JPS61228443A - Heat developeble color photosensitive material - Google Patents

Abstract

PURPOSE:To form a heat-developable color photosensitive material low in the min. density in the light, superior in color separability, and raw stock storage stability by forming a layer contg. photosensitive silver halide and specified 2 kinds of compds. on a support. CONSTITUTION:The layer formed on the support contains photosensitive silver halide and the compds. represented by formula A and I, and the compd. of formula A lowers the density in the light of a transferred image, that is, the min. density, and greatly improves discrimination. Main factors of coloring in the min. density part is considered to be in that the oxidation product (having quinone structure) of a color developing agent, being intrisically immobile, reacts with various kinds of additives present in the film, and their decomposition products, and it is partially converted into an easily mobile type, and attached to the dye fixing layer. Presumably, the compd. of formula A preferentially reacts with the oxidation product of the color developing agent as compared with the additives,such as bases, to convert it into a less mobile type, and it can effectively lower the min. density.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a heat-developable color photosensitive method that forms a dye image in a negative relationship to a silver image by heating in a substantially water-free state. It relates to materials, and in particular to heat-developable color photosensitive materials using dye developers.

(Background Art) A photographic method for obtaining a color positive image using a dye developing agent, that is, a compound containing a hydroquinone type developing agent and a dye in its molecule, is disclosed in US Pat. tots issue, same j, 44/j, j4c$ issue, same 3,! In addition to the wet developing method described in Tada, Ibu reference, etc.,
Also known is a method using heat development, which is described in U.S. Pat. No. 63-0147. To describe this thermal development color photography method in more detail, a light-exposed light-sensitive element containing at least a light-sensitive silver halide, a .zeta. When heated and developed in a state that does not contain dye, the dye developer becomes immobilized in the area where development has occurred.
If a dye developer that maintains its mobility is transferred to an image receiving element, a positive image will be formed regardless of the intensity of light.

Here, the dye developer is believed to be oxidized by forming an oxidant, thereby substantially inhibiting transfer.

However, in thermal development color photography using this dye developer, transfer is not sufficiently inhibited, and the density of bright areas that should normally be transparent or white increases (that is, the minimum density value increases). It also had the major drawback of poor color separation.

By the way, U8 patent No. 3. No. 73,716 describes that in a diffusion transfer color photograph using a dye developer, which is processed with an aqueous alkaline processing composition, the transfer of the oxidized form of the dye developer can be inhibited by using an onium compound. ing.

This onium compound certainly has the effect of improving bright areas even in thermal development systems, but it causes problems when it significantly lowers the image density (<Stt large density), and also causes desensitization of the photosensitive element. It was found that it has. On the other hand, Tokko Akida! -≠Oizt No. 1 states that compounds having active methylene groups or active methine groups have the effect of improving brightness and color separation in diffusion transfer color photographs using dye developers that are processed with aqueous alkaline processing solutions. There is a statement to that effect. However, the compounds having active methylene groups or active methine groups described in the above-mentioned patents are mobile compounds soluble in alkaline aqueous solutions or water without ballast groups. When such a mobile compound without a pallast group was applied to a heat-developable color photographic system, /) no improvement effect on bright areas was observed, or even if an improvement effect was observed, it was extremely small; ) It has been found that there are various problems such as:) the effect cannot be exerted only on the white objective layer of each color-sensitive layer constituting the photosensitive element; and 3) the storage stability of the photosensitive element is deteriorated.

(Object of the Invention) Accordingly, an object of the present invention is to provide a heat-developable color photosensitive material that has a low minimum density in bright areas, excellent color separation, and excellent shelf life.

(Disclosure of the Invention) The above-mentioned object of the present invention is to provide a heat-resistant silver halide solution having at least a photosensitive silver halide, a compound represented by general formula (A), and a compound represented by general formula (I) on a support. This is achieved by developing color photosensitive materials.

General formula (A) Represents a group that provides a hydroxyl group.

General formula (I) Y -C-C)12-Z The compound of the general formula (I) of the present invention greatly improves the bright areas of the transferred image, that is, the lower minimum density and the Sidisk IJ termination. Although the mechanism is not clear, the main cause of coloration in the minimum density area is that the oxidized form (quinoy form) of the dye developer, which is originally immobile and is produced by oxidation, is further present in the film. It is presumed that the dye reacts with various additives and decomposed products of the additives (e.g., bases, etc.), partially changes into a mobile compound, and stains the dye fixing layer. The compound of general formula (I) of the present invention preferentially reacts (possibly addition reaction) with the oxidized product of the dye developer than the above-mentioned additives such as bases, and is substantially less mobile (preferably ballasted). As a result, it can be assumed that the effect of effectively lowering the minimum concentration will be expressed.

Specific examples of Y in general formula (I) include alkyl groups and aryl groups, which may have a substituent. Examples of substituents include alkyl groups, alkoxy groups,
Examples include acylamino group.

Specific examples of Z in general formula (I)K include shea and the like. Here, Bl and B2 represent a hydrogen atom, an alkyl group having up to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms. These R and R may be further substituted, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an oxycarbonyl group, a cyano group, a carboxylic acid group, a sulfonic acid group, an acylamino group, etc. .゛Specific examples of compounds of general formula (I) useful in the present invention are shown below, but the present invention is not limited thereto.

■-2 α -j ■-μ C (JOC14H2°C) i3U 1-r COOC,, H33 ■-ta1-/Kol-/ J 1-/≠ ■-/! 1-/bu-t70H2C(Jul 1-/ri■-co1 ■-23 ■-co≠ 1-J j α The compound represented by the general formula (I) of the present invention can be used in a wide range of applications. However, it is usually Q, 0! mol to 2 Q mol, preferably 0 per mol of the dye developer of general formula (A).
．． 1 mol to 10 mol. Note that the compound represented by general formula (I) is a known compound and can be easily obtained.

The compound of the present invention represented by general formula (I) is usually dissolved in an organic solvent that is sparingly soluble in water (e.g., ethyl acetate, tricresyl phosphate, dibutyl hetatalate), and then
It is emulsified and dispersed and added in the form of an emulsion (at this time, it may be co-emulsified with a dye developer or emulsified alone).

Among the compounds of the present invention, compounds that exhibit surface-active properties and form micellar gold (for example, compound examples (-/j to l-
In the case of 20), it can be added directly to water alone, dissolved in a water-miscible organic solvent (for example, methanol, ethanol, dimethylformamide, tetrahydrofuran), or in water and the above-mentioned organic solvent.

Although the compound represented by general formula (I) may be present in any layer of the light-sensitive material, it is particularly preferable that the compound represented by general formula (I) be present in the same layer as the dye developer of general formula (A).

Next, a compound represented by the general formula (A) (dye developer)
I will explain in detail.

Here, R, R2, and Ra are each selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, and a halogen atom. represents an fc group, and the alkyl and aryl groups in these groups can further include an alkoxy group, a hydroxyl group, a halogen atom, a cyano group, an acyloxy group, an alkoxycarinyl group, an acylamino group, a carbamoyl group, a substituted carbamoyl group, and a sulfamoyl group. , a substituted sulfamoyl group, an alkylsulfonylamio group, an arylsulfonylamino group, a ureido group, or a substituted ureido group.

However, at least one of R1, R2, and R3 represents a hydrogen atom.

G represents a hydroxyl group or a group that provides a hydroxyl group by heating and/or a base.

In a preferred embodiment of the present invention, substituents a1, FL2
, R3 is a substituent selected from a hydrogen atom, an alkyl group with a carbon number of Hiro or less, an alkoxy group with a carbon number of μ or less, and an alkylthio group with a carbon number of μ or less, and G is a hydroxyl group or a trialkylsilyl ether of a hydroxyl group. , carboxylic acid ester, carbonic acid ester, sulfonic acid ester, and phosphoric acid ester are the selected hydroxyl group precursors.

The linking group X is preferably a simple link or a divalent residue shown below. 0 alkylene, -〇-1-
S-1-C-1-SO□-1-N)iCO-1-Full*
vy-fjH(CCI)-, alkylene-NE(S(
J□-17 *L/7-8 (J2NH-, Alkyne-CONH-1-NHCUNH-1Dye is an image-forming dye or a precursor thereof.

Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes,
Mention may be made of metal-chelated or non-metal-chelated dyes, such as styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, xanthine dyes.

Examples of image-forming dyes include the following.

Example of yellow dye: US patent! ,! No. 97.200, 3.30 r.

No. 12, same≠, 0/3,433, same≠, Ko≠j, 0
No. 4A, /! &, No. 402, same≠.

13ri, 3i3, room attendant, /ri! , Tade No. 2, same 44,
/441. All I, same 1t, /1llr, l, 4A
J No., Room Clerk, Jjt, No. 322; Tokukai Sho! ／−／／≠2
No. 30, No. j4-7107: Re5earchD
isclosure Noah 1.30 (/7F),
What is described in the /J$77 (/P77) issue.

Example of magenta dye: US Patent 3. ≠ni’! , No. 107, s, r4L≠.

Hari-go, same! , No. 932,310, 3. ri3i, iu
No. a, same j,? 32.301, same 3゜P! Hiroshi, ≠7
No. 6, same≠, Ko 33, 237, same tA 213',
10P issue, same ≠, λ! O, Ko≠6, same≠, l≠2. r
yi issue, same da, 207, 10≠ issue, same≠, -r7. -F
λ issue; Tokukaisho! Koh 104.7 Tips issue, same! --104
No. 727, same! 3-Jj, 4ko No. 1, 1j-El,,
10μ issue, 74-73.0!7, 74-710bu0, sr-/J reference, 16-/23! Jt No., as described in the same No. jj-//377W.

Example of cyan dye: US patent! , No. 4414, 272, 3. riλri.

No. 740, same da, 0/3. T! ! No. 1, 26t, No. 25, same, /7/, No. -20, same≠.

JliLko, μ3! No., same a, ias, tri No. 1, same μ
, liri! , Pfl No. 1, 44. /4C7, j4c4 number, same, tl/Lr, bu≠ko number; British patent/, 11
/ .

No. 131; Tokukai Sho! ≠-Tata 4cJ/issue, same! 2-11
No. 27, same! ! -17rJj No. 3-7IIJ32
No. 3, same! Hiro-data 4cJI No., same j6-710bu 1; European Tsuno patent (RPC) tJ.

No. 037, same! 3,0 san〇 issue, Tokukai Sho! Tar/4!0!
≠ Issue; Research Disclosure (R+asearc
h Disclosure )/7, A jO(
What is described in /ri No. 71) and /4, 4A77 (/ri 77).

The characteristics required for image-forming dyes are: /) having nine hues suitable for color reproduction; λ) having a large molecular extinction coefficient;
3) stability against light, heat, and other additives such as a dye release aid contained in the system; and μ) ease of synthesis. For specific examples of preferred image-forming dyes that meet these conditions, please refer to JP-A-Sho! Tar/410
It is listed in No. 1.

Alternatively, a chelate dye may be formed using a dye capable of forming a metal chelate in a dye fixing layer containing a metal salt (post-chelation method).

This type of dye is described in the patents listed below.

U.S. Patent No. 11, 2! 0, 2 J11 ≠, 3 Hiro ≦.

/11. Same, 34 Abu, lbu 11 same≠,! ! f7゜I
tlo, same It, 3!7, 4c12, same II, 1419
゜Da 3! , same da, ≠ko o, pro, same, pi07゜ri31. Same≠, 4A34.7 Tata; Tokukai Sho! 3-31
! 33, same 1! -13722, same j7-/μt co! 0,
Same 77-! r/I/-P, same 17-/1r437, same!
7-! f/4A? , 77-/r! , 4'33, same! 7
-/'462jO, samez7-irz.

Go, same 7-/! Ibu37, same! 7-/1103ri,
same! 7-/12731. Same j-7-/r/lp4, same!
r-/43?31. Same 11-/, 2jj37, same! I-
/43?31. same! I-/639sr, same! lr-/1
JWjlr, same! r-/74434, same! r-/7+3
7. Same! r-171fi3r.

11-2097141, jlr-2097442,
same! Tur≠t7bujl SamejTurf2IO Specific examples of the dye developer used in the present invention are shown below.
It is not limited to these.

OH (I). H(ri)
OH H CH3 (6). □(JH (ri) (l/) OH OH (/4A) OH (/riOH (/')
CM (JC3H, (iso) OH (λO) OH H (Kob) (JH (Kor) (Kob) (3) OH OH (j4c) (3riOH 3Ct (2bed=nNf (80□) 1 lip] (JH80, OH3 Be=Ken N=N802 0□N N)i ω Regarding the method of synthesizing the dye developer, see the above-mentioned U.S. Patent No. 3.13.
Da, No. 7M4A, No. J, /71. Takota, No. 3. Ri2
See also U.S. Patent No. 3.
The dye developing agent used in the present invention can be synthesized according to these synthesis methods, which are described in detail in No. 1, No. I, Try, Tyt, etc.

Two or more types of the dye developing agents of the present invention may be used in combination. In this case, one or more types may be used in combination to produce the same color, and it also includes the case where 2's or more are used in combination to produce black.

The dye developer of the present invention has a total of 10 to irt7
The range of m2 is appropriate, and more preferably /! from ki to zy
It is appropriate to use it within a range of 7m.

The dye developer of the present invention may be used in the same layer as the silver halide emulsion, or may be included in a layer adjacent to the emulsion layer.

In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is a so-called auxiliary silver salt developer, which has the ability to act cooperatively with the dye developer to promote silver development.

Useful auxiliary developers include hydroquinone, tert-butylhydroquinone, and more! - Alkyl-substituted hydroquinones such as dimethyl hydroquinone, catechols,
These include pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid g-conductor L N .

Hydroxylamines such as N′-di(2-ethoxyethyl)hydroxylamine, pyrazolidones such as /-722-3-pyrazolidone-hiro-methyl-der-hydroxymethyl-l-phenyl-3-pyrazolidone, reductones, Hydroxytetronic acids and the like are useful.

Among them, /) less stain, 2) the general formula (I)
Pyrazolidones are particularly useful auxiliary developing agents because the effects of the compounds represented by the following formula are likely to be noticeable. The auxiliary developer may also be precursorized to be activated by heat or by base.

Auxiliary developers can be used in a certain concentration range.

A useful concentration range is 0.0001 times molar to 20 times molar based on coated silver, and a particularly useful concentration range is 0.00
/ times mole to 3 times mole.

The color photographic light-sensitive material of the present invention preferably includes a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer, or a combination of a green-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared-sensitive emulsion layer; Each emulsion layer is composed of a yellow dye developer, a magenta dye developer, and a cyan dye developer, respectively.
An emulsion layer that is sensitive to light of 0 nm or more, particularly 7440 nm or more).

Silver halides used in the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide.

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. That is, it is particularly preferable to use pure silver iodide which shows a lumpy turn when subjected to X-ray diffraction of silver iodide.

Silver halide containing one or more types of halogen atoms is used in photographic light-sensitive materials, but in ordinary silver halide emulsions, the silver halide grains form a complete mixed crystal. For example, in a silver iodobromide emulsion, when X-ray diffraction of the grains is measured, patterns of silver iodide crystals and silver bromide crystals are not found, but X-ray patterns are found at positions corresponding to the mixing ratio.

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

Such silver halide can also be obtained, for example, by adding a silver nitrate solution to a potassium bromide solution to first form silver bromide grains, and then adding potassium iodide.

Two or more types of silver halide having different sizes and/or silver halide compositions may be used in combination.

The silver halide grains used in the present invention preferably have an average grain size of from o,oot μm to 70 μm, more preferably from o,ooi μm to 3 μm.The silver halide grains used in the present invention may be used as is. In addition, compounds such as sulfur, selenium, tellurium, etc., chemical sensitizers such as compounds such as gold, platinum, /R radium, rhodium and iridium, reducing agents such as tin chloride, etc., or combinations thereof. For details, see “The theory of
the Photographic Process
"U edition, 7μ pages of Chapter 5 by T. H. James.
It is written on page 4.

In the present invention, the coating amount of photosensitive silver halide is suitably 1 to 7 m in terms of silver.

A sensitizing dye may be used to spectral sensitize silver halide to a specific wavelength range as described above. The dyes used include
cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hexonol dyes. Particularly useful bottle pigments include cyanine pigments,
It consists of pigments belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

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

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

A particularly preferred embodiment of the present invention is one in which an organic silver salt oxidizing agent is present.
or more, preferably 1 when heated to ioo°C or more.
A silver image is formed by reacting with the above-mentioned image-forming substance or a reducing agent coexisting with the image-forming substance if necessary.

By coexisting with an organic silver salt oxidizing agent, a photosensitive material with better discrimination can be obtained.

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.

Examples of such organic silver salt oxidizing agents include JP-A-5R-Z
There are some examples described in rzμ3, such as the following.

Silver salts of organic compounds having a carboxy group can be mentioned first, and typical examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.

In addition, there are compounds having a mercapto group or a thione group, and silver salts of derivatives thereof.

In addition, there are silver salts of compounds having imino groups. For example, silver salts of benzotriazole and its derivatives described in Japanese Patent Publication No. 30270 and No. 4tt-/rμlt, such as silver salts of benzotriazole, silver salts of alkyl-substituted benzotriazoles such as silver salts of IJ azole, and silver salts of methylbenzotriazole. salt,! - Silver salts of halogen-substituted benzotriazoles, such as silver salts of chlorobenzotriazole, town salts of carboimidobenzotriazoles, such as silver salts of butylcarboimidobenzotriazole, US Pat.

l described in the specification of Coco No. 0,70, 2. Hiro-triazole/-)1? - Silver salts of tetrazole, silver salts of carbazole, silver salts of saccharin, silver salts of imidazole and imidazole derivatives, etc.

Organometallic salts such as silver salts and copper stearate described in Research Disclosure No. 170/702 are also organometallic salt oxidizing agents that can be used in the present invention.

For details on how to produce these silver halides and organic silver salts, and how to mix both, please refer to Research Disclosure/
No. 70 1702 Riya Tokukai Akira! 0-32 octopus? , Tokukai Sho pi-pco! Kota, Tokukai Sho≠2-/32koμ, Tokukai Shoj
07-/72/l, US patent! , No. 700.4Ljr.

In the present invention, the coating amount of photosensitive silver halide and organic silver salt is suitably 10 to IOf/m" in total in terms of silver.

The binders used in the present invention may be contained alone or in combination, and hydrophilic binders are preferably used.

Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as 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.

Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time.

Among them, inthiuroniums represented by low hydroxyethyl inthiuronium trichloroacetate described in U.S. Patent No. J, JO/, 671, U.S. Patent No. J, 4
Bis(isothiuroniums such as i,r-(3,t-dioxaoctane)bis(intiuronium trichloroacetate) described in No. 670, West German Patent No. 2./
Otsu λ, 7/thiol compounds described in reference publication, US Patent No. ≠.

Low aminocortiazolium trichloroacetate described in No. 012,240, λ-amino! - Thiazolium compounds such as bromoethyl-cortiazolium trichloroacetate, US Pat. No. 44. O20,1A2
Bis(λ-amino-λ-thiazolium)methylenebis(sulfonylacetate) described in No. 0, co-amino-λ-
Compounds having λ-carboxycarboxamide as an acidic moiety, such as thiazolium phenylsulfonylacetate, are preferably used.

Furthermore, Belgian patent no. 74. azole thioethers and blocked azolinthionic compounds as described in U.S. Pat. -thione compounds, and other U.S. Pat. Also preferably used are the compounds described in J, 711, J, 177, and RμO.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are l and co.

≠-triazole, /H-tetrazole, thiouracil and /, 3. ≠ - Compounds such as thiadiazole.

Examples of preferred toning include! -Amino/, J, u-
Thiadiazole-corchiol, 3-mercapto-l,
Co, 4A-triazole, bis(dimethylcarbamyl)
Disulf()', 4-methylthiouracil, l-phenyl-cochitraazoline-! -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.
1,0.1 mole.

Various bases or base precursors can be used in the image forming method of the present invention. Bases or base precursors are believed to promote redox reactions between photosensitive silver halides and reducing dye developers, and their use is particularly advantageous in promoting development. .

Examples of preferred bases include hydroxides, co- or tertiary phosphates, borates, carbonates, quinolates, metaborates of alkali metals or alkaline earth metals as bare bases; Examples include ammonium hydroxide; hydroxide of primary alkylammonium; hydroxide of other metals, etc. Organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines). ); Aromatic amines (N-alkyl substituted aromatic amines, N-hydroxylalkyl substituted aromatic amines and bis(p-(dialkylamino)7enyl)methanes)
, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, especially p K
Preferably, a is 1 or more.

Examples of base precursors include salts of organic acids and bases that decompose by decarboxylation and decomposition by heating, compounds that decompose and release amines by reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmann rearrangement. Preferably used are those that cause some kind of reaction and release a base. Preferred base precursors include British Patent No. Tatar, ? Salt of trichloroacetic acid described in Hiroori No. etc., U.S. Patent No. ≠, O
Salts of α-sulfonylacetic acids as described in BuO9 Ko No. 20, salts of propiolic acids as described in JP-A No. 37, U.S. Patent No. μ, O♂! , ≠ 2, the 2-carboxycarboxamide visiting conductor described in No. 2, and a salt with a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base as the base component (JP-A No. 5237) ), a special application using Rossen rearrangement in 1974 r-μ! , No. 160, JP-A-Sho!, which produces nitriles upon heating, as described in JP-A-Sho! Examples include aldoxime carbamates described in Patent No. 117437.

Other British Patent Nos. Tata r, t≠! No. 3, U.S. Pat.
220. r4Al, No. 421, JP-A No. 10-22゜421,
Also useful are the base precursors described in British Patent No. 2,07, No. ♂O, etc.

Specific examples of base precursors particularly useful in the present invention are shown below.

Guanidine trichloroacetate, Methylguanidine trichloroacetate, Potassium trichloroacetate, Guanidine phenylsulfonylacetate, Guanidine p-chlorophenylsulfonylacetate, Guanidine p-meta/sulfonylphenylsulfonylacetate, Potassium phenylpropiolate, Cesium phenylpropiolate, Peranidine phenylpropiolate , guanidine p-chlorophenylpropiolate, co,≠-dichlorophenylpropiolate diguanidine, p-phenylene-bis-propiolate diguanidine, phenylsulfonylacetate tetramethylammonium, phenylpropiolate tetramethylammonium.

These bases or base precursors can be used in a wide variety of ways. The useful range is calculated by converting the coated dry film of the photosensitive material into weight! O weight - or less, more preferably,
It ranges from 0,0/wt% to ≠O wt%.

It goes without saying that the above bases or base precursors can be used not only for promoting development, but also for other purposes, such as adjusting the pHO value.

The above-mentioned components constituting the heat-developable photosensitive material of the present invention can be placed at any appropriate position.

For example, one or more of the components can be disposed in one or more layers in the light-sensitive material, if desired. In some cases, it may be desirable to include certain amounts (proportions) of reducing agents, image stabilizers and/or other additives, such as those described above, in the protective layer.

In this case, it is possible to reduce the total movement of additives between layers of the photothermographic material, which may be advantageous.

The support used in the light-sensitive material and the dye-fixing material used in some cases in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogues, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. Contains film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. US Patent 3. t3a, orri issue, same number J, 7
2! , No. 070 is preferably used.

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 (J, j-dihydroxydioxane, etc.) ), activated vinyl compound (/, j
, j-) lyacryloyl-hexahydro-@+)
IJ azine, /, J-vinylsulfonyl-2-propanol, etc.), active halogen compounds ゛(co2μm dik4-hydroxy-9-) 17 azine), mucohalogen acids (mucochloric acid, mucophenoxychlor) acids, 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.

In a system in which the transfer aid is externally supplied, 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 in such a way that the image-receiving layer is wetted 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.

Other compounds that can be used in the light-sensitive material in the present invention, such as sulfamide derivatives, cationic compounds having a pyridinium group, surfactants having a polyethylene oxide chain, sensitizing dyes, antihalation and irradiation dyes, hardening film Regarding agents, mordants, etc., European Patent No. 76, ≠ Octopus No. 66, -12, West German Patent J,
J/j.

Jrz issue, Tokukai Shojter itμ4Aμ! Same issue! Turf! Those listed in Ko≠Hiroshi O issue can include Kongo.

Furthermore, the methods cited in the above-mentioned patents can be used for methods such as exposure.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, or laser light sources,
Various light sources can be used, such as a CRT light source, a fluorescent tube, and a light emitting diode (LED).

When using an LED as an exposure means, it is difficult to obtain blue light using an LED, so in order to reproduce a color image, for example, three types of LEDs emitting green, red, and infrared light are used for exposure. The heat-developable photosensitive material may be designed so that yellow, magenta, and cyan dyes are released from the respective photosensitive layers that are sensitive to these lights. That is, if the green-sensitive area (layer) contains a yellow dye-providing substance, the red-sensitive area (layer) contains a magenta dye-providing substance, and the infrared-sensitive area (layer) contains a cyan dye-providing substance. good. However, the light emitting characteristics of the LED, the spectral sensitivity characteristics of the photosensitive material, and the coloring characteristics of the photosensitive material are not necessarily limited to this combination, and various combinations are possible.

Examples of methods for exposing the heat-developable photosensitive material include the following methods. The first method is to use an original image such as a line image such as a drawing or a photographic image with a level p4t, and perform contact printing over the original image.

In addition, electrical signals of images taken by a video camera, etc., images sent from a television station, or original images read by a light-receiving element such as a phototube or COD, and image signals stored in the memory of a computer or other device are required. After performing so-called image processing, which is processed according to the
It is also possible to expose the image to a T or FOT (fiber optics cathode ray tube) and print the image on a heat-developable photosensitive material either by contacting it or by using a lens. Reference rJO2).

Alternatively, scanning may be performed by the method described below, and scanning exposure may be performed by controlling all light emission of a j5 LED or a semiconductor laser light source, or by modulating a laser beam or the like based on the processed image signal.

1) For example, as described in JP-A No. 17-711733 or JP-A No. 17-711733 or JP-A-17-711733, light sources such as LEDs and semiconductor lasers are arranged in the circumferential direction of a disk-shaped rotor, A method of scanning by rotating this rotor and moving it in the direction of the rotation axis.

11) As is known in so-called scanners, etc.
A scanning method in which a photosensitive material is wound around a drum, the drum is rotated, and a head is provided with a light source or the light from the light source is guided by an optical fiber, etc., by moving in the direction of the rotation axis of the drum.

111) A method in which a light beam from a laser light source or the like is vibrated using an optical deflector such as a carpano mirror or a rotating polygon mirror, and the photosensitive material is scanned by moving it perpendicular to the direction of deflection.

Furthermore, exposure can also be carried out by applying an image signal to a matrix or array of liquid crystals and controlling the light from a light source, as described in % Gansho J-1-/≠Koko λ.

The heating temperature in the heat development process is approximately 0°C to approximately 2°C.
It can be developed at c, but especially about ito"c to about /IO"
C is useful. The heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but it is particularly preferable to set the heating temperature to a temperature that is about 0.degree. C. lower than the temperature in the heat development step.

As a heating means in the development and/or transfer step, a heating plate, an iron, a heating roller, a heating element using carbon, titanium white, etc. can be used.

The present invention will be explained in more detail below with reference to one example, but the present invention is not limited thereto.

Example 1 Comparative photosensitive coatings A-/ and B-/ were made by coating the following layers in the order listed on a polyethylene terephthalate film support.

Photosensitive coating A-/l) Benzotriazole silver (0,3417 m2 in amount of silver)
), silver iodobromide (in the amount of silver, 7 J r/m2)
Gelatin (A I 97m"), dye developer compound example (J4t) (0,3497m2), structure W below
Auxiliary developer C0, Orf/1n2) represented by structure X, antifoggant (0,/717m
), a surfactant represented by the structure Y below (0, co2
layer 2) containing gelatin (/, 4 f/ff! 2) and a base precursor represented by the structure Z below (0, 6f/m2)
(Note) (I) Auxiliary developer (Structure W) (2) Antifoggant (Structure X) (3) Surfactant (Structure Y) (4) Base precursor (Structure Z) Photosensitive coating A -/in layer (I), the dye developer compound example (coB
Comparative photosensitive coatings A-J and B, 2ft, were prepared as follows.

In the photosensitive coating A-/, layer (I) is Tokkosho≠! −
≠A mobile compound (2) with the following structure described in issue 0/14
, Hiromm o I 7m'') Photosensitive coating B-2 In the photosensitive coating B-/, layer (I) is
≠A mobile compound with the following structure ■ described in issue 0/14 (J
,! Photosensitive coatings according to the invention A-j to A-r and B-J to
B-4f was prepared as follows.

Photosensitive coating A-J In the photosensitive coating A-/, layer (I) has the general formula (I
) Photosensitive coating A-da Photosensitive coating A-/Ni (layer (I) has the general formula %
A photosensitive coating containing the general formula %) Photosensitive coating A-1 Photosensitive coating A-1 In addition to the photosensitive coating A-/, the layer (I) also contains the general formula %) Photosensitive coating material A-4 Photosensitive coating material A-4 Photosensitive coating material A-7 Photosensitive coating material A-7 Photosensitive coating material A-7 Photosensitive coating material in which layer (I) also contains the general formula %) /, the layer (I) has the general formula (I
Photosensitive coating A-4 Photosensitive coating A-4 In the photosensitive coating A-/, the layer (I) has the general formula % formula % ) In the photosensitive coating A-/, the layer (I) also contains the general formula %) In the photosensitive coating A-/, the layer (I) also contains the general formula %) ) is the general formula (I
) Compound example 1-/r (ko, 4'mmO17m2)
Photosensitive coating material B-z Photosensitive coating material B-z Photosensitive coating material A-/in which layer (I) also contains the general formula %) In /, the layer (I) also contains the general formula %) Photosensitive coating B-7 In the photosensitive coating A-/, the layer (I) also contains the general formula % ) In the photosensitive coating A-/, the layer (I) is a photosensitive coating also containing the general formula % ) and then laminated with polyethylene in which titanium dioxide is dispersed. By applying the following layers on a paper support:
A dye fixing material was created.

/) Poly(methyl acrylate) N, N, N
-Trimethyl-N-vinylbenzylammonium chloride (ratio of methyl acrylate and vinylbenzylammonium chloride is /”, /) j, j 97 m2
and gelatin fJ, Jf/m containing layer Then the above photosensitive coating A-/-A-1! and B-/~B-r
, using a tungsten bulb, 70 lux at 000 lux.
Image-wise exposure for seconds. Thereafter, it was heated for 20 seconds on a heat block heated to l≠o'C.

Next, the dye-fixing material was soaked in water, superimposed so that the film surface was in contact with the sample, heated for 10 seconds on an RJ'C heat block, and then the dye-fixing material was peeled off from the photosensitive material.

For A-/~A-r, a magenta positive image was obtained, and for B-/~Br, a yellow positive image was obtained. For the positive images 'i, A-/-A-r, the density against green light was measured, and for B-/, B-4, the density against blue light was measured using a color densitometer. Table 1K below shows the results.

Table 1 shows that the photosensitive coating containing the compound of general formula (I) of the present invention has a significantly lower minimum density than the comparative photosensitive coating. It can be seen that a clear positive image with good termination can be obtained.

Example 2 A comparative photosensitive coating (I) and an inventive photosensitive coating (2) were made by coating the following layers in the order listed on a polyethylene terephthalate film support.

Photosensitive coating (I) [for comparison] /) Benzotriazole silver (001797m in silver amount)
), red-sensitive silver iodobromide (l in quantity of silver).

0゜3), Dye developer compound example (Jri(0゜3)
297m L gelatin (J, 1117m), an adjunctive phenomenon represented by the structure W above (0, coly/
” 2), an anti-capri agent represented by the above structure X (
0#cof/m2), a surfactant represented by the above structure Y (0,1797m''), a base precursor represented by the above structure Z (0,4Jf/lN>), and tricresyl phosphate (/ , / 97m”
) containing gelatin (o, ryf/m2) and a base precursor (0,3
3) layer containing benzotriazole silver (0.J4cf/” in amount of silver)
)
), Dye developer compound example (J/) (-4cf/ at 0°
n2), gelatin y (2,0617 m2), the above structure W
An auxiliary developer represented by (0.10f/m2), an antifoggant represented by the above structure X (0.2Of7m2)
), a compound represented by the above structure Y (o, tyy/m
2), the base precursor (o
, 4co2/m 2 ) and tricresyl 7 phosphate (o.

1297 m ) gelatin (0,1797 m ) and the structure 2 above
Layered benzotriazole silver containing a base precursor (0,3if/m) (O6≠λr/m in amount of silver)
, blue-sensitive silver iodobromide (06t4Ay7m2 in amount of silver)
, Dye developer compound example (Jf) (0°3451/m2)
, gelatin (t, e2t/m"), auxiliary developer represented by the above structure W (O0l t/m")%, antifoggant represented by the above structure X (0,2 17 m2)
, the thermal solvent represented by the structure Y (O, coit/m2
), the base precursor represented by structure 2 (0,
11497 m2) and tricresyl phosphini) (
t) gelatin (0,17 f/m") and the above structure 2
Base precursor expressed as (0,3λf/1n2)
In the layer photosensitive coating (I) containing t, layer (I), layer (3) and layer (5) each contain l-20f of a compound of general formula (I).
Each /, 1297m", Oori 1f/m2, l.

A coating identical to photosensitive coating (I) except that it contains 417 m2. The photosensitive coatings (I) and (2) above were then imaged for 10 seconds at CoOOQlux using a tungsten bulb. exposed to light. Thereafter, it was heated for 0 seconds on a heat block heated to l≠00. Next, the same dye-fixing material used in Example 1 was soaked in water, layered so that the film surface was in contact with the above sample, and heated for 75 seconds on an RZOC heat block, and then the dye-fixing material was removed from the light-sensitive material. Upon peeling off, positive yellow, magenta and cyan dye images were obtained on the dye fixing material.

This positive value was measured using a color densitometer.

The results are shown in the table.

Claims (1)

[Scope of Claims] A heat-developable color photosensitive material comprising at least a photosensitive silver halide, a compound represented by the following general formula (A), and a compound represented by the following general formula (I) on a support. . General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_1, R_2, R_3 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group,
Represents a group selected from an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, and a halogen atom. (However, at least one of R_1, R_2, and R_3 represents a hydrogen atom.) X represents a divalent residue or a simple link that connects the benzene ring and Dye. Dye represents an image-forming dye or a precursor thereof. G represents a hydroxyl group or a group that provides a hydroxyl group by heating and/or a base. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [Here, Y represents an aliphatic group or an aromatic group, and Z represents an electron-withdrawing group. However, at least one of Y and Z shall contain a diffusion-resistant group having 6 to 30 carbon atoms. ]