JPS6111741A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a transferred color image of high quality by incorporating a matting agent into a nonphotosensitive hydrophilic colloidal layer as a protective layer so as to strip a dye fixing material from a photosensitive material without damaging both the materials. CONSTITUTION:The photosensitive material contg. photosensitive silver halide, a binder and a dye donor, compound has a nonphotosensitive hydrophilic colloidal layer as a protective layer on a layer contg. photosensitive silver halide. A matting agent is incorporated into the protective layer. The matting agent is disconnected solid particles of an inorg. or org. material dispersible in a hydrophilic org. colloidal binder and known well in the field of photographic technique. The average particle size of the matting agent is about 0.1-10mum, the coated amount is about 5-500mg/m<2>, and the thickness of the protective layer is preferably regulated to about 1/10-1/2 of the average particle size (average diameter) of the matting agent so as to improve the strippability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a thermal in-process color photosensitive method in which silver halide is developed by heating in a substantially water-free state, and a dye image is formed as a result of the development. Regarding materials.

(Prior art) So-called conventional technology in which silver halide is developed in a strongly alkaline aqueous solution.
Unlike type photosensitive materials, in heat-developable photosensitive materials, after exposure, silver halide is developed by heating in a substantially water-free state, and as a result of the development, mobile dyes are formed or released in the form of an image. . This mobile dye moves (thermal transfer) to a dye-fixing material superimposed on the photosensitive material and is eventually fixed to the dye-fixing layer to obtain a transferred color image. To view the color image obtained in this way, the photosensitive material and the dye fixing material are usually peeled off, but even if you try to peel it off, the outermost layer (protective layer) of the photosensitive material and the dye in contact with it will be removed. There was a problem in that the fixing layer adhered and could not be peeled off, resulting in damage to both layers9 and the image being damaged (adhesion failure).

OBJECTS OF THE INVENTION It is therefore an object of the present invention to ensure that when the dye-fixing material is peeled off from the light-sensitive material after thermal transfer of the mobile dyes resulting from thermal development, both materials are not damaged and the image quality is improved. An object of the present invention is to provide a heat-developable photosensitive material that provides a transferred color image.

(Means for Solving the Conventional Technical Problems) As a result of extensive research, the present inventor has found that the object of the invention is to provide at least a photosensitive silver halide, a binder, and a photosensitive halogen compound on a support under high temperature conditions. A photosensitive material containing three types of compounds (hereinafter referred to as "dye-donating compounds") that generate or release a mobile dye in response to or inversely to this reaction when silver oxide is reduced to a chain. A protective layer consisting of a non-photosensitive hydrophilic colloid layer is provided on the silver-containing layer,
It has been found that this can be effectively achieved by a heat-developable photosensitive material characterized by containing a matting agent in the preservation layer.

(Effects of the Invention) By incorporating a matting agent into the protective layer, the conventional problem of adhesion failure between the coated surfaces of the dye fixing material and the photosensitive material has been solved.

This effect is significant in embodiments where the dye is transferred under elevated temperature conditions. In the case of dye transfer, the high temperature state is to
0c or more is appropriate. The high temperature state may be formed using the effect of heating for development, or may be formed by heating anew.

This is because if a photosensitive material and a dye-fixing material are brought into contact with each other and kept in a high temperature state, physical and chemical adhesion at the contact surfaces will progress and the releasability will deteriorate.

(Detailed Description of Means) Conventionally known matting agents can be used as the matting agent added to the protective layer of the photosensitive material of the present invention.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of inorganic or organic material dispersible in a hydrophilic organic colloidal binder. Examples of inorganic matting agents include oxides (e.g. silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (e.g. sulfates and carbonates, specifically barium sulfate, carbonate, etc.). (calcium, magnesium sulfate, calcium carbonate, etc.), silver halide particles that do not form an image (silver chloride, silver bromide, etc., and may further include a small amount of iodine atoms as a halogen component), glass, and the like.

Examples of organic matting agents include starch, cellulose esters (eg, cellulose acetate propionate, etc.), cellulose ethers (eg, ethyl cellulose, etc.), and synthetic resins. Examples of synthetic resins include dispersions of water-insoluble or sparingly soluble synthetic polymers, such as 1, alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates, glycidyl acrylates, chrycidyl methacrylates, acrylamides, methacrylamides, and vinyl esters. (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene Polymers containing combinations of sulfonic acids and the like as monomer components can be used.

Among them, -limethyl methacrylate is preferred.

The average particle size of these matting agents is approximately 0. /~1Ot
The i-position is suitable, preferably o, z, rμ, more preferably /-4μ.

The amount of matting agent applied is approximately jrRfi ~ 100■/m2
is appropriate.

The thickness of the protective layer containing the matting agent is preferably about 1/10 to about 1/2 of the average particle size (average diameter) of the matting agent.

The protective layer may be multi-layered, in which case the matting agent is contained in the outermost layer, and in the case of a two-layered structure, for example, oil droplets are preferably dispersed in at least one of these layers. .

The appropriate size of the oil droplets is approximately 0.0/n~20ti.
0. Ojg to 10tt is preferable.

As the substance that forms oil droplets with, high-boiling organic compounds that are usually used for dispersing photographic couplers are useful, and the high-boiling organic compounds preferably have a boiling point of /IOoC or higher at normal pressure, such as U.S. Patent Co., 32λ, 027
Phthalic acid alkyl esters (dibutyl phthalate, dioctyl 7-talate, etc.), su/
acid esters (diphenyl 7-osphate, triphenyl phosphate, tricresyl 7-os 7ate, dioctyl butyl phosphate), esters of citrate (e.g. acetyl tributyl citrate), benzoic acid esters (
(e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate),
Examples include trimesic acid esters (eg, tributyl trimesate).

In the protective layer, for example, a slip agent, an ultraviolet absorber, an organic fluoro compound, an anti-staining agent (eg, a hydroquinone derivative, etc.), a development stopper, a development inhibitor-releasing compound, etc. may be added.

Furthermore, additives such as ultraviolet absorbers, stain inhibitors, and development inhibitor-releasing compounds are preferably contained in the oil droplets.

As ultraviolet absorbers, for example, benzoxide compounds substituted with aryl groups (for example, U.S. Patent J, 33
3.7 Rihiro and JP-A-Shoj't-λ//lμ), ≠-thiazolidone compounds (for example, U.S. Pat. No. 3,
31≠, 7 tag number, those described in 3゜312.411), benzophenone compounds (for example, JP-A-Sho≠4-2
71φ), cinnamate ester compounds (for example, US Patent No. 3.7oz, rot No. J, 707.3
7! ), butadiene compounds (e.g. those described in U.S. Pat.
Benzoxidole compounds (e.g. U.S. Pat. No. 3.700)
．． 4<, those described in No. tj) can be used.

Additionally, U.S. Patent 3. ≠Tata.

The books described in No. 742 and JP-A-Shoj≠-≠113j can also be used. UV-absorbing couplers (e.g. α
- naphthol-based cyan dye-forming couplers), ultraviolet absorbing polymers, etc. may also be used.

More specifically, the above-mentioned benzotriazole compound is, for example, one represented by the following general formula [I], and specific examples of this compound are given in the above-mentioned JP-A-Sho! I-2
///≠Described in No. 1.

General formula CI) The coating amount of the ultraviolet absorber is approximately 0.00/~2 to the hydrophilic organic colloid (binder) used in the protective layer.
(weight ratio) is preferable. Incidentally, the coating amount of the binder is preferably about 0.i to 39/m''.

Examples of the slippery agent include higher alkyl sodium sulfate, higher fatty acid higher alcohol ester, carbowax, higher alkyl phosphate ester, and silicone-based compounds. In particular, US Patent No. 1, 1re2.117, US Pat. /
2/, OAO No. 3, Za 10, 1. The compounds described in Kou Q, JP-A-11-1971-71423, etc. are particularly effective when used alone or in combination of one or more.

The amount of slip agent applied is approx. A suitable value is 200 .mu./TrL2.

The organic fluoro compound includes a chain or cyclic compound containing at least 3 fluorine atoms and at least 3 carbon atoms, and any type of cationic, nonionic, or anionic betaine type can be preferably used.

Representative organic fluoro compounds used in the present invention include, for example, U.S. Pat.
464. GUAR No. 3,73, RI 24/-, GUAR No. 3,771,126゛, GUAR No. s, rso, 4<
<a, British Patent No. 1.3.30.

314, issue, JP-A-11-1064! /Recorded in the specification etc.

For representative examples of these organic fluoro compounds, please refer to Tokko Sho! It is described in column r to column 7 of the specification of No. 7-ta OjJ.

A particularly preferred organic fluoro compound is an anionic organic fluorine-containing surfactant.

The amount of organic fluoro compound added is the protective layer to be coated/1r.
L2 Toshi 0. /~zoo■dashi, preferably /~20
It's 0 da.

Examples of hydroquinone derivatives include Tokugansho! l-2
2/2 ItO issue (Showa srrt/monthly 2nd day Fuji Photo Film ■Application) No. of the specification! It is possible to use hydroquinone derivative mixtures having freezing points below 100 oC, as described on pages 2j to 2j.

In addition, as a development stopper that quickly neutralizes the base or reacts with the base to reduce the base concentration in the film and stop the development, for example, Tokugansho! t-λ/G.

, Ri 2 No., same J 4ct, 3 oz No., same Zy-tj
, No. 1.311, No. 19-Ire, tel., can be used.

As the hydrophilic organic colloid (binder) used in the protective layer of the light-sensitive material of the present invention, those commonly used in photographic layers can be used.

That is, it is advantageous to use gelatin as the hydrophilic organic colloid, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate, starch derivatives, etc. Sugar derivatives; various synthetic highly hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used.

Gelatin derivatives include various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, poly, alkylene oxides, and epoxy compounds. The product obtained by reacting is used. A specific example is U.S. Pat. No., same s, / rt,
r<6, same J, J/2,113, British patent r#/
, ul II No. i, o33. It is written in the tr issue, same i, oo yu, and 7 in the hiro issue, tokuko dakoko tza 4/-j issue, etc.

The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. Particularly preferred are graft polymers with polymers that are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate. Examples of these are U.S. Pat.
It is described in No. 7, A, YST, and TR of the same issue.

In addition to lime-processed gelatin, acid-processed gelatin, l"Bull, Soc, 5ci-Photo, Ja
Enzyme-treated gelatin as described in PanJ4/page 6.30 (l. 66) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The dye-providing compound used in the present invention may be added to the silver halide-containing layer or to a layer adjacent to the silver halide-containing layer.

The dye-providing compound useful in the present invention is represented by the following formula (I).

D-Y (I) "Diffusivity changes" means that (1) the dye-providing compound is originally non-diffusive, and it itself changes to diffusivity;
or (2) a diffusible dye is partially released, or (2) an originally diffusible dye-providing compound is converted to non-diffusible. It means that.

Also, depending on the nature of Y, this change may occur when Y is oxidized or reduced, and both can be used appropriately depending on whether the emulsion used in combination is a negative emulsion or a direct positive emulsion. .

An example of the diffusivity changing due to the oxidation of Y is P-sulfonamide naphthols (including p-sulfonamide phenols, JP-A-Sho≠I-JJ).

No. 124, No. 13-10,734, European Patent No. 76,
≠ Specific examples are listed in the Octopus issue), 0-sulfonamidophenols (including 0-sulfonamidonaphthols,
Tokukai Shoj/-//3. Aλφ No. 74-/2, 4≠2
No., j4-/J, No. 730, jt-/6. /J/ issue, same j7-≠.

No. 0IIJ, No. 17-410, US, Part 0! J.

No. 3/2, European Patent Nos. 7A and 4 (specific examples are described in Octopus No.), Hydroxysulfonamide heterocycles (JP-A-Shoj
/-10≠, 3 Reference No. 3, European Patent No. 76, ≠ 2λ No. 3), 3-sulfonamindoles (JP-A-Sho J-/-IOu, J+3, JP-A No. 13-1j) , 730
No., j4'-/30゜12.2, No. 17-4101
No. 1, European Patent No. 7A, specific examples are described in the reference number)
Examples include so-called dye-releasing redox substrates such as.

As another example, after Y is oxidized, a dye is released by intramolecular nucleophilic attack, as disclosed in Japanese Patent Application Laid-Open No. 7-20, 7.
No. 31, and the intramolecularly assisted substrate described in Japanese Patent Application No. 17-/77/PI.

Another example is a substrate that releases a dye by an intramolecular ring-closing reaction under basic conditions, but does not substantially release a dye when Y is oxidized (JP-A-Shoj. /-63.tlI has a description of a specific example). Furthermore, as a modification of this, a substrate in which the diisoxacilone ring is rewound by a nucleophilic reagent to release a dye is also useful (Japanese Patent Application Laid-open No. 21-21, J2-DA).

Specific examples are listed in the RI issue).

Another example is a substrate in which the dye moiety is released due to dissociation of acidic protons under basic conditions, but when Y is oxidized, the dye does not substantially release (
%Kaisho 33-J, No. 033, same ≠-/J (1), specific examples are described in Octopus No. 7).

On the other hand, examples of the diffusivity changing due to reduction of Y include the nitro compound described in JP-A No. 33-/10,127 and the nitro compound described in JP-A-33-/10. ♂, No. 27,
US, μ, 3jl, Kohiro issue, same≠, 311, j2
The quinone compounds described in No. 2 can be mentioned. These are reduced by a remaining reducing agent (referred to as an electron donor) that is not consumed during the heat development process, and a dye is released by molecular attack of the resulting nucleophilic group. As a modification of this, a quinone-type substrate is also useful, in which the dye moiety is released by dissociation of the acidic proton of the reduced product (JP-A-KOKAI Hiroshi Akihiro/JO).

'? Specific examples are described in No. 27 and No. 76-/j da 1.3). When using a substrate whose diffusivity changes upon reduction as described above, it is essential to use a suitable reducing agent (electron donor) that mediates between the exposed silver halide and the dye-donating compound. Specific examples thereof are described in the above-mentioned publicly known materials. In addition, a substrate in which an electron donor exists in the substrate Y (referred to as an LDA compound)
is also useful.

Dye-donating compounds that release mobile dyes and form image irons by utilizing coupling reactions with reducing agents oxidized by redox reactions with silver halides or organic silver salts at high temperatures are also useful. (These are described in European Patent No. 72,0
14, West German Patent No. 3, J/7, 1rjJ, European Patent No. 47, 4Ijtj).

Further, as another dye-donating compound, there may be used a compound that undergoes a redox reaction with silver halide or an organic silver salt at high temperature, and as a result, the mobility of the compound having a dye moiety changes. It is described in Gansho J-39,4100.

In addition, regarding compounds that release mobile dyes upon reaction with iron ions in photosensitive materials, patent application Shozr-! ! , No. 12λ.

Many of the above compounds form an image-like distribution of mobile dyes in light-sensitive materials through heat development, and these image dyes are transferred to a dye-fixing material (so-called diffusion transfer) for visualization. The method for doing this is described in the patents cited above or the patent application Sho Sr-≠2. O Octopus No. 1
1-11. ．． /7-2 etc.

Silver 10-genide used in the present invention includes silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, silver iodide, and the like.

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, particularly preferred silver halide is one containing silver iodide crystals in a part of the grains. In other words, it is particularly preferable to use silver iodide which shows noiturns of pure silver iodide when subjected to X-ray diffraction.

Silver halide containing I.sub.2 atoms or more is used in photographic light-sensitive materials, but in ordinary silver halide emulsions, the .sub.2 steel grains form a complete mixed crystal. For example, when measuring the X-ray diffraction of the grains of a silver iodobromide emulsion, no /ξ turns of silver iodide crystals or silver bromide crystals are observed, but an X-ray pattern is formed at positions corresponding to the mixing ratio.

Particularly preferred silver halides in the present application are silver chloroiodide, silver iodobromide, and silver chloroiodobromide, which contain silver iodide crystals in their grains and therefore exhibit an X-ray pattern of silver iodide crystals.

A particularly preferred embodiment of the present invention is one in which an organic silver salt oxidizing agent is also used.

By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color at a much higher density.

The silver halide used in this case does not necessarily have the characteristic of containing pure silver iodide crystals when silver halide is used alone, and all silver halides known in the art may be used. be able to.

Specific examples of such surface-like silver salt oxidizing agents are well known to those skilled in the art of heat-developable photosensitive materials, and examples include the following.

1) Silver salt of an organic compound having a carmexyl group.

Typical examples include silver salts of aliphatic carboxylic acids.

2) Silver salts of compounds and derivatives thereof having mercapto or thione groups.

3) Silver salt of a compound having an imino group.

4) [Research Disclosure
hDisclosure) J, vol, /70. /ri7
Silver salt as described in issue 16/7022 of the month issue.

In addition to the above organic silver salts, organic metal salt oxidizing agents such as copper stearate can also be used.

In the present invention, after exposure of the photosensitive material, the resulting latent image is exposed to light at a moderately elevated temperature, e.g. It can be clarified by heating. As long as the temperature is within the above range, either high or low temperatures can be used by increasing or shortening the heating time. Especially about I10”
Temperature ranges from about 160°C to about 160°C are preferred.

The heating means may be a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc., or the like.

In the present invention, a specific method for forming a υ-color image by heat development is to move a hydrophilic mobile dye. For this purpose, the light-sensitive material of the present invention may have a built-in dye fixing layer, but it is effective to superimpose a dye fixing material having at least a dye fixing layer on a support. As for the timing of superimposition, the photosensitive material is imagewise exposed and heated uniformly, and then the fixing material is stacked and the mobile dye can be transferred to the fixing layer; The fixed materials may be overlapped and heated uniformly.

The dye fixing layer can contain, for example, a dye mordant for dye fixation. Various mordants can be used as the mordant, and polymer mordants are particularly useful.

In addition to the mordant, it may also contain a base, its precursor, a binder, a hot solvent, etc.

Examples of polymer mordants include polymers containing secondary and tertiary amino groups, polymers with nitrogen-containing heterocyclic moieties, and polymers containing these quaternary cation groups, with a molecular weight of about z.
, ooo~, 2oo, oo.

The appropriate one is special 1/C10,000,10,00
0 is preferred.

For example, U.S. Patent No. 1444, identical.

4! -111, 4AJO No., same J, /≠r, It/ No.,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat.
Same J, 11? , No. 094, 44, /21.

Evening 3r issue, British patent l, Cocoa, Hiro! A polymer mordant capable of crosslinking with gelatin, etc., disclosed in Specification No. 3, etc.;
US Patent 3. Risr, yri No. 3, same J, 72/, 1
No. 12, same No. 2,721,01,3, Japanese Patent Application Publication No. 1974-
No. 111221, No. 74 (-IQ!jλri No., No. 7)
Aqueous sol type mordant disclosed in US Pat. No. 26,027, etc.; US Pat. Water-insoluble mordant disclosed in the specification of RR, ORTR; T-Co3 070
No. or U.S. patent≠.

(Imidazole mordant as described in III, No. 6117; U.S. Pat.
-/37333) A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc.;
No. 09.490, J, 71g'.

No. 111, same! , 1,172, No. 1112, 3
．． crt, 707. No. J, j! No. 7,046,
3゜27/, /≠7, 3. λ7/, /Hiroshi issue, JP-A-ShojO-7/332, same! No. J-30321, same j
Ko/! ! ! No. 21, same! J-/No. 27, same! 3-70
The mordants disclosed in No. 2 can be mentioned.

Other US patents, 67! , Jet issue, same.

Mention may also be made of the mordants described in rr, t, izt specifications.

Among these, it is preferable to use imidazole mordants as described above.

Gelatin is a typical binder for the dye fixing layer, and various known gelatins such as those from Gelatin Co., Ltd. and those mentioned above may be used. For example, it is also possible to use gelatin produced by different methods of producing gelatin, such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained lanoceratin such as phthalation or sulfonylation. In addition, if necessary, it can be used after being desalted. Use as a replacement for gelatin or in combination,
Water permeable polymeric binders in the mordant layer as described in US Pat.

The mixing ratio of the polymer mordant and gelatin and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. However, mordant/
Gelatin ratio is 20/if0 to 10/20 (weight ratio), mordant application amount is O0! ~I g/m'' is preferable.

A white reflective layer may be coated on the dye fixing material.

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, methylol dimethylhydantoin, etc.), dioxane derivatives (λ, 3-dihydroxydioxane, etc.) , activated vinyl compound (/, J
, j-triacryloyl-hexahydro-5-)! J7
active halogen compounds (u,<4-dichloro-t-
Hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer. As the dye transfer aid, a liquid or a hot solvent that can dissolve the dye to be transferred at least in a heated state can be used.

That is, when the dye to be moved is a hydrophilic dye,
A hydrophilic liquid or a hydrophilic hot solvent can be used, and in the case of lipophilic pigments, organic solvents, oils, lipophilic hot solvents, etc. that can dissolve the lipophilic pigment can be used.

Further, depending on the degree of hydrophilicity or lipophilicity of the dye, suitable amounts of a hydrophilic liquid, a hydrophilic heat solvent, a lipophilic solvent, and a lipophilic heat solvent may be mixed and used.

The dye transfer aid may be used by moistening the dye fixing layer and/or photosensitive layer, preferably the dye fixing layer, with the aid during thermal transfer, or it may be directly incorporated into the layer in advance, or it may be added to a polymer or crystal. It may be adsorbed to water, or incorporated as crystal water or microcapsules.

Hydrophilic or lipophilic solvents used as dye transfer aids include water or basic water-soluble solvents including inorganic alkali metal salts such as caustic soda, caustic potash, and soda carbonate; methanol, ethanol, propatool, phthanol, benzyl; Tetrahydric alcohols such as alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, fluoropylene gellicol, and glycerol; ethers with alcoholic OH groups such as furyl alcohol, methyl cellosolve, and cellosolve; acetone, acetylacetone, and methyl ethyl ketone Ketones such as , hexanone, cyclohexanone; methyl acetate, ethyl acetate,
Examples include esters such as butyl acetate, methyl benzoate, and n-butyl sinate; and nitrogen-containing solvents such as diethylamine, dibutylamine, pyridine, and quinoline.

In a photographic material containing a dye-donating compound in which the dye to be transferred is hydrophilic, when a dye transfer aid is incorporated into the photosensitive material or/and the dye fixing material, the dye transfer aid may be a hydrophilic thermal solvent. The hydrophilic dye can be transferred and fixed onto the dye fixing material by heating in the presence of the dye.

In the image forming method in which the dye is transferred to the fixed dye layer by heating in the presence of a hydrophilic hot solvent, the transfer of the mobile dye may start at the same time as the release of the dye, but after the release of the dye is completed. There may be. Therefore, heating for transferring the dye may be performed after the heat development or at the same time as the heat development.

Heating water for dye transfer 1. From the viewpoint of storage stability and workability of photosensitive materials, the temperature is 40'C--2go'C, so in the present invention, a solvent that can function as a hydrophilic thermal solvent in this temperature range is appropriately selected. be able to. It goes without saying that hydrophilic thermal solvents need to be able to help dyes move quickly during heating, but if we also consider the heat resistance of photosensitive materials, the requirements for hydrophilic thermal solvents are The melting point is Hiroo 0c, xzo'c, preferably ≠o0c~koo'c, more preferably ≠00~/jO
“c.

The above-mentioned hydrophilic thermal solvent is a compound that is in a solid state at room temperature but turns into a liquid state when heated, and has an (inorganic/organic) value>l and a water solubility at room temperature of 1 or more. is defined as a compound of Here, inorganic and organic are:
It is a concept for predicting the properties of compounds, and its details can be found, for example, in the field of chemistry.
It is described in. As a hydrophilic heat solvent, (inorganic/
It is an essential condition that the (organic) value is 7 or more, preferably 2 or more.

On the other hand, from the viewpoint of the size of one molecule, it is considered preferable that there be molecules that can move by themselves without hindering the movement of the moving dye. Therefore, it is preferable that the molecular weight of the hydrophilic heat solvent is small, about -200
Hereinafter, the more preferred molecular weight is about 100 or less.

The hydrophilic thermal solvent is sufficient as long as it can substantially assist the transfer of the hydrophilic dye generated by heat development to the dye fixing layer. Incorporating it into the photosensitive material of
It can be contained in both the dye fixing layer and the photosensitive layer, or an independent layer containing the hydrophilic thermal solvent can be provided in the photosensitive material or in an independent dye fixing material having a dye fixing layer. From the perspective of increasing the efficiency of dye transfer to the dye fixing layer, hydrophilic thermal solvents are suitable for dye fixing layer and/or
It is also preferable to include it in a layer adjacent to the layer.

The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols, such as methanol, ethanol, etc.

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

Specific examples of the hydrophilic thermal solvent and particularly preferred examples thereof are described in Japanese Patent Application Laid-open No. 1983-11-21, pages 44 to 1! Compounds described on page 1 can be mentioned.

These hydrophilic heat solvents can be used alone or in combination of two or more.

The hydrophilic thermal solvent is added to the photosensitive material or dye-fixing material in an amount of approximately io of the total coating film thickness excluding the hydrophilic thermal solvent.
~300 weight units, preferably ~200 weight units, particularly preferably 30~l! It can be used within the range of O weight ratio.

Example 1 A thermal photosensitive material prepared by coating a support with a first layer having a dark blue pattern as shown in Table 1 below and a second layer (protective layer) having a composition as shown in Table 2, respectively. was created.

*1 Nitricresyl phosphate *3: ψ-methylsulfonylphenylsulfonylacetate guanidine *4: (isocgHlgo)3P=0*5: N(L'2H6)3 Third layer, third layer and Benzotriazole silver emulsion formulation used in the 7th layer: 219 gelatin and 13.2 g of benzotriazole to 3 parts water
Dissolve in 000ml. This solution is maintained at 4Ao0c and stirred. A solution of silver nitrate/7.17 dissolved in water is added to this solution over a period of 2 minutes.

The pa of this benzotriazole silver emulsion is adjusted, sedimented and excess salt removed. Thereafter, the pH was adjusted to 6.3 to obtain a benzotriazole silver emulsion with a yield of 4 tools.

Formula of the silver halide emulsion used in the fifth layer: A well-stirred gelatin aqueous solution (gelatin in water/000 g)
Aqueous solution 10 containing potassium iodide and potassium bromide in g and ammonia dissolved and kept warm at jOoC
00111 and an aqueous silver nitrate solution (7 moles of silver nitrate dissolved in water/000d) were added simultaneously while keeping the pAg constant. In this way, the average particle size is 0. A monodisperse silver iodobromide octahedral emulsion (j moles of iodine) of 7 μm was prepared.

After washing with water and desalting, chloroauric acid (Horosui salt)! ~ and sodium thiosulfate-2~ were added, and gold sensitization and sulfur sensitization were performed to'c. The yield of the emulsion was 1,000 kg.

Formula of the silver halide emulsion used in the third layer: A well-stirred gelatin aqueous solution (209 g of gelatin in 100 θ1 of water)
(containing 3g of sodium chloride and kept at 7j'C)
An aqueous solution containing 100 yd of sodium chloride and potassium bromide and an aqueous silver nitrate solution (silver nitrate o, r
tamol dissolved therein) and the following dye solution (I) were simultaneously added at equal flow rates over aO minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (10 moles of bromine) having a dye adsorbed thereon having an average grain size of 0.3 μm was prepared.

After washing with water and desalting, 9-hydroxy-t-methyl-1,3,Ja,7-titrazaindene 201119 was added to sodium thiosulfate 111, and chemical sensitization was performed at 6o'C. The yield of emulsion was 4oog.

Dye solution [I] The silver halide emulsion used in the first layer was prepared using the same recipe as the silver halide emulsion used in the third layer, except that no dye solution was used. .

Prescription of gelatin dispersion of dye-providing compound: Yellow dye-providing compound (A) was used as a surfactant, and Kono.
Weighed 0, zg of sodium phosphoric acid-coethylhexyl ester sulfonate and 10g of triiso-nonyl phosphate, added 30 ml of ethyl acetate, and heated to about 60°C to dissolve.

Make a homogeneous solution. 10 of this solution and lime-processed gelatin
% solution ioog and then dispersed with a homogenizer at 10.00 OR, P, M between io sorting. This dispersion is called a yellow dye-providing compound dispersion.

A dispersion of a magenta dye-providing compound was prepared in the same manner as described above, except that the magenta dye-providing compound (B) was used and 7°g of tricresyl phosphate was used as a high-boiling solvent. A cyan dye-providing compound dispersion was prepared using the cyan dye-providing compound (C) in the same manner as the yellow dye dispersion.

(A) (B) (C) Prescription of dispersion A: A mixture of compounds (A), (B), (C) and (D) (ultraviolet absorbers) having the following structures [mixing ratio, compound (
A) Two compounds (B): Compound (D) = λ: l:/:/
: 12g was dissolved in dioctyl phthalate/jt9 and ethyl acetate tg at 7t'c, and this solution was diluted with jO'c.
Contains sodium triisopropylnaphthalene sulfonate/fl heated to! It was added to 100 cc of an aqueous gelatin solution with stirring, and then dispersed by passing it through a colloid mill three times to prepare a dispersion liquid A.

Compound (A) Compound (B) Compound (C) Compound (D) [Compound (A) is Tinuvin PS, Compound (B) is Tinuvin-320, Compound (C) is Tinuvin-326,
Compound (D) is commercially available as Tinuvin-327 (trade name, both manufactured by Cipacaigy). ] The photosensitive materials coated with the protective layers of Table 2 4/-/FAl are referred to as photosensitive materials (1) to (4), respectively.

Next, we will discuss how to prepare the dye fixing material.

Poly(methyl acrylate-N,N,N-)dimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) 109 is dissolved in λ00ynl of water,
10% lime-processed gelatin, ioog was mixed uniformly.

This mixed solution was uniformly applied to a wet film thickness of POBTrL 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.

The above multilayered color photosensitive material (B%G using tungsten bulbs in 11 to (4) and continuously changing density)
, H for 1 second at 2,000 lux. Thereafter, it was heated uniformly for 30 seconds on a heat block heated to /4tO°C.

Next, water was supplied to the film side of the dye fixing material at an amount of 01/11 rL2, and then the heat-treated photosensitive coatings were superimposed on the fixing material so that the film surfaces were in contact with each other. ro
After heating for 6 seconds on a heat block at 0C, the dye fixing material is peeled off from the photosensitive material, and B, G,
Yellow, corresponding to the H three-color separation filter, respectively.
Magenta and cyan color images were obtained.

At this time, clear color images were obtained with photosensitive materials (3) and (4), but with photosensitive materials (1) and (2), the emulsion layer of the photosensitive material adhered to the dye fixing material together with the protective layer. The image quality was compromised.

Example 2 The same dye fixing material, heat-developable photosensitive layer, and intermediate layers (7th layer to 3rd layer) as in Example 1 were prepared. A plurality of time-keeping layers having the compositions described below (Table 3) were further coated on the j-th layer of the heat-developable photosensitive layer as a layer 1 and a layer 7.

29F *Special agent: CH2-00C-nC11H2al CH-00C-nC11H23 CH2ooc ncllT(23 **Organic fluoro compound: Na0aS-CH-COOC)T2-(CFz)a H
CH2(:00CH2-(C,F2)6 H base precursor: Same as base precursor *3 in Table 1.

Dispersion A: Same as Dispersion A in Table 2.

Dispersion B: Compound (I)/(Lfj) was added to 100 g of gelatin/% aqueous solution, and milled to about 0.00 tz.

Glass beads l having an average particle size of oog for 70 minutes. Ga Separate raspies to obtain dispersion B. Obtained.

Compounds) The photosensitive materials (5) to (8) thus obtained were exposed and thermally developed in the same manner as in Example 1, and then transferred to a dye fixing material. Good color images were obtained with light-sensitive materials (6) to (8), but with light-sensitive material (5), the emulsion layer and protective layer remained on top of the dye-fixing material, resulting in a loss of image quality. .

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Showa Showa J February//Date 1, Case Indication Showa! 2nd year patent application No. 1J/10!
r No. 2, Title of the invention: Heat-developable photosensitive material 3, Relationship with the person making the amendment Patent applicant: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address: 2-26-30-4, Nishi-Azabu, Minato-ku, Tokyo 106 Subject of amendment The description in column 5 of "Detailed Description of the Invention" of the description and the section of "Detailed Description of the Invention" of the description of contents of the amendment will be amended as follows.

(1) @gupage ~l! After "...can be defined" in the seventh line, "among them, matting agents suitable for use in the present invention are preferably ones that are less deformed by heat. Use of inorganic matting agents is particularly preferred. Insert "Gives the result."

(2) Page 2, line lj ", Calcium carbonate" Delete.

(3) From page 1/line P, “Also, an organic matting agent...” to page 1! In the ioth line of the page, the description up to "..., olefin," has been changed to "Also,
The organic matting agent is preferably one that does not soften during transfer.

Examples of such organic matting agents include cellulose ester NFIJ, cellulose acetate probione, etc.), cellulose ether (fF
(IJ, t-kethylcellulose, etc.), synthetic resins, etc.

Examples of synthetic resins include alkyl methacrylate, alkoxyalkyl methacrylate, glycidylmethacrylate, acrylamide, and methacrylamide.

that's all

Claims (1)

[Claims] On a support, at least photosensitive silver halide, a binder, and 3 compounds that produce or release a mobile dye in response to or inversely to this reaction when the photosensitive silver halide is reduced to silver under high temperature conditions. A heat-developable photosensitive material having seeds, which has a protective layer consisting of a non-photosensitive hydrophilic colloid layer on a photosensitive silver halide-containing layer, and a matting agent is contained in the protective layer. material.