, and a backing layer.

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 is a surface latent image type LL
It may be an emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating side and optical fogging. It may also be a so-called funnel 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~
2μ, especially 0.2 to 1.5μ is preferred. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or any other form.

Specifically, U.S. Pat. No. 4,500,626 No. 504
f4, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (19
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, selenium sensitization methods, etc. for emulsions for conventional light-sensitive materials can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing bicyclic compounds (!! l!!
).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g7m' in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Patent No. 4,500,626;
There are benzotriazoles, fatty acids, and other compounds described in 534111 and the like. Also, JP-A-60-11323
Silver salts of carboxylic acids having a furkynyl group such as silver phenylpropiolate described in No. 5, and JP-A-61-2490
Acetylene silver described in No. 44 is also useful. Organic silver salt is 2
You may use more than one species in combination.

The above W1 silver salts can be used in combination in an amount of not more than 0.01 LIO mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 1 in terms of silver.
0g7m2 is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD】76
43 (1978) pp. 24-25, nitrogen-containing carvone W1s and phosphoric acids described in JP-A-59-168442, or mercapto compounds and phosphoric acids described in JP-A-59-111636. Metal salts thereof, acetylene compounds described in JP-A No. 62-87957, and the like can be 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 hemioxonol dyes.

Specifically, U.S. Pat.
I 7029 (1978) pages 12-13 and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, 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, as described in the US Pat. No. 3,615,641, JP-A-63-2
3145 etc.).

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

The amount added is generally about 10-1 to 10-2 mol per mol of silver halide.

A hydrophilic material is preferably used as the pigment in the constituent layer of the photosensitive material or dye fixing material. Examples include those described on pages 26) to (28) of JP-A-62-253159. Specifically, transparent to translucent hydrophilic pine nuts are preferable, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, dextran, pullulan, etc.
Natural compounds such as l11 and polyvinylfurfur,
Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, JP-A-62-
245260, i.e., a homopolymer of a vinyl monomer having -COOM or -3O3M (M is a hydrogen atom or an alkali metal), or a copolymer of these vinyl monomers with each other or with other vinyl monomers ( For example, sodium methacrylate, ammonium methacrylate, Sumikagel L- manufactured by Sumima Kagaku Co., Ltd.
5H) is also used. Two or more of these binders can also be used in combination.

When using 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 20 per 11
The amount is preferably 10 g or less, more preferably 7 g or less.

Constituent layers (including adhesive layers) of photosensitive materials or dye-fixing materials contain additives 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. Various polymer latexes can be included. Specifically, Japanese Patent Publication Nos. 62-245258 and 62-13
Any of the polymer latexes described in No. 6648, No. 62-110066, etc. can be used. In particular, using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point for the back layer can prevent curling. can get.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donating compound having reducing properties, which will be described later, is also included (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, columns 30-31, same No. 4゜330.617
No. 4,590,152, JP-A-60-1403
No. 35, pages (17) to (18), 57-40245
No. 56-138736, No. 59-178458, No. 59-53831, No. 59-182449, No. 59-182450, No. 60-119555, No. 6
From No. 0-128436 to No. 60-128439,
No. 60198540, No. 60-181742, No. 6
No. 1-259253, No. 62-244044, No. 62
There are reducing agents and reducing agent precursors described in European Patent No. 220,746A2, pages 78 to 96, and the like.

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

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or an electron transfer agent may be added as necessary to promote open electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of precursors can be used.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).

Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or ami/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 7-el/-ols, 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 added on the reducing side is 0 per mole of silver.
．． 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

In the present invention, silver can be used as the image forming material. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating compound. can.

Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions.

The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction; this diffusion-resistant group may form a polymer chain. Specific examples of color developers and couplers are given by James [The Theory of the Seven Otographic Processes] 4th Edition (T.
theory of the P I+ot.

grapbic Process”) pages 291-334 and 354-361, JP-A-58-123533
No. 58-149046, No. 58-149047, No. 59-111148, No. 59-124399,
No. 59-174835, No. 59-231539, No. 59-231540, No. 60-2950, No. 60-
No. 2951, No. 60-14242, No. 60-2347
4, No. 60-66249, 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. This type of compound can be represented by the following general formula (LT).

(Dye-Y) n-Z (L r )Dye represents a dye group, -temporally shortened dye group or dye precursor group, Y represents a mere bond or linking group, and Z represents an imagewise Correspondingly or inversely to the photosensitive silver salt having a latent image, a difference is created in the diffusivity of the compound represented by (Dye-Y)nZ''C, or Dye is released, and the released Dye and (Dye -Y) n Attenuates a group having properties that cause a difference in diffusivity between -Z, n represents 1 or 2, and when n is 2, two Dye
-Y may be the same or different.

Specific examples of the dye-providing compound that is attenuated by the general formula (Ll) include the following compounds (1) to (2).

Note that ■ to ■ below are those that form a diffusive dye image (bottom dye image) in reverse response to silver halide development.
(2) and (2) form a diffusive dye image (negative dye image) in response to silver halide development.

■U.S. Patent Nos. 3,134,764 and 3,362.
No. 819, No. 3,597,200, No. 3.544
, No. 545, No. 3,482,972, etc., 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.

■As described in U.S. Patent No. 4,503,137, it is also possible to use non-diffusible compounds that release diffusible dyes in an alkaline environment but lose that ability when they react with silver halide. . Examples include U.S. Patent No. 3,980
Compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions, such as those described in U.S. Patent No. 4,199,3
Examples include compounds that release a diffusible dye through an intramolecular rewinding reaction of the inoxazocune ring described in No. 54 and the like.

■US Patent No. 4,559,290, European Patent No. 220
．． As described in No. 746A2, U.S. Patent No. 4,783,396, Publication No. 87-6199, etc., a non-diffusible dye that releases a diffusible dye by reacting with the reducing agent that remains unoxidized during development. Compounds of can also be used.

Examples include U.S. Patent No. 4,139,389, U.S. Pat. Compound releasing diffusible dye by nucleophilic substitution reaction, U.S. Pat. No. 4.232.107, JP-A-5
No. 9-101649, No. 61-88257, RD24
025 (] 99884, etc., a compound that 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 No. 4,343,893;
No. 4,619,884, etc., a compound whose single bond is cleaved to release a diffusible dye after reduction, and a compound that diffuses after electron acceptance, described in U.S. Patent No. 4,450,223, etc. Examples include nitro compounds that release a diffusive dye, and compounds that release a diffusible dye after accepting electrons, as described in U.S. Patent No. 4,609,610 and the like.

Also, more preferably, European Patent No. 220.7
No. 46A2, Published Branch No. 87 6199, U.S. Pat.
No. 783.396, JP-A-63-201653, JP-A No. 63-201653
Compounds having an N-X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule as described in Japanese Patent Application No. 106885-1982, etc. A compound having SQ, -X (X has the same meaning as above) and an electron-withdrawing group in the molecule, P○-X bond (X has the same meaning as above) in one molecule described in JP-A-63-271344
and a compound having an electron-withdrawing group, vf Kaikai 3-271
No. 341, C-X° bond (X' is
(synonymous with or representing -S○2-) and a compound having an electron-withdrawing group is preferred. Also, patent application No. 62-3199
Compounds described in No. 89 and No. 62-320771 that release a diffusible dye by cleavage of a single bond after reduction due to a π 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 No. 22
0,746A2 or compounds (1) to (3), (7) to (10) described in U.S. Patent No. 4,783,396
, (12), (13), (15), (23)-(26)
, (31), (32), (35), (36), (40
), (41), (44), (53) to (59), (64
), (70), compound (11) of published branch root 876199
~(23) etc.

■A compound that is a coupler that has a diffusible dye as a leaving group and releases the diffusible dye upon reaction with the oxidized form of a reducing agent (D
DR coupler). Specifically, British Patent No. 1,330,
No. 524, Special Publication No. 48-39.

No. 165, U.S. Patent No. 3,443,940, U.S. Patent No. 4.
There are those described in No. 474,867, No. 4,483.914, etc.

■Ha! A compound (D
RR 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. A typical example is U.S. Pat.
No. 28,312, No. 4,053,312, $4,
055,428, 4,336,322, JP 59-65839, 59-69839, 53
No. 3819, No. 51-104, 343, RD1746
No. 5, U.S. Patent No. 3,725,062, U.S. Patent No. 3,72
No. 8.113, No. 3,443,939, JP-A-58
-116,537, US Pat. No. 57,179,840, and US Pat. No. 4,500,626. D.R.R.
Specific examples of compounds include the aforementioned U.S. Patent No. 4,500,
The compounds described in columns 22 to 44 of No. 626 can be mentioned, among which compounds (1) to (3), (10) to (13), and (16) to (1
9), (28) to (30), (33) to (35), (3
8) - (40), (42) - (64) Kaho i L i. *Ta. <National U Permit No. 4.639,408 No. 37-39
The compounds listed in the column are also useful.

In addition, dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Journal 19
May 1978 issue, pp. 54-58, etc.), 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.), Wife Dye (U.S. Patent Road 3,9
No. 85,565, No. 4,022,617, etc.) can also be used.

(Left below) Hydrophobic additives such as dye-donating compounds, IT#, and dispersible reducing agents can be introduced into the layers of the photosensitive material by known methods such as those described in U.S. Patent No. 2,322,027. I can do it. In this case, Japanese Patent Application Laid-open No. 59-83154,
No. 9-178451, No. 59-178452, No. 59
-178453, 59-178454, 59-
178455, No. 59-178457, etc., if necessary, at a boiling point of 50°C to 1°C.
It can be used in combination with a low boiling point organic solvent of 60°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, ice per 1 g of binder, and even O, Sc
cc or less, particularly 0.3 cc or less is suitable.

Dispersion methods 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.

When dispersing a hydrophobic compound in a hydrophilic colloid, various surfactants can be used.
-157636, pages (37) to (38), those listed as surfactants 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 U.S. Pat.
No. 0,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding 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, the relationships described in US Pat.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat.
and mordants described in JP-A-61-88256, pages (32) to (41), JP-A-62-244043, JP-A-62-244043, and JP-A-62-244043;
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in U.S. Patent No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling, low-temperature solvent can be used as a plasticizer, a slippery agent, or a peelability improving agent between the light-sensitive material and the dye-fixing material. Specifically, pages (25) and 6 of JP-A-62-253159.
There is one described in No. 2-245253.

Furthermore, various silicone oils (
All silicone oils can be used, from 7-methyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane. For example,
[Modified silicone oil] published by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils described in technical data P6-18B, especially carboxy-modified silicone (trade name X-22-
3710) etc. are effective.

Also, JP-A-62-215953 and JP-A No. 63-46449.
The silicone oil described in this issue 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 chroman-based compounds, coumaran-based compounds, and 7-7-ol compounds (e.g., Hingood 7).
Examples include engineering 7-l[), hydroquinone derivatives, hindamine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Examples of ultraviolet arpi absorbers include benzotriazole compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as U.S. Pat. No. 3,352,681), and benzo-7-based compounds (such as U.S. Pat. No. 3,352,681). No. 46-2784, etc.), other Jikai Mei No. 54-48535, No. 62-1
There are compounds described in No. 36641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
Same No. 4,245,018 No. 3-36m, Same No. 4,25
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A No. 61-88256, pages (27) to (29), JP-A No. 63
No. 199248, Japanese Patent Application No. 62234103, No. 62
There are compounds described in No.-230 S 95 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. .

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

A fluorescent whitening agent may be used in the photosensitive material or dye fixing material. In particular, a fluorescent whitening agent is incorporated into the dye-fixing material, but it is preferably supplied from outside the photosensitive material. Examples include K. VeenkataramanJi “Th
e Chemistry of 5ynthetic,
Examples include compounds described in Dyes J, Volume V, Chapter 8, JP-A-61-143752, and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds,
Examples include naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

EF used in constituent layers of photosensitive materials and dye fixing materials! As the film agent, U.S. Pat.
Dural debris described in 61-18942 and the like is removed.

yr) Specifically, aldehyde hardeners (formaldehyde, etc.), azilinone hardeners, epoxy hardeners (nylsulfonylacetamide) ethane, etc.), N-methylol hardeners (tumethylol urea, etc.) ), or a polymer hardener (compound 41 described in JP-A No. 62-234157).

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 include improved slipperiness,
Existing for the purpose of preventing static electricity, improving peelability, etc.8! Fluoro compound
It may contain things. Typical examples of growing fluoro compounds include fluorine-based surfactants described in Japanese Patent Publication No. 57-9053 No. 8 to 17I/gA, Japanese Patent Application Publication No. 61-20944, No. 62-135826, etc.; Examples include hydrophobic heptad compounds such as oily hepta-compounds such as base oils and solid fluorine compound resins such as tetra-7-polyethylene resins.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used as JP-A-61-8825.
In addition to the compounds described on page 29 of No. 6, 'ftM No. 110064/1986, No. 62-62, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
There is a compound described in No. 110065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, a colloidal binder, and the like. Specific examples of these additives are given in JP-A-61-
No. 88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive materials. 8! Promotion of dye transfer from the layer to the dye fixing layer, etc.! Based on their physicochemical functions, they are classified as bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions. Ru. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,67
8,739 No. 38-40! It is described in.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines through intramolecular nucleophilic substitution reactions, Rossen rearrangement, or Benkmann rearrangement. Specific examples thereof are described in U.S. Pat.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, compounds capable of complex-forming reaction with the sparingly soluble metal compounds and metal ions constituting the second sparingly soluble metal compound described in European Patent Publication No. WI 4210.660 and U.S. Patent No. 4,740,445. (referred to as complex-forming compound)
Combinations of the above and compounds that generate bases by electrolysis as described in JP-A No. 61-232451 can also be used as base precursors. The former method is particularly effective.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

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 E'f 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 inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples thereof include electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, nitrogen-containing heterocyclic compounds, mercap F compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
It is described on page 32).

As the support for the dye-fixing material of the present invention, one that can withstand the processing temperature is used. −
For boat fishing, paper and synthetic polymers (films) can be used.

Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (for example, tosoacetyl cellulose), or films containing pigments such as titanium oxide, as well as polypropylene, etc. Film-based synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, 21-tipped paper (especially cast coated paper), metals, fabrics, glass, etc. are popular. I can stay.

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 (29) to (3)
The supports described on page 1) can be used.

The surface of these supports may be coated with a wood-philic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black, or other antistatic agent.

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and copying machines. A method in which the original image is scanned and exposed through a slit using an exposure device, etc., a method in which image information is transmitted via an electric signal to a light-emitting diode, various lasers, etc., and exposed to light; a method in which image information is transmitted to a CRT, liquid crystal display, electroluminescence There is a method of outputting the image to an image display device such as a display or a plasma display and exposing the image directly or through an optical system.

As mentioned above, light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., such as U.S. Pat. No. 4,500,6.
The light source described in No. 26, column 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. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, [jaD20. Inorganic compounds such as
Urea derivatives, =) loaniline derivatives, such as ionanitrobilinone-N-Oquindo derivatives of 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61
Compounds described in No.-53462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

In addition, the above-mentioned image information includes image signals obtained from a video camera, electronic still camera, etc., a television signal represented by the Nippon Television Signal Standard (NTSC), and an image signal obtained by dividing an original image into a large number of pixels using a scanner. , C.G., C.
Image signals created using a computer such as AD can be used.

The photosensitive material and/or the dye fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
1 145544 can be used. These conductive layers can also be used as antistatic layers. function.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180°C. 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 step can be in the range from the temperature in the heat development step to room temperature, but is particularly preferably 50° C. or higher and up to a temperature about 10° C. lower than the temperature in the heat development step.

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

Also, JP-A-59-218443, JP-A No. 61-2380
56, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is ε
The boiling temperature of the solvent is preferably 0°C or higher and below the boiling temperature of the solvent. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters can be used. Also, low boiling, α
A solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperatures is incorporated into the light-sensitive material or dye fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye fixing material.
It may be built into both. Also, the layer to be incorporated is an emulsion layer,
It may be an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

Examples of hydrophilic heat solvents include ureas, viridines, amino acids, sulfonamides, imides, alnyls,
There are oximes and other heterocycles.

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or copying process include touching a heated block or plate, a hot plate, a photopresser, a hot roller, a halogen lamp heater, an infrared lamp heater, and a far-infrared lamp heater. This may include contacting the device or passing it through a high-temperature atmosphere.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye fixing material and applying the pressure are described in VT Kaikai 1 147.
The method described in No. 244, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 59-75247,
Apparatuses described in Japanese Patent No. 59 No. 177547, No. 59 No. 181353, No. 60 1i395i, Japanese Utility Model Application No. 62-25944, etc. are preferably used.

Specific examples will be described below, but the present invention is not limited to these examples.

[Example 1] A method for preparing a dispersion of zinc hydroxide will be described.

12°5 g of zinc hydroxide with an average particle size of 0.1 μm
As a dispersant, 1 g of carboxymethyl cellulose and 0.1 g of sodium polyacrylate were added to 100 m of a 4% gelatin aqueous solution.
In addition, it was ground in a mill for 30 minutes using glass beads with an average particle size of 0.75 m. The moth and glass beads were separated to obtain a dispersion of zinc hydroxide.

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

Add 10 g of the electron transfer agent below, 0.5 g of polyethylene glycol, nonyl phenyl ether as a dispersant, and 5 g of Demol NO manufactured by Kao Soap ■ to a 5% aqueous gelatin solution, and mill using glass beads with an average grain size of 0.75 m. hand,
Milled for 60 minutes. Separate the glass beads, average particle size O
A 14μ dispersion of electron transfer agent (■) was obtained.

Electron Transfer Agent■ Next, we will discuss how to make a gelatin dispersion of a dye-donating compound.

Yellow, magenta, and cyan were each dissolved by heating at approximately 60" C as per the above recipe to form a homogeneous solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, 0.6 g of sodium dodecylbenzenesulfonate, and 50 m2 of water After stirring and mixing, use a homogenizer for 10 minutes.
Dispersion was performed at 110,000 rpm. This dispersion is called a gelatin dispersion of a dye-providing compound.

Dye-donating compound (1) Electron donor■ CH C.I.

High boiling point solvent ■ Electron transfer agent precursor ■ Compound ■ COC+Jzs(n) C0CIJzs(n) Next, the preparation of a gelatin dispersion of the electron donor ■ in the intermediate layer will be described.

Add 20g of the electron donor below, 5.9g of the compound below, 1.8g of the compound below, and 8.5g of the high-boiling solvent above to cyclohexanone 30#1, heat and dissolve at 60°C, and dissolve uniformly. It was made into a solution. 1 of this solution and lime-treated gelatin
After stirring and mixing 100 g of 0% aqueous solution, 0.8 g of sodium dodecylbenzenesulfonate, 0.3 g of sodium bisulfite, and 30 d of water, the mixture was mixed with a homogenizer for 10 minutes.
Dispersion was performed at 10,000 rpm. This dispersion is called a gelatin dispersion of electron donor (1).

JH Compound ■ 0 (n)C+sHx+-C-N-ON CH.

Next, a method for preparing a photosensitive silver halide emulsion (■) (for blue-sensitive emulsion layer) will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide, and lo (CHz) in 800 cc of water)
) ts (CHz) 1s (CHz) 0.3 of zOH
g and kept warm at 55℃), the following (1) solution and (
2) The liquids were added simultaneously over a period of 30 minutes. Thereafter, the following solutions (3) and (4) were simultaneously added over 20 minutes. Further, after starting the addition of the liquid (3), the following dye solution was added over a period of 18 minutes from 5 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and PAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,
Optimal chemical sensitization was carried out by adding 3a,7-chitrazaindene and chloroauric acid. Thus the average particle size, 0.4
600 g of a monodispersed tetradecahedral silver iodobromide emulsion of 0 μm was obtained.

dye solution 0.12g 0.12g is dissolved in 160cc of methanol.

Next, a method for preparing a photosensitive silver halide emulsion (■) (for green-sensitive emulsion layer) will be described.

A well-stirred aqueous solution (gelatin 2 in 730 d of water)
0g, potassium bromide 0.30g, sodium chloride 6g and the following chemical A 0.015g were added. Add the following solution (1) and solution (II) simultaneously to
Added at equal flow rate over 0 min. (■) After the addition of the solution, a methanol solution of the following sensitizing dye ([1)] was added. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm was prepared.

After washing with water and desalting, add 20g of gelatin and adjust the pH to 6.4.
After adjusting PAg to 7.8, chemical sensitization was performed at 60°0°C. The chemicals used at this time were 1.6μ of triethylthiourea and 4-hydroxy-6-methyl-1,3,3a.
, 100 g of 7-chitrazaindene and the ripening time was 55 minutes. The yield of this emulsion was 635 g.

(Drug A) CHl sound CH.

(Sensitizing Dye C) Next, a method of preparing a photosensitive silver halide emulsion (■) (for red-sensitive emulsion layer) will be described.

A well-stirred gelatin aqueous solution (gelatin 20g, potassium bromide 0.3g, sodium chloride 6g in 800ml water)
(g) and the following chemical A30■ were added and kept at 65°C), the following solutions (1) and (II) were simultaneously added at equal flow rates over 30 minutes. After that, the following (I[[)
Solution and solution (IV) were added simultaneously over 30 minutes. Furthermore, starting from 3 minutes after the start of addition, the following dye solution 160% was added to the solutions (I [I) and (IV) over a period of 20 minutes.

After washing with water, desalting, lime treatment, adding 22 g of ossein gelatin to adjust the pH to 6.0 and pAg to 7.7, and then adding sodium thiosulfate and 4-hydroxy-6-methyl-1,3
,3a,7-chitrazaindene, adding chloroauric acid to 60
Optimally chemically sensitized at °C. In this way, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.5 μm was obtained. The yield was 635g.

H3 Dye solution 67111 g of the following dye (a) and 1331 g of dye (b) were dissolved in 200 ml of methanol.

Dye (a) Dye (b) Next, a method for preparing a photosensitive silver halide emulsion (TV) will be described.

The temperature of the aqueous gelatin solution was kept at 45°C from 65°C.1 The amount of dye solution added was changed from 160 paper to 22ON, but the process was exactly the same as that for photosensitive silver halide (III), and the photosensitive halogen for the red-sensitive emulsion layer was heated. I made a silver oxide emulsion. The average particle size was 0.31μ, and the yield was 635g.

Using the above emulsion dispersion, a coating solution was prepared as follows.

First layer (red-sensitive emulsion layer) 236 g of photosensitive silver halide emulsion (I) and 760 g of photosensitive silver halide emulsion (TV) were dissolved at 38°C. Next, add a 0.15% aqueous solution of the following anti-capri agent
1 After another 5 minutes, dissolve the gelatin dispersion of the cyan dye-providing compound at 45°C, add 3734 g of the above mixture, and add the thickener ■
A 3% aqueous solution of 112 was added to prepare a coating solution for the first layer.

Antifoggant ■ Thickener ■ Second layer (intermediate layer) in SO2 300 g of a 14% aqueous solution of phthalated gelatin of the present invention, 700 g of a 14% aqueous solution of lime-treated gelatin, Electron donor ■
720 g of gelatin dispersion was dissolved at 40°C. Next, 905 g of a dispersion of zinc hydroxide dissolved at 45°C, 64d of a 5% aqueous solution of the following anionic surfactant [phase], 146Id of a 5% aqueous solution of the following compound (1),
5% aqueous solution of dextran 229yd, 3% thickener ■
35 yd of an aqueous solution was added to prepare a coating solution for the second layer.

Surfactant [phase] Na0sS CHCOQCHzCH(CzHs)Ca
H*CHzCOOCHzCH(CJs)CJw compound■ (n=8.5) 3rd layer (green-sensitive emulsion layer) 1000g of photosensitive silver halide emulsion (It) was heated to 38°C
Dissolve in a 0.15% aqueous solution of antifoggant ■ 21111
1 and after 5 minutes, add 1% aqueous solution of potassium bromide 220
rRIl, 2839 g of a gelatin dispersion of a magenta dye-providing compound dissolved at 45°C, and 100 d of a 3% aqueous solution of thickener (2) were added to prepare a coating solution for the third layer.

4th layer (intermediate layer) 300 g of 14% aqueous solution of phthalate compound gelatin of the present invention
, 700 g of a 14% aqueous solution of lime-treated gelatin, 246 g of a gelatin dispersion of the fft transfer agent (■), 746 g of a gelatin dispersion of the electron donor (■), and 2116111 of water! Add 4
It was melted at 0''C.Next, 65 pieces of a 5% aqueous solution of surfactant [phase], 236 pieces of a 5% aqueous solution of dextran, 101 pieces of a 3% aqueous solution of thickener (2), and 4 pieces of the following hardener @ % aqueous solution was added to prepare a coating solution for the third layer.

Hardener @C)Iz ==CI(SOtGHzCONHz (CH
z) tNHcOcHzsOzcLcHz 5th layer (blue-sensitive emulsion layer) Photosensitive silver halide hole side (1) 1000g was dissolved at 38°C, 0.14% methanol solution 1791i of the following antifoggant ■ was added, and the mixture was heated for 5 minutes. Thereafter, 2564 g of a gelatin dispersion of a yellow dye-providing compound was dissolved at 45°C and added thereto, and 15 d of a 3% aqueous solution of thickener (1) was added to prepare a coating solution for the fifth layer.

Antifoggant @ 6th layer (protective layer) 30 θg of a 14% aqueous solution of phthalated gelatin of the present invention, 700 g of a 14% aqueous solution of lime-treated gelatin.

91 g of a gelatin dispersion of a silica matting agent (8 g of silica with an average particle size of 3 tI dispersed in 100 g of an 8% lime-treated gelatin aqueous solution) was melted at 40°C, and 1247 g of a dispersion of zinc hydroxide and 1247 g of a dispersion of zinc hydroxide were heated at 45°C. Add the solution dissolved in
Furthermore, 5% aqueous solution of surfactant [phase] 110111, 10% aqueous solution of compound [phase] 274d, dextran 5%
% aqueous solution 170 ml, and 3% aqueous solution of thickener ■ 16-
was added to prepare a 6N coating solution.

Compound [Phase] (n = 30) Using the above coating liquid, apply the coating liquid from the 1st layer to the 6th layer with the layer structure shown in Table 1 so that each layer has the wet film thickness shown in the table. , photosensitive material 101 was produced.

Table 1 (Photosensitive material 101) Structure of support (1) Next, as a comparative example, lime was added instead of the 14% aqueous solution of phthalated gelatin added to the second, fourth, and sixth layers of the photosensitive material 101. A photosensitive material 102 was prepared in exactly the same manner except that a 14% aqueous solution of treated gelatin was used.

Further, as shown in Table 2, photosensitive materials 103 and 104 were prepared in exactly the same manner as photosensitive material 102, except that polymer latex P-1 or P-4 of the present invention was added.

C00CHzCHs Next, an image receiving material was prepared as shown in Table 3.

Table 3 Structure of image receiving material Structure of support (2) Silicone oil (1) CHs C83CHs CL-Si-0-11→5i-0tn-5i CH3
(CHz)+□C00N C113(CHt)IzC
OOH surfactant law (1) (r+1-12.6) Surfactant (2) CsF+tSO□NC)(
tcOOKl C,L Surfactant (3) CH's C+ +HisCONHCH2CH2CHJ @CH2
COOeL Surfactant (4) Js HibikiCHzCOOCH2CHC4He Na0iS CHCOOCHzCHCJqJs Fluorescent brightener (1) 2.5-bis(5-tert-butylbenzoxazolyl (2))thiophene surfactant (5) Jt CsF + tsOxN − (CHtCHtOh(CI
lt) rsOaNa water-soluble polymer (1) Sumikagel L5-H (manufactured by Sumitomo Chemical ■) Water-soluble polymer (2) Dextran (molecular weight 70,000) Mordant (1) High boiling point solvent (1) Hardener (1) Matting agent ( 1)9 Silica matting agent (2)'' benzoguanamine resin (average particle size 15μ) The above photosensitive materials 101 to 104 and image receiving material were processed using the image recording apparatus described in Japanese Patent Application No. 137104/1982.

That is, the original image [Y, M, Cy whose density changes continuously]
and a test chart in which a gray wedge is recorded] is scanned and exposed through a slit, and the exposed photosensitive material is immersed in water kept at 35°C for 5 seconds, squeezed with a roller, and then immediately separated from the image-receiving material and film. They were stacked so that the surfaces were in contact.

The temperature was adjusted so that the temperature of the surface of the film that had absorbed water was 80°C, and when it was heated for 15 seconds using a drum and peeled off from the image-receiving material, a clear color image corresponding to the original image was obtained on the image-receiving material. .

Table 4 shows the results of measuring DmaxSDmin of Y (yellow), M (magenta), and Cy (cyan) in the gray part.

Table 4 Next, a curling property test was conducted using the following procedure.

Each of the photosensitive materials 101 to 104 is 20C11X20
Cut into sheets of C11 size, place on a laboratory bench in an environmental test room with the film side facing up, and store at a low temperature and low humidity (15°C, 20%).
RH), and at room temperature (25°C, 50% RH), how much the edge of the photosensitive material rises above the surface of the desk.
It was measured.

desk The results are shown in Table 5.

Table 5 Next, the photosensitive material was wound up into a roll and
It was stored under RH conditions for 10 days.

As a result, the photosensitive material of the present invention did not show any traces of adhesion to the bank surface.

From the above results, it can be seen that the photosensitive material of the present invention has higher image quality and better storage stability, and has particularly good curling properties.

Patent applicant: Fuji Photo Fi4 Rem Co., Ltd. Date: 1991

Claims (2)

[Claims] (1) A paper support having a thickness of 200 microns or less has at least a photosensitive silver halide, a dye-donating compound, and an amino group-deactivated gelatin derivative on one side, and on the other side of the support, A heat-developable color photosensitive material characterized by not having a hydrophilic binder. (2) having at least a photosensitive silver halide, a dye-providing compound, a hydrophilic binder, and a polymer latex on one side of a paper support having a thickness of 200 microns or less, and on the other side of the support; A heat-developable color photosensitive material characterized by not having a hydrophilic binder.