JPS61113058A - Photographic material - Google Patents

Abstract

PURPOSE:To obtain a heat developing photosensitive material which is free from the distortion of an image and uneven density by using a polyester film of which the elongation in a heated state is decreased to a specified value as a substrate. CONSTITUTION:Such polyester film of which the elongation in the longitudinal and transverse directions at 120-180 deg.C is -0.5-+0.5% is used as the substrate. The adjustment of the elongation is made possible by devising the condition a for heat setting after stretching. The conditions for the heat setting vary with the condition for longitudinal and transverse stretching and can be deter mined mainly by the transverse relaxation rate after the transverse stretching as well as the temp. and time of the heat treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester films used in photographic materials that undergo heat treatment.

More specifically, the present invention aims to provide a method for controlling the elongation of a polyester film at the developing temperature to obtain uniformity in development.

Polyester films, typified by polyethylene terephthalate, are usually produced by the λ-axis stretching method, and the main process is longitudinal stretching → transverse stretching → heat setting/heat relaxation. Various stretching methods are known in the art, and longitudinal stretching is described, for example, in U.S. Pat. J7ri issue,
3.627.572, p, o, 2o, ≠λ1, 2.
77ri, Rur No. 3, Ko, tri 2.7 No. 3, Patent Publication J
O-1432, 344-/Tatabu, 31-≠23≦
No., etc. Further, regarding the temperature conditions, stretching ratio, gripping device method, heating method, etc. related to the lateral stretching method, see, for example, US Patent No.

θ! ri, 6hiro 7, 2.9104AIIr4AI, -
.

Tata J, No. 779, J, 041. ! λ No. 31J! 7
, ulrt issue, u, 0 hiro 2. ! l, ri number, 3゜a44
a, ire issue, patent publication 37-134! No. 7, No. 370, Patent Publication μtar.

Sir No. J3-94.072, etc.

An example of the method for producing polyethylene terephthalate represented by the above patent is shown below.

A conventional method for producing a λ-axis stretched film of polyethylene terephthalate is as follows. That is, the sheet-like polymer pushed from the extruder and the die is cooled in a casting drum, then preheated while passing between a group of preheating rolls, and stretched and cooled in the direction in which the film travels, that is, the longitudinal direction.

The longitudinal stretching is carried out by passing the film through a set of nip rolls and utilizing the difference in peripheral speed of the nip rolls. Next, the film is gripped with grips attached to infinite buttons at both ends, introduced into a tenter, preheated, stretched in the transverse direction, and heat treated.

The stretching temperature is go'C to lso0c, and the heat treatment temperature is generally IIO to coro0c.

Polyester films made by such a method have been conventionally used as supports for photosensitive materials because of their excellent dimensional stability at room temperature and slightly higher temperatures (eg, tOoC).

However, the conventionally known polyester film
When used in a photosensitive material that is heat-treated at a temperature of 0.6 yen or higher, the resulting image may be distorted or uneven, which is disadvantageous.

Furthermore, recently, a method has been known in which a diffusible dye is formed in the form of an image by heating and transferred to a dye fixing layer (for example, European Patent Publication No. 74.'79
In this method, distortion and unevenness are particularly severe when ordinary polyethylene terephthalate is used as a support.

An object of the present invention is to provide a heat-developable photosensitive material with no image distortion or unevenness, and particularly to provide a method for obtaining a color image without image distortion or density unevenness by total heating.

The purpose of the present invention is to achieve an elongation rate of 10, S% to 100 in the longitudinal and transverse directions at a temperature of 7.2 ONl♂o'C.

This is achieved by heat treating the photographic material using a polyester film such as 5% as the total support.

This elongation rate is preferably 10.1% to +0.3%, particularly preferably -0.3% to +0.2%.

The above elongation rate can be adjusted by adjusting the heat setting conditions after stretching.

The heat setting conditions vary depending on the longitudinal and transverse stretching conditions, but can be determined mainly by the transverse relaxation rate, heat treatment temperature, and time after transverse stretching. All of these conditions are known and described in the patents cited above.

Vertical and horizontal elongation is 120-/10”C under unrestrained conditions.
K/minute, measure the dimensions in the heated state, -2j0
Compare with the dimensions in C. -(minus) indicates contraction, +(
Plus) indicates growth.

Since it is known that polyester films used as supports for photosensitive materials have excellent dimensional stability between room temperature and around 00C, and that they thermally expand at higher temperatures,
The use of polyester films as supports for thermal image forming materials is completely unexpected.

When the heat-set polyester film of the present invention is used as a support for the material of the present invention, the surface of the polyester film may be treated or an undercoat may be applied to provide strong adhesion between the polyester film and the binder layer. It is normal to have layers. In particular, when the photosensitive layer is hydrophilic F-, (1) chemical treatment, mechanical treatment, corona discharge treatment, j- flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
After treatments such as activated plasma treatment, high-pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment, a photosensitive layer is applied to obtain adhesive strength; (2) an undercoat layer is provided, and then There are two methods for applying the photosensitive layer. In this case, it is advantageous to carry out the surface treatment before applying the undercoat layer.

(For example, U.S. Patent Nos. 4L?r, 4(7),
744A, s2o No. 3,07.1,1713, J.
1443, 172/No. J, /II! , 10! No. 3,
/4!1,2472, J, JtO, 1I411r,
J, 374. Ko Ot issue, 3. ≠7! l/ri No. 3, 3, μ
tλ133! No., British Patent No. 71#, 3bu No. 5, tr
oy, ooz, Belgian Patent No. 463゜171, etc., Special Publication No. 4I7-244, 270, Tsunoda, 3rd Annual Adhesion Study Group (170), Caldwell et al. J,
Po1y, Sci,, C-λ Reference/! (/riA?
), Iyengar, J., Appl.

(Refer to Polyester, Sci, / /Co311 (/rij7), etc.) In addition, various efforts have been made to apply the undercoat layer, and as a first layer, it adheres well to polyester and is durable. The so-called multilayer method, in which a layer containing a resin with low chemical properties is provided, and a hydrophilic resin layer is applied as a second layer on top of the layer.
There is a single I-method in which only one resin layer containing both hydrophobic groups and hydrophilic groups is applied.

All of these methods have been well studied and include copolymers starting from vinyl chloride, vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., as well as polyethyleneimine and epoxy resins. , grafted gelatin-nitrocellulose, and many other resins have been investigated for their suitability.

In order to further improve the performance, methods have been taken such as including a large amount of a highly polar, high boiling point, and expensive etching agent, a solvent that swells or dissolves the polyester, in the undercoating solution.

These etching agents include, for example, aromatic nuclei (benzene ring, naphthane term, pyridine ring, pyrrole ring, or condensed rings thereof or alkyl, alkoxy, acyl, nitro, cyano, etc.), hydroxy, formyl, carboxy, alkoxycarbonyl, hydroxyalkyl, aminoalkyl, haloalkyl, etc.), or alcohol, ketone, carboxylic acid, ester, aldehyde, etc. (for example, British Patent No. 772.400, 771.117 ,
7J'j, 7fr, 797, I/-, 2j, U.S. Pat. be.

Further, as the undercoat i, latex of a synthetic polymer copolymer may be used.

In the present invention, the above-mentioned hydrophilic treatment of the polyester film is desirably carried out at a low temperature, for example, 1000 C or lower, preferably lower than the glass transition temperature (Tg) of the polyester. This is to maintain the f of the prepared polyester film to be '1i-O,j~+〇,jq6.

Photographic materials to be subjected to the heat treatment referred to in the present invention include materials used in methods for obtaining photographs by heat development, such as heat-developable photosensitive materials, and materials used when thermally transferring diffusible dyes obtained from image-like VC. Included are materials having an image-receiving layer, such as dye-fixing materials used in the systems described in European Patent Nos. 7J, ≠ 2 and 79.014.

The temperature of the heat treatment performed in the present invention is preferably 72,006 or higher, and particularly preferably 1μ00C or higher.

The most preferred polyester film used in the present invention is polyethylene terephthalate film.

Further, the effects of the present invention are particularly remarkable in heat-developable photosensitive materials.

The heat-developable photosensitive material used in the present invention has at least a photosensitive silver halide, a binder, and a reducing agent on a support. Among them, in order to form a color image, a dye-providing substance that releases or forms a mobile dye upon heating is further contained.

In this case, the dye-donating substance may function as a reducing agent.

Another embodiment of the heat-developable photosensitive material used in the present invention includes at least one photographic layer comprising a photosensitive diazo compound, a binder, and a coupling component with the diazo compound on a support.

In the method using a heat-developable diazo photographic material, the photosensitive material 1 contains a photosensitive diazo compound, a coupling component with the diazo compound, and a substance that generates a base upon heating, that is, a base precursor, and these have a temperature of 100 to 2oo 0C. When heated to a certain degree, a shivering reaction occurs and an azo dye is formed.

A method using a heat-developable diazo copying material was disclosed in Japanese Patent Application Laid-Open No. 1989-
11212, 72-70 Tatako 1, j7-μ5
oya issue, same jj-/JJOjJ issue, same j ko 1joo
ia, special public show jtt-/9t io-0, same da 3-ko 1172≦, same si-μO≠jj, same gu J'-4A1.202, same≠≠-2♂t63 It is described in etc.

Diazonium salts, coupler compounds with diazo compounds, stabilizers, etc. used in the present invention are described in the above-mentioned patent publications.

In the present invention, the light-sensitive material is used, if necessary, with a dye fixing element that fixes the dye.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
It may be silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition within the particles may be uniform, or may have a multiple structure with different compositions on the surface and inside (as disclosed in JP-A No. 7-23/1999, same re
-io♂j3J issue, same! Day lI♂? jS issue, same! Day! No. 2237, U.S. Pat. No. 33,017! R and European Patent Nos. IOO, RRP). Further, tabular grains having a grain thickness of 0.1 μm or less, a diameter of at least o.t μm, and an average aspect ratio of 5 or more (U.S. Pat. No. 11,4
t/4A, No. 310, No. 44,173! , ≠ Tade and West German Published Patent Application (OL8) No. 3,24A/.

j! 7A/etc.), monodispersed emulsions with a nearly uniform grain size distribution (JP-A-Sho, t7-171236, 5r-
7oorat issue, same! r-/44129, International Publication 1
310 Coj J rk/No., European Patent No. t#, 4I
/ J) 3 and the same No. 73. ! 77AI) may also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing monodisperse emulsions of 2fa or more with different grain sizes.

The grain size of the silver halide used in the present invention preferably has an average grain size of o, ooi μm to 708 m;
More preferably, the distance is from 0000/μm to 38m. These silver halide emulsions can be prepared by acid method, neutral method, or 7tl emulsion.
It may be prepared by any of the ammonia methods, and the reaction method between the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A back mixing method in which particles are formed in an excess of silver ions or a Chondral double jet method in which the pAge is kept constant can also be employed. In addition, in order to accelerate grain growth, the degree of addition, addition @, or addition rate of silver salts and halogen salts may be increased (see Japanese Patent Publication No. 2003-110001, No. 23 Kota, No. 5r-1sr/2). No., U.S. Patent No. J, tjO,
No. 717, etc.).

Epitaxial junction type silver halide grains can also be used (JP-A-Sho!t-/J), 24! No., U.S. Patent No. p, ori<z, ar.

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, silver chloroiodide, silver iodobromide, silver chloride iodide, silver iodobromide, silver iodobromide, etc. Silver oxide 1r: Preferably for toilet use.

Such a silver salt can be obtained, for example, by adding a nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide to obtain silver iodobromide having the above-mentioned properties.

In the stage of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent.
Organic thionythyl derivatives described in No. 11314 or sulfur-containing compounds described in JP-A No. 13-44≠31 can be used.

In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

Further, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (lIl, fV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Tardel water washing method or the precipitation method can be applied.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (%
11-/-) μm 24jJA No. 11-2/1t4I44).

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. An internal latent image emulsion suitable for this purpose is disclosed in U.S. Pat. octopus.

No. 130, No. 3, 76, No. 276, Special Public ShojIf-
No. 31317 and Tokukai Sho! 7-/, 3bubu 4t1 issue, etc. Preferred nucleating agents for combination in the present invention are those described in U.S. Patent No. 3. cocoa.

No. 132, same No. G, 24! ! , No. 037, No. 1゜co3
1. II No. 1, No. ≠, No. 211,031, No. 44.
J74. JJ4! No. O! Hi-OL 8th girl, 63! , 31
It is stated in No. 6 etc.

The coating amount of the photosensitive silver halide used in the present invention is in the range of silver conversion 'Jl/ki to 109/m2.

In the present invention, an organic metal salt that is relatively stable to light can be used in combination with the photosensitive silver rhodanide as an oxidizing agent. In this case, it is necessary that the photosensitive silver rhodanide and the organic metal salt be in contact with each other or at a close distance. Among these organic metal salts, organic silver salts are
It is particularly preferably used. When organic metal salts are used together in this way, the photothermographic material has rθ0C1 preferably /θ
When heated to temperatures above 0C, it is believed that the organometallic oxidizing agent also participates in redox using the silver halide latent image as a catalyst.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include aliphatic or aromatic carbo/acids, compounds containing a mercapto group or a thiocarbonyl group carrying an α-hydrogen, and compounds containing an imino group. Examples include.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, manic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lylic acid, and oleic acid. Typical examples include silver salts derived from the acids adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid or camphoric acid.

Halogen atoms or hydroxyl group substituted products of these fatty acids,
Alternatively, silver salts derived from aliphatic carboxylic acids and the like having thioether groups can also be used.

Frog salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3. j-dihydroxybenzoic acid, o-lm- or p-methylbenzoic acid, co-dichlorobenzoic acid, acetamidobenzoic acid, p-
Phenylbenzoic acid, gallic acid, tannic acid, phthalic acid,
Representative examples include silver salts derived from terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid, or 3-carboxymethyl-l-methyl-l-thiazoline-corchion. As a silver salt of a compound having a mercapto or thiocarbonyl group, 3-mercapto-7
-7 enil 1. Co, l-triazole, -merkabutobenzimidazole, komelkabuto j-aminothiadiazole, komelkabutobenzothiazole, S-
Alkylthyl 7-oglycolic acid (carbons m12 to 22 of alkyl group)
, dithiocarboxylic acids such as ditheoacetic acid, thioamides such as thiostearamide, j-carboxy-7-methyl-phenyl-hiro-thiopyridine, mercaptotriazine, comelcabutobenzoxazole, mercaptooxadiazole or 3-amino- ! -B/Jilchio 1. Also≠-triazole and other US patents! , /, 2j
Silver salts derived from mercapto compounds described in , J74, etc. can be used.

As a silver salt of a compound having an imino group, Japanese Patent Publication No. 444
4-40.270 or uJ-/Ir4417° or derivatives thereof, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole,! -Halogen-substituted benzotriazoles such as chlorobenzotriazole, carboimidobenzotriazoles such as butylcarboimidobenzotriazole, nitrobenzotriazoles described in JP-A-Sho Jfl-//IAJ issue, JP-A-Show! I-//
J'bu-/r- Sulfobenzotriazole, carboxylic acid benzotriazole or its salt, or hydrogine benzotriazole described in JIr, U.S. Patent No. G, Co 20.70
/, 2. μ-triazole/1-1-
Typical examples include silver salts derived from tetrazole, carbazole, zatukarin, imidazole and derivatives thereof.

In addition, organometallic salts other than silver salts such as silver salts and copper stearate listed in 1'LI)/70, 2 (where 7 is the year and month), and patent application Shojrf-2co/63j. Silver salts of carboxylic acids containing an alkyl group, such as the phenyl acids mentioned above, can also be used in the present invention.

The organic silver salts mentioned above are photosensitive, preferably 0.0 to 10 moles per mole of silver rhodanide, preferably O1θl to 1
Moles can be used together. The commercial coating rate for photosensitive silver halide and orientated scissors is 10 to 109/m2.

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. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus,
Thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring in these nuclei A fused nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus,
A benzosennazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-j-one nucleus, a thiopidantoin nucleus, and a cortioxazolidine-2 nucleus as a nucleus having a ketomethylene structure.
, 41-dione nucleus, thiazolidine, l-dione nucleus,
S-a-membered heterocyclic nuclei such as rhodanine nuclei and thiobarbic acid nuclei can be used.

These sensitizing dyes! rj, lit may be used alone, but
Combinations thereof may also be used, 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 substance that does not substantially absorb oJ visual light and exhibits supersensitization. For example, aminosteryl compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. Patent No.

ri 33, 3 ri no. 0, same no. 3. t3! , No. 721, etc.), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. U.S. Patent No. 3.6-J/-/! , t/3 issue, t/3, 4/! , Hiroshi No. 1, same No. J,
AI7, 2nd No. 3, same No. 3. t3! Particularly useful are the combinations described in , No. 7.21.

In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, they may be directly dispersed in the emulsion, or they may be dispersed alone or in a solvent such as water, methanol, ethanol, acetone, methyl cellosolve, etc. It may be dissolved in a mixed solvent and added to the emulsion. Alternatively, they may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol, then dispersed in water or a hydrophilic colloid, and this dispersion may be added to the emulsion. Furthermore, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. Further, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved. Also, when added to an emulsion, it may be added at the same time as a mixture, or
It may be added separately or simultaneously with other additives.

The timing of adding it to the emulsion is during chemical ripening or -J,
It may be before or after the formation of silver halide grains according to U.S. Pat.

The amount added is generally about lo-8 to 10 moles per mole of silver rhodanide.

In the present invention, when photosensitive silver halide is reduced to silver under high-temperature conditions, a compound that is completely formed or released as a dye in response to or inversely to this reaction, that is, a dye. Goldstone the donor substance.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that react with a developer. This system that utilizes all of the coupler, in which the oxidized product of the developer produced by the branching-reduction reaction between the silver salt and the developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of developers and couplers include:
For example, by T. H. James, The
ory of thephotographic p
rocess''!th, Ed1 Kota 1-33 Gobege, and 3111-34/Beige, by Makoto Kikuchi, "Photography Chemistry", Vth edition (Kyoritsu Shuppan), pages 2r4L - Kota J, and the like.

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds can be found in Research Disclosure magazine, 1970! It is written in the Monthly Issue, J-G-SR Page, (RD-#ritt), etc.

Furthermore, azo dyes used in heat-developable silver dye whitening methods can also be cited as examples of dye-donating substances.

Specific examples of azo dyes and bleaching methods are provided in U.S. Patent No. ≠, 2.
31. 37, Research Disclosure magazine, 1971≠month issue, pages 30-3- (EtD-/≠733
) etc.

Also, U.S. Patent No. 3. RS, its issue, 4t.

Leuco dyes described in No. 022.1.17 and the like can also be cited as examples of dye-donating substances.

Further examples of other dye-donating substances include those that release or diffuse diffusible dyes in an imagewise manner, such as those useful in the systems described in European Patent 7J, ≠ 1, 7, 041 Compounds with functions can be mentioned. The effects of the present invention are particularly remarkable in these two methods.

This type of compound can be represented by the following general formula (L I , l).

(Dye - to cause a difference in the diffusivity of the compound represented by (Dye-X)ny, or
ye is released and released 7' (Dye and (Dye-X)
n represents a group having a property that causes a difference in diffusivity with Y, n represents 1 or -, and when n is -, the two Dye-Xs may be the same or different.

Specific examples of the dye-donating substance represented by the general formula [Li3 include, for example, hydroquinone-based developer-1! - A dye developer in which a drug and a dye component are linked is disclosed in US Patent No. 3.
/3'l, No. 71.41, No. 3,312. I/ri issue,
Same No. J, jri 71.2θO, same No. J, j4t4Z
, jVj No. J, 4tr2, RI No. 72, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in Japanese Patent Application Laid-Open No. 2003-120003, etc., and a substance that releases a diffusible dye through an intramolecular rewinding reaction of isoxacilone ring is Tokukai Showa 4ty-///
, t, 2rg, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

Furthermore, in these methods, development and dye release or diffusion occur in parallel, so it is very difficult to obtain an image with a high SZN ratio. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have dye-releasing ability, and is made to coexist with a reducing agent or its precursor, and after development, it is reduced by the reducing agent that remains unoxidized. A method has also been devised in which a diffusible dye is released using a method of releasing a diffusible dye. Zakoa, j44-/J (7,ri27, j4-/buri, 31λ
No. tJ-45. ! It is described in No. 33.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. , 330°, tJ4 (No., Tokko Sho≠r-
3, No. 141, U.S. Pat. American special pestle No. 3. Ko, 27. It is described in JJL No. 17, etc.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised. Representative examples are shown below along with literature. Definitions in the general formula are described in each respective literature.

N HS 02 D y e U.S. Patent Nos. 3.2 Cor, 3i-, etc. U.S. Pat. , 4A Co., etc. H U.S. Patent No. ≠, 336,322 Japanese Patent Application Publication No. 13-31/2013 JP-A No. 13-31/2013 JP-A No. 336-322 Showa 5i-io, No. 3443 0H Ballast JP-A Showa J/-1011. Jg No. 3 NH302-Dye Research Disclosure Magazine / No. 741'4j' H U.S. Patent No. 3,7λj, No. 012 H H U.S. Patent No. 3,7 Cot, No. 113 Ba1last U.S. Patent No. 3. Hiro≠3. Ri3ri-Dye Tokukai Sho! I-//l,! Any of the various dye-donating substances described in No. 37 and above can be used in the present invention.

Specific examples of imaging materials for use in the present invention are described in the patent documents cited above.

In the present invention, the dye-donating substance is disclosed in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in , No. 2,0 Core.

In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

Examples include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters ( octyl benzoate), alkyl amides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate,
Dioctyl azeley)),)! J mesic acid esters (
(e.g., tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 50°C.
After dissolving in a 0C organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl zolopionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., the hydrophilic Dispersed into colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in Japanese Patent Publication No. Shoj/-321jJ and Japanese Patent Application Laid-open No. Shoj/-J Tatako No. 3 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it.

The amount of high boiling point organic solvent used in the present invention is IO? Below, preferably! V
It is as follows.

In the present invention, it is desirable that the light-sensitive material contains a reducing substance. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxytetronic acid, hydrazines, hydrazides, borane-amine complexes, no-hydroquinones, In addition to amine phenols, catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, ≠-amino-j-pyrazolones, etc., T, I'', James,
“The theory of the ph
otographic process” It H
The reducing agents described in I, Ed, pages 2/-33u can also be used. In addition, Japanese Patent Application Publication No. Sho J7-/31.73 and J7-170. ．． No. 2vj, U.S. Patent No. ≠, 330
, No. 4/7, etc., can also be used.

Combinations of various developers can also be used, such as those disclosed in U.S. Pat. No. 3,03, fA.

In the present invention, the amount of reducing agent added is o per mole of silver.
, oi ~ 20 mils 20 mono 1 ku 017 ~ 10 moles.

Image formation accelerators can be used in the present invention. 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 mobile dyes, and photosensitive material layers. It has functions such as promoting the movement of the dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it has the following functions: base or base precursor, nucleophilic compound, oil, hot solvent, surface active agent,
It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, seven compounds have the same number of functions. There are many.

(a) Bases Examples of preferred bases include, as inorganic bases, alkali metal or alkaline earth metal hydroxides, co- or tertiary phosphates, borates, carbonates, quinolates, metaborates. ;Ammonium hydroxide: 4! hydroxides of alkylammonium; hydroxides of other metals; examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines @( N-alkyl substituted aromatic amine M
, N-hydroxylalkyl-substituted aromatic amines and bis[p-(dialkylamino)phenylcomethanes]
, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, especially p K
a! The above are preferred.

Examples of base precursors include salts of organic acids and bases that decompose by decarboxylation when heated, compounds that decompose and release amines through reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmann rearrangement. Those that cause a reaction and release a base are preferably used. Preferred base precursors include the salts of trichloroacetic acid described in British Patent Nos.
The salt of α-sulfonylacetic acid described in θ, No. 11.20, patent application No. 111-! salts of propiolic acids described in U.S. Pat. Salts with decomposable acids (%Gan Sho 5R-1 Rijri No. 7), hydroxamic carbamates described in Japanese Patent Application Sho 5R-P3RTO that utilize Rossen rearrangement, and patent application Sho JL- that generates nitriles by heating. 3/, A/4! Examples include aldoxime carbamates described in No. In addition, British Patent No. t, ri≠j, U.S. Patent No. 31.2, -
3 Za-1rat issue, Tokukai Sho! Also useful are the base precursors described in British Patent No. 0-22T Coj, British Patent No. 1,07, ITO, and the like.

Water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols, It is also possible to use salts or precursors of the compounds mentioned above.

(d) Oil A high boiling point organic solvent (so-called plasticizer) used as a solvent during emulsification and dispersion of hydrophobic compounds can be used.

(e) Hot solvents Solid at ambient temperature, melting near the development temperature and acting as solvents, such as ureas, urethanes, amides, pyrudines, sulfonamides, sulfones, sulfoxides, esters, and ketones. It is a compound of the class, ether class.
A solid material with an o 0c or less can be used.

JP-A-19-7≠3117 pyridinium salts,
Ammonium salts, phosphonium salts, JP-A-Shojter!
Examples include polyalkylene oxides described in No. r723/.

Imides, eight nitrogen-containing items described in Japanese Patent Application No. Shoj♂-31437, Japanese Patent Application No. Shoj7-. Examples include thiols, thioureas, and thionidels described in No. 2222μ7.

The image formation accelerator may be incorporated into either the light-sensitive material or the color patch fixing material, or may be incorporated into both.The layers in which it is incorporated also include the emulsion layer, intermediate layer, protective layer, dye fixing layer, and They may be incorporated into any layer adjacent to them.

The same applies to the case where the photosensitive layer and the dye fixing layer are all on the same support.

Image formation accelerators can be used alone or in combination, but generally a greater accelerating effect can be obtained when several types are used in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base or reacts with the base to stop development due to the base concentration in the film after proper development, or a compound that interacts with silver and silver salts to inhibit development. 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 when heated, nitrogen-containing heteroterminal compounds, mercapto compounds, and the like. For acid precursors, for example, patent application Shoj♂-2
Examples include oxime esters described in Japanese Patent Application No. 1,921 and Japanese Patent Application Shojter No. 4!1301, and compounds that release acids through Rossen rearrangement as described in Japanese Patent Application Shojter No. 4!1301. Examples of electrophilic compounds that stimulate reactions include Tokugansho! -≠
) - Compounds, etc.

The above-mentioned development stoppers are particularly effective when a base precursor is used, which is preferable.

In that case, the value of the ratio (molar ratio) of base precursor/acid sol cursor is preferably /120-20//, / /
j −j / / is more preferable.

Further, in the present invention, it is possible to use a compound that simultaneously stabilizes the image while activating the development.

Among them, isothiuroniums represented by λ-hydroxyethyl isothiuronium trichloroacetate described in US Patent No. J, 30/771r, US Pat. /, f-(3,t-
Bis(isothiuronium)s such as dioxaoctane)bis(trichloroacetate in isothiuronium), West German Patent Publication No. 2. Thiol compounds described in /A2゜71/, US Patent No.≠.

0/2, 2-amino-λ-thiazolium Φ trichloroacetate described in JtO issue, Coamino! - Thiazolium compounds such as buomoethyl-cochiazolium trichloroacetate, US patent -≠ 2- Hiroshi Dai, 040,! Compounds having a cocarboxycarboxamide as an acidic moiety, such as bis(,2-amino-thiazolium)methylenebis(sulfonylacetate) and λ-aminocortiazolium phenylsulfonylacetate described in No. 20, etc. Preferably used.

Furthermore, azole thioether and blocked azolinthionic compounds described in Belgian Patent No. 761,071,
U.S. Patent No. 3. 3. Ijt's Hiroshi-Origari-Runault Luvamilukotetrazoline! -thione compounds, etc. U.S. Patent No. 3゜r3p, opt No. 3
, f&! , No. 711, No. 3,177, and Ripo No. 1 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are /, 2゜q-triazole, lH-tetrazole, thiouracil and /,3
．． Compounds such as 44-thiadiazole. Examples of preferred toning include j-amino-7,3,4t-thiadiazole-corchiol, 3-mercapto-/, j,
≠-triazole, bis(dimethylcarbamyl) disulfide, t-methylthiouracil, l-phenyl-λ-
Tetraazoline! -Thion, etc. Particularly effective toning agents are compounds capable of forming black images.

The concentration of the toning agent contained varies depending on the type of photothermographic material, processing conditions, desired image, and other factors, but generally it is about 0.00 per mole of silver in the photosensitive material.
It is 0.1 mole.

The binders used in the present invention can be contained alone or in combination. A hydrophilic binder can be used for this binder.

Hydrophilic binders are typically transparent or translucent, such as gelates, gelatin derivatives, cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinyl Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as pyrrolidone and acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others.

The coating amount of the binder of the present invention is /m'' or less than #) oy, preferably less than #'1 ioy, more preferably 72 or less.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is less than or equal to solvent/cc, preferably less than or equal to 0.1 cc, and more preferably less than or equal to 0. Jcc or less is appropriate.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, metherodimethylhydantoy, etc.), dioxa/derivatives (co, 3- dihydroxydioxane, etc.], active vinyl compounds (/, 3.j-triacryloyl-hexahydro-3-tria-μ!-dine, 113-vinylsulfonyl-coprobanol,
/, J-bis(hinylsulfonylacetamido)ethane, etc.), active rhodan compounds (2,l-dichloro-t-
Hydroxy-S-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related Contains film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Patent No. 3゜t3p, ory, No. 3
,72! , No. 070 is preferably used.

In the present invention, when using a dye-providing substance that releases all of the image-wise mobile dye, a dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer.

In a system in which all of the transfer aid is supplied externally, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used as the dye transfer aid. Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used.

The dye transfer aid may be used by wetting the image-receiving layer with the transfer aid.

If the transfer aid is incorporated into the photosensitive material or dye fixing material, there is no need to supply the transfer aid from the outside.

The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is incorporated into the light-sensitive material or dye-fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
The dye-donating substance represented by l)? If it contains,
Since the dye-donating substance is colored, it is not necessary to further include anti-irradiation, anti-halation substances, and various dyes in the light-sensitive material, but it is necessary to improve the sharpness of images. In order to make
-JG Octopus Publication, U.S. Patent No. 3. Ko! 3,92/issue,
Same No. 25jλ7.61.3, Same No. ko, F,, tj,
It is possible to contain filter dyes, absorbent substances, etc., which are described in various specifications such as No. ♂7.

In addition, it is preferable that these dyes are thermally decolorizable.
For example, U.S. Patent Nos. 3 and 7, No. 0/R, U.S. Pat.
Dyes such as those described in 4'jt, No. 00, I, tit, p. 32 are preferred.

The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an A
It can contain an H layer, a release layer, etc. For various additives, see Research Disclosure magazine VOI, /7
1. Additives listed in No. 70.2 of 1971, such as plasticizers, dyes for improving sharpness, AH dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, There are additives such as anti-fading agents.

The photographic element of the present invention is comprised of a light-sensitive element that forms or releases a dye upon heat development and, optionally, a dye-fixing element that fixes the dye. In particular, in systems that form images by diffusion transfer of dyes, a light-sensitive element and a dye-fixing element are essential. It is roughly divided into a form in which it is coated and a form in which it is coated on the same support.

There are two types of forms in which the photosensitive element and the dye-fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. In the case of the former peel-off type, after image exposure or heat development, the coated surface of the photosensitive element and the coated surface of the dye fixing element are overlapped, and after the transferred image is formed, the sensitive wing element is immediately peeled off from the dye fixing element. do. Depending on whether the final image is of a reflection type or a transmission type, the support of the dye fixing element can be selected as an opaque support or a transparent support.

Furthermore, a white reflective layer may be coated if necessary.

In the case of the latter type that does not require peeling, it is necessary to have a white reflective layer interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. It may be painted on any of the elements. The support of the dye fixing element needs to be a transparent support.

A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is such that the photosensitive element does not need to be peeled off from the image-receiving element after the transfer image is formed.

In this case, a photosensitive layer is placed on a transparent casing or an opaque support.
A dye fixing layer and a white reflective layer are laminated. In a preferred embodiment, for example, transparent or opaque support/photosensitive layer/
White reflective layer/dye fixing layer/, transparent support/dye fixing layer/
Examples include a white reflective layer/sensing layer.

Another typical form in which the light-sensitive element and the dye-1 constant element are coated on the same support (see, e.g., JP-A-47J)
There are forms in which part or all of the photosensitive element is peeled off from the dye-fixing element, as described in Canadian Patent No. For example, a release layer is coated at an appropriate position.

The photosensitive element or the dye fixing element may be in the form of an electrically conductive heating element Ink as a heating means for thermal development or diffusion transfer of the dye.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors yellow, maze/red, and 7/, the light-sensitive element used in the present invention has at least three layers, each sensitive to a different spectral region. It must have a silver rhodanide emulsion layer.

Typical combinations of at least three light-sensitive Rogge/silveride emulsion layers sensitive to different spectral regions include a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer; a green-sensitive emulsion layer; Emulsion layer, combination of red-sensitive emulsion layer and infrared-sensitive emulsion layer, combination of blue-sensitive emulsion layer, green-sensitive emulsion layer and infrared-sensitive emulsion layer, W-sensitive emulsion layer, red-sensitive emulsion layer and infrared There are combinations of light-sensitive emulsion layers, etc. Note that the infrared light-sensitive emulsion layer refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 7 μonm or more.

The light-sensitive material used in the present invention may have an emulsion rfi sensitive to the same spectral region divided into two or more layers depending on the sensitivity of the emulsion, if necessary.

Each of the above emulsion layers and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer contains a dye-donating substance that releases or forms a yellow hydrophilic dye, and a dye-donating substance that releases or forms a magenta hydrophilic dye. It is necessary to contain any seven types of dye-donating substances and dye-donating substances that release or form cyan hydrophilic dyes. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form hydrophilic dyes of different hues.

Dye-donor of the same hue as desired:! It is also possible to use a mixture of il-λ or more types. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary.

In particular, the protective RTI (PC) usually contains an organic or inorganic matting agent to prevent adhesion.

This protective layer also contains a mordant, a UV absorber, etc.
3- You can leave it alone. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent, a UV absorber, and a white pigment such as TiO2 to prevent color mixing. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing overall sensitivity.

In order to impart all of the above color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity.

The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

Furthermore, a water absorption layer or a dye transfer aid-containing layer may be provided in order to fully contain a dye transfer aid if necessary, or to control the dye transfer aid. These 1- may be adjacent to the dye fixing layer, or may be applied via an intermediate layer.

The dye fixation N used in the present invention may be adjusted to 74' if necessary.
- It may be composed of two or more layers using mordants having different mordant powers.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or base precursor to promote dye migration, a hydrophilic thermal solvent, an antifade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stability Dispersed vinyl compound for increasing
A fluorescent brightener or the like may also be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, water-soluble polyvinyl compounds such as degistrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Synthetic polymeric substances etc. are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In addition to the above, the dye fixing element may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose. These layers may be coated not only in the dye-fixing element but also in the photosensitive element. The configurations of the reflective layer, neutralization layer, and neutralization timing layer described above are described, for example, in U.S. Pat. r
iy No. 3.3t2, 1.21, same No. J, 44/
j, A! μ, Canadian Patent No. 2♂, JJ Patent No. 1, etc. are described.

Furthermore, it is advantageous for the dye fixing element of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing l-, or may be included in a separate layer.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder.

Materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTc thermistors, tin oxide, and lead oxide. Transparent or opaque thin films can be formed using known methods. can be made. In the latter method, a resistor with desired temperature characteristics can be produced by dispersing conductive particles such as gold particles, carbon black, or graphite in rubber, synthetic polymer, or gelatin. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, etc.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat generating element/support /photosensitive element support/heat generating element/photosensitive element support/heat generating element/intermediate layer/photosensitive element support/photosensitive element/heat generating element support/photosensitive element/intermediate layer/heat generating element j 71 The image receiving layer in the present invention includes a dye fixing layer used in heat-developable color light-sensitive materials, and can be arbitrarily selected from commonly used mordants, among which polymer mordants are particularly preferred. Here, the polymer mordants include polymers containing tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, and polymers containing primary cation groups thereof.

Polymers containing vinyl nitrates and one unit gold having a tertiary amino fund are described in Japanese Patent Application No. Sho J, R-/4-0/-, Japanese Patent Application No. 5 R-Ittisj, etc., and have a tertiary imidazole fund. Specific examples of polymers containing one vinyl monomer unit include Tokoku No. 1 Musume No. 31-224'197;
♂-JJ, No. 2o7/, U.S. Patent No. Hiroshi, λtco, 305
No., No. 3, //, t, /24! No. 3. /I
II, No. 041, etc.

Preferred examples of polymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent No.
1&, 10/No., No. 1, Ori3゜sr-04t1, No. 1. Jriμ, Ribu No. 1, U.S. Patent No. 4
', / 2u, No. 314, same No. p, ils, /,
No. 2, No. 273.163, No. ≠, μjO1
, No. 2 Cog, JP-A No. 4L, R-Col-lr, Coco-J, etc.

Preferred specific examples of polymers containing one vinyl unit having a quaternary ammonium salt include U.S. Pat. ! r, No. 996, special request! I-/At
/3j issue, same jlr-IA? Olko, same j1-232
It is described in No. 070, Jl-, 2J-07, and J-Tata No. 1420.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, backing layer, and other layers are prepared for each layer using the dipping method, air knife method, curtain coating method, or U.S. Patent 3. The entire photosensitive material can be prepared by sequentially coating onto a support by various coating methods, such as the hopper coating method described in No. 25', and drying.

Additionally, if necessary, US Pat. Two or more layers can also be applied simultaneously by the method described in θRI No. 1.

Radiation including visible light can be used as a light source for image exposure for recording an image on a heat-developable photosensitive material. In general, light sources used for normal color printing include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CR'f' light sources, fluorescent tubes, and light-emitting diodes (LEDs).
Various light sources such as can be used.

The heating temperature in the heat development process is about ro0c to about 0c
It can be developed at c, but especially about 1O0C to about tto0c.
is useful, and within this range, 1ao0c or more is preferred, and 1106C or more is particularly preferred. The heating temperature in the transfer process can be transferred in the range from the temperature in the heat development process to room temperature, but in particular, the heating temperature in the heat development process is approximately 1
A temperature lower than O0C is more preferable. As a heating means in the development and/or transfer process, a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc. can be used.

A dye transfer aid (for example, water) is added between the photosensitive layer of the Iri heat-developable material and the dye fixing layer of the dye fixing material to promote image transfer. It is also possible to apply a dye transfer aid to one or both of the layers before superimposing them.

Examples of the method for applying the dye transfer aid to the photosensitive layer or the dye fixing layer include a roller coating method or a wire per coating method as described in JP-A No. 1989-11-JJ-07; A method of applying water to a dye-fixing material using a water-absorbing member as described in TSR No. 02, patent application Akio! A method of applying a dye transfer aid by forming beads between a heat-developable photosensitive material and a dye-fixing material as described in Japanese Patent Application Sho Jr.-J!
10, in which a bead is formed between a water-repellent roller and a dye fixing layer to apply a dye transfer aid, and other methods include a dipping method, an extrusion method, and a method of ejecting it as a jet from pores. Various methods can be used, such as a method of applying the bond and a method of applying the bond in a compressed manner.

The dye transfer aid may be measured in advance and given in an amount within the range as described in Japanese Patent Application No. 11-372O, or
The amount can be adjusted and used by applying sufficient amount and then squeezing it out by applying pressure with a roller or the like or drying it by applying heat.

For example, there is a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out by passing between pressurized rollers, and then the material is superimposed on a photothermographic material.

Heating means in the transfer process include heating that passes between hot plates or in contact with a hot plate (for example, JP-A-Sho!0-j, 2-buj
j), heating by rotating and contacting a heated drum or heated roller (e.g., JP-A-1J-107-1), heating by passing through hot air (e.g., JP-A-Sho! 3-3 Core No. 37) , Heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source with a roller, belt, or guide member (for example, Japanese Patent Publication No. 4A≠-1!
≠ (sign) etc. can be used. Alternatively, a layer of an electrically conductive material such as graphite, carbon black, or metal may be applied to the dye-fixing material in an overlapping manner, and an electric current may be passed through this electrically conductive layer to heat it directly.

The heating temperature applied in the transfer step can be in the range from the temperature in the heat development step to room temperature, but in particular t
o0c or higher, to'c higher than the temperature in the heat development process
A lower temperature is preferred.

The pressure when overlapping the heat-developable photosensitive material and the dye-fixing material and bringing them into close contact varies depending on the embodiment and the materials used.
0, /-/o Okg/ax preferably /-
zOkg/as is appropriate (for example,
! ! (described in issue No. BUYI).

Various methods can be used to apply pressure to the photothermographic material and the dye-fixing material, such as passing it between a pair of rollers or pressing it using a plate with good smoothness. Furthermore, the roller and plate used to apply pressure can be heated within a range from room temperature to the temperature used in the thermal development process.

Example 1 Polyethylene terephthalate was extruded by a conventional method to obtain 1O
J at O0C, 1x longitudinal stretching, then /30°C
After that, this thin film was stretched by 3 times in the transverse direction and stretched in the co-axis direction.Then, this thin film was heated and fixed at a temperature of 1μ30C to form a polyethylene terephtha V-) film A with a film thickness of ioooμ.
made.

Film B was made in exactly the same manner as above except that the heating fixation temperature was set to 0.

This film AXB was subjected to a hydrophilic treatment by the method described below. Liquid a is maleic anhydride copolymer (Ga
ntrez AN) as a starting material, butylamine was used in equimolar amounts, and methyl ethyl ketone was used as a solvent to adjust the concentration to 70% by weight. Solution B: 1 ethylene glycol diglycidyl ether, phenoxydiethylamine
A dimethylformamide solution having a concentration of 0% was prepared according to a conventional method.

Undercoat liquid composition: A liquid, 2 c parts, liquid 3
Part C: 10 parts of water. Samples C and D were prepared by applying this undercoating liquid to both sides of the film AX B at a rate of 100,111 per 7 square meters, and then drying in a oven.9.

Sample E was prepared in the same manner as above except that Film B was coated with the above undercoat solution and dried at tro°C for 3 minutes.

The elongation rates of samples C, D, and H were calculated by measuring the dimensions at -2joC and the dimensions during heating for 1so0ci. The results are shown in the table below.

-4! - From the above results, sample D is 1. It was shown that the expansion and contraction ratio was extremely small in the heated state of tOoC.

Example 2 The following photosensitive material was coated on the polyethylene terephthalate film prepared in Example 1.

This article describes how to make benzotriazole silver emulsion.

21f gelatin and 13.21 parts benzotriazole to 3 parts water
Dissolves in 000@l. The solution is kept at ≠00C and stirred. Add silver nitrate/71 to this solution and 700.7 of water! Add the solution dissolved in it over 2 minutes.

The pH of this benzotriazole silver emulsion is
and allow to settle to remove excess salt. Then the pH was adjusted to t.

3, a benzotriazole silver emulsion with a yield of pooy was obtained.

Next, a method for preparing a silver halide emulsion for the fifth layer will be described.

Aqueous gelatin/l stirred well! (Water 10100O
Dissolve gelatin-Of and ammonia in 5o0c
An aqueous solution lθ00g1 containing potassium iodide and potassium bromide (kept warm at
oWt (in which 1 mol of silver nitrate was dissolved) was simultaneously added while keeping pAgffi constant. In this way, the average particle size is 0. A monodispersed silver iodobromide octahedral emulsion (j mol of iodine) of jμ was prepared.

After washing with water and desalting, gold and sulfur sensitization was performed at 0c by adding chlorauric acid (Horhydrochloride) j■ and sodium thiosulfate 2■. The yield of the emulsion was 1.0 kQ.

Next, I will talk about how to make the emulsion for the third layer.

A well-stirred gelatin aqueous solution (gelatin in water/000 wt, 201 and sodium chloride 3?@mi7j
tθOml of an aqueous solution containing sodium chloride and potassium bromide (kept at 0C) and a silver nitrate aqueous solution (water A
O,ry moles of silver nitrate dissolved in OOmt) and the following dye solution (1) were simultaneously added at equal flow rates over ≠θ minutes. In this way, the average particle size is 0.3
A monodisperse cubic silver chlorobromide emulsion with 1μ of dye adsorbed (bromine t.

(mol%) was prepared.

Sodium thiosulfate after washing with water and desalting! ■Tobi-hydroxy-l-methyl-/, 3.3a, 7-chitrasaindene 2
Chemical sensitization was carried out using AooC with the addition of 0■. The yield of emulsion was 100f.

Dye solution ([)′ Next, the method for preparing the emulsion for the first layer will be described.

A well-stirred aqueous gelatin solution (containing 20f gelatin and 3v sodium chloride in 10100O of water and keeping it warm at 7j0C) was mixed with AOOml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous solution of silver nitrate (water tθ0wt1). At the same time, a solution of silver nitrate (O0S) was added at an equal flow rate over μθ minutes. In this way, the average particle size is 0, . A monodisperse cubic silver chlorobromide emulsion (bromine rO mol ratio) of 3 μm was prepared.

After washing with water and desalting sodium thiosulfate
Chemical sensitization was carried out at 0c by adding 20μ. The yield of the emulsion was too.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

If the yellow dye-donating substance (A) is used as a surfactant, sodium succinate-2-ethyl-hexyl ester sulfonate o, zf, )! Weigh 1 oy-5 of j-isononyl phosphate and add 30. Add if and heat to dissolve at about t o OC to form a homogeneous solution. After stirring and mixing this solution and 100 ml of lime-processed gelatin ios solution, the mixture was mixed with a homogenizer for 10 minutes. ooooo
Disperse using FLPM. This dispersion is called a dispersion of a yellow dye-donating substance.

A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that a magenta dye-providing substance (B)k was used and tricresyl phosphate was used as a high boiling point solvent at a total of 7°sy.

A cyan dye-donor compound (C) was prepared in the same manner as the yellow dye dispersion.

Using these materials, color photosensitive materials having a multi-layer structure as shown in the following table were prepared. In the table, back 1- is a conductive heat generating layer containing carbon black.

(A,) (B) 0C16H33” Screen 1: (1soC9H□90) 3F=0 Screen 3:
Hiro-Methylsulfonylphenylsulfonylacetate guanidine cage 4: Kao Atlas Demol Hemat 5 = Next, the method of making the dye fixing material will be described.

Poly(methyl acrylate-N,N,N-)samethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is t', i) Dissolve iog in 20011 water,
iogy lime-processed gelatin, 1ooy was mixed uniformly. This mixed solution was uniformly applied to a wet film thickness of 9θ μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material having a mordant layer.

B and G, in which a tungsten bulb is used in the multilayered color photosensitive material, and the density changes continuously.

1 at 200θ lux through a three-color separation filter of R
Exposure for seconds.

Thereafter, a DC voltage of JooV was applied to the packed layer for 20 seconds through electrodes spaced apart from each other.

Next, water was supplied in an amount of 0 ml per 1 m to the membrane side of the dye-fixing material, and then the above-mentioned photosensitive material, which had been subjected to electrical heating, was stacked on the fixing material so that the membrane surfaces were in contact with each other. r
After heating on a heat block at θ0C for 4 seconds, the dye fixing material was peeled off, and yellow, magenta, and cyan color images corresponding to the decomposition filter were obtained on the fixing material.

This color image was uniform and clear for sample D, but for sample C,
With E, there was a lot of unevenness and an insufficient image could be obtained.

From the above, it has been proven that a uniform image can be obtained for the first time in the heat-developable photosensitive material using polyethylene terephthalate as a support with the elongation f of the base of the present invention adjusted.

Claims (1)

[Claims] A photographic material that is heat-treated using a polyester film as a support having an elongation rate of -0.5% to +0.5% in the longitudinal and lateral directions at a temperature of 120 to 180°C.