JPS5974547A - Thermodevelopable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a sharp color image in a simple manner by forming a layer contg. photosensitive silver halide, a hydrophilic binder, a dye releasing adjuvant, a dye donor, or a cationic compd. on a support. CONSTITUTION:Photosensitive silver halide, a hydrophilic binder, a dye releasing adjuvant, and at least one of a reducing dye donor releasing a hydrophilic dye and a cationic compd. having a pyridinium group are contained in a layer formed on a support. The cationic compds. each having a pyridinium group represented by formulae I , II (A is a methylene chain preferably having 1-16C, -O-, -NHCO-, phenylene, or -C(OH)H-; B is alkyl, aralkyl, or H; R, R' are each H or 1-5C alkyl; X<2-> is a divalent anion; and Y is monovalent anion) are preferable among such usable compds.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a thermally developed image.The present invention particularly relates to a method for forming a color image by thermal development. In the heat-developable color light-sensitive material containing Color I[1], the dye released by heat development is thermally diffused and transferred to the dye-receiving support.
This paper concerns a new method for obtaining a single image.

The photographic method using silver halide sound has been the most conventional since it has superior photographic characteristics such as sensitivity and gradation compared to other photographic methods such as electrophotographic method and diazo method. It has been widely used. In recent years, photosensitive materials using silver halide have been developed. Techniques have been developed in which images can be obtained easily and quickly by changing the tI image forming processing method from the conventional wet processing using a developer solution to a dry processing using heating or the like.

Heat-developable photosensitive materials are well known in the art; u.S. Pat.
j, No. 2.9041, H3,3o/,i.

No. 71, No. 3. ．． 9P, 2, No. 0.20, No. 3. Hiroj7
No. 075, British Patent No. 1, /J/, No. 101, No. 7, /lr7,777, and Research Disclosure magazine / June 27r issue, pages 2 to /j (RD-/7
o Kota).

Many methods have been proposed for obtaining color images. Regarding a method of forming a p-color image by combining an acetylated developer and a coupler, US Pat. No. 3,13/, Cor. , U.S. Patent No. 3.7t/, 270, p-amine phenolic reducing agents are described in Belgian Patent No. 102. J/R issue and Search This Flower magazine is 7t years old? Monthly issue 3/,
On page 32, a sulfonamide phenol thread threading agent is proposed. In US Pat.

However, in such a method, a color image of reduced silver and a color image are simultaneously generated in the light area after heat development.
There was a drawback that the iit flR became cloudy. To solve this problem, there are methods to remove the silver image through liquid processing, or to transfer only the dye to another layer, for example, a sheet that is equivalent to the image-receiving layer. It has the disadvantage that it is not easy to transfer only the dye.

In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a planer salt, and releasing the dye by heat development is described in the 71r issue of Leather Closure Magazine! G~sr page I
(described in , D-/ri6t. With this method, Q,
This is not a common method because it is difficult to suppress the release of dye in areas that are not exposed to light, making it impossible to obtain clear images.

Furthermore, regarding the method of forming positive color images by the silver color cumulative white method using heat development, for example, see Research Disclosure magazine/Re7, page 3.2 (RD-/≠≠ 33), same magazine / 1976 / month issue / j ~
/j page (RD-/l, 2.27), US Patent No. ≠,
,23jt,ri! No. 7 and other publications describe useful dyes and bleaching methods.

However, this method requires extra steps and materials, such as stacking and heating activator sheets to speed up the bleaching of the dye, and the resulting color image may still coexist during storage during the eclipse period. However, it has the disadvantage that it gradually undergoes reductive bleaching due to the release of free buttons.

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

No. 6t, No. 0.22, 1. / No. 7. However, this method has the disadvantage that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage.

The present invention provides a new method for forming color images by heat development, and also solves the drawbacks of hitherto known H materials.

That is, an object of the present invention is to obtain a new +I! color image by thermally transferring a hydrophilic dye released by thermal development to an image receiving material containing a mordant. A method for forming IIpi is provided.

The object of the present invention is to provide a clear color 1mm image using a simple method.
This provides a method for obtaining images.

It is an object of the present invention to obtain long-term stable color Il! I
This provides a method for obtaining an I-image.

An object of the present invention is to provide a method for obtaining high color images in a short time.

゛ These objectives are to provide at least a photosensitive silver halide, a hydrophilic binder, a dye release aid, a reducing dye-donating substance that releases a hydrophilic dye, and a cationic compound having a pyridinium group on a support. This can be achieved by a heat-developable color photosensitive material containing one.

Among the cationic compounds having a pyridinium group used in the present invention, those represented by the following general formula are preferred.

(1) (It) A is a methylene chain (preferably carbon number/~/6), -0-
, -NHCO-, -0CO-, phenylene.

Original product consisting of -CH- or a combination of each Hail to the children.

Besides, it also rains hydrogen atoms.

R and R' each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

X-- is a covalent anion (e.g. sulfonate ion, oxalate ion, carbonate ion, sulfite ion, HPO4), Y
- produces a heptavalent ion (e.g. halogen ion, perchlorate ion, acetate ion).

Preferred compounds represented by (1) and (ll) include the following.

(1) (2) (8) (9) (11) (13) (14) (10) (12) (15) (16) (18) (19) CN-C'H2-CH-CH2-0 -1;CH-CH2
The cationic compound having a pyridinium group is known per se and can be produced by methods described in related literature. Cationic compounds having a pyridinium group described in the following known documents can also be used in the present invention. PSAJournal, 5ectionB
3 A (/Tata3).

usp 2. t4AI, 4017 usp 3.
Otsu 7/.

Cog 7, Tokko Showa 4 to Hiro-3007≠, Tokko Showa 11. Gutata03゜In general, cationic compounds having a pyridinium group can be used at a certain concentration. Concerning the useful concentration of the compound used in the present invention, it is from o, i% by weight to 10% by weight, preferably from 1% by weight to 10% by weight, based on the hydrophilic binder.

In the present invention, by using a heat-developable color light-sensitive material containing a cationic compound having a pyridinium group, a color N image with a low minimum moisture content and maximum density can be obtained in a short time. is a feature.

The heat-developable color photosensitive material of the present invention simultaneously provides a silver image having a negative-positive relationship with the original and a diffusible dye in the area corresponding to the silver image, simply by performing heat development after image exposure. be able to.

That is, when the heat-developable color photosensitive feed of the present invention is exposed to light in a bag and heat-developed, an oxidation-reduction reaction occurs between the organic silver salt oxidizing agent and the reducing dye-donating substance using the exposed photosensitive silver halide as a catalyst. This causes a silver image to appear in the exposed area. In this step, the dye-donating substance is oxidized by an organic silver salt oxidizing agent to become an oxidant. This oxidant is cleaved in the presence of a dye release aid, resulting in the release of a hydrophilic, diffusible dye. Therefore, in the h-circled area, a silver image and a diffusible dye are obtained, and a color image is obtained by transferring this diffusible dye.

All reactions that release the diffusible dyes of the present invention are carried out under conversion. This release reaction of the diffusible dye is thought to be caused by the attack of a so-called nucleophile, and is usually carried out 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 high reaction rate even during conversion. This remarkable reaction rate was an unexpected discovery. Further, the dye-donating additive of the present invention can undergo a redox reaction with a halogenated forging or a heavy machinery silver salt oxidizing agent without the aid of a so-called auxiliary developer. This is an unexpected result based on the knowledge up to saw l'L at the temperature near the cylindrical portion.

The reducing dye-donating container that releases the hydrophilic diffusible dye used in the present invention has the following general formula (% formula %) (1) where R must be a reducing agent that can be oxidized by an organic silver salt oxidizing agent. It contains a dye part for image formation that has a hydrophilic base.

The extrinsic substrate (几) in the dye-donating substance R-802-D was oxidized to a saturated calomel electrode in polarographic half-wave height measurement using acetonitrile as a solvent and sodium perchlorate as a support. It is preferable that the firing position is /, ko or less. Preferred redundant groups (1) are the following general formulas (If) to (IK).

H H H- H- ■ 几3 Here, Bl, R2, R3, and 几4 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkyl paper, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, Acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl group, N-substituted carbamoyl group, N-substituted sulfamoyl group, halogen atom, alkylthio crystal, arylthio group. The alkyl group and aryl group moiety in these groups can be further expressed as an alkoxy group, a halogen atom, a hydroxyl group, a cyanide group, an acyl group, an acylamino group, a substituted carbamoyl group, a substituted carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, an alkylsulfonylamino pattern, an arylsulfonyl group, etc. It may be substituted with an amino group, a substituted ureido group, or a carbalkoxy group.

In addition, the acid and amino groups at 7 in the company are protected by protecting groups that can be regenerated by the action of nucleophiles. may have been done.

In a further preferred embodiment of the present invention, the reducing substrate 1t
is expressed by the following formula (X).

Here, G represents a hydroxyl group or a group that provides a hydroxyl group upon hydrolysis.几10 represents an alkyl group or an aromatic group.

XIO is an electron-donating substituent when n = /, and when n = 3, it can be the same or different substituents, and when 7 of them are electron-donating groups, the or the third one is an electron donating group or a halogen atom,
Even if X itself forms a fused ring, OR,! : May form a ring.

The total number of carbon atoms in R and X is t or more.

Among those included in formula (X) of the present invention, in a more preferred embodiment, the reducing substrate R is represented by the following formulas (Xa) and (Xb).

Here, G represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. R11 and ai2 may be the same or different, and each is an alkyl group, or R11 and R
12 may be connected to form a hole.

R13 represents hydrogen or an alkyl group, and BIO represents an alkyl group or an aromatic group. Xll and X12 may be the same or different and each represents a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group, or an alkylthio group;
t may be connected to form a ring.

R10 Here, G is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis, 几 is an alkyl or aromatic group, X is a hydrogen atom, an alkyl group, an alkyloxyacetic acid, a halogen group, an acylamino group, or an alkylthio group. Is it a ring connected with LIO? It may be formed.

Specific examples included in (X), (Xa) and (Xb) are US Hiromu, O Tata, Hiro2g, Tokukai Sho! 6-/2Allλ
It is listed in the same issue and Taro/Otsu/No. 30 respectively.

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

(However, 9 dimensions (), X, R and n are the formula (X
) has the same meaning as G, X, Ft. ) of the present invention (
Among those included in XI), in a more preferred embodiment, the reducing substrate ()L) has the following formulas (Xla) to (X
IC).

However, G is a hydroxyl group, a group that gives hydroxyl 'Jkk by hydrolysis; 1 R and R may be the same or different and each represents an alkyl group or an aromatic group; may form a ring:] 23 represents hydrogen, an alkyl group or an aromatic group; 24 represents an alkyl group or an aromatic group; B25
represents an alkyl group, alkoxy, alkylthio, arylthio, halogen atom, or acylamino group; p is 0. /or B24 and B25 may combine to form a condensed ring; B21 and B24 may combine to form a condensed ring; B21 and 1L25 may be bonded to form a condensed ring, and B21.1(,22,B
The total carbon number of 23,4 几 and ILp is greater than 7.

CI-IR"" Also, G is a hydroxyl group or a hydroxyl group is obtained by hydrolysis: R represents an alkyl region or an aromatic group; B32 represents an alkyl group or an aromatic group; B33 represents an alkyl converted alkoxy or an alkyl thio group; , represents an arylthio group, a halogen atom or an acylamino group; q is 0. / or -; 1t and R may be combined to form a condensed ring<,
H, 31 and B32 may be combined to form a condensed ring, or IR and R may be combined to form a condensed ring; and the total carbon q prime number of B31, R32, and R2H is from 7 Thick.

In the formula, G represents a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; 1 R represents an alkyl school or an aromatic book; 2 R represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom, or Represents an acylamino group: r is 0. / or co-represents a carbon tertiary carbon atom in the combined ring that represents a combination and also participates in bonding to the phenol (or its precursor) mother nucleus, and also a carbon atom in the hydrocarbon ring (However, the above-mentioned tertiary carbon atoms are excluded) may be partially substituted with oxygen atoms, or the hydrocarbon ring may have a substituent, or the aromatic ring may be fused. The total number of carbon atoms is 7 or more.

The above (XI), (Xla) to (Xlb) K-inclusive Salel specific examples are disclosed in Japanese Patent Application Laid-Open No. 2003-110001. /3/, same 17-4jO1 same! 7-170≠3.

The essential part of formula (1) and formula (IV) is the para-(sulfonyl)aminophenol moiety.

A specific example is US Patent 3. ri2t, 3/ko issue,
Same≠, No. 076.122, No. /31゜Pλ, No. ≠, 2jtt, /, No. 20, US Patent Publication BE! /,
473, which are also effective as the reducing &I[(I()) of the present invention.

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

Here, Ba1last represents a diffusion-resistant group.

G represents a hydroxyl method or a precarner of a hydroxyl group.

G1 forms an aromatic ring and forms a naphthalene ring together with a benzene ring. n and nl are each different integers.

Specific examples included in the above X1 are described in US-4', or3°3/, 2.

The reducing substrates of formulas (V), (■), (Xa) and (IX) are characterized by containing a heterocycle, and specific examples include US Gu, /R, 23! , Tokukai Akira! 3-≠A
7JO, US≠lλ73. The! ! These include those listed in . A specific example of the reductive disposition represented by formula (Vl) is US! ,/+ri.

There is a description in λ.

The following properties are required for the reducing agent.

1. It is rapidly oxidized by an organic silver salt oxidizing agent and efficiently releases a diffusible dye for image formation through 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. Therefore, the reducing hematin R has large hydrophobicity. .

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

4. Easy synthesis.

Next, preferred specific examples of containers that satisfy these conditions will be shown. In the examples, NH- represents a linkage with a dye moiety.

0l-(OH OH OH OH OH No.3FI7 1-1 OH OH Dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes.Representative examples are shown by hue.Please note that these dyes can be processed by development. It can also be used in a temporarily shortened form that can sometimes be recolored.

Yellow Rst R52 t52 0H Magenta 01 is also □ H ”52 R52 5a Cyan Q NH2O 0H In the above formula, It, □ ~ I (+56 are each a hydrogen atom,
Alkyl group, cycloalkyl group, aralkyl group, alkoxy group, aryloxy group, aryl group, acylamino group, acyl group, cyano group, hydroxyl group, alkylsulfonylamino grade, ri-ru-sulfonylamino paper, alkylsulfonylamino paper, hydroxyalkyl cyanoalkyl group,
Alkoxycarbonylargyl group, alkoxyalkyl group, aryloxyalkyl group, nitro range, halogen,
Sulfamoyl 7k, N-substituted sulfamoyl group, carbamoyl i, N-1 carbamoyl group, acyloxyalkyl group, amino group, substituted amino group, alkylthioya,
Represents a substituted paper selected from arylthio, and the alkyl and aryl & moieties in these substituted papers are further) - rogene atom, hydroxyl group, cyano group, acyl group, acylamino group, alkoxy group, carbamoyl group, It may be substituted with carbamoyl paper, sulfamoyl &, fZf-substituted sulfamoyl group, carboxyl base, arylsulfonylamino group, arylsulfonylamino ureido group.

Hydrophilic groups include hydroxyl group, carboxyl group, sulfonate group,
Phosphoric acid group, imide chloride, hydroxamic acid gel, quaternary ammonium group, carbamoyl paper, substituted carbamoyl paper, sulfamoyl k, substituted sulfamoyl cage, sulfamoylamino group, substituted sulfamoylamino group, ureido group, substituted ureido group, Examples include alkoxy scraps, hydroxyalkoxy groups, and alkoxyalkoxy groups.

In the present invention, it is preferable that hydrophilicity is significantly increased by dissociating protons under salt-wiping conditions (PKa (/, 2), among which phenolic hydroxyl acetate, carboxyl A, sulfo group, phosphate group, imidoya, hydroyanamic acid group, (substituted) sulfamoyl group,
(Substituted) sulfamoylamine groups, etc. are included.

The characteristics required for a color chart for image formation are: /) having a hue biased for color reproduction, 1.2) having a large molecular extinction coefficient, 3) controlling light, heat, and dye release aids contained in the system, etc. stable against additives, easy to synthesize,
Examples include. A specific example of a high-quality color for forming an image that satisfies these conditions will be shown below. Here H2N
-S O2 represents the bonding part with the reducing paper material.

Ye 11 ow Magenta SO□NH2 H H an OH OH Next, specific examples of preferable color-imparting materials will be shown.

41191tl (3) OC16H33 (5) 01-1 H (7) (8) CHa C4H9(11 H C4H,jtl (11) H H C4H8fil (13) (14) (15) H H 11, t tl (18) 1-1 C4Hg(tl (19) H C4H9(tl (20) C3H1t(tl
(21) (′°). o143 (24) (25) (26) H OC16H33 0C161)33 (30) (34) OU16H33-n ()C16H3a n (36) OC□6H33 (37) (38) N (41) OH (42) QC1aHa a n CH3CHa 1 C-CI(2-C-CHa 1 CHa CHa 16H33n (43) OH (44) 0C16H33-n (45) αll:18H37-n (46) (47) QC16H33n 0C16H33-n (52) (53) OC16H33 61113 (56) OH OH OC16H33 (58) 01( OC16H33 (59) OH C31(7 0(-"taHaa C(CH3) 3 II H 0 In addition, IJ84t, 0!!, Il, 2F, ice lf1 Doakiri&-/u&!, !, Same J'J-/l=/3
0. Same tg-/l/3/, same 37-tjO, same ter 1-
1 Ura 3, USA, ri, 2g, 3/ko, USJ, 07 Otsu, j, 2ri, US Published Pate
ntApplicationB 311,673
, tJ8≠, /3! r, Ri2ri, US41. /91. ．．
2J! , Tokukai Akira”-4tJ7Jθ, USJ, Core 3.♂
j! , USILL, /Hirori.

l Octopus, υSI1. /4t, 2. ♂ri/, USJ, Ko!
Compounds described in ZA, /2θ, etc. are also effective.

Furthermore, USJ, 0/3,633, USJ, /it, t
Ori, '[Ji94L, /4'za, 6≠/, USJ.

Il,! , ri+7, USJ, /≠J, Aμ3, US+,
/r3,7rr, UslI, aag, piti, US4
1,261.42! r, U8tl, xar, oxj1 JP-A-34-71072, j6-ko j737, rz-
i3t7a+, same r! r-/3111IA, the same λ-
Dye-donating substances that emit yellow dyes, such as those described in 10t7co7, 31-//Geta 30, are also effective in the present invention. Also USJ.

the law of nature! μ, 176, USJ, Ri3ko, 3zao, USJ,
? 3/ , /4'4', IJ8J ,? 3.2.3
1/, US Hiromu, 21. T, 6 φ, USJ, Kota! , RiOri, Tokukai Sho, +4-7Jθ! 7, same k1. -7IO4
01 same j! −／j≠zzo, same ta! -San〇≠Oλ, same!
Tar3trO Hiromu, same! 3-ko 3tko t1 samejko 104
72, 1 33/41.2, same ta! -! Dye-donating substances that release magenta dyes, such as those listed in No. 33 Kota, are also effective in the present invention. Still USJ, 2.2? ,7/
sO, IJ811.0/3.63'5Us3. Rihiro, 2
, Ff7, US4< , 273.

qol, USJ, /μff, A Hiroko, USJ, /13.
7 ta≠, U84', /≠71 month t4t, USμ.

/Otsur,,231. US, λhirot, ≠/g, USJ,
Korot, 6λ! , Japanese Unexamined Patent Application Publication No. 1997-7101,/.

same! 3-'1L7123, same j2-1127, same! 3-
Dye-donating substances that release cyan dyes such as those listed in No. 113323 are also effective in the present invention.

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

Generally, the dye-donating substance of the present invention is obtained by condensing the amino group of a reducing crystalline substance with the chlorosulfonyl group of the image-forming dye.

Depending on the type of paper, nitro,
It can be introduced by reduction of the nitroso, azo group or ring opening of the benzoxazole, and also as a free base.
It can also be used as a salt of an inorganic acid. On the other hand, the chlorosulfonyl group in the image-forming dye moiety can be derived from the sulfonic acid or sulfonate 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 reducing substrate R and the image-forming dye moiety is generally carried out using pyridine, picoline, lutidine, triethylamine, diisopropyl in an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, permethylpyrrolidone, or acetonitrile. It can be carried out in the presence of an organic base such as ethylamine at a temperature of Q to zo 0c, and usually the desired dye-donating substance can be obtained in an extremely high yield. An example of its synthesis is shown below.

Synthesis Example t: Synthesis of 4-Hydroxy-λ-methylbenzoxazole 306 g of Hiro-dihydroxyacetophenone and 00 ml of hydroxylamine hydrochloride/6≠21 sodium acetate were mixed and heated under reflux for an hour. Pour the reaction solution into io1 of water, count the number of precipitated crystals, and calculate λ.

μm dihydroxyacetophenone oxime 37≠2 was obtained.

This oxime 30? f Dissolved in 4100 ml of acetic acid, /
While heating and stirring at 200C, hydrogen chloride gas was blown into the solution for 2 hours. After cooling, the precipitated crystals were collected and washed with water to obtain t-hydroxy-comethylbenzoxazole/79.

Synthesis Example 2: t-Hexadecyloxy-comethyl is the 6-hydroxy-comethylbenzooxazole synthesized in Synthesis Example 1 of 1.0? , /-bromohexadecane 3t
, t9, potassium carbonate λ≠, 02, N, N-dimethylformamide/20 mQ was poured at 0° C. and stirred for 5 hours.

Separate the solids from the reaction solution and add the filtrate to gemethanol j00r.
Opened in nQ. The precipitated crystals were collected and t-hexadecyloxy-comethylbenzoxazole 4tj,0
Got 9.

Synthesis Example 3: 2-acetylamino-! - Synthesis of hexadecyloxyphenol t-hexadecyloxy-λ-methylbenzoxazole obtained in Synthesis Example 2 / / / 9, ethanol / 300
m1. ．． 33% hydrochloric acid//OmQ, water jjOml were mixed and stirred for a certain period of time. After cooling, the precipitated crystals are collected in a furnace and coacetylamino! -hexadecyloxyphenol//39%.

Synthesis Example 4: Coacetylamino≠-t-butyl-!
-Synthesis of hexadecyloxyphenol Co-acetylamino-hexadecyloxyphenol obtained in Synthesis Example 3 30.0? , Amberlis l/l (registered trademark of Rohm and Haas, Inc., USA) 20. Of,
300 mQ of Torxone was mixed, and while stirring and heating at ♂O to 206C, imbutene was blown into the mixture for 5 hours. After removing the solid, concentrate the P solution and add n-hexane to the residue.
When Omu was added, crystals were precipitated. Taking P, coacetylamino≠-t--Z-thyl-! -hexadecyloxyphenol23. Got 2 evenings.

Synthesis Example 5: Synthesis of 2-amino-g t-butyl-j-hexadecyloxyphenol The λ-acetylamino group prepared in Synthesis Example 4 was converted into butyl-hexadecyloxyphenol 23°0? , ethanol/2oroρ, 3! Mix %iM acid 1=mff, and leave for 5 hours? The mixture was stirred and refluxed. After cooling the reaction solution, the precipitated crystals were collected and processed into Koaminogut--/
Chill! -Hexadecyloxyphenol hydrochloride! 3.
We get λ2.

Synthesis example 6:! -t-butyl router hexadecyloxy-co[-1(,2-methoxyethoxy)-! -Nitrobenzenesulfonylamino] Synthesis of phenol Co-amino + -1-buheru obtained in Synthesis Example 5! -hexadecyloxyphenol salt m salt+, +2 and 2-
(2-methoxyethoxy)-! -Nitrobenzenesulfonyl chloride 3. /f to N.

Dissolved in N-dimethylacetamide/, 2 mQ,
Pyridine λ,! After adding rnQ, 2j0C for 1 hour
It was stirred with When the reaction solution was poured into dilute hydrochloric acid, a curved material was precipitated. When 30 mQq of methanol was added to this curved material, it crystallized, so it was treated as F.

Haruhiro,! ? .

Synthesis Example 7: 2-[,t-amino-no(2-methoxyethoxy)benzenesulfonylamino]-μ-t-butyl-! -Synthesis of hexadecyloxyphenol The compound ioy obtained in Synthesis Example 6 above was mixed with ethanol AOmO
1, add about 0.21% of 70% palladium-carbon catalyst, and add water! ! Press in until 2/■2, to
'C for 4 hours. Next, the catalyst was removed by heating and allowed to cool, crystals were precipitated and the mixture was removed.

Yield 7. Yo? .

Synthesis Example 8: 3-cyano-Hiro-[gu(2-methoxyethoxy)-! -Sulfophenylazo]-/-Synthesis of phenyl-terpyrazolone 7J Add j-amino-,2-(,!-methoxyethoxy)benzenesulfonic acid to a solution of sodium oxide, 09 and water. Add sodium nitrite/3. An aqueous solution of ♂9 (,t□mc,) was added.

Separately, a solution of 1 tOrnU of string salt and 4 t 00 n+1 of water was prepared in dM, and the above solution was added dropwise to this at a concentration of 500 ml or less.

Thereafter, the reaction was completed by stirring at t'c34 for 30 minutes.

Separately, sodium hydroxide/l, 09, water, 200 ml,
.

Sodium acetate! 3, Of and methanol, 200
The solution of m1+ was combined 5 times, and 3-cyano-/-phenyl-
Terpyrazolone 37. Of was added thereto, and the prepared diazo solution was added dropwise at a temperature below 1Q 0C. After the dropwise addition was completed, the mixture was stirred for 30 minutes at 10oC or less, and then stirred at room temperature for 7 hours.
The precipitated crystals were collected, washed with 200 rall of acetone, and air-dried.

yield! ;2,09 nl,p,,2A3~. 2Aj0
C Synthesis Example 9: 3-cyano-≠-[gu(nomethoxyethoxy)-! Synthesis of -chlorosulfonylphenyla7") -/-phenyl-terpyrazolone 3-cyano-<z-((+-methoxyethoxy-j-sulfophenylaso]-7-phenyl-! -N,N-dimethylacetamide was added dropwise to a mixed solution of pyrazolone J'7.0?, acetone 2!Om9, and phosphorus oxychloride!OmQ at 9710°C or below.After the dropwise addition, the mixture was stirred for about an hour and then washed with ice water i, olO Pour the precipitated crystals one by one, then add 100 ml of acetonitrile.
Washed with mQ and air dried.

Yield Hiro A, 79 m, p, /g/-/13 °C Synthesis Example 10: Synthesis of dye donor *' (xl) 3-g of sulfonylamino-≠-1-butyl-!-hexadecyloxyphenol t was dissolved in 30 ml of N,N-dimethylacetamide to obtain 3-cyano-+-[≠-(nomethoxyethoxy)-] obtained in Synthesis Example 9. !-chlorosulfonylphenylazo)-/-phenylterbylazolong, 6f is added, and then pyridine! Added a female. After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. N,N-dimethylacetamide-
7. Recrystallize from methanol. ! I got 2.

rn, p, /J'tahe/ri/'C Synthesis Example 11: Synthesis of dye-donating substance (2) No[!] obtained in Synthesis Example 7 -amino-λ- (nomethoxyethoxy)
Benzenesulfonylamino-Hiro-1-butyl-! -Hexadecyloxyphenol 632 was dissolved in 30 mQ of N,N-dimethylacetamide, and 3-cyano-g(!-
chloro2-methylsulfonylphenyl 7so)-/-(
F-chlorosulfonylphenyl)-terpyrazolone! ,
09 was added, and then pyridine jmO was added.

After stirring for 7 hours (4 hours) at room temperature, the reaction solution was poured into dilute hydrochloric acid,
The number of precipitated crystals was counted. Recrystallization from acetonitrile yielded ♂, 1I9.

m, p, /1711 to /41 0C Synthesis Example 12: Dye-donating substance (synthesis of one co-amino-pt-butyrotate hexatecyloxyphenol hydrochloride, μ9 and ≠-C3-chlorosulfonyl-≠
-(2-methoxychetoxinephenylaso')-,2-
(N,N-diethylsulfamoyl)-termethylsulfonylamino-/-naphthol 6,j9 to N,N-
Pyridine/- dissolved in 20ml dimethylacetamide
2mQf was added. /h after stirring at zt 0C.
The reaction solution was poured into dilute hydrochloric acid. l? The ejected solid rP was collected and purified by silica gel column chromatography (eluted with a chloroform-ethyl acetate (Koni/) mixed solvent).

yield! ,Ko? .

Synthesis Example 13: Synthesis of dye-donating substance (17)
00ml and added pyridine/-2. to this! -(3-chlorosulfonylbenzenesulfonylamine)-2-(N-t--1tylsulfamoyl)-≠-(
, 2-methylsulfonyl-≠-nitrophenylua")"
)-7-f phthol 20f/ was added. After stirring for 1 hour,
ice water! θOmQ, and recrystallize the precipitate with isopropyl alcohol-acetonitrile (/:l).
I got it.

Synthesis Example 14: Synthesis of dye-donating substance (19) λ-[j
-amino-no(no-methoxy-shethoxy)benzenesulfonylamino]-≠-t-phthalate hexatecyloki7phenol 3/, f/,! +-(3-chlorosulfonylbenzenesulfonyl 7mi/)-41-(J-methylsulfonyluder-nitrophenylazo/f'iN,N-Dissolved in 100ml of dimethylacetamide and added pyridine 2/mc.10 After stirring for 2 minutes, methanol/200 mQ was added and water/00 mQ was added.The precipitated resinous material solidified after a while, so it was taken out.
) Recrystallize the mixed yarn +/, j? Obtained.

Synthesis Example 15: Synthesis of Compound Example (4o) a) S. t
-Dihydroxy-Hiro-Synthesis of t-butylacetophenone t-Butylhydroquinone III was dissolved in acetic acid≠00m0, and boron trifluoride (B
Fa) was introduced for about 3 hours. After the reaction was completed, the mixture was poured into 1/l of ice water and the precipitated viscous solid was collected. One of these solids!
N - N a O H 4 0 0 mQ. The insoluble portion was filtered off. The ν solution was made acidic with dilute hydrochloric acid, and the precipitated crystals were collected, washed with water, and then recrystallized from aqueous methanol.

Number tryrtz%) Ib) 2,! Synthesis of -dihydroxy-g-t-butylacetophenone, oxime The nine ketone 212 obtained in a) above was dissolved in 70 m ethanol.
Q, Sodium acetate, 2≠2 and heated to dissolve, and while stirring, add hydroxylamine hydrochloride 2 to 70 mC of water.
．． The solution was added to the solution and refluxed for about 7 hours. After the reaction is complete! The precipitated crystals were poured into 0.0 ml of ice water and recrystallized from benzene-hexane.

Number position /71 (74%) c)1. -t-butyl-! -Synthesis of hydroxy-no-methylbenzoxazole The oxime/4Af obtained in b) above was dissolved in 100 mη of acetic acid, and dry hydrochloric acid gas was introduced while heating +JD, 1.
! Time passed quickly. After the reaction was completed, the mixture was poured into ice water for 200 hours, and the precipitated crystals were washed several times in the fc furnace.

Income Ta2 (70%) d) 4-i-butyl-! -hexadecyloxy-2
-Synthesis of methylbenzoxazole The benzoxazole obtained in C) above t. 1 in dimethylformamide
l! The solution was dissolved in water and stirred with anhydrous potassium carbonate lr2 and hecypdecyl bromide at 00C for 4 hours. After the reaction is complete, remove the inorganic substances and add methanol/! to the p liquid! .

mD. When the mixture was cooled on ice, crystals precipitated. By removing P from this, the title compound was obtained.

Collection tta'. f (Section 4.2) e) Synthesis of no-amino-1-1-butyl≠-hekitedecyloxyphenol hydrochloride iQd) Benzoxazole compound 7.

32 total ethanol) L/30 ml 11.1 concentrated hydrochloric acid. 2
It was run for 3 hours with 0m9. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were washed with water and then with acetone.

Number 6.29 (22%) f) Synthesis of Compound Example (40) The hydrochloride t2 obtained in the above e) and the sulfonyl chloride ♂, r2 of the dye having the following structural formula were mixed with dimethylacetamide jOml.
, pyridine≠ml was added, and the mixture was stirred at room temperature for 7 hours. After the reaction was completed, the precipitated crystals were poured into dilute hydrochloric acid and washed with water. After drying, the residue was purified by silica gel chromatography to obtain substantially 2.29/components of the title compound.

Dye sulfonyl chloride: SOα Synthesis Example 16: Synthesis of dye-donating container (42) Synthesis example 15 above (in di, J-t-butyl-!-hydroxy-nomethylbenzoxazole was replaced with J-t-
Octyl! 0-Hexadecylation was performed using -hydroxy-λ-methylbenzoxazole. Next, a color patch-providing substance (42) was obtained by the same treatment as in Synthesis Example xs (el and ff+).

The reducible dye-donor material releasing the diffusible dye of the present invention can be used at a certain range.

A generally useful saturation range is from about 0.01 mole to about V moles of dye-providing material per mole of silver in the silver halide or silver halide and organic silver salt oxidizing agent.

Concentrations particularly useful in the present invention are about 0.03 to about 1 mole per mole of silver.

In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is a so-called auxiliary chemical, which is oxidized by a silver halide or sulfate oxidizing agent, and its oxidized product has the ability to oxidize the reducing collagen in the dye-donating substance. It is.

Useful f... co-developers include hydroquinone, tertiary
Butyl hydroquinone! ,! - Alkyl-substituted hydroquinones such as dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Historically, methyl gallate, ascorbic acid, ascorbic acid derivatives, N.

Hydroxylamines such as N'-di(,2-ethoxyethyl)hydroxylamine, /-phenyl-3-pyrazolidone, Hiro-methyl-ghydroxymethyl-/-
Pyrazolidones such as phenyl-3-pyrazolidone, reductones, and hydroxytetronic acids are useful.

The auxiliary developer can be used within a certain degree range.

A useful concentration range is from 0.0/times mole to -2Q times mole relative to the organic silver salt oxidizing agent, and a particularly useful coating range is o, i
It is twice the mole to twice the mole.

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

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

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

Silver halide containing 1.2 or more halogen atoms is used in negative-looking WIJt materials, but in ordinary silver halide emulsions, the silver halide grains are completely mixed crystal 7 . For example, when measuring X-ray diffraction of the grains of a silver iodobromide emulsion, no patterns of silver iodide crystals or silver bromide crystals were found, and X-ray patterns were found at positions corresponding to the mixing ratio between the two. Turn is hail.

Particularly preferred silver halides in the present application are chloroiodide, silver iodobromide, and silver chloroiodobromide containing silver iodide crystals in their grains.

Such silver halide, for example, silver iodobromide, can be obtained by adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains without stirring, and then adding potassium iodide.

Silver halide grain size is from 0,007μm to 2μm
and preferably 0.00/μnl to 7 μm.

The silver halide used in the present invention is one of them! In addition, compounds such as sulfur resistant, selenium, tellurium, gold, etc. may be used.
Chemical sensitization may be achieved through the use of chemical sensitizers such as compounds such as platinum, noradium, rhodium or iridium, reducing agents such as tin halides, or combinations thereof. For more information, see “The Theory of the
Photographic Process” Hong version,
'1'', written by H. James, Chapter!/II-ta~/1,
It is described on page 9.

The silver halide and the dye-providing substance may be present in the same layer, or a layer containing silver halide may be provided on the layer containing all the dye-providing substances.

In the present invention, the photosensitive silver halide is preferably jOrq to 109/m2 in total in terms of silver.

In the photosensitive material of the present invention, when an organic silver salt is added to the photosensitive material, the maximum density of the image becomes high, and the reaction rate is also fast. salt, and when heated in the presence of photosensitive silver halide to a temperature above 0'C, preferably above 10°C,
A silver image is formed by reacting with the above-mentioned image-forming substance or, if necessary, with a reducing agent coexisting with the image-forming substance.

Examples of such common salt intoxicants 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 single-group carboxylic acids include silver salts of behenic acid, silver salts of stearic acid, silver salts of oleic acid, silver salts of lauric acid, silver salts of capric acid, copper salts of myristic acid, and silver salts of palmitic acid. salts, silver salts of maleic acid, silver salts of fumaric acid, silver salts of tartaric acid, silver salts of furoic acid, silver salts of linoleic acid, silver salts of linoleic acid, silver salts of oleic acid, silver salts of adipic acid, sebacin These include silver salts of acids, 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 groups are also effective.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, silver salts of 3゜terdihydroxybenzoic acid, silver salts of 0-methylbenzoic acid, m-
Silver salt of methylbenzoic acid, silver salt of p-methylbenzoic acid, 2
．． Silver salts of substituted benzoic acids, such as silver salts of hiro-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid, silver salts of gallic acid, silver salts of tannic acid, and silver salts of phthalic acid. Salt, silver salt of terephthalic acid, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of pyromellitic acid, US Patent No. 3.7g! , silver salts such as 3=carboxymethyl-gumethyl-guthiazoline-corchion described in No. 30, US Pat. No. 3,33o.

Examples include silver salts of aliphatic carboxylic acids having a thioether group, which are described in the specification of No. 4AJ.

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

Example t tri 3-mercapto-gouphenyl-/2
Hiro-triazole silver salt, normercaptobenzimidazole silver salt, normercapto j-aminothiadiazole silver salt, 2-mercaptobenzthiazole "'
+111, -2 Silver salt of (S-ethyl glycolamide) benzthiazole, S-alkyl (72 to 2 carbon atoms)
．． 2 alkyl 8) Silver thioglycolate etc. JP-A-Sho≠
Silver salt of thioglycolic acid described in No. 1-21, 22/,
Silver salts of ditheocarboxylic acids such as silver salts of dithioacetic acid, silver salts of thioamides, tercarboxy-/-methyl-λ-7
silver salt of enyl≠-thiopyridine, silver salt of mercaptotriazine, silver salt of λ-mercaptobenzoxazole,
Silver salt of mercaptooxadiazole, US Pat.

/JJ, J7! Silver salts described in the specification, for example /.

λ, 3-amino-! which is a 4t-mercaptotriazole derivative. -Silver salt of benzylthio/, ≠-triazole, U.S. Patent No. 30/, 47, No. 3
-(Cocarboxyethyl)-μm methyl-μm thiazoline-A silver salt of a thione compound such as a silver salt of a cothion.

In addition, there are silver salts of compounds having imino h (for example, equity 111), Gugu J O, 270, same≠tar/I
! '17-/ Silver salts of benzotriazole and its derivatives described in Publication A, for example, silver salts of alkyl-optional benzotriazoles such as silver salts of -benzotriazole and silver salts of methylbenzotriazole, and silver salts of j-chlorobenzotriazoles. (such as base salts), silver salts of rogen-substituted benzotriazoles, silver salts of carbimidobenzos such as silver salts of butylcarboimidobenzotriazole), silver salts of IJ azoles,
US%#'fll, J-20゜7oy-@Details 4 mouths self-published 1. -1 Hiro-triazole, t-) 1-tetrazole silver salt, carbazole complex salt, saccharin! l1lJ
There are salts, complex salts of imidazole and imidazole derivatives, etc.

Also, Research Disclosure■01170゜ri7
Organometallic salts such as silver salts and stearic acid described in Za6f-June-no-ya 170 Kota are also organometallic salt oxidizing agents that can be used in the present invention.

The heat development process a in the knife heat of the present invention is not fully clear (1), but it can be considered as follows.

When the photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver halide. About this-,'r.

“ 'l” be 'l'heo by James if,
ry of thePbotograpbic
Process” 3rdEdition ll
/) 10s negative to 1arB.

"By heating the CF material, the reducing agent, in the case of the present invention, the dye-donating agent, is oxidized with the help of the alkaline agent released by heating, and the I' etc. 14; nucleus is used as a catalyst. , silver halide still reduces silver halide and silver salt oxidizing agent to produce metallic silver, which itself is polymerized. al (drug (dye release aid in the present invention)) attacks and the dye is released.

The silver halide and organic silver salt oxidizing agent that serves as the starting point of the traced image are
In reality, it is necessary to exist at a good effective distance.

Therefore, it is desirable that the silver halide and (a) chloride oxidizing agent exist in the same layer.

It is also possible to mix silver halide and an organic chloride oxidizing agent, which are formed separately, and apply it by mixing the solution. It is also effective to mix the halogen-containing compound into the prepared organic silver salt oxidation series with γ, 1≧
In addition, a method of forming halogen silver with silver from an organic silver salt oxidizing agent is also effective.

For details on how to make these silver halides and organic silver salt oxidizing agents, and how to mix both, please refer to Rizutitei R Taroja No. 70.2, JP-A Showa 0-32-2, and JP-A Showa 0-32-2. Evening/-≠, 2! , 2? , USA) 1zeJii'F 3+
700, Guj♂ν”, Tokukai Akira <z Turf! , 22 Hiroyuki,
It is described in JP-A-30-77.2//y.

In this light + r horn, the organic silver salt oxide R11 used as necessary is 200 mol JJ per 1 mol of silver halide, and the photosensitive silver halide and the oxidized silver salt 1 ゜Total in terms of silver in the agent! Omg~10i
/ / m is facing.

41 examples of 1'-1-silver halide of Mokuuniaki's oxidizing agent and the following binder are used.

One sheet of the ma/ko dye-bearing crop 'ei is also placed in the following binder.

The binder &J used in the present invention can be used alone or in combination. A hydrophilic binder can be used as the binder. '/1
A7J (Typical binders include hydrophilic colloids with translucent color, such as gelatin, gelatin derivatives, cellulose derivatives, and polysaccharides such as starch and gum arabic. These include natural substances and synthetic salt compounds such as polyvinylpyrrolidone, a water-soluble polyvinyl compound derived from acrylamide polymers.Other synthetic polymeric compounds, especially in the form of latexes, increase the dimensional stability of photographic materials. There are dispersed vinyl compounds that can

Various dye release aids can be used in the heat-developable color photosensitive material of the present invention. A dye release aid is one that can nucleophilically attack a dye-donating substance oxidized by a silver halide or organic silver salt oxidizing agent and release a diffusible dye. A water releasing compound is used.

Among these dye release aids, the base or base release agent not only promotes the total dye release but also promotes the redox reaction between the silver halide or organic silver salt oxidizing agent and the dye donating substance. Particularly useful.

Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines,
Mention may be made of N-hydroxyalkyl-substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanes. Also, US Patent No. λ, ≠10. The Hirohiro Oto issue contains betaine tetramethylammonium iodide and diaminobutane dihydrochloride as disclosed in U.S. Patent No. 3.
Organic compounds containing amino acids such as urea and t-aminocaproic acid are described and useful in the t,≠IIL column. The base releasing agent is one that releases a salt releasing component upon heating. A typical example of a base release agent is the British patent! Pi
, described in the YT issue. Preferred base release agents are salts of carboxylic acids and organic bases; useful carboxylic acids include trichloroacetic acid, trifluoroacetic acid; useful bases include guanidine, lysine, morpholine, p-toluidine, d-picoline, and the like. . U.S. Patent No. 3゜22
Guanidine trichloroacetic acid described in Nos. 0 and ♂<2+ is particularly useful. Tokukai Akira again! 0-. Aldonamide well 1 described in the 12t2 publication is preferably used because it decomposes at high temperature to produce a base.

A water-releasing compound is a compound that decomposes during thermal development to release water and replaces a compound that has a vapor pressure of 70 1-rel or more at a temperature of 100 to 00°C. These compounds are particularly known in the transfer printing of textiles, and include NH4F described in Japanese Patent Publication No. ShojO-41'3♂2.
e(S04)2.12H20 and the like are useful.

These dye release aids can be used in a wide variety of ways. 17100 to 70 times molar ratio to silver, especially //2
It is preferable to use it in a range of 0 to 2 times.

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, isothiuroniums represented by 2-hydroxyethyl isothiuronium and trichloroacetate described in U.S. Patent No. 3,3θ/, t7g', and 7. Bisisothiuriums such as I-(3,t-dioxaoctane)his(intiuronium trifluoroacetate), West German Patent No. 2
．． /ls2,7/ Thiform compounds disclosed in Ko No. 1, λ-amino-λ- described in U.S. Patent No. 0/2,21rO
Thiazolium compounds such as thiazolium trichloroacetate, λ-aminoterbromoethyl-2-thiazolium trichloroacetate, US%? Hu P,
oto,≠Bis(,2-amino-λ-
Thiazolium) methylene bis(sulfonylacetate)
, compounds having α-sulfonylacetate as the acidic moiety, such as λ-aminocorchiazolium phenylsulfonylacetate, US Pat. No. a, otr♂.

! 5> Compounds described in No. J and having a no-carpoxyl-rupoxyamide moiety as the acidic moiety are preferably used.

These compounds or mixtures can be used in a wide variety of ways. It is preferably used in a molar ratio of 17,100 to 70 times, particularly 7,720 to 2 times, relative to silver.

The heat-developable color photosensitive material of the present invention can contain a heat solvent. As used herein, 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 examples of the thermal solvent include compounds that can serve as solvents for developing agents, and compounds with high dielectric constants that are known to accelerate the physical development of silver salts. Useful thermal solvents include U.S. Pat. No. 3,3≠7.
67J numbered polyglycols such as average molecular weight/
! 00S-λoooo polyethylene glycol, derivatives such as oleate ester of polyethylene oxide, beeswax, monostearin, high dielectric constant compounds having -802-1-〇〇- groups, such as acetamide,
Succinimide, ethyl carbamate, urea, methyl sulfonamide, ethylene carbonate, U.S. Patent No. 3
゜Otsu 7. the law of nature! Polar substances described in issue 2, lactone of ghydroxybutanoic acid, methylsulfinylmethane, tetrahydrothiophene-7,/-dioxide, Research Disclosure magazine / 7, December issue 2t, -2g, /, 10- Decanediol, menal anisate, biphenyl perate, etc. are preferably used.

In the case of the present invention, the color-donating substance is colored;
Although it is not so necessary to incorporate irradiation and/or ration-preventing substances or dyes into the light-sensitive material, in order to further improve the sharpness, it is recommended to '-, 3
7F J issue and US time & FFi 3+ “3, ri 2/
No., same λ,! 27. rza No. 3, same λ.

Written on each statement such as JLS, No. 172, etc.
Filter dyes can also contain IP-absorbing materials. Preferably, these dyes are thermally decolorizable, such as U.S. Pat. , No. 00, No. 3, 6/Evening, 4
Dyes such as those described in No. 4J, No. 2 are preferred.

The photosensitive feed according to the present invention may optionally contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a galvanic layer, a protective layer, an intermediate layer, AHIfJ,
It can contain a foil p layer and the like. Various additives include “Re5earch Disclosure” Vel
/70 1. Additives such as plasticizers, sharpness improving dyes, A)
(Dye, sensitizing color chart, matting agent, surfactant, fluorescent whitening agent, anti-fading agent, etc.)

Similar to the heat-developable photosensitive material according to the present invention, a protective layer, an intermediate layer,
For the undercoat layer, pack layer, and other W4, each coating solution is mixed with M solution and applied by dipping method, air knife method, curtain coating method, or hopper coating as described in U.S. Patent No. 3,6♂/2 tag specification. The photosensitive +A material can be prepared by sequentially coating the base material on a support using various coating methods such as the above-mentioned coating method, and drying it.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat.

Various exposure means can be used for the heat-developable photosensitive material according to the present invention. The latent image is obtained by imagewise nWS of radiation including visible light. In general, the light sources used for normal color printing, such as tungsten lamps, halogen lamps such as iodine lamps, xenon lamps, lasers), and CRT)'e; sources, fluorescent tubes, and diodes Canned food etc. can be used as a source.

As an original drawing, lines such as technical drawings are used! Not only the ll image, but also the photo with the gradation corrected! II image may also be used. It is also possible to photograph portraits of people and landscapes using a camera. The engraving from the original drawing may be printed in close contact with the original, or it may be subjected to reflective printing, or it may be enlarged and printed.

Images taken with a video camera or image information sent from a television station are sent directly to a CRT or FOT, and this image is formed on a thermal image material using a close contact or a lens, and then printed. is also possible.

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. This LED is
It is difficult to create something that emits blue light in one effect. In this case, to reproduce a color image, three LEDs that emit green, red, and infrared light are used, and the parts of the sensitive material that are exposed to these lights emit yellow, magenta, and cyan dyes, respectively. Just design it.

That is, the green-sensitive portions (layers) should contain a yellow dye-providing substance, the red-sensitive areas (shields) should contain a magenta dye-providing substance, and the infrared-sensitive areas (layers) should contain a cyan dye-providing substance. Yes. Other combinations are possible depending on your needs.

In addition to the above method of directly counting or projecting the original image, it is also possible to put the original image illuminated by a light source into the memory of a computer, etc. using a light-receiving element such as a Kusei tube or CCU. After applying so-called image processing to process the information as necessary, this image information is reproduced on a CRT and used as an image-like light source.Based on the processed information, three types of LEDs are directly activated. There is also a method of exposing it to light.

After birth of a heat-developable color photographic element, the resulting latent image is, for example, about 0° at about θ0C to about 2jθ0C! The element can be developed by generally heating the element at elevated temperatures, such as from seconds to about 300 seconds. As long as the temperature is within the above-mentioned range, either high or low temperatures can be used by increasing the heating time or by using field pongee. Especially about /1
A temperature axis of 00C to about /loc is for the south. 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 υ color image by thermal development is thermal diffusion transfer of a hydrophilic diffusible dye. For this purpose, the heat-developable color light-sensitive material contains on a support at least a silver halide, a 4i% silver salt oxidizing agent, a dye-donating substance which is also a speeding agent, a hydrophilic binder, and a color patch release aid. It is composed of a photosensitive layer (1) and an image-receiving layer (11) capable of receiving the hydrophilic and diffusible dye formed by layer (1).

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 (It) 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 (
11) can be torn off.

However, in another specific method, after imagewise exposure, a 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, "a lower temperature than the development temperature" includes room temperature, and preferably ranges from room temperature to a temperature about 4 to'c lower than the heat development temperature. For example, heat development temperature/2o ac, transfer temperature to
'c etc. are equivalent.

In addition, only the photosensitive layer (1) is imagewise exposed, and then the image receiving i@
There is also a method in which (II) is combined and uniformly heated and developed.

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

The polymer mordants used in the present invention include polymers containing secondary and tertiary amine groups, polymers containing heterocyclic moieties, and polymers containing these 4A-class cation groups, with a molecular weight of 000 to 20°. , ooo, especially 10,0
00 to evening o, oooO thing.

For example, American-ness. 1-F2. Tag, j otohiro, same λ.

4t♂4L, No. 4130, same 3. /≠g, Otsu/issue, same 3.7! Vinylpyridine polymers and vinylpyridinium canone polymers disclosed in U.S. Pat. Z2 evening, 22g issue, 39g! ri, 094, same≠, /, 2♂.

Evening 3g issue, British special i [/, 277, t/l! Polymer mordants capable of crosslinking with gelatin, etc., as shown in No. R3, et al.; US d13. Rijtl, Tata! issue,
Same 2 7; 2/, ♂ No. 52, Same λ, 7 Riza, No. 063,
Tokukai Shosy-//! ra2r issue, same! ≠−lgu! j2!
Aqueous sol type mordant disclosed in US Pat. No. 1, No. 617-7.2t027, etc.: US Pat. ♂r, or
Water-insoluble mordant disclosed in No. g Specification:;
A reactive mordant capable of forming a covalent bond with a dye disclosed in U.S. Patent No. 33, etc.;
No. 3, 7g and Zatata No. 3, 6≠2. ≠g2
J14F, same 3rd. ≠tza, No. 706, same 8g3. Ta!
7. Otsu No. 6, same No. 3, 27/, /≠7-bow, same No. 3,
No. 277.1IIr, Unexamined Japanese Patent Application Shoj 07/Jj
, No. 2, same, t 3-303.2r, same, t2-11
Examples include mordants disclosed in Japanese Patent No. 552g, Japanese Patent No. 3-72 Evening, and Japanese Patent No. 13-102.

and other U.S. Patents λ, t7j, No. 3/, same.

112, /j4 specification may also be mentioned.

Among these mordants, those that are difficult to move from the mordant layer to other layers within the suspension layer are preferred, such as those that crosslink with the matrix such as gelatin, water-insoluble mordants,
and aqueous sol (or latex dispersion) type mordants can all be used.

Particularly preferred polymer mordants are shown below.

(1) Groups that have j-class ammonium & and can be covalently bonded to gelatin (for example, aldehyde release, chloroalkanoyl method, chloroalkyl group, vinylsulfonyl group, pyridinium propionyl group, vinyl carbonyl, so alkylsulfonoxy group) For example, (2) a copolymer consisting of a repeating unit of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated monomer, and a crosslinking agent (e.g. d: hisalkanesulfonate, bisarenesulfonate) reaction product with.

RI Rt:H, at least λ alkyl groups may be bonded to form a petero ring.

X: anion (the above alkyl groups and aryl groups include substituted ones) (3) Polymer represented by the following general formula X: about 0. ．． 2j to about J Morti y: about θ to about O Molti 2: about 10 to about Tata Morti A: monomer having at least λ ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated monomer Q: N , PR1, R2, 几3: Alkyl active, cyclic hydrocarbon cell, and at least two of Rt to R3 may be combined to form a ring. (These groups or ring devices may be substituted.) , 41 Copolymer consisting of tar, tb+ and +c+ al X: Hydrogen atom, alkyl group or halogen atom (alkyl group may be substituted) lb ) Nisder acrylate (C) Acrylonitrile (5) A water-insoluble polymer having //3 or more repeating units represented by the following general formula R1, R2, ) La: Each represents an alkyl group,
) The total number of carbon atoms in L1 to R3 is 7 or more. (The alkyl crystals may be substituted.) X: Anion As the gelatin used for the mordant j, various known gelatins can be used. For example, it is also possible to use gelatin produced using different gelatin production methods, such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. If necessary, it can be desalted before use.

1) The mixing ratio of the light polymer mordant and gelatin and the amount of the polymer mordant are determined by the W' of the dye to be mordanted.
A person skilled in the art can easily determine the mordant/gelatin ratio depending on the type and composition of the polymer mordant, the image forming process used, etc.
/, 20 (bundle ratio), θ for mordant application,! ~19/
It is preferable to use it in m2/).

The image receiving layer 1rJ (II) may reflect a white reflective layer. For example, a layer of titanium dioxide dissolved in gelatin can be placed on top of a mordant layer on a transparent support. The divalent titanium layer forms a white opaque layer, and a reflective color image can be obtained by viewing the transferred color image from the transparent support side.

A typical image receiving material for magnification 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 to transfer the dye from the photosensitive layer to the image-receiving layer. As the transfer solvent, water and a basic aqueous solution containing sodium hydroxide, potassium hydroxide, and an inorganic alkali metal salt are used. Also used are low-boiling solvents such as methanol, N,N-dimethylformamide, acetone, and diisobutylketone, and mixed solutions of these low-boiling solvents and water or basic aqueous solutions. Transfer solvent is image receiving 1
- may be used by moistening it with a solvent, or it may be incorporated into the material as crystal water or microcapsules.

Example 1. 1 Lt09 of gelatin and 24 g of KBr are dissolved in 3000 mQ of water. Keep the solution at to'c and stir.

Next, a solution of silver nitrate 3K2 dissolved in water θOm9 was added to the above solution over a period of 70 minutes.

Then, add 2 liters of KIJ and Jf dissolved in 100 ml of water.
Add in minutes.

The pH of this silver iodobromide emulsion is adjusted, and the emulsion is precipitated to remove excess salt. After that, adjust the pH to t and θ and the yield will be 4'o.
An OP silver iodobromide emulsion was obtained.

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

A dye-donating substance having the following structure is used as a 109 (t)CH 9 surfactant, and sodium succinate-1-ethyl-hexyl ester sulfonate is used as a surfactant. tf, toIJ-cresyl phosphate (TCP) was weighed to 20 g, 20 rne of cyclohexanone was added, and the mixture was heated and dissolved to about t'c.

After stirring and mixing this solution and 100 ml of 10% gelatin solution, 10,0001 L of gelatin was mixed with a homogenizer for 70 minutes.
Disperse in PM. This dispersion liquid is called a dispersion of a dye-providing substance.

Next, a method for preparing a photosensitive coating will be described.

(a) A silver iodobromide emulsion! ?
(b) Dye-donating PA dispersion 3. Sake 2 (C1 guanidine trichloroacetic acid 220μ dissolved in methanol 2mQ lack 7f (dl) 107% aqueous solution of the present compound (4)
+al~(d) of comQ or higher were mixed, heated and dissolved, and then applied to a wet film thickness of 60 μm on a polyethylene terephthalate film having a thickness of iroμ. After drying this coated sample, it was imagewise exposed for 7 c seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated uniformly for 30 seconds on a heat block heated to 7200C. This sample is designated as A.

Next, remove the compound of the present invention in tdl and replace it with water λmQ
A sample prepared by adding , was used as B, and the same operation was performed.

Next, a method for forming an image-receiving material having an image-receiving layer will be described.

Poly(methyl acrylate-N, N, N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) 109 is dissolved in 200 mQ of water,
/θti lime-treated gelatin 201100f/ was mixed uniformly. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 20 μm. After drying, this sample was used as a darkening material.

After soaking the image-receiving material in water, the above-mentioned heated photosensitive material A,
B-i, the membranes were stacked so that their surfaces were in contact with each other.

After heating on a s'o 0c heat block for 6 seconds, the receiving material was peeled off from the light-sensitive material, and a negative magenta color image was obtained on the receiving material. The accuracy of this negative image was measured using a Macbeth transmission gravel meter ('rD-tog), and the following results were obtained.

Boiled sample Maximum concentration Minimum concentration A (invention) /, tg O0/7 B (comparison) 0,33 0. /l (Indicates the concentration with respect to green light.) The above results show that the compound of the present invention provides an extremely high concentration.

Example 2゜Benzotriazole t,! 2 and gelatin 102 parts water 10 parts
Dissolve at 100O. Keep this solution to oc and stir. Next, a solution of silver nitrate r, ty dissolved in 100 mQ of water is added to the above solution for 2 minutes.

Next, add potassium bromide/, 22 to water! Add the solution dissolved in OmQ for 2 minutes. The deflated emulsion is pH adjusted and settled to remove excess salt. Then the pH of the emulsion was adjusted to t,
Adjusted to o. The yield was 2009.

The photosensitive coating was prepared as follows.

la) Bensito, 1,1 azole silver emulsion containing photosensitive silver bromide 109 (bl
Dispersion of dye-donating substance 3.59 (same as Example 1) (C) A solution of 250 ml of guanidine trichloroacetic acid dissolved in 2 m9 of ethanol (dl) 10% aqueous dispersion of the compound (4) of the present invention -
m9 or more (al~(dl) was mixed, and then Example 1
The same operations and processing were performed. The results are shown below.

Sample concentration Maximum concentration Minimum concentration C (invention)/, rit O,/8' D (comparison) 0.3! 0. /j (green) indicates the concentration relative to shi. ) Example 3 The following results were obtained by carrying out exactly the same operation as in Example 2, except that the following compound was used in place of compound (4) of (di) of sample tc+.

The above results show that the compounds of the present invention are effective in providing high maximum concentrations with low minimum concentrations.

,1 A preferred embodiment is as follows.

1. Photosensitive silver halide, organic silver salt oxidizing agent, hydrophilic binder, dye release aid, silver halide or organic silver salt oxidizing agent that is reducible to the support and releases hydrophilic dye. A heat-developable color photosensitive material characterized by containing a dye-donating substance and at least one cationic compound having a pyridinium group.

2. A feed in which the cationic compound having a pyridinium group according to the claims and the preceding paragraph is represented by the following general formula.

(1) (II) A is a methylene chain, -0-1-l<HCO-1-OCO
-1-C14-Phenylene and its products■ Hail atomic groups consisting of each combination.

B is a saturated or unsaturated alkyl group, an aralkyl paper, or a hydrogen atom.

a and it' represent a hydrogen atom or a carbon atom/~j alkyl group.

X-1 represents a divalent anion, and Y- represents a heptavalent anion.

3. The diffusion transfer thermal mass color photosensitive material as claimed in the claims, which contains a reducing agent for an organic silver salt oxidizing agent, if necessary.

4. A heat source as claimed in the claims, characterized in that the dye-donating property capable of reducing a silver salt oxidizing agent and releasing a hydrophilic diffusible dye is represented by the following general formula (1). Developed color feeling 5'6 material.

R, -8O2-D (1) Here, R represents a reducing substance that can be oxidized by an organic silver salt oxidizing agent, and D represents an image-forming dye.

5. A heat-developable color characterized in that the reducing dye in the dye-donating material R-802-D of item 4 has an oxidation-reduction magnetic potential of 2 V or less with respect to a saturated calomel electrode. photosensitive material.

6. A heat-developable color feeling yt characterized in that the acceptability property R in the dye-donating storage 'R-802-1) of item 4 is represented by the following general formulas (II) to (IK); material.

01-] 0) f H- 11- 1 R2 Here, 几1 and R2 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group, and an alkyl group. Sulfonylamino number, arylsulfonylamino number, aryloxyalkyl I! +(, alkoxyalkyl group, N-1 substituted carbamoyl A, N-substituted sulfamoyl paper, halogen atom, alkylthio number, represents a device 11!, selected from arylthioya, and these M11
The alkyl group and aryl group moiety in NM are further alkoxy, ), rogen, hydroxy, cyan, acyl, acylaminotachibana, substituted carbamoyl, substituted sulfamoyl, alkylsulfonylamino, arylsulfonylamino, and substituted ureido. It may also be substituted with carbalkoxy.

7. The D part in the dye-donating substance R-802-D of item 4 is hydrophilic azo, azomethine, anthraquinone, naphthoquinone, styryl, nitro, quinoline, carbonyl,
A heat-developable color photosensitive material as claimed in the claims, characterized in that it is a phthalocyanine dye.

8. A heat-developable color material, characterized in that the dye-releasing aid claimed in the claims is a base, a base-releasing agent, or a water-releasing compound.

9. A heat-developable color photosensitive material, characterized in that the reducing agent as claimed in the claims is capable of oxidizing the reducing group R as defined in claim 3 in its oxidized form.

10. A heat-developable color photosensitive material, wherein the organic silver salt oxidizing agent according to the claims is a silver salt of a carboxylic acid derivative or a nitrogen-containing heterocyclic compound.

11 Thermal developable color i+i! characterized in that the hydrophilic binder in the claims is gelatin and gelatin derivatives! )'c material.

12.C1 released diffusible dye in the claim box,
An image forming method characterized in that the image is transferred to an image-receiving material using water or a salinity-prone aqueous solution.

13 Transfer image 1 using a mordant on the image-receiving material in Section 12
An image forming method characterized by 14J images of a house.

14. Thermal developable color effect, characterized in that the organic silver salt oxidizing agent of item 10 is a silver salt of a nitrogen-containing heterocyclic compound)
material.

Claims (1)

[Claims] a hydrophilic binder, a hydrophilic binder,
1. A heat-developable color photosensitive material characterized by containing a dye-releasing aid, a reducing dye-donating agent that releases a hydrophilic dye, and at least one cationic compound having a pyridinium group.