JPS5957231A - Thermodevelopable color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color image by forming on a support layer contg. at least a phoaosensitive silver halide, a hydrophilic binder, a dye-releasing aid, and a dye donor reducing an org. silver salt oxidizing agent and releasing a hydrophilic dye, and a polyethylene glycol type surfactant, and thermally transferring said dye released by thermal development to an image receiving layer contg. a mordant. CONSTITUTION:The thermodevelopable color photographic senstivie material can produce a silver image having a negative-positive relationship to an original and a diffusible dye at the positions corresponding to said silver image at the same time only by imagewise exposure and the following thermal development. The reducing dye donor releasing a hydrophilic diffusible dye has formula ( I ) in which R is a reducing moiety oxidizable with silver halide, D is a dye group having a hydrophilic group and forming a dye image, and the reducing moiety R preferably has <=1.2V oxidation reduction potential to a satd. calomel electrode in the determination of a polarographic half-wave potential using acetonitrile as a solvent and sodium perchlorate as a supporting electolyte, and exemplified by formula (II)-(IV), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of forming color images by thermal development. In particular, in a heat-developable color photosensitive material containing a dye-providing substance that releases a diffusible dye upon heat development, the present invention provides heat diffusion transfer of the dye released by heat development onto a dye-receiving support. This paper relates to a new method for obtaining color images.

The photographic method using halogen-1 is superior to other photographic methods such as the Ashi photographic method and the diazo photographic method, as it is superior in customizing photographs such as sensitivity and gradation adjustment, and has traditionally been the most It has been widely used. In recent years, the image forming process of YJ materials using silver halide has been changed from the conventional wet processing using a developing solution to a dry processing using heating etc., making it easier and faster to process the image. KWi, which can obtain II images, has been discovered.

Heat-developable photosensitive materials are well known in the art, and a description of photothermographic materials and processes thereof is provided in U.S. Patent No. 3. /ter, 20μ issue, j, 30/, 47g issue, 3rd
．． 3 Octopus, No. 020, No. 3. In DAJ7゜071, British Patent Nos. I, i3/, IOT, No. 1.767.777, and Research Disclosure magazine, June 7J' issue ~/j page (RD-/7o Kota) Are listed.

Many methods have been proposed for producing color images. A method of forming a color image by combining an oxidized developer and a coupler is disclosed in a US patent @
3. No. s3/, 2gt uses a p-phenylenediamine reducing agent and a phenolic or active methylene coupler; US Patent No. 3.7t/, 270 uses a p-aminophenol reducing agent; Belgian Patent No. J/ri issue and search disclosure magazine/27! February issue 3
/, page 32 proposes a sulfonamidophenol reducing agent, and in US Pat.

However, this method has the disadvantage that the color image becomes dark because the reduced image and the color 11iii image are simultaneously generated in the areas where the dew after heat development occurs. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer.

In addition, a nitrogen-containing heterocyclic group is added to the dye, and a silver salt is produced in the form 1jy.
A method to make dyes free by heat development is introduced in 2013. Monthly issue tμ~rig page) t, IJ-/944. With this method, it is difficult to suppress the release of dye in areas not exposed to light, and a clear image cannot be produced using iLF, so it is not a common method.

Furthermore, regarding the method of forming positive color images using the heat-sensitive whitening process, for example, see Suto-Chi Disclosure Magazine/Rep.
4L4tjJ), same magazine, December 1976 issue, pages 1-1j (1 is also D-/!-core), US Patent No. ≠, 231.
Useful dyes and bleaching methods are described in No. 57.

However, this method requires extra steps such as heating the viscous ratio agent sheet to accelerate the whitening of the dye and +J material, and the resulting color image does not last long during long-term storage. However, it had the disadvantage that it was gradually reductively bleached by the coexisting free 141I silver and the like.

Further, regarding the method of forming color images using leuco dyes, for example, US Pat. Ril! .

, 1+ evening issue, No. ≠, o, 2λ, t/7 issue. But not this way! It is difficult to stably incorporate Jiko dye into the photocoat material, which has the disadvantage of gradually becoming colored during storage.

The present invention uses color lI! by heat development. This provides a new method for forming II images and solves the drawbacks of the hitherto known single materials.

Overall, an object of the present invention is to provide a new image forming method in which a color image is obtained by thermally transferring a hydrophilic dye released by thermal development to an image receiving feed containing a mordant.

An object of the present invention is to provide a method for obtaining clear color images using a simple method.

An object of the present invention is to provide a method for obtaining stable color images over a long period of time.

Such terms include at least a photosensitive silver halide, a hydrophilic binder, a dye release aid, and a dye-donating agent that is reducible to an organic silver salt oxidizing agent and releases a hydrophilic dye. This is achieved by a heat-developable color photosensitive material characterized by containing a polyethylene glycol type non-circular activator.

The heat-developable color photosensitive material of the present invention can simultaneously develop a silver image that has a negative-positive relationship with the original and a diffusible dye in the area corresponding to the silver image by simply performing heat development after image exposure. It's a monkey that can grow.

That is, the rA standard image color photosensitive first image development of the present invention is introduced,
When heat-developed, a reaction occurs between the exposed photosensitive silver halide and the reducing dye-donor substance, and IjMIIIJI mounds are formed in the exposed areas. In this step, the dye-donating substance is oxidized by silver halide to become an oxidant. This oxidant cleaves in the presence of a dye-releasing agent, resulting in the release of a hydrophilic, diffusible dye. Therefore v
In the Njyt section, a silver image and a diffusible dye are separated, and a color image is obtained by transferring this diffusive color patch.

The anti-L+-1 release of the diffusible dyes of the present invention is all carried out in an inversion layer at elevated temperatures. This release reaction of the diffusible dye is thought to be caused by the attack of a so-called nucleophile, and is generally known to occur in a liquid.

In the present invention, although it depends on the type of color patch-providing compound, the compounds listed as preferred examples showed a good reaction rate even during layer inversion. This high response rate is an unexpected finding. Furthermore, the nitride-donating compound of the present invention can undergo a redox reaction with silver halide without the aid of a so-called auxiliary developer.

This is an unexpected result based on previous findings at temperatures near the cold temperature.

The above reaction proceeds particularly well in the presence of an organic silver salt oxidizing agent and exhibits a bright color development. Therefore, it can be said that it is a particularly preferable embodiment to coexist an organic silver salt oxidizing agent.

The reducing dye-donating substance that releases the hydrophilic diffusible dye used in the present invention has the following general formula (1) where R represents a reducing agent that can be oxidized by silver halide; D is an image-forming dye i having a hydrophilic group
Hail to ts.

Dye-donating substance) Reducing substrate in L-802-13 (1
1) In polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte, the redox reaction on a saturated calomel electrode was
It is preferable that the voltage is 2V or less. Favorable degeneracy & ga(
R) is the following general formula (It) to l).

H- H- l mo 3 here), 1 , R2, R, 3, ) mo 4 are each hydrogen atom, alkyl group, cycloalkyl paper, aryl school, alkoxy group, aryloxy group, aralkyl group, acyl crystal,
Acylamino paper, alkylsulfonylamino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl &, "-substituted carbamoyl group, N-substituted sulfamoyl group, halogen atom, alkylthio crystal,
Represents a group selected from arylthio groups, and the argyl group and aryl group moiety in these islands can further be an alkoxy group, a herogen atom, a hydroxyl group, a cyano group, an acyl group,
It may be substituted with an acylamino group, substituted carbamoyl group, substituted sulfamoyl group, alkylsulfonylamino group, arylsulfonylamino group, substituted ureido group or carbalkoxy group.

Furthermore, the hydroxyl groups and amino groups in the nitric acid may be protected with a recyclable protective paper by the action of a nucleophilic reagent.

In a historically preferred embodiment of the present invention, the reducing group '11 (
, is expressed by the following formula (X).

Here, G represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis.几 stands for an alkyl group or an aromatic group.

When n=1, XlO represents an electron-donating substituent; when n=2 or 30, it may be the same or different substituent; 3 is an electron-donating group or a herogen atom, and X
10 may form a fused ring by itself or may form a ring with (JR).

The sum of the total carbon numbers of both 1 mo 10 and Xi 2 O is 1 or more than t.

Among those included in formula (X) of the present invention, in a more preferred embodiment, the reducing substrates are represented by the following formulas CXa) and (Xb).

Here, G stands for hydroxyl koji or a compound that gives a hydroxyl group by hydrolysis. Ru and Ru may be the same or different, and each is an alkyl group, or it and H may be linked to form a ring.

3 ■ represents a hydrogen atom or an alkyl paper, and R represents an alkyl group or an aromatic appearance. and 2 may be connected to form a ring.

Here, G is a hydroxyl cage or a group that gives water by hydrolysis 1 (, 1G is an alkyl or aromatic group, X
represents a hydrogen atom, an alkyl group, an alkyloxy, a halogen, an acylamino paper, or an alkylthio group,
X and R may be connected to form a ring.

Specific examples included in (X), (Xa), and (Xb) are IJS4t, or! , 4t Koza, Tokukai Akira 6-/λ
6≠λ, and t+-1ti3°, respectively.

In another more preferred embodiment of the present invention, the reducing substrate (R) is represented by the following formula (XI).

(However, the code G, X10.1 (10, Iu and n
is G,X, )1. of formula (X). , which is synonymous with 6
) Among those included in (XI) of the present invention, in a more preferred embodiment, the reducing substrate (I() is represented by the following formula (XI)
It is represented by a) to (XIC).

- +t2 except that G is a hydroxyl group, or 8 which gives hydroxyl by hydrolysis: B21 and R may be the same or different and each represents an alkyl group or an aromatic group: tt21 and B
22 may be combined to form a ring; R25 represents a hydrogen atom, an alkyl group or an aromatic group; 1t24 represents an alkyl paper or an aromatic group; 14
25 represents algyl, alkoxy, alkylthio, arylthio group, halogen, or acylamino group; p is 0. / or co; 1Mo24 and B25 may be combined to form a condensed ring<, R21 and 1 (24 may be combined to form a condensed ring<, R21 and H,25 may be bonded to form a condensed ring, H,21,1)22, R2
The total number of carbon atoms of 3, R24 and 3 is greater than 7.

CH2R3, where G is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis: 1 R represents an alkyl group or an aromatic group; 2 R represents an alkyl group or an aromatic group; 3 1 also represents an alkyl group, an alkoxy group, alkylthio paper,
represents an arylthio group, a halogen atom or an acylamino group; q is 0 and/or co; even if R and R combine to form a condensed ring, i<, )? ,
and H may combine to form a condensed ring <, 1(31
and R133 may be combined to form a condensed ring:
Ka I (31, H, 32, l (, 33 has a total number of carbons of 7
bigger.

In the formula, G represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; B41 represents an alkyl group or an aromatic group; B42 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a haloken ikyoshi, or an acylamino group. represents a group; represents a group, and also represents a phenol (or its precursor)
The carbon atom (---C-) in the condensed ring that participates in bonding to the mother nucleus is a tertiary carbon atom that forms one of the key points of the metal ring.
carbon atoms, and some of the carbon atoms in the hydrocarbon ring (excluding the above-mentioned tertiary carbon atoms) may be substituted with oxygen atoms, or a substituent may be present in the hydrocarbon ring. may be attached, or an aromatic ring may be fused to the parent group; the total number of carbon atoms in the group is 7 or more.

Specific examples included in the above (XI), (Xla) to (Xlb) are JP-A No. 6-/613/, J-7-4 jO1
Same j same 7-da 0 hiro 3 is published.

The essential parts of formula (lit) and formula (IV) are para-
(sulfonyl)aminophenol moiety.

Specific examples include U8J, Ri, 2♂, 3/ko, TJ.
S4L, 07t, Takota, US Publicis
hedPatent Application l
(31/ 673, US4t, /jt, P, 2F, u
s4t, art.

Examples of the reducing substrates disclosed in 1-0 are also effective as the reducing substrate (R) of the present invention.

In another more preferred embodiment of the present invention, the reducing substrate ()L) is represented by the following formula (Xll).

Here, Ba1last contains a diffusion-resistant group.

G represents a hydroxyl group or a precursor of a hydroxyl group; G1 represents a group that represents an aromatic ring and forms a naphthalene ring together with a benzene ring; n and m are different integers.

A specific example included in XII above is us-4! , us3
It is described in ゜3/ko.

Reducing substrates of formulas (V), (■), (■) and l) are
It is characterized by the inclusion of a heterostructure, and specific examples include tJs Hiroshi, /ri♂, , 23t, JP-A-1983-≠4.
7. ? O, tJsμ, core 3. ? ! ! These include those listed in . A specific example of the reducing substrate represented by formula (Vl) is described in US 4Z, /≠2°8 Octopus.

The following are the special orders required for the reduction case (-).

1. It is rapidly oxidized by silver halide and efficiently releases a diffusible dye for image formation at °C by the action of a dye release aid.

2. The dye-donating substance is immobilized in a hydrophilic or hydrophobic binder, and only the released dye needs to be diffusible. thing.

3. It has excellent stability against heat and dye release aids, and does not release image-forming dyes until oxidized.

4. Easy synthesis.

Next, a preferred specific example of It that satisfies these conditions will be shown. In the examples, N[-J- represents a linkage with a dye moiety.

(J) (04H9Lt) 0 H 14 H (JtJ CHa-C-Ctla 3H7 1-1 CH3-C-CH3CH3 H Ue16833 OH OH (Jl( 01) (JH (JIJ (Month 4 QC□6l-133 (JH OH) OH Ntl- O[I OH- l-1- C5H1, (tl Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthragynone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, and carbonyl dyes. There are pigments, phthalocyanine color charts, etc., and three representative examples are shown by hue.
It can also be used in a temporarily shortened form such as I fii2.

Yellow 11+2 N0 (JH Magenta Ul also 1 1 too l \ H 4 H・2 1 too 2 3 1 Cyan tt2 t63 (Jl-1(J NHI also 1 (Jl(J N) Kashi 1(z 3 2 OHU NuH , 1 02N (] N) (I is also 20 N
l20 (Jt-1 in the above formula) 1 to ■t6 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, etc. A, aryl group, acylaminoya, acyl^(, sia7) group, hydroxyl base, alkylsulfonylamino^(, arylsulfonylamino group, alkylsulfonyl method, hydroxyalkyl Hiroshi, cyanoalkyl camellia, alkoxycarbonylalkyl group, alkoxy Alkyl group, aryloxyalkyl group, nitro paper, halogen, sulfamoyl group, N unit sulfamoyl group, carbamoyl group, "-itt substituted carbamoyl group, acylmexyalkyl group, amino group, substituted amino group, alkylthio group, arylthio group, The alkyl and aryl groups in these substituents are further substituted with halogen, hydroxyl, acyl, acylamino, alkoxy, carbamoyl, and substituted. It may be substituted with a carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxyl group, an argylsulfonylamino group, an arylsulfonylamino group, or a ureido group.

Hydrophilic groups include hydroxyl group, carboxyl group, sulfonyl group,
Phosphorus opening group, imide group, hydroxyl ψm acid base, quaternary ammonium 8, carbamoyl group, substituted carbamoyl group, sulfamoyl group, t* substituted sulfamoyl paper, sulfamoylamino group, substituted sulfamoylamino group, ureido group, Examples include substituted ureido groups, alkoxy groups, hydroxyalkoxy groups, and alkoxyalkyl groups.

In the present invention, it is particularly preferable to use a substance whose hydrophilicity is significantly increased by dissociating protons under salt conditions (
P Ka (/J), which includes a phenolic hydroxyl group, a carboxyl group, a sulfamoyl group, a phosphoric acid group, an imide group, a hydroxyl group, a (substituted) sulfamoyl group,
(Includes sulfamoylamino groups, etc.)

The characteristics required for image-forming dyes are: 1.2) having a hue that passes through zero color reproduction; 1.2) having a large molecular extinction coefficient;
3)) Stable against t1 heat and dye release aids and other additives contained in the system, ≠) Easy to synthesize;
Examples include. Examples of preferable image-forming dyes satisfying these conditions are shown below.
802 represents a binding portion with a reducing substrate.

8 (J2NH2 Magenta (JCHa (J 0H 802N) 12 01] (J.H. S(]NH 2 H Cyan 02NH2 (J.H. (]H 02 Next, specific examples of preferred dye-providing substances will be shown.

11 C4H, Jt) (2) 0C16H33 C4H, (1) 1-I IJ U 41(9(tl (J) ((4H C4Hgl tl H OC16083 (15) H (16) H shi4t19(tl H H U 4H9 (tl 0 (24) H 5) (26) OC16H33 幀) ((6) 1-3 OC16H33 word 0C16H33-n ()C16H33-n UCl3) 133 113 L; ti3 (40) (1 (44) H OC16H33' (JH (Jc18H37-n (46) (48) H (JCt6Has 4 (JH UC16833-n) → (]H (57) UClaHaa (59) 3H7 00 0016831 (62) 1-1 @ OH (→ 0 day Q Keni) OH +1 )] As the dye-donating substance of the present invention, the above specific example Nojt
(: also, U311-.013.IA2r, JP-A-14
-/roll 4t), same t4-/l/30. same! 6-/6
/ 3/, same-t 7-4 r O% direction-t 7
4' 0 'I j, LISJ, octopus 1, 3/ko, U
Sgu, 07 otsu,! -Ta, US Published
Inotent AI)I)1 1catio
nB3 evening! ,473,US4t,/J! , Taλri,
USIf, / PI, 23! , especially til'J'hr
'=33- II 673O, VSg, λ73. I! !
r, IJS≠, /≠ri.

r λ, US ≠, /≠-1g ri/, US da, ko! 1',
Compounds described in /20 and the like are also effective.

Furthermore, U8g, 0/3,633, US≠, lIt, t
OY, US4I, /1111,1,111. USμ
, / Ar, yr 7, I no 8 μ,
i 4A t, + g 3, Uel
, /13, 7! r! r, (), 3
Hiroshi, j 4Z A, 4/, /
4! , LIS4t, J4F, 4.1t, IJS44,
2171.

43Q□, special 11111 white J'[-7/θ7ko, l;,
, l J' 6 '−j! 737, same sr-/Jza7
4Lμ, same! ! -/jgr+2, same! Co 106727
Dye-donating substances that emit yellow dyes, such as those described in Japanese Patent Publication No. 2003-112033, are also effective for the invention. Also, US3.5j Hiro, tI'/4, IJSJ, Ri3ko, 310°U83. U'3/, /II-Hiroshi, U83. 3.2,317, US<j-,,2tt,62μ,[
18≠, ko, t jo.

Marori, Tokukai Akira, tlI-7, 90 tough, same! 6-7)
0601 Tata 1/311g evening 0, same evening 2 Hiro O≠0.
2. Same j! -3611'04L, same jj-236,21
゜Same! Cor 10. A727, same 5r-33i≠ko, same k
j-! Dye-donating substances that release magenta dyes such as those listed in 33.22 are also effective in the present invention.

IJSJ again? , 2, 760SUSμ, 0/J
.

A J , t % [J L') J , ri≠2. ri17, LISIIt, Core 3, 70&'%US≠,
i4tg, +daλ, US Hiromu.

/ J' j, 7 j 4', US! it, /
Hiro 7, t! %, tJ84Z, /4J9.2j
rXUS4t, j#4,44/4Z, IJF4! ,,
24. ! ', 62! , Japanese Patent Publication No. 36-7/06/,
Same j3-≠7t23, Same j' No 1 #27, Same 13-/
Dye-donating substances that release cyan dyes, such as those listed in '73323, are also effective in the present invention.

Next, the method for synthesizing the dye-donating substance will be described.

In general, the dye-donating substance of the present invention is prepared by condensing the reducing amino acid of the amino acid and the chlorosulfonyl group of the image-forming dye moiety.

Dogen Case'jlJR's amino number can be introduced by reduction of nitro, nitroso, or azo groups or ring opening of benzoxazole in accordance with the basic strains, and can be introduced as a free base or as an unaltered acid. can also be used. On the other hand, the chlorosulfonyl group of the mt image-forming dye moiety can be derived from the sulfonic acid or sulfonic acid salt of the dye by a conventional method, ie, by the action of a chlorinating agent such as phosphorus oxychloride, phosphorus pentachloride, or thionyl chloride.

The condensation reaction between the coloring matter moiety for forming 1a and 1a is generally carried out using dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone,
In acetonitrile, the first proton e4m solvent, in the presence of organic bases such as pyridine, picoline, ludine, triethylamine, and diisobrobyl ether, oz.
It can be carried out at a temperature of o'e, and usually the desired dye-donating substance can be obtained in very good yield. An example of its synthesis is shown below.

Synthesis Example 1: Synthesis of '-hydroxy-comethylbenzooxole, ≠-dihydroxyacetophenone 3062, hydroxylamine tA H salt/AIIf/, sodium acetate 32t9, ethanol/000. mQ, and water 10
0 ml+, were mixed and heated to reflux for μ hours. The reaction solution was poured into 10 liters of water, and the precipitated crystals were counted to yield 3/4 t of cog-dihydroxyacetophenone oxime.

He lived 2 years.

This oxime 309 was dissolved in 1100 ml of acetic acid,
While heating and stirring at λo'C, hydrogen chloride gas was blown in for 2 hours. After cooling, the precipitated crystalline P 1-1 was then washed with water to obtain 6-hydroxycomethylbenzoyl 1-1.
It's an insult to Tozor/7f.

Synthesis Example 2: Synthesis of 6-hexadecylated oxy-comethylbenzoxazole l-hydroxy-comethylbenzoxazole synthesized in Synthesis Example 1/r, θ9,/-promohextidecane 3z
,the law of nature? , potassium carbonate, Of,N,N-dimethylacetamide/Omp was stirred at OoC for an hour. Separate the solids from the reaction solution and pour the filtrate into methanol! 0
I opened it on 0ruQ. The precipitated crystals were collected by F, and 6-hexazosyloxy-comethylbenzoxazole≠j,
I got 09.

Synthesis Example B: Synthesis of '-acetylamino-j-hexadecyloxyphenol 6-hexazosyloxy-λ-methylbenzokitizole/l/f/, ethanol/JOOm9
, JJ% hydrochloric acid l10m0. ,water! Mix jOrm, s
The mixture was stirred at r to'c for 1 hour. After cooling, crystalline P[,-2-acetylamino-! -hexadecyloxyphenol l/32 was obtained.

Synthesis Example 4: Coacenalamino<z-t-butyl-
! -Synthesis of hexadecylbouquinphenol 2-acetylaminoterhexadecyloxyphenol obtained in Synthesis Example 3 30.0? , Amberlist/! (Song title registered by Rohm and Haas, USA) 10.0? ,
Mix 300rnQ of toluene, heat and stir with ♂O-taQ0C, and add isobutyne! I blew time. After removing the solid, liquid F was concentrated, and the residue contained n-hexitine J!
Crystals were precipitated when O was added. In terms of number of households, --acetylamino-<z-t-butyl-! -Hekiidecyloxyphenol, 2J, t9 was obtained.

Synthesis Example 5: , 2-Amino-g-t-butyl-! -Synthesis of hexadezyloxyphenol Synthesis example ≠ Coacetelamino obtained in ≠ -1-phthyl! -Hexadecyloxyphenol 3°Of, xtanol/co 0ml, and 26mQ of 37% hydrochloric acid were mixed, and the mixture was stirred and refluxed for 3 hours. After the reaction solution was cooled, the precipitated crystals were counted and found to be coamino≠-t-butyl! -Hexadecyloxyphenol hydrochloride-3,22 was obtained.

Synthesis example s: 4A-t-phthyl! Synthesis example of -hextidecyloxy-co[λ-(co-methoxychetoxy)-t-nitrobenzenesulfonylamino]phenol! Koaminoh≠-t-butyru obtained from ! - Hexadecyloxyphenol Shiori, Hiroshi? and J-(
,2-methoxyethoxy)-! -Nitrobenzenesulfonylchlori'T'3. /9 is N.

After adding pyridine and jmQ to N-dimethylacetamide/JmQ, the mixture was stirred at 0C for 2 nights. When the reaction solution was poured into dilute hydrochloric acid, an oily substance precipitated.

When methanol (30 mQ) was added to this oil, it crystallized and was collected.

Fill the hat! 9゜Synthesis Example 7: Synthesis of -1[j-amino-,2-(,2-methoxyethoxy)henzenesulfonylamino]-≠-t-bunaruta-hexadecyloxyphenol Compound obtained in Synthesis Example 6 above/ θ9 (1' ethanol tO
mO,l: /J, 70%) ξRadium-carbon catalyst approx. 0-! f 'ltk+L7': (') Chi, hydrogen 1
kj! The catalyst was press-fitted for 12 minutes and pressed with a finger for 6 hours.Then, the catalyst was removed while hot, and when it was allowed to cool, crystals precipitated, so it was removed.

Yield 7.52° Synthesis Example 8: J-cyano-μm [gu(comethoxyethoxy)-j-sulfophenylazo]-/-phenyl-! -Synthesis of pyrazolone In a solution of sodium hydroxide♂, 09 and water, 200 ml! -Amino-2-(,2-methoxyethoxy)benzenesulfonic acid ≠2 was added, and then sodium nitrite/
3. A solution of 60 mQ of porcelain hydrochloric acid and water≠00 me was prepared in addition to an aqueous solution of ♂t (tOm+#), and the above solution was added dropwise to this at a concentration of 500 mQ or less. Thereafter, the mixture was stirred for 30 minutes at below j0C to complete the reaction.

Separately, sodium hydroxide/l, Of, yJ<ko00rnl
, sodium acetate 33.09 and methanol, 200
Prepare a solution of m1+, 3-cyano-/-phenyl-j
- 37.09 g of pyrazolone was added, and the prepared diazo solution was added dropwise at IO@C. After the completion of the dropwise addition, the mixture was stirred for 30 minutes at 10'C or less, and then stirred for 1 hour at room temperature, and the precipitated crystals were collected by F, washed with acetone J 00 mO, and air-dried.

Number position jt2. Of m, p, 2tJ-itz'c Synthesis Example 9: 3-cyano-cou[Hiro-(coastoxyethoxy)-! Synthesis of -chlorosulfonylphenylazo)-/-phenyl-y-pyrazolone 3-cyano-hiro-[(≠-methoxyethoxy!-sulfophenylazo]-7-phenyl- obtained in Synthesis Example t above)
! -Pyrazolone ri, oy, acetone, 2! OmQ
, and phosphorus oxychloride! Add N and N to the Orn# mixed solution.
-Dimethylacetamide! OmQ was added dropwise below jOoC. After the addition, the mixture was stirred for about 1 hour and gradually poured into ice water. After separating the precipitated crystals, acetonitrile 10
It was washed with 0ml and air dried.

Yield 416.79 m, p, /J'/ ~113°C
Synthesis Example 10: Synthesis of dye-donating Monoga (1) Co[!] obtained in Synthesis Example 7 -Amino, 2-(comethoxyethoxy)benzenesulfonylamino-μm t-butyl-j-hexadecyloxyphenol 6.32 to N,N-dimethylacetamide 30 m9. 3-cyano-hiro-[gu(nomethoxyethoxy)-!] was obtained by following the synthesis example.
-chlorosulfonylphenyl aso]-/-phenyl-!
- Added vilazolong, 62, and more pyridine! Added m9. After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected in a furnace. 7. Recrystallize from N,N-dimethylacetamide-methanol. ! I asked if it was hot.

+n, p, /A'ter/9/'C Synthesis Example 11: Synthesis of dye-donating substance (2) 2-[j-amino-no(2-methoxyethoxy)benzenesulfonylamino- obtained in Synthesis Example 7 a-t-butyl-j-hexadecyloxyphenol 6.39 to N,N-dimethylacetamide 30
-, 3-cyanoder-(!-chloronomethylsulfonylphenylaso)-/-(4'-chlorosulfonylphenyl)-terpyrazolone j, 09 was added, and then pyridine r+nl! added.

After stirring at room temperature for 1 hour, the reaction solution was poured into diluted hydrochloric acid, and the precipitated crystals were collected. After recrystallization from acetonitrile, lA9 was obtained.

m, p, / ≠ b-~-l 4-[
TA 0 (゛Synthesis Example 12: Synthesis of dye-donating substance (1) No-amino-Hiroshi-t-i-thyl-j-hexadecyloxyphenol hydrochloride≠, Hiroshi 2 and Hiroshi-[3-chlorosulfonyl-4(-( ,2-methoxyethoxy)phenylazo]-no(N,N-diethylsulfamoyl)-
! -Methylsulfonylamino/-naphtholt,! 2
to N,N-dimethylacetamide JOm11. Pyridine Hiroshi, 2alt was added to the solution. After stirring for 1 hour at Jt'C, the reaction solution was poured into dilute hydrochloric acid. The precipitated isomer was collected and subjected to silica gel column chromatography (
It was purified by chloroform-ethyl acetate (2:/) mixed solvent).

yield! , 2゜Synthesis Example 13 Two dye-donating substances (one synthetic no-amino-at-7'thyl-j-hexadecyloxyphenol hydrochloride //, t9 is N,N-dimethylacetamide 10
Dissolved in 0 mQ and added pyridine 7.2rIIQ. To this, t-(j-chlorosulfonylbenzenesulfonylamino)-,2-(N-1-butylsulfamoyl)-μ
m(-2-methylsulfonylluce-dito-phenyla/
)-/-naphtholcoOf was added. After stirring for 1 hour,
4. Pour into ice water and recrystallize the precipitate with isozorobyl alcohol-acetonitrile (/:/). I got f9.

Synthesis Example 14: Synthesis of dye-donating substance 09) No(1-amino-no(,2-methoxyethoxy)benzenesulfonylamino)-≠-1--/thirunohexadecyloxyphenol 3/,!g,r -(J-chlorosulfonylbenzenesulfonylamino)-μm(λ-methylsulfonyl≠-nitrophenylazo)-/-naphthol 3
the law of nature.

/f to N,N-dimethylacetamide 100m0. and added pyridine 2/me. After stirring for several minutes, 2jOmQ of methanol and ioom of water were added. The precipitated resinous material solidified after a while, so P was removed. This was recrystallized from a toluene-methanol-water (/4:Hiroshi:3) mixed system to yield 4 tons/year.

Synthesis Example 15 Synthesis of Compound 40 a), 2. Synthesis of J--dihydroxy-≠-1-butylacetophenone 1-Butylhydroquinone was dissolved in 00 ml of acetic acid and heated to 0.0C, then boron trifluoride (HlI''s) was introduced for about 3 hours.

After the reaction is complete, pour the precipitated viscous solid into P/l of ice water.
I took it. This solid was dissolved in 8400 ml of 2N-NaU, and the insoluble portion was removed. Make the furnace liquid acidic with cloth hydrochloric acid,
The precipitated crystals were washed several times with water and then recrystallized from aqueous methanol.

Accommodation: 4ft (A, T) b), 2. Synthesis of t-dihydroxy-≠-t-butylacetophenone and oxime H1 The ketone obtained in 1.a), 219, was dissolved in 70 m ethanol.
7.2 g of hydroxylamine hydrochloride was dissolved in 70 m of water by heating and dissolving it with 4!9 of sodium acetate, and stirring.
A solution dissolved in No. 11 was added and refluxed for about 1 hour. After the reaction was completed, the precipitated crystals were poured into 00 mQ of ice water and recrystallized from benzene-Heggisen.

Condensation line /79 (7g%) c)! , -1-butyroux! Synthesis of -Hydroxyco-methylbenzoxazole The oxime 1H2 obtained in Section 1 b) was treated with io acetic acid.

Dry hydrochloric acid gas was introduced while heating to dissolve rδ during nIQ. /! Refluxed for an hour. After the reaction was completed, it was poured into 100 mQ of ice water, and the precipitated crystals were taken out of the furnace and washed with water.

Yield? ? (70ch) d) 4-1-butyl-! - Hexadecyloxy - Synthesis of methylbenzoxazole 10% of the benzoxole t and 2 obtained in C) was dissolved in dimethylacetamidota and 10% of the solution was added with anhydrous potassium carbonate ♂t and hexadecyl bromide 19 The mixture was stirred at ~yot'c for 6 hours.

After the reaction is complete, remove the inorganic substances and add methanol/jO to the furnace liquid.
After adding mQ and cooling on ice, crystals were precipitated. The title compound was obtained by extracting the product.

Yield ♂, J'f (42%) e) Synthesis of no-amino-1-1-butyro-hexadecyloxyphenol hydrochloride 7.3 g of the benzoxazole compound obtained in step d) above was mixed with ethanol and 30 ml. X
Mizuki hydrochloric acid-〇 m9. The mixture was refluxed for 3 hours. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were washed with water and then with acetone.

Yield 6. f) Synthesis of Compound Example 40 Hydrochloride t2 obtained in 1.e) and sulfonyl chloride ♂, 2 of the dye with the following structural formula were mixed with dimethylacetamide jOrn.
Dissolve in Q, add pyridine l/Ln+F and incubate at room temperature for 7 hours.
Stir for hours. After the reaction was completed, the precipitated crystals were poured into dilute hydrochloric acid and washed with water.

After drying, it was purified by silica gel chromatography to obtain substantially the title compound of component 2, 2? It's i4.

Dye Sulfonyl Chloride: Synthesis Example 16: Synthesis of Color Donor Substance (42) Above Synthesis Example/
In j(d), 6-t-butyl-! -Hydroxycy instead of g-t-octyl-! -Hydroxy, O-hexadecylation was performed using 2-methylbenzoxazole. Next, one dye-donating substance (supplementary material) was prepared by the same treatment as in Synthesis Example 1 (el and ge).

The reducible dye-donating substance that releases the diffusible dye of the present invention can be used within a certain concentration range.

Generally useful concentration ranges are:
From about 0.01 moles to about V moles of dye-donating substance. The concentration of iris that is particularly useful in the present invention is from about 0.03 mole to about 1 mole per $1 mole of halogenide.

In the present invention, a reducing agent can be used as necessary. In this case, the reducing agent is a so-called auxiliary developer, which is oxidized by the oxidizing agent and its oxidized form is the degenerating agent in the dye-donating substance. + It has the ability to oxidize the substrate.

Useful auxiliary developers include hydroquinone, tert-butylhydroquinone, and more! - Alkyl-substituted hydroquinones such as dimethyl hydroquinone, catechols,
Pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone 9:U
% Alkoxy-substituted hydroquinones such as methoxyhydroginone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Historically, methyl gallate, ascorbic acid, ascorbic Ia derivatives,
N.

Hydroxylamine X11, such as N'-di-(+2-ethoxyethyl)hydroxylamine, /-phenyl-
Pyrazolidones such as 3-virasoliton, μm methyl-hiro-hydroxymethyl-/-phenyl-3-pyrazolidone, reductones, and hydroxytetronic acids are useful.

Tsukudasuke developer can be used within a certain silver degree range. A useful once range is Q for silver halide.

0/fold mole to 20 fold mole, and a particularly useful one-time range is O0/fold mole to Hirofold mole.

Examples of silver halides include silver chloride, silver chlorobromide, silver chloroiodide, silver silver, silver iodobromide, silver iodide, and silver iodide.

Particularly preferred silver halides in the present invention are those containing silver iodide crystals in ten parts of the grains.

That is, it is particularly preferable to use silver halide that shows a pattern of pure silver iodide when subjected to X-ray diffraction.

Silver halide containing one or more halogen atoms is used in photographic light-sensitive materials, and in the silver halide emulsion of 111Ig, a complete mixed crystal of silver halide grains is formed. For example, when measuring X-ray diffraction of the grains of a silver iodobromide emulsion, there are no patterns of silver iodide crystals or silver bromide crystals, but an X-ray pattern is found at a position between the two, depending on 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.

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

The grain size of silver halide is from 0.00/ltm to μ
m, preferably from 0.00/μm to l.

The silver halide used in the present invention may be used as is, but chemical sensitizers such as mochiko, selenium, tellurium compounds, gold, platinum, radium, rhodium, iridium, etc. may be chemically sensitized by the use of reducing agents such as tin halides or combinations thereof.

For more information, see The Theory of the Ph.
otographicProcess”u version, T, [1
, No. 1 written by James! It is described in the chapter/geta page ~/l.

,+ A particularly preferred embodiment of the present invention is one in which an organic silver salt oxidizing agent is present, which is a silver salt that is relatively stable to light, and is resistant to heat in the presence of photosensitive silver halide. When heated to yzo 00 or higher, preferably 1OO0C or higher, the above-mentioned 11!111N formation actually or if necessary I[! II Image Formation A bronze statue is formed by reacting with a reducing agent coexisting with the material. By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material with a higher degree of purity.

The amount of organic copper salt oxidizing agent (I/In) is 0-ioomole, preferably 0.2 to 10 mole, per mole of silver halide.

Examples of such organic silver salt oxidizing agents include the following.

It is a silver salt of an organic compound having a carboxyl group, and representative examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.

Examples of aliphatic carboxylic acids include silver salts of behenic acid, silver salts of stearic acid, silver salts of oleic acid, fM salts of laflic acid, fM salts of capric acid, silver salts of myristic acid, silver salts of palmitic acid, Silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid, silver salt of linoleic acid, silver salt of oleic acid, silver salt of adipic acid,
These include silver salts of sepacic acid, silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, and silver salts of camphoric acid. Furthermore, silver salts substituted with halogen atoms or hydroxyl atoms are also effective.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, 3°! -Silver salt of dihydroxybenzoic acid, silver salt of 0-methylbenzoic acid, m-
Silver salts of substituted benzoic acids, such as silver salts of methylbenzoic acid, silver salts of p-methylbenzoic acid, silver salts of co-, hiro-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, and silver salts of p-phenylbenzoic acid. , silver salt of gallic acid, silver salt of tannic acid, silver salt of phthalic acid, silver salt of terephthalic acid, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of pyromellitic acid, US Patent No. J, 7rr, 3-carboxymethyl-Hiroshi-Menalu≠-Thiazoline-Corchion etc. described in JO No. 1, US Patent No.! , 330゜663 specification, silver salts of carboxylic acids having a thioether group; and the like.

In addition, Mercap)! Alternatively, there are silver salts of compounds having a thione group and derivatives thereof.

For example, 3-mercapto-μm phenyl-1,co.

≠-Silver salt of triazole, silver salt of Nomer Kabutobenzimidazole, Nomer Power Pouto! - silver salt of aminothiadiazole, silver salt of nomerkabutobenzthiazole,
JP-A Showll-2g of silver salts of λ-(S-ethylglycolamide)benzthiazole, S-al, f(alkyl esters having 72 to 2.2 carbon atoms) thioglycolate, etc.
Silver salts of dithiocarboxylic acids, such as silver salts of thioglycolic acid and silver salts of dithioacetic acid, silver salts of thioamides, etc. described in No. 2.2j,! -Methylphenyl≠-Thioviridine mortar, silver salt of mercaptotriazine, silver salt of normercaptobenzoxazole, silver salt of mercaptooxediazole, US Pat.

L Co. 3, 27 ≠ No. 3, 27≠ Silver salts with few details, for example, L.

2. 3-amitsu!, a Hiro-mercaptotriazole derivative! -benzylthio/, 2.4j-triazole silver salt, 3-(-calphokidiethyl)-≠-methyl-≠-thiazoline-2thione described in U.S. Patent J, 30/, 671, etc. It is a silver salt of a thione compound.

In addition, there are silver salts of compounds having imino groups. For example, Tokuko Akihiro'l-30270. 4Is-iflint
Silver salts of benzotriazole and its derivatives described in publications, such as silver salts of benzotriazole, silver salts of alkyl-substituted benzotriazoles such as silver salts of methylbenzotriazole, and silver salts of halogen-substituted benzotriazoles such as silver salts of terchlorobenzotriazole. Silver salts, silver salts of carbimidobenzotriazole, such as silver salts of butylcarboimidobenzotriazole, U.S. Pat. - Silver salts of tetrazole, silver salts of carbazole, silver salts of setukaline, silver salts of imidazole and imidazole derivatives, etc.

Also, Research Disclosure VoI/7. Olli 7
Organometallic salts such as silver salts and copper stearate, which are published in J'wo Tsuki no Oori/No. 7022, are also organometallic salt oxidizing agents that can be used in the present invention.

The thermal development process during heating in the present invention is sufficiently slow and can be considered as described above.

When a photosensitive material is irradiated with Y:, an image is formed on the photosensitive silver halide. Ill about this.

“The Theory of
thePhotographic Process
"Jrd Edition, pages 101 to 1att.

By heating the light-sensitive material, a reducing agent, in the case of the present invention, a dye-donating substance, is oxidized to an organometallic salt oxidizing agent or a silver halide, with the help of an alkaline agent released by heating, using the sore nucleus as a catalyst. Machine Jinpeng oxidation 41J is produced to produce silver or metal, which itself is oxidized. This oxidized dye-donating reservoir is attacked by a hydronuclear reagent (dye release aid in the present invention) and the dye is released.

The silver halide and organic silver salt oxidizing agents that serve as the starting point for development are
In practice, it is necessary to exist at a self-effective distance.

Therefore, it is desirable that the silver halide and the organic silver salt oxidizing agent exist in the same layer or in adjacent layers.

It is possible to prepare a coating solution by mixing separately formed silver halide and organic silver salt oxidizing agent before use, but it is also not effective to mix the two and mix them in a ball mill for a long time. be. Another effective method is to add a halogen-containing compound to the prepared organic silver salt oxidizing agent and form halogen silver with the silver from the organic silver salt oxidizing agent.

For information on how to make these silver halides, the oxidizing agent of Kirigin salt, and how to mix both, please refer to RESETCH DISCLOSURE/No. L-Hiro 25J, US special TF 3s700, Vrr
No., JP-A No. 1982-17 No. 2, and JP-A-50-17 No. 6.

In the present invention, the coating amount of the 90-sensitized silver halide and the organic silver salt oxidizing agent is silver (converted into two, the total is j011f~/0
97 m2 is appropriate.

The oxidizing agent ii &5'f of the present invention, a silver halide, an organic silver salt, is prepared in the binder described below. A dye-providing substance is also dispersed in the binder described below.

The binders used in the present invention can be contained alone or in combination. This binder has
Hydrophilic materials can be used. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, cellulose conductors, natural substances such as starch, thiosaccharides such as gum arabic, and polyvinyl colloids. Includes synthetic polymeric materials such as pyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric compounds include dispersed hinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes.

Various dye release aids can be used in the heat-developable color photosensitive material of the present invention. A dye-releasing agent is one that can nucleophilically attack the dye-donating substance oxidized by an organic silver salt oxidizing agent and release a diffusive color patch. is used. Among these dye release aids, bases or base release agents are particularly useful because they not only promote dye release but also the redox reaction between the organic silver salt oxidizing agent and the dye-donating substance. .

Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines,
Mention may also be made of hydroxyalkyl-substituted aromatic amines and bis(p-(dialkylamino)phenylcomethanes). Also, U.S. Pat.
No. 4 includes betaine tetramethylammonium iodide and diaminobutane dihydrochloride.
Organic compounds containing amino acids such as urea and t-amitsukazolonic acid are described and useful in No. JJET, No. 4 & H.F. The base release agent releases the salt IF component when heated. Examples of typical base releasing agents are described in British Patent No. Tata ♂, No. 2μ. Preferred base releasing agents are salts of carboxylic acids and organic salts, and useful tC carboxylic acids include trichlorol! Useful bases include guanidine, piperidine, morpholine, p-toluidine, novicoline, and the like. Particularly useful is guanidine trichloric acid, published in US #Fl-No. 3.2.20, rμ No. 6d. Also, JP-A-10-1999
Aldonamides having a temperature of -124°C described in the publication are preferably used because they decompose at high temperatures to produce bases.

A water-releasing compound is a compound that decomposes during thermal development and releases C water.
These compounds are substitutes for compounds that have a vapor pressure of 10') or more at a temperature of 00 to 200" C. These compounds are particularly known in the transfer printing of textiles, and are NH4Fe (+0
4) 2・icoH2 (J etc. are for η.

These dye release aids can be used in a wide variety of ways. A molar ratio of 17 ioo to silver.

It is preferably used in a range of 20 to 1 times.

The polyethylene glycol type non-density surfactant used in the present invention is characterized by having an ethylene oxide repeating unit in the molecule, and particularly preferably one having 5 or more ethylene 4-1-ide repeating units. is desirable.

Nonionic surfactants that meet the above conditions are widely used in fields other than the above, and their structural properties and synthesis methods are well known. Representative known documents include 8urf
actant 5science 5eriesvO
View 1. Non1onic 5urfact
ants(Edited by Martin J
,8chick.

Marcel Dekker Inc./! P.A.
7), 5surface Active Ethy
lene OxideAdducts (8chi;uf
eldt, N person Per gamonPress
The nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention.

Preferred polyethylene glycol type nonionic surfactants are alcohol ethylene oxide adducts,
Alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, /1] fat ethylene oxide adduct, polypropylene glycol ethylene oxide Addenda can be given. Examples of alcohol ethylene oxide adducts include those made from synthetic alcohols such as lauryl alcohol, cetyl alcohol, and oleyl alcohol, and natural alcohols such as coconut reduced alcohol and beef tallow monoalcohol. Also included are oxo alcohols and secondary alcohols with methyl branches. Both the single composition and the mixture are effective with no difference in performance.

Examples of the alkylphenol ethylene oxide adduct include nonylphenol, dodecylphenol, octylphenol, octylcresol, and the like. Both branched alkylphenols and straight alkylphenols are effective.

Fatty acid ethylene oxide adducts are also called polyethylene glycol ester type nonionic surfactants.
Examples include those made from higher fatty acids such as lauric acid and oleic acid.

As raw materials for polyhydric alcohol fatty acid ester ethylene oxide adducts, partial esters of polyhydric alcohols and fatty acids such as glycerin and sorbitol can be mentioned.

Examples of ethylene oxide adducts of alkylamines and fatty acid amides include those made from laurylamine, oleic acid amide, and the like.

Examples of polypropylene glycol ethylene oxide adducts include those using polypropylene glycol having a molecular weight of 1,000 to 2,000 as a raw material for hydrophobic paper.

The preferred polyethylene glycol type nonionic surfactant of the present invention is specifically represented by the following general formula.

u-(J-eCH2CH2U-+mHm=λ~100 几 is an alkyl group and may have an unsaturated bond, preferably the number of carbon atoms is ≠~λ, and hydrogen may be substituted with fluorine. R is It may also represent a polyhydric alcohol.

3 R tlR 2 # ” 3 may be the same or different, and each represents a hydrogen atom, )~rogen atom, carboxyl group, acyl group, alkoxycarbonyl group, alkyl group, alkyl group, afrecoxy group, etc. Represents phenyl.Hydrogen is replaced with fluorine and can also be expressed as Iz'.■
Two of 1 to 3 may form a carbon ring.

1 is an alkyl group, preferably carbon number/-. 20, R2 represents hydrogen 1 Kyoko, alkyl/~-20), fluorine-substituted alkyl group, phenyl school, alkyl-substituted phenyl group, or (OH□C12 (J ＼H curtain).

1(,C-(J(('H2CH20-)mH m
=J~1001 (1) represents an alkyl group, preferably an alkyl group having a carbon number of v to λ.

(J I (+1 is an alkyl group, preferably one with a carbon number of 1 to λO, 2 is a hydrogen atom, an alkyl group (carbon number / ~ 0)
, represents a fluorine-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a (CH20H2υ+mH 2 group).

Specific examples of the polyethylene glycol type nonionic interfacial viscosity agent used in the present invention are as follows.

C,I-1,5(,tJυ-ee12CL-12(J+
□5HCHC0(J((Jj2CH20), -HI3
23 CHC(JtJ(C)12C1-120-)2o)11
23 CHC(JO-(C1-1, Cl-120+,.HI3
35 CHCCJU÷CI-J2C)], (J-) 36
H1781 C1,)138000-(CH2C)120-), o)
1 polyoxyethylene polyoxypropylene cetyl ether C4)1, +C)] 2CH2U〼□. F no C4)
], (CH2CH□Ou, .H O2) 117 (CH2CH20-)4. HC1□t-1
25+C)J20H20-), 5H018H37+”2
CH20+30H Polyoxyethylene glycerin monostearate These nonionic surfactants can be used alone or as a mixture of two or more.

The polyethylene glycol type nonionic surfactant of the present invention is preferably used in an amount of equal weight or less, preferably 50% or less, based on the hydrophilic binder.

It is not clear how the polyethylene glycol type nonionic surfactant of the present invention is effective. There is a theory that it acts as a solvent for color image-forming substances, but it is effective for both hydrophilic and lipophilic color image-forming substances, so a unified explanation cannot be given.

Further, in the heat-developable color light-sensitive material of the present invention, a compound which activates development and simultaneously stabilizes the image can be used. Among them, 2 described in U.S. Patent No. 3,30/671
- Hydroxyethylisothiuronium, isothiuroniums represented by trichloroacetate, U.S. Patent No. J
, 64, No. 470, bisisothiolium compounds such as l,za-(3,t-diokido-octane)bis(isoduronium trifluoroacetate), West German Patent No. 1,
/ 7.2.7/≠ thiol compounds disclosed in US Pat. −
Thiazolium compounds such as bromoethyl-cortiazolium trichloroacetate, U.S. Patent No. ≠, oto
Compounds having α-sulfonylacetate as an acidic moiety, such as bis(no-amino-cortiazolium)methylenebis(sulfonylacetate) and '-amino-λ-thiazolium phenylsulfonylacetate described in , a, zo issues, United States Patent No. a, or? .

Compounds having a no-carboxycarboxamide as the acidic moiety described in No. 26 are preferably used.

These compounds or mixtures can be used in a wide range of applications. It is preferably used in a molar ratio of //100 to 70 times, particularly in the range of 0 to - times l/co.

The heat-developable color photosensitive material of the present invention can contain a heat solvent. A "thermal solvent" is a non-hydrolyzable organic material that is solid at ambient temperature but exhibits a mixed melting point with other components at or below the heat treatment temperature used. Useful thermal solvents include compounds that act as solvents for developing agents and compounds known to promote the physical development of silver salts with substances having a sieve dielectric constant. 3,3≠7.
67! Polyglycols described in No. r, for example, average molecular weight/jt00~. 2oooo polyethylene glycol,
Derivatives such as oleate ester of polyethylene oxide, beeswax, monostearin, -8(J2-1-C
Compounds with a high dielectric constant having a υ group, such as acetamide, cylinmide, ethyl carbamate, urea,
Methylsulfonamide, ethylene carbonate, U.S. Patent No. 3°t67, Ri! Extreme substances in the journal, ≠-hydroxybutanoic acid lactone, methylsulfinylmethane,
Tetrahydrothiophene-/,/-diokioid, Research Disclosure Magazine 1276/, February issue, 26
Preferably used are /, IO-decanediol, methyl anisate, biphenyl perate, etc. described in page 1.

In the case of the present invention, in addition to the dye-donating substance being colored,
Although it is not so necessary to incorporate irradiation or antihalation substances or dyes into light-sensitive materials, in order to improve the sharpness of rainbows, it is necessary to incorporate irradiation and antihalation substances and dyes into the light-sensitive material, but in order to improve the sharpness of rainbows, Japanese Patent Publication No. R-J4 Octopus and U.S. Patent No. 3. Ko! 3, Ri, No. 27, same! Core, Yu♂3, same.

It is possible to contain filter dyes and absorbent substances, which are described in various specifications such as No. 172.

Preferably, these dyes are thermally decolorizable, such as those described in US Pat. No. 3,762. Oi-ri No. 3, 7 Hiroj, θOri No. 3, 61.5', 4t3
．． Dyes such as those described in No. 2 are preferred.

The photosensitive material according to the present invention can be heat-developable if necessary.
Various additives known as additives and layers below the photosensitive layer, such as anti-static layer, conductive layer, protection 1-1 intermediate 1! , an AH layer, a cover layer, etc. Various additives include “Re5earch Disclosure” V
Additives described in No. 70.29 of June 01/70/971, such as plasticizers, sharpness-improving dyes ζ
Examples include AH dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, and antifading agents.

Similar to the heat-developable photosensitive layer according to the present invention, for the protective layer, intermediate layer, bottom layer, pack layer and other layers, respective coating solutions are prepared and coated using the dipping method, air knife method, curtain coating method, or coating method. A photosensitive feed can be prepared by sequentially coating a support on a support using a phase process, such as the hopper coating method disclosed in US Pat. No. 61/2, and drying.

Furthermore, if necessary, two or more layers can be applied simultaneously by the methods described in U.S. Pat. .

Various exposure means can be used for the heat-developable photosensitive material according to the present invention. 1 layer low is mm of radiation including visible light.
Obtained by spherical exposure. In general, light sources used for regular color printing, such as tank lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, and T light sources, fluorescent tubes, light emitting diodes, etc., are used as light sources. I can do it.

The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be carried out by contact printing overlapping the original drawing, reflection printing, or enlargement printing.

In addition, images taken with a video camera, etc., and image information sent from a television station can be directly transferred to a CRT or F' (J
It is also possible to print the image on a heat-developable material by placing it on a heat-developable material by contacting it or using a lens.

[Also, there has been a great deal of progress recently], and ED (light emitting diodes) are being used as exposure means and display means in various types of equipment. It is difficult to make an LED that effectively emits blue light. In this case, to reproduce a color image, three types of LEDs are used that emit green, red, and infrared light, and the parts of the sensitive material that are exposed to these lights emit yellow, magenta, and cyan dyes, respectively. The design is good.

That is, the green-sensitive area (layer) should contain a yellow dye-donating substance, the red-sensitive area (layer) should contain a magenta dye-providing substance, and the infrared-sensitive area (1-) should contain a cyan dye-providing substance. good. Other combinations are also possible as required.

In addition to the above-mentioned method of directly attaching or projecting the original image, the original image illuminated by a light source can be read using a light-receiving device such as a light source or COD and stored in the memory of a computer, etc., and this information can be processed as necessary. After applying so-called image processing, this Il! IJ image information is CL(,T
There is also a method of using it as an image-shaped light source, or directly emitting light from the three LE: IJ lights based on the processed information.

After 40,000 elements of thermal development color, Tamezuka was superior.
For example, development can be carried out by heating the entire element at a moderately elevated temperature, such as from about r0@C to about 2 kO'' (2C about 300 seconds). As long as the temperature is within
Temperature ranges from 100C to about 100C are useful. The heating means may be simply a hot plate, an iron, a hot roller or the like.

In the present invention, a specific method for forming a color image by thermal development is thermal diffusion transfer of a hydrophilic diffusion coloring chart. For this purpose, a heat-developable color photosensitive material has a photosensitive layer (1) on a support containing at least silver halide, an organic silver salt oxidizing agent, a dye donating substance which is also a reducing agent, a hydrophilic binder and a dye release aid. ), and an image-receiving layer (1) that can receive the hydrophilic and diffusible dye formed by the layer
n).

The above-mentioned photosensitive layer (1) and image-receiving layer (It) may be formed on the same support, or may be formed on separate supports. The image-receiving layer (II) can also be peeled off from the photosensitive layer (1). For example, after imagewise exposure of a heat-developable color photosensitive material, uniform heat development is performed, and then an image-receiving layer (
If) can be torn off.

In another specific method, after imagewise exposure, the image-receiving layer (II) can be superimposed on the photosensitive layer (1), which has been uniformly heat-developed, and the dye can be transferred at a temperature lower than the development temperature. In this case, "lower temperature than the development temperature" includes room temperature, and preferably refers to a temperature from room temperature to about ≠00C lower than the thermal development temperature. For example, thermal development temperature i, zo oc, transfer temperature? 0°C
etc. are equivalent.

Alternatively, only the photosensitive layer (1) is imagewise exposed, and then the image-receiving layer (
If), there is also a method of overlapping and uniformly heating and developing.

The image-receiving layer (II) contains a dye mordant. Various mordants can be used in the present invention, and a useful mordant can be selected depending on the physical properties of the dye, transfer conditions, other components contained in the photographic material, etc. I can do it. The mordant used in the present invention is a high molecular weight polymeric mordant.

The polymer mordants used in the present invention include polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, and polymers containing these V-class cation numbers, and have a molecular volume of r, ooo-x.

o, ooo, especially 10.000 to to, ooo.

For example, U.S. Patent Co., Tagza, Taro Hirogo, Doko.

μg≠, Kou 30, same 3. /μg, 06/ issue, same s, 7
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in No. rt, ri≠ Specification Frog et al.: US Watch 3. /,,2! r, l, 9g issue, same 3. ♂j
ri, Ori No. 6, same≠, /, 2g.

j, No. 31, British Patent/, 277, Da! 3. A polymer mordant capable of crosslinking with gelatin etc. disclosed in the specification of No. 3, etc.; Tata♂, Tata! No., same λ, y, zi,
rzko, sameko, 7ri J, 063, JP-A-Shoj4A-
//! No. 221, same tp-i4LA! r-2, sameta 4
'-/, an aqueous sol-type mordant disclosed in 2tO Core No. Jyoji; U.S. Patent No. 3. water-insoluble mordant disclosed in the US Pat.
7GJ', No. 76 (Unexamined Japanese Patent Publication No. Shoj≠-/No. 3731.3)
A reactive mordant capable of forming a covalent bond with the dye disclosed in Specification 1, etc.; furthermore, US Pat. 'ytrr, rj! Gin, Mukai M3.64A2,
'It J No., Same Wr' + "1#, No. 706,
Same 1j,! , t 7 , No. 06, same No. J, .
27/, /≠No. 7, same No. 3. ．． 27/, /Hiro Ir No., JP-A No. 7/332, No. 13-303.21,
Same, T, No. 2-111121, Same Ta, No. 3-72j, Same Ta! The mordant disclosed in No. 10.2 can be mentioned.

Miscellaneous U.S. Patent Co., 471. j/No. 4, the same.

1r12. /! The mordant described in the specification of No. Zeng can also be mentioned.

Among these mordants, other 1-
It is preferable to use a mordant that is difficult to migrate, and for example, a mordant that crosslinks with a matrix such as gelatin, a water-insoluble mordant, and an aqueous sol (or latex dispersion) type mordant can be preferably used.

Particularly preferred polymer mordants are shown below.

111 Polymers having a ≠ grade ammonium group and a group capable of covalently bonding to gelatin (e.g., aldehyde group, chloroalkanoyl group, chloroalkyl group, vinylsulfonyl group, pyridinium propionyl group, vinyl carbonyl group, alkylsulfonoxy group, etc.) For example, (2) reaction of a copolymer consisting of a heptad repeating unit represented by the following general formula and another ethylene-infused unsaturated heptad repeating unit with a crosslinking agent (e.g. bisalkanesulfonate, bisarenesulfonate) product.

1(li:)l, alkyl number R1 group, aryl number, Or l is also from 3 to 5 At least λ are combined to form a heterocycle You may.

X: Anion (The above alkyl paper and aryl paper include substituted ones.) (3) Polymer star 3 represented by the following general formula 20 mol% 2: about 10A - about 2% A: Seven monomers having at least one ethylenically unsaturated bond B: Ethylenically unsaturated monomer capable of co-contamination Q: N, P'l, R2, R11: An alkyl group, a cyclic hydrocarbon group, or at least two of R1-[3 may be combined to form a ring. (These groups and rings may be substituted.) +41 Copolymer la+ consisting of (at, (b) and (C1) ) (bl Acrylic ester (C1 acrylonitrile (5)) A water-insoluble polymer having //J or more repeating units represented by the following general formula H, 1, t also 2, R3: each represents an alkyl group,
The total number of carbon atoms in R x = R3 is 72 or more. (The alkyl group may be substituted.) X: Anion The gelatin used in the mordant layer may be any of the known gelatins. For example, there are different gelatin manufacturing methods such as lime-treated gelatin and acid-treated gelatin, or
It is also possible to use gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment.

The mixing ratio of the polymer mordant and gelatin of the present invention and the coating weight 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. You can, but
The mordant/gelatin ratio is 0/10 - 0/20 (also ratio), and the loincloth is θ,! It is preferable to use it at ~♂9/m2.

The image receiving layer (11) may have a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided over the mordant Iso on a transparent support. The titanium dioxide layer forms a white opaque layer and the transfer color im+
By viewing the + image from the transparent support side, a reflected color image can be obtained.

A typical receiver 11!1 material for diffusion transfer is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a transparent support.

A transfer solvent can be used for transferring the coloring matter 3Y; J- to the image-receiving layer. The transfer solvent includes water, regenerated soda, regenerated potassium, and salt If containing an inorganic alkali metal salt.
An aqueous solution of f is used. Also, methanol, N, N-
Low boiling point solvents such as dimethylformamide, acetone and diisobutyl ketone, and mixed solutions of these low boiling point solvents and water or basic aqueous solutions are used. The transfer solvent may be used by moistening the image-receiving layer with the solvent, or may be incorporated into the material as crystal water or microcapsules.

Example 1 Dissolve benzotriazole is, jt9 and 10f of gelatin in 10oQIn of water twice a month. Keep this solution to oc and stir. Next, a solution prepared by dissolving silver nitrate r, jt in 100 nil of water is added to the above solution for 2 minutes.

Next, a solution of potassium bromide/co2 in water is added over 2 minutes. The adjusted emulsion is settled by p)l adjustment to remove excess terms. Then the pH of the emulsion was adjusted to 6.
．． Adjusted to 0. The yield was 1□Of.

Next, a method for making a gelatin dispersion of a color image forming substance will be described.

A color image-forming material having the following structure is ioy as a surfactant: sodium succinate-2-ethyl-hexyl ester sulfonate. , tf,) leak resyl phosphate (Tel')-□t was weighed, and ethyl acetate J
Add Oml and dissolve at about 60°C to make a homogeneous solution.

After stirring and mixing this solution and 70-bath solution 10O9 of lime-treated gelatin, io, o
ool is also dispersed in PM. This dispersion is combined with the actual dispersion of the dye donor.

Next, we will discuss the method for controlling photosensitive debris.

(Al benzotriazole silver containing photosensitive silver bromide)
I emulsion 1oilbl
Dispersion of color image-forming substances 3. Evening 2 (C) Guanidine trichloroacetic acid, 2! O■ to ethanol, 2m
A solution of 100 mQ of the compound of the present invention dissolved in water goo (+8) to (d) was mixed and dissolved by heating). It was applied to a film thickness. After drying this coated sample, io was applied at 2000 lux using a tungsten bulb.
The image was exposed to light for seconds. Thereafter, it was heated uniformly for 30 seconds on a heat block heated to i, zo oc. This sample is designated as A.

Next, except for the compound of the present invention in (d), a sample prepared by adding Mizukosei instead was used as B, and the same operation as above was performed.

Next, a method for producing an image-receiving feed having an image-receiving layer will be described.

Dissolve 10f of poly(acrylic acid mether-N, N, N-trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) in 100 ml of water,
096 was uniformly mixed with lime-treated gelatin 1009. Spread this mixture onto a polyethylene terephthalate film.
It was applied uniformly to a wet film thickness of 20 μm. After drying, this sample was used as an image receiving material.

After soaking the image-receiving material in water, the photosensitive material A is heated as described above;
B were stacked one on top of the other so that their membrane surfaces were in contact with each other.

After heating on a TO'C heat block for 6 seconds, the image-receiving material was peeled off from the photosensitive material, and a negative magenta color image was obtained on the image-receiving material. This negative image was measured using -7 Kuben transmission once ttt ('I' D-Y0+), and the following results were obtained.

Sample shop Maximum # degree Minimum girl hair A (this invention)
Ko, 10 0. /IB (comparison) 0・
31 0. From the results shown in /J and below, it can be seen that the compounds of the present invention provide extremely high concentrations even at low temperatures.

Example 2 The following results were obtained by carrying out the same operation as in Example 1 except for using the following compounds.

From the above results, it was found that the compounds of the present invention have superior effects compared to compounds outside the present invention.

Example 3 In place of the color image forming material of Example 1, a storeroom io having the following structure was used.
A dispersion of a color image forming substance was prepared in the same manner as in Example 1 using t.

t-1 The following results were obtained.

From the above results, it was found that the compound of the present invention provides a significantly high maximum concentration even at low temperatures.

Example 4 In place of the emulsion in Example 1, an emulsion prepared as follows was used. Gelatin 4109 and KHr, 249 in water JO
Dissolves in OOmρ. Keep this 1w solution at to''c and stir.

Next, add 70 m of silver nitrate to 34 c97 water.
Add to the above solution m in minutes.

Thereafter, a solution prepared by dissolving Klj,j9 in 100rnQ of water was added over a period of time.

The silver iodobromide emulsion thus prepared is adjusted in temperature and precipitated to remove excess salt.

The pH was adjusted to t and o to obtain a silver iodobromide emulsion with a yield of 41,009.

The photosensitive coating was made as follows.

(at mj't, silver iodobromide emulsion
zg(b) Dispersion of dye-providing substance 3. evening? (Same as Example 1) tel Guanidine trichloroacetic acid 0. ．． Compounds of the invention 0, . A solution prepared by dissolving 2 g of water≠mg was mixed with (al~tdl), and then the same operations and treatments as in Example 1 were performed.The results are shown below.

Preferred embodiments are as follows.

1. The heat-developable color photosensitive feed as claimed in the claims, wherein an organic silver salt oxidizing agent is present on the support.

2. The heat-developable color photosensitive material according to Embodiment 1, which contains, if necessary, a reducing agent for an organic silver salt oxidizing agent.

3. The dye-donating property that can reduce silver halide and release a hydrophilic diffusive color system is expressed by the following general formula (1)
The heat-developable color effect of the claims characterized in that it is represented by 714 materials.

R-8D2-D (1) Here, R represents a reducing substrate that can be oxidized by an organic silver salt oxidizing agent, and D represents an image-forming dye.

4. A thermal block imaging color photosensitive material characterized in that the reducing power of the dye-donating substance R-8LJ2-D of item 3 is 2 V or less in terms of redox potential with respect to a saturated calomel electrode. .

5. A heat-developable color photosensitive tA material, characterized in that the reducing cage in the dye-donating substance R-802-1) of item 3 is represented by the following general formulas (I[) to (K). .

U)I U)l H-Nt1-2 Here, R1, H, and 2 are each hydrogen atom, alkyl group, cycloalkyl, aryl group, alkoxy group, aryl group, aralkyl group, acyl group, anruamino group, Alkylsulfonylamino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl group, N-substituted carbamoyl &, “-substituted carbamoyl group,
It represents a substituent selected from halogen atoms, alkylthio groups, and arylthio koji, and the alkyl groups and aryl groups in these substituents can be further substituted with alkoxy groups, halogen atoms, hydroxyl and cyano groups, acyl groups, and acylamino groups. It may be substituted with a substituted carbamoyl group, a substituted carbamoyl group, a substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group, or a carbalkoxy group.

6. The D portion in the dye-donating substance 1 (-8 (J2-1) in Section 3 is a hydrophilic azo, azomethine, anthraquinone, naphthoquinone, styryl, nitro, quinoline, carbonyl, or phthalocyanine dye. A heat development color photosensitive material as claimed in the patent claims.

F. A heat-printable color sensitive material, characterized in that the patented dye release aid is a salt release agent, a salt release agent or a 7J release compound.

8. The retroactive agent in the claims is the oxidized form of Embodiment 1r.
A heat-developable color photosensitive material, characterized in that it is capable of oxidizing the reducing substrate H in item 3 of iZ.

9. Organic 1Iili of Embodiment 1! 1. A heat-developable color photosensitive material, wherein the salt oxidizing agent is a carboxylic acid donor or a silver salt of a nitrogen-containing heterocyclic compound.

10. A heat-developable color photosensitive material, wherein the hydrophilic binder as claimed in the claims is gelatin or gelatin derivative.

11. An image forming method according to the claims, characterized in that the released diffusible dye is transferred to an image-receiving material using water or a basic aqueous solution.

12. An image forming method characterized in that a mordant is used in the image-receiving material according to item 11 to obtain a transferred image.

13. A heat-developable color effect '#, characterized in that the organic silver salt oxidizing agent of item 9 is a silver salt of a nitrogen-containing heterocyclic compound;
material.

14. The claimed polyethylene glycol type nonionic surfactant is an alcohol ethylene oxide adduct;
Alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, ethylene oxide of /IIJ1311 A heat-developable color photosensitive material characterized by being an adduct, a polypropylene glycol ethylene oxide adduct, and a mixture thereof.

15. A heat-developable color photosensitive material, characterized in that the polyethylene glycol type nonionic surfactant according to claims w & 14 contains 5 or more repeating cells of ethylene glycol.

Patent applicant: Fuji Photo Film Co., Ltd. 1937/
/Monday/Monday/Monday Mr. Commissioner of the Japan Patent Office, Small Case Display, Showa J7 Patent Application No.
2. Name of the invention Heat-developable color photosensitive material 3. Relationship with the person making the correction Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact address 106 Tokyo No. 4, 2-26-30 Nishi-Azabu, Miyakominato-ku, Subject of amendment: Section 5 of ``Detailed explanation of the invention'' in the specification 1, @Correct contents In the section of ``Detailed explanation of the invention'' of specification 1, the following Correct as expected.

/) 3rd negative line 77th r RD = /ri66” trR
D-#ri66" is corrected.

K) No.! "For organic silver salt oxidizing agents" on page/line G
Delete J) i? y page 1/line no.

4A) Change “organometallic oxidizer” on page ioz/line 7 to “
Corrected to "silver halide."

"Organic metal" on page 17 to /r of iOS is corrected to "organic silver salt."

6) Insert the entire line ``if an organic silver salt oxidizing agent is used together'' before ``1st development'' on the negative 2nd line of iot.

7) On page 107, line 20, delete "1 by an organic oxidizing agent".

l) Insert ``Silver halide also [7〈wa''] in front of ``Silver halide oxidation April'' in line j of page io.

ri) @/Page 34, line 3, 14t/Page 3, line 141
, /page jth line, 1° color image forming substance Jt in the table on page 1≠2
-r color-donor substance”.

10) No. 137. Page, line 20, amend it to "Lung field lysis" (heat lysis).

//) Delete "Lime treatment" on page 137, line 1.

/2) Page 137, line 73 [, zoomz > water uml
r (combined 1 solution) 1k Corrected as ``solution dissolved in Mizuhiro mf'.''

/J) Daiichi Hiro! "Primary" on the 6th line of the page is corrected to "said".

/4L) No. 14! ! General formula (I
I) or IX)? f-Delete・lj) Page 1III, 1st line to /Jth line 1. You may place here. ” and delete it.

199-

Claims (1)

[Claims] On the support, photosensitive silver halide, hydrophilic binder,
A heat-developable color photosensitive tA composition comprising a dye release aid, a reducing dye-donating substance that releases a hydrophilic dye, and a polyethylene glycol type nonionic surfactant.