JPS59157636A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain a bright color image with a simple method by migrating the movable hydrophilic dyes released by heating to a dye fixed layer in the stage of contg. substantially no water. CONSTITUTION:A photosensitive material have the two binder layers, adjacent to each other, contg. photosensitive silver halide and/or dye donative materials which exhibit a reducing property with photosensitive silver halide and release hydrophilic dyes by reacting with the photosensitive silver halide when heated, on a base. The photosensitive material in which the molar amt. of the dye donative material coated on he binder layer A on the side where the light for exposing comes in of the two binder layers is smaller than that of the other binder layer B is heated in the stage of contg. substantially no water simultaneously or after the exposing to form the movable dyes like an image. The photosensitive silver halide is contained in either layer in the above-described binder layer group and a satisfactory result is obtd. if the ratio between the amt. of the silver coated on the binder layer A/that on the binder layer B is larger than 1/10.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new method for forming dye images by heating in a substantially water-free state.

The present invention further provides a novel method containing a dye-donating substance that reacts with a photosensitive silver halide oxidizing agent and/or an organic silver salt oxidizing agent by heating Vc in a substantially water-free state to release a hydrophilic dye. It relates to photosensitive materials.

The present invention particularly relates to a new method for obtaining a complete dye image by transferring dyes released by heating to a dye fixing layer.

Photographic methods using silver halide have been used most widely since they have superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. has been developed.

Heat-developable photosensitive materials are well known in the art, and for more information on heat-developable photosensitive materials and their processes, see, for example, Basics of Photographic Engineering (published by Corona Publishing Co., Ltd. in 1999)! ! Page 3 ~ J'11
Page, 1971 ≠ Month issue video information '70 page, Neble
tts Handbook of Photography
y and Reprography 7th Ed.

(Van No5trand Re1nhold
Company), pages 32-33, U.S. Patent No. 3. /!
Ko, 2θ4t−+#j.

No. 3, 30/, t7r, j, 392.020,
No. 3', No. 4I-17,073: British Patent No. 1. /31
．． No. 10, No. 1. /1,7,777, and Research Disclosure magazine, June 71, page (RD-17o2).

Many methods have been proposed for obtaining color images using a dry process. Regarding a method of forming a p-color image by combining an oxidized developer and a coupler, U.S. Pat. , U.S. Patent No. 3.74/,-70, p-amine phenolic reducing agents are described in Belgian Patent No. 102. Sulfonamide phenol reducing agents were also reported in the Evening/Return issue and Research Disclosure Magazine/Re7I issue J/, JJ Page, as well as U.S. Percentage No. ≠, 02/.

In the λ≠θ issue, a sulfonamide phenol reducing agent and 4
A combination with an equivalent amount of turnip is proposed.

However, in this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem that the color image becomes cloudy. 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, but it is necessary to distinguish between unreacted materials and the dye. It has the disadvantage that it is not easy to transfer only the dye.

In addition, a method of introducing nitrogen-containing heterocyclic haze into the dye, forming a silver salt, and releasing the silver strands by heat development was published in Research Des Closure Magazine / 7♂°! Monthly issue zp-~ttr page RD-1t, 9ttVc is listed. With this method, it is difficult to suppress the release of dye in areas that are not exposed to light, and a clear image cannot be obtained, so it is not a common method.

Further, regarding the thermal silver dye bleaching method KL and the method of forming positive color images, for example, see Research Disclosure magazine/Re7, p.
33), the same magazine li 7 in 2018/February issue l≠～/yo page (R
D-/sλ-7), U.S. Patent No. G, Co3! , No. 57, etc., describe useful dyes and bleaching methods.

However, this method requires extra steps such as stacking and heating an activator sheet to accelerate the bleaching of the dye, and the resulting π-color image may coexist during long-term storage. Methods for forming color images using O. yco pigments, which have the drawback of gradual reduction and whitening in free castings, are disclosed, for example, in U.S. Patent No. 3. Ri II.

No. 565, No. ≠, o2. z, described in tt7-@. However, with this method, it is difficult to stably incorporate the leuco dye into the photographic dye, and the dye gradually turns Kflt color during storage.

The present invention provides a new method for forming deep dye images by heating in a substantially water-free state, and overcomes the drawbacks of hitherto known dye images. be.

That is, an object of the present invention is to provide a new image forming method in which a mobile hydrophilic dye, which is released upon heating, is transferred to a dye fixing layer in a substantially water-free state to obtain a dye image. It is something to do.

The object of the present invention is to provide a new photosensitive material containing a dye-donating substance that releases a mobile dye by reacting with photosensitive silver halide in a substantially water-free cage upon heating. It provides:

Another object of the present invention is to provide a heat-developable color photosensitive material which has high sensitivity and reduces deterioration of sensitivity over natural aging.

Another object of the invention is to provide a simple method (KLF) for obtaining sharp color images.

The object of the present invention is to coat a photosensitive silver halide film on a support.
or a layer of λ mutually adjacent binders containing a dye-donating substance which is reducible to photosensitive silver halide and which reacts with the photosensitive silver halide upon heating to release a hydrophilic dye. Among these λ binder layers, the coating molar amount of the dye-providing substance in the binder layer (A) on the side into which the exposure light enters is smaller than that in the other binder layer (B). The coating amount in one layer of the above-mentioned λ binder is achieved by a method of heating the photosensitive material at the same time as exposure or after exposure in a state substantially free of water to form a movable dye in the form of an image. The difference may be any amount as long as the effect of the present invention of high sensitivity can be achieved, but if the coating molar amount of the binder layer (A)/coating mole amount of the binder layer (B) is ≠/2. The effect of the present invention can be clearly recognized, and 3/7 is more preferable, and even 0//0 is enthusiastically effective.

When there are three or more mutually adjacent binder layers, the above coating amount relationship may hold seven or more, and n mutually adjacent binder layers.

When there is one layer of matching binder, a maximum of n-7 can be formed. Also, if there are three or more binder layers adjacent to each other,
When the force of the light enters, it is desirable that the relationship of the present invention is established between two adjacent binder layers as close as possible to the side from which the light enters. When the binder layer corresponds to the above-mentioned binder layer (A), desirable effects are exhibited.

The effects of the present invention are particularly remarkable when adjacent λ binder layers in which the relationship of the present invention is established contain dye-donating substances that release dyes of the same color.

In this case, the above-mentioned preferred embodiments hold true in adjacent binder layers containing dye-providing substances from which dyes of the same color are released.

It is possible to have any number of same-color dye-donating single-layer groups on a support, which are related to the present invention, but since three subtractive primary colors are often used to express various colors, there are three. It's advantageous.

The photosensitive silver halide is contained in any layer in the binder layer group. In a single layer of two adjacent binders that have the relationship of the present invention, the binder (B) layer can be formed without containing photosensitive silver halide, and in this case, it can be made highly sensitive. Furthermore, when the coating amount of photosensitive silver halide in the binder ('A) layer is larger than that in the binder CB) layer, the degree of high sensitivity is particularly significant, which is advantageous. However, the present invention is not limited to this, and if the ratio of the amount of coated silver in the binder layer (A)/the amount of coated silver in the binder layer (B) is larger than / / / OJ, the effect of increasing the sensitivity of the present invention will be apparent. I can admit it.

In the present invention, adjoining refers to a case in which the above-mentioned λ binder layers are in direct contact with each other, or a binder layer that does not contain either photosensitive silver halide or a dye-donating substance to the extent that they can have a chemical relationship when heated. This includes the case where they are adjacent to each other through a layer (for example, a very thin layer, preferably θ, ≠ μ or less, a layer made of gelatin, or a material that can be melted by heat).

The dye image of the present invention refers to a multicolor or monochrome dye image, and the monochrome image in this case includes a monochrome image obtained by mixing two or more types of dyes.

In the image forming method of the present invention, a silver image and a movable dye can be simultaneously provided in the area corresponding to the silver image by simply heating after image exposure. That is, in the color image forming method of the present invention, imagewise exposure is performed, and heat development is performed in a state substantially free of water.
& An oxidation-reduction reaction occurs between the original silver halide and the reducing dye-donating substance, producing a silver image in the exposed area. In this step, the dye-donating substance is oxidized to form an oxidant, so that a hydrophilic mobile dye is released, and in the exposed area a silver image and a mobile dye are obtained. At this time, the presence of a dye release aid accelerates the above reaction. A rainbow dye image is obtained by moving this mobile dye to, for example, a dye fixed layer. The above is a case where a negative type emulsion is used, but when an autopositive emulsion is used, the process is the same as when a negative type emulsion is used, except that a silver image and mobile dye are obtained in the unexposed areas. be.

In the present invention, it is believed that the diffusivity of the rainbow dye-providing substance increases upon heating, and reaches within the action range of the halogenated moiety in the silver halide emulsion layer, causing a redox reaction.

In this case, the diffusion of the rainbow dye-providing substance can be promoted by using a hot solvent, which will be described later.

The polymerization-reduction reaction of the present invention between the photosensitive silver halide and the dye-donating substance and the subsequent dye-releasing reaction are characterized in that they occur at high temperatures and in a dry state substantially free of water. be. Here, "under high temperature" refers to a temperature condition of to0c or higher, and "dry state containing substantially no water" refers to a state in which the system is in equilibrium with moisture in the air, but there is no supply of water from outside the system. This state of affairs is 'The theo'
ry of the photography
process′′ +thEd, (Edited
by 'l', ) (, James, Macmilla
n) Described on page 37≠. It is 7 in the 10th edition that a sufficient reaction rate is shown even in a dry state that does not substantially contain water.
This can be confirmed by the fact that the reaction rate of the sample dried under vacuum for days did not decrease.

Conventionally, the dye release reaction has been thought to be caused by attack by a so-called nucleophile, and is usually carried out in a liquid with a high pH of pHlo or higher. However, it is unexpected that one aspect of the present invention shows a high reaction rate at high temperatures and in a dry state substantially free of water. Furthermore, the dye-donating substance of the present invention can undergo an oxidation-reduction reaction with silver oxide without the aid of a so-called auxiliary developer.

this is.

This is an unexpected result based on previous knowledge of wet development at temperatures around room temperature.

In the present invention, the use of an organic chain salt oxidizing agent is advantageous in that it accelerates the development of silver halide and the dye release reaction during heating and increases the color density.

When using this, the above effects are exhibited no matter which layer it is added to.

The reducing dye-donating substance that releases the hydrophilic diffusible dye used in the present invention has the following general formula % (%) where Ra represents a reducing substrate that can be oxidized by silver halide, and D contains a dye part for image formation that has a hydrophilic group.

The reducing substrate in the dye-donating substance Ra SOz D (
Ra ) is the redox potential relative to a saturated calomel electrode in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte.
, 2V or less is preferable. Preferred reducing substrates (Ra) have the following general formulas (II'') to (IX).

H H- H- fLa where RaXRa, Ra, and Ra each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an arylox/group, an aralkyl group, an acyl group, an acylamino group, an alkylsulfonylamino group, or an aryl group. Represents a group selected from a sulfonylamino group, an aryloxyalkyl group, an alkoxyalkyl group, an N-substituted carbamoyl group, an N-substituted sulfamoyl group, a halogen atom, an alkylthio group, and an arylthio group, and the alkyl group in these groups The group and the aryl group moiety further include an alkoxy group, a halogen atom, a hydroxyl group, a cyano group, an acyl group, an acylamino group, a substituted carbamoyl group, a substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group, or a carboxy7 group. may be replaced with .

' Furthermore, the hydroxyl group and amino group in Ra may be protected with a protecting group that can be regenerated by the action of a nucleophilic reagent.

In a more preferred embodiment of the present invention, the reducing group 7 substance R
a is represented by the following formula (X).

Here, G represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. Ra represents an alkyl group or an aromatic group. n is an integer between / and 3.

0 X represents an electron-donating substituent when n=, /, and may be the same or different substituent when the number is 2 or 30, and when one of them is an electron-donating group, it represents an electron-donating substituent. The third one is an electron donating group or...a rogen atom,
X may form a fused ring by itself or may form a ring with ORa.

The total number of carbon atoms of both Ra and X is g or more.

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

Here, Ga represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. ll'l, a and Ra may be the same or different, and each may be an alkyl group, or Ra and Ra may be linked to form a ring.

3 Ra represents a hydrogen atom or an alkyl group, and Ra represents an alkyl group or an aromatic group. X and X 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, and furthermore, Ra2 and may be formed.

Ga Here, Ga is a hydroxyl group or a group that gives 0 hydroxyl group by hydrolysis, Ra is an alkyl or aromatic group,
X represents a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an anruamino group or an alkylthio group, and X2 and R%0 may be linked to form a ring.

Specific examples included in (X), (Xa), and (Xb) are US≠, 0! ! ; ,≠2g, JP-A-5T-i,
These are described in Z Otsu No. 11.2 and 1 Tsuji J Otsu No. 73130, respectively.

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

(However, the symbols Ga, X, Ra and n are expressed by the formula (
It has the same meaning as 02, X, and Ran of X). ) Among those included in (XI) of the present invention, in a more preferred embodiment, the reducing substrate (Ra) has the following formula (X[a
) to (X[c).

i' where Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; R11 and 几a may be the same or different and each represents an alkyl group or an aromatic group; Ra and Ra
may be combined to form a ring; R2a5 represents a hydrogen atom, an alkyl group, or an aromatic group; a2a4 represents an alkyl group or an aromatic group; R represents an alkyl group, an alkoxy group, represents an alkylthio group, an arylthio group, a rogen atom, or an acylamino group; p is 0. / or Kodashi; Ra and Ra may be combined to form a condensed ring.
Ra and Ra may be combined to form a condensed ring.
Ra and Ra may be combined to form a condensed ring,
and Ra, RaXaa.4 The total carbon number of Ra and (Ra)p is greater than 7.

However, Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; 1 Ra represents an alkyl group or an aromatic group; R3a2 represents an alkyl group or an aromatic group; 3 Ra represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group; represents a group, an atom or an acylamino group; q is 0, /-! , or co; Ra and Ra may be combined to form a condensed ring.
Ra,! :Ra may combine to form a condensed ring<
, FL%1 and R%3 may combine to form a condensed ring; and the total number of carbon atoms in Ra XRa 1 (Ra,)q is greater than 7.

Ga In the formula, Ga represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; R11 represents an alkyl group or an aromatic group; R4a2
represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a rogen atom, or an acylamino group; r is 0, l″li or 2; The carbonized atom in the condensed ring that participates in bonding to the phenol (or its precursor) core (---C-> is a tertiary carbon atom constituting one element of the condensed ring, and Carbon atoms in hydrocarbon rings (
However, some of the above-mentioned tertiary carbon atoms (excluding the tertiary carbon atoms) may be substituted with oxygen atoms, or the hydrocarbons may have substituents, or furthermore, aromatic rings may be fused. No. 1 Ra or Ra and the above T---C- group may form a condensed ring. However, R11, (R'a") r
Specific examples included in (X[), (X[a) to (X[b)] above are disclosed in Japanese Patent Applications Shoj6-/Otsu/3/, Shoj67-&j
O, same j7 'I-0≠3.

The essential part of formula (III) and formula (IV) is the .xilar(sulfonyl)amine phenol moiety.

A specific example is US3. 21.3/2, USI
I-, 07 Otsu, J2'7, US Publish
dPatent Application B
33/, Otsu73, USp, /3r, riλri, [JSl
/L, 2! The.

The reducing substrates disclosed in Section 1.20 are also effective as the reducing substrate (Ra) of the present invention.

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

Here, Ba1last contains a diffusion-resistant group.

Ga represents a hydroxyl group or a hydroxyl group precursor.

Ga forms an aromatic ring, and forms a group that forms a naphthalene ring together with the benoise/ring. Mouth and m are l or λ
Hail an integer that turned out to be.

Specific examples included in the above are US-tl, os3゜3/
It is described in 2.

The reducing substrates of formulas (■), (■), (■), and (IX) are characterized by containing a petero ring, and specific examples include US≠, 1,23! f, Japanese Patent Publication No. 53-≠47
3o, US≠, 273, Za! Examples include those listed in j. In the formula (Vl).

Specific examples of the reducing substrates represented are US≠, 100%.

There is a description in Zari 2.

The following properties are required for the reducing substrate Ra.

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

2. The dye-donating substance must be difficult to diffuse in a hydrophilic or hydrophobic binder, and only the released dye needs to be diffusible. Therefore, the reducing substrate R has a large hydrophobic property. to have

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 Ra that satisfy these conditions will be shown. In the examples, NH- represents a linkage with a dye moiety.

C4H9(t) CH-C-CH3 3 3H7 CH-C-CH3CH3 1 CH-C-CH3 NH3 0C engineering. H33 N.H. N.H. OC engineering. H33 0C06H3゜ NH- N.H.

NH- Dyes that can be used as image forming dyes include Id azo dyes, azomethine dyes, anthraquinone dyes, naphthoquino 7 dyes,
There are styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalo/anine dyes, and representative examples are shown on the dye side. It should be noted that these dyes can be used in a temporarily shortened form that can be multicolored during development processing.

Yellow〈 / 152 53 R3aa ( 2 1(, aR%3 2 Ra ■Mo533 Iself' -C-C-C-NHI II II II 11 Magenta 1 Ra 1 Ra \ H R08' 1 Ra ■ Su HRa \1 0 Ua OHONHRa R03゜1 Ra H 5156 In the above formula, Ra-aa is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, respectively. group, hydroxyl group, alkylsulfonylamine group,
Arylsulfonylamino group, alkylsulfonyl group,
Hydroxyalkyl group, cyanoalkyl group, Alfky/
carbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, haloke/, sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group,
N-f substituted carbamoyl group, aryloxyalkyl group,
Represents a substituent selected from an amine group, a substituted amino group, an alkylthio group, and an arylthio group, and the alkyl group and aryl group moiety in these substituents further includes a halogen atom, a hydroxyl group, a cyano group, an acyl group, and an acylamino group. group, alcoquine group, carbamoyl group, substituent lupamoyl group
The group, y, may be substituted with rufamoyl x, substituted sulfamoyl group, carphokyl group, alkylsulfonylamine group, arylsulfonylamino group or ureido group.

Hydrophilic groups include hydroxyl group, carboxyl group, sulfo group,
Phosphoric acid group, imide group, hydroxamic acid group, quaternary ammonium group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, sulfamoylamino group, substituted sulfamoylamino group, ureido group, substituted ureido group, Examples include an alkoxy group, a hydroxyalkoxy group, an alkoxyalcokyne group, and the like.

In the present invention, it is particularly preferable to use basic groups (such as phenolic hydroxyl groups, calhomonol groups, sulfo groups, phosphoric acid groups, imido groups, and hydroxamic acid groups) whose hydrophilicity increases significantly through proton dissociation. , (replacement)
Includes sulfamoyl group, (substituted) sulfamoylamine group, etc.

The characteristics required for image-forming dyes are: /) having a hue suitable for color reproduction; 2) having a large molecular extinction coefficient;
3) stability against light, heat, and other additives such as a dye release aid contained in the system; and ≠) ease of synthesis. Specific examples of preferred image-forming dyes satisfying these conditions are shown below. Here H2N-8O3
represents a binding site with a reducing substrate.

yellow SO□NH2 02NH2 H Magenta OCH3 02NH2 NHCOCH3 H H H3 Cyan SO2NH゛2 H H Next, specific examples of preferred dye-donating substances will be shown.

(2; C4H9(suC4H9(L) (4) OC16-H33 (11) OH C4H9([) (13) (14) (15) (16) \ C4H9(t) \ C4H9([) C4H9(L) C4H9(L) (21) (22) (23) H (25) H Sushi16Fi33 (28) OH oe□6H33 0C16H33
()OC16H33n (35) (36) OC06H33 (38) CH3C:kl 3 (39) (40) H Cl6H330CH3 (43) (44) OC16H33-n (45) (46) (47) 02 0C46H33-Ro 0C16H33-Ro (53) (54) ○H (55) (56) H (58) (゛). H CH-C-CH3 3H7 (61) o) (OC□6H33 (aa) oH \ 16H33 (6 (67) (69) H QC,, H33(n) (70) H H (71) H of the present invention In addition to the above-mentioned specific examples, as dye-donating substances, USA, orz, u21.
2, same J-&-/l/30. Same jA -/311 Same j7
-1. IO, same j7-≠0113.3, ri21.3/2
,US4',θ76,! 2US Publish
d patent Application! /,l,
73, USll, 133. riλri, --≠, l'1g,
23j', JP-A-53-1A1.730XUSII,
273, Ijj, US44, /44ri.

192, Ui9! ,/! u, 19/, US4',,!
Compounds described in tg, 120, etc. are also effective.

Additionally, US μ, 013 , l, 33, US Hiro, 154
．． 609, us+, /ur, I, Hiro/, USA.

/ Aj, 917, US<z, 1tar, ts
a3, USA, ttr3. ysr,,USp,xp4
, a/a, US≠, 26g, , <25XUS≠, Cog 5
, 02g, Japanese Unexamined Patent Application Publication No. 1983. -71072, J-4-23
737, same S star/jf71u, same 33-/3'/-I
Q, 32-106727, same! r/-//Hirori 3
Dye-donating substances that emit yellow dyes such as those described in O and the like are also effective in the present invention. Also US3゜rijtA, ≠
76,UStA,ri32,3za0XUS3,ri3/,/
lIl/-1US3,? 32.31/, US4',
, 2tl , 1, 21t, [JS! ,) #ta, ta0ri, JP-A-5 Otsu-730!7, same r6-7io401 same!
j-/31A Doyo 01 SS-≠OφOλ, 63-3
tr011. Same evening 3-237.21. Same jλ-10 Otsu 7
λ7, same! ! -33/Hiroshiλ・, same evening 3--! Dye-donating substances that release mazenota dyes such as 332 are also useful in the present invention. Also U83, Ri2ri, 7tO
X US≠, 0/3, &36, US3, ri121
ri g7, US≠, 273°7ovXIJ8p, /ri
-ir, At1x, US4', /f3, 7s4LXU
S≠, /≠71ta≠Hiroshi, USHiroshi.

/l,j,231. USIA, 21-1. ．． 44/! ,
US4', 2&J, J, 2J-, JP-A-66-7io4
i, same j3-≠7g23, same evening 2-18j27, same j3
Dye-donating substances that release cyan dyes, such as those listed in 7 Hiroshi 33.23, are also effective in the present invention.

Two or more types of dye-donating substances may be used in combination.

In this case, two or more of the same pigments may be used in combination, and two or more of the same pigments may be used in combination to produce black.

The total amount of dye-donating substances is 10 m9/m to 7
It is appropriate to use the tag in the range of g/J, preferably 2
It is advantageous to use a range from orng/J to lOg/TrL2.

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

Generally, the dye-donating substance of the present invention is obtained by condensing the amine group of the reducing substrate Ra with the chlorosulfonyl group of the image-forming dye part.

The amine group of the reducing substrate Ra can be introduced by reduction of nitro, nitroso, or azo groups or ring opening of be/dioxazole depending on the type of substrate, and can be used as a free base or 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 oxychloride/pentachloride/or thionyl chloride.

A condensation reaction between the reducing substrate Ra and the image-forming dye moiety,
Generally dimethylformamide, dimethylacetamide,
In an aprotic polar solvent such as dimethylsulfoxide, N-methylpyrrolidone, acetonitrile, etc., in the presence of an organic base such as pyridine, picoline, lutidine, triethylamine, diinopropylethylamine, etc., with a polarity of 0-600c. Usually, the desired dye-providing substance can be obtained in extremely good yield.

An example of its synthesis is shown below.

Synthesis Example 1: Synthesis of O-hydroxy-λ-methylbenzoxazole 2+ gauge hydroxyacetophenone 30I! +7゜Hydroxylamine hydrochloride/l, ltf/, sodium acetate 32ff, ethanol/0 (1) Oytttz
and j 00 ml of water were mixed and heated under reflux for ≠ hours. Pour the reaction solution into 101ml of water, count the precipitated crystals,
λ.

37≠g of ≠-dihydroquine acetophenone oxime was obtained.

This oxime 30f was dissolved in acetic acid≠00 ml, and 72
While heating and stirring at 0°C, hydrogen chloride gas was blown in for 2 hours. After cooling, the precipitated crystals were collected and then washed with water to obtain O-hydroxy/-λ-methylbenozoxazole/79.

Synthesis Example 2 = Synthesis of O-hexadecyloxy-2-methylbenzoxazole Synthesis example/6-hydroxy-2-methylbenzoxazole/g, oyX i-bromohexadeca/3
1. ．． 9! , potassium carbonate 211. Of.

N,N-dimethylformamide/λOml was stirred at QoC for ≠j hours. The solid was separated from the reaction solution, and the P solution was poured into methanol J0011. By counting the precipitated crystals, 6-hexazofluoroxy-λ-methylbentoxazole tx;,090 was obtained*.

Synthesis Example J: -2-acetylamino-! , -Synthesis of hexadenyloxyphenol Otsu-hexadecyloxy-2-methylbenzoxazole obtained in Synthesis Example 2/1g, ethanol/300@l,
110ml of 33% hydrochloric acid. Mix sso ml of water,
In the evening, the mixture was stirred at J-to-0c for an hour. After cooling, the precipitated crystals were collected and coacetylamino! -Hexaf noroxyphenol//3f obtained fc.

Synthesis example≠: Synthesis of 2-acetylamino-Hiroshi-[-butyl-hexadecyloxyphenol] λ-acetylamino obtained in Synthesis Example 3! - Hexatecyloquinephenol 30, Of, 7 number list/evening (
(U.S. Rohm & Haas registered trademark) 20.0g
, 700 ml of toluene were mixed, and isobutylene was blown into the mixture for 5 hours while heating and stirring at 0 to 0C. After removing the solid, P'ri.

was concentrated, and 30ml of n-hexane was added to the residue to precipitate crystals. In terms of number of households, coacetylamino≠−t
-Fuchiru! -hexadecyloxyphenol23. I got it for free.

Synthesis Example J2 Synthesis of 2-amino-cou[-butyl-terhexadecyloxyphenol] l-acetylamino-@-L-butyl-j-hexadefluoroki/phenol obtained in Synthesis Example ≠ 23° og, ethanol/, 20 ml of hydrochloric acid Ame was mixed for 3 days, and the mixture was stirred and refluxed for 5 hours. After cooling the reaction solution, the precipitated crystals were separated into 2-amine-Hiro-t--7" chill-
j-Hexadezoluoquinphenol hydrochloride 230.2f
I got /.

Synthesis Example B: Synthesis of ≠-[-butylterhexade;nruoxy-λ-(2-(2-methoxyethoxy/)-t-nitrobenozenosulfonylamino]phenol 2-Amino-≠- obtained in Synthesis flJ) 1-Butyroux!-
Hexadecyloxyphenol hydrochloride Hiroshi, ≠g and 2
-, (2-methoxyethoxy)-ternitrobenzenesulfonylchlorIJ)"J,/gwon.

Dissolved in N-dimethylacetamide 12πt, pyridine,! ml was added and stirred at 0C for 7 hours and 2 nights. When the reaction solution was poured into dilute hydrochloric acid, an oily substance precipitated. When 30 ml of methanol was added to this oil, it crystallized and was collected.

Yield: 5g0 Synthesis Example 7: Synthesis of 2-(j-amino-λ-(2-methynethoxy)henzenesulfonylamino]-≠-1-butyl-j-hexadezoluoquinphenol Synthesis Example 6 above The compound iog obtained in 6 oπl of ethanol
After adding about 0.05g of 70% ξ radium-carbon catalyst, hydrogen! The mixture was pressurized to rjkg/cm 2 and stirred at 60°C for 6 hours. Next, the catalyst was removed while hot, and when it was allowed to cool, crystals were precipitated and the catalyst was removed.

Yield 7. j//.

Synthesis Example g: Synthesis of 3-cyano-≠-[≠-(2-methoxyethoxy)-j-sulfophenylazo]-/-phenyl-j-pyrazolone In a solution of sodium hydroxide f, 09 and water, 200ml Add j-amino-2-(2-methoxynoethoxy)benzenesulfonoic acid, ≠1, and add sodium nitrite/3
．． An aqueous solution (s Oml ) of 100 ml was added.

Separately, prepare a solution of concentrated hydrochloric acid 1=Omt and water≠00H1,
The above solution (g) was added dropwise to this at less than sOc. then s
The reaction was completed by stirring for 30 minutes at a temperature below 'C.

Separately, 16.0g of sodium hydroxide, 200ml of water, 33ml of sodium acetate, Ofl and 200ml of methanol.
Prepare a solution of shoulder l, 3-cyano-/-phenyl-5-
Pyrano Rono 37. θg was added, and the above-prepared diazo powder was added dropwise at a temperature of 1000 or less. 100C or less after completion of dripping (3
After stirring for 0 minutes and then stirring at room temperature for 1 hour, the precipitated crystals were separated, washed with 200 ml of acetone, and air-dried.

Yield 32.09 m, p, 2A3~2A! 'C synthesis example: 3-cyano-Hiro-[≠-(2-methoxyethoxy)-! Synthesis of -chlorosulfonylphenylaso]-/-phenyl-j-pyrazolone
Yo-pyrazolone! ;/, 09, N,N-dimethylacetamide jOd was added dropwise to a mixed solution of acetono2jfOgl and phosphorus oxychloride j01gl at a temperature below 00C.

After the dropwise addition, the mixture was stirred for about 1 hour and gradually poured into ice water/O2O. Remove the precipitated crystals from the F side and add 100 g of acetonitrile.
1 and air dried.

Yield tfiA, 79 m, p, /I/ ~ /13
°C Synthesis Example 10: Synthesis of Dye Donor Substance (1) λ-[j-amino-2-(2-methoxyethoxy)benzenesulfonylamino-tx -t-phthylVj-hexadecyloxy obtained in Synthesis Example 7 Phenol t, 3g N, N
-3-cyano-+ -[≠-C2-methoxyethquin>-r-chlorosulfonylphenylaso]-/-phenyl-j-pyrandelone≠, 6 g, dissolved in 30 ml of dimethylacetamide and obtained according to the synthesis example. and then added pyridi/jπt. After stirring at room temperature for 7 hours, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Recrystallized from N,N-dimethylacetamide-methanol7.
! I got f.

m, I), /I ml 10Q Synthesis example //: Synthesis of dye-donating substance (2) Synthesis example 7
λ-[j-amino-λ-(2-methoxy/ethoxy/
) Pe/ze/sulfonylamine-≠-[-phthyl-hexade/ruoxyphenol A, 3 g was dissolved in 30 ml of N,N-dimethylacetamide, and 3-cyano-≠-(
j-chloro-, z-methylsulfonylphenyl aso)-
/-(Hiro-chlorosulfonylphenyl)-3-L'
Lasolone S and OG were added, and pyridino J ml was further added.

After stirring at room temperature for 7 hours, the reaction solution was poured into dilute hydrochloric acid.
The number of precipitated crystals was counted. Recrystallization from acetonitrile gave f, -≠g.

m, p, /≠≠~/4Lta 0Q Synthesis Example/22 Synthesis of dye-donating substance (1o) λ-Amino-pt-butyl-! -Hexadedyloki/phenol hydrochloride Gu, Gu! and Hiro-[3-chlorosulfonyl-
Gu(λ-methoxyethoxy)phenylazocy 2-C
N,N-diethylsulfamoyl)-j-methylsulfonylamino-/-naphthol t,ry was dissolved in 20 g of N,N-dimethylacetamide and 2 g of pyridine It was dissolved.
Added l. After stirring at 2j0Q for 7 hours, the reaction solution was poured into dilute hydrochloric acid. The precipitated solid was collected and purified by silica gel column chromatography (eluted with a mixed solvent of chloroborum-ethyl acetate (,t:/)i).

Yield 1. ,．． 2Q.

Synthesis Example/3: Synthesis of dye-donating substance (17)
00g1 and added pyridine/lλ shoulder t. This is added to 5-(3-chlorosulfonylbenzenesulfonylamine)-,2-(N-[-butylsulfamoyl)-≠-(
Normethylsulfonyl-Hiro-nitrophenyl aso)-/
-f-phthol 20f was added. After stirring for 1 hour, add 5 ml of ice water.
00Hi, and the precipitate was washed with inpropyl alcohol-7.
I got Setoni f.

Synthesis example/ψ2 Synthesis of dye-donating substance (19) 2-[j
-Amino-2-(λ-methoxyethoxy)benzenesulfonylamino)-pt--i'decylj-hexate/
oxyphenol 3/. EfX j-C3-chlorosulfonylbenzenesulfonylamino)-≠-(2-methylsulfonyl-≠nitrophenylazo)-/-naphthol

/da was dissolved in N,N-dimethylacetamide iooHz and pyridino u/@l was added. After stirring for 0 minutes, methanol/L = , 2 j O me% water 100@
Added l. The precipitated resinous material solidified after a while, so it was mixed several times. This is toluene-methanol-water (
/ A: Hiroshi = 3) mixed system °shi recrystallize Hiroshi /, 39
Obtained.

Synthesis Example 13 Synthesis of Compound ≠ O a) Synthesis of 2,s-dihydroxy7-hiro-[-butylacetophenone[-butylhydroquinone ♂3 fl t-vinegar rll'A
Boron trifluoride (BF3) was dissolved in 0.0 °C and heated to 10 - 0 °C 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. This solid was diluted with 2N NaOHl.

The insoluble portion was removed. The P solution was made acidic with dilute hydrochloric acid, and the precipitated crystals were washed several times with water and then recrystallized from aqueous methanol.

Yield lrf (65%) b) Synthesis of 2,j-dihydroxy7-44-L-butylacetopheno/oxime The ketone λ/f obtained in a) above was added to 70 ml of ethanol.
, and 2 hd of sodium acetate, and while stirring, a solution prepared by dissolving 7/2 f of hydroxylamide hydrochloride in 70 g of water was added, and the mixture was refluxed for about 1 hour. After completion of reaction 30
It was poured into 0 gt of ice water, and the precipitated crystals were recrystallized from Tokasu Shibe/Zen-Hexa/.

Yield /7f (74%) C) Synthesis of O-[-butyl-5-hydroxy-2=methylbenozoxazole The oxium/≠g obtained in b) above was mixed with acetic acid io.

Introducing dry hydrochloric acid gas while dissolving it in mt and heating it,
Refluxed for i,s hours. After the reaction was completed, the precipitated crystals were poured into 200 ml of ice water and washed with water.

Yield Free (70 sections) d) At-butyl-j-hexadecyloxane 7! -Synthesis of methylbenozoxanol The benzoxazole compound obtained in C) above was mixed with dimethylformamide.
The solution was stirred for 4 hours at 10°C to 10°C with gg of anhydrous potassium carbonate and 1/g of hexade/lupromide.

After the reaction is completed, the inorganic substances are removed and Eg. methanol ir
When cInl was added and cooled on ice, crystals were precipitated. By counting this, the title compound was obtained.

Yield 1+. lrf (4λ%) e) Synthesis of 2-Amino-s-t-butyl-Hiro-hexadecyloxyphenol hydrochloride Benzoxazole compound 7 obtained in d) above.

3 g was refluxed for 3 hours with 3,011 liters of ethanol and 2 CJl of concentrated hydrochloric acid. - After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were washed with water and then with acetone.

Yield 2.7F! (72%) f) Synthesis of Compound Example Hiro O The hydrochloride ty obtained in e) above and the sulfonyl chloride r, rg of the dye having the following structural formula were combined with dimethylacetamide j O
#ll was added, pyridine/≠ml was added, and the mixture was stirred at room temperature for 1 hour. After the reaction period R, 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 2.2f of the title compound having substantially the same components.

Dye sulfonyl chloride: Synthesis example/l: Synthesis of dye-donating substance (42) In the above synthesis example/sd), ot-L- instead of 7-t-butyl-4-hydroxy-comethylbe/zoxazole O-hexadecylation was performed using octyl-terhydroquino-nomethylbenzoxazole. Then, a dye-donating substance (42) was obtained by the same treatment as in Synthesis Example 1se) and f).

The dye-donating substance of the present invention is disclosed in U.S. Patent No. 2,322.02.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl tucrate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (eg acetyl tributyl citrate).

High boiling point organic solvents such as benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) , or an organic solvent 1 having a boiling point of about 30°C to 160°C, such as ethyl acetate,
After dissolving in lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc.
Dispersed in hydrophilic colloids.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants are listed as surfactants elsewhere in this book. You can use what you have.

The amount of the high boiling point N31 solvent used in the present invention is 10 g or less per 1 g of the dye-providing substance used.

Preferably it is 5g or less.

In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is a so-called auxiliary developer,
It is oxidized by a silver halide and/or organic silver salt oxidizing agent, and its oxidized product has the ability to oxidize the reducing substrate Ra in the two-dye donor substance.

Useful auxiliary developers include hydroquinone, t-butylhydroquinone, alkyl-substituted hydroquinones such as 2,5-dimethylhydroquinone, catechol, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, methoxyhydroquinone, etc. There are alkoxy-27'-substituted hydroquinones and polyhydroxybenzene derivatives such as methylhydroxynafculene.

Furthermore, hydroxylamines such as methyl gallate, ascorbic acid, 2-ascorbic acid derivatives, N,N''-di(2-ethoxyethyl)hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl- Pyrazolidones and reductones such as 1-phenyl-3-virapritone.

Hydroxytetra acids are useful.

Auxiliary developers can be used in a range of concentrations. A useful concentration range is 0.0 for silver. ooos (g mole-2
0 times molar, particularly useful concentration ranges include o, ooi
It is twice the mole to four times 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.

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

Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary silver halide emulsions, silver halide grains form a complete mixed crystal. For example, when measuring X-ray diffraction of the grains of a silver iodobromide emulsion, no pattern of silver iodide crystals or silver bromide crystals is found, but an X-ray pattern is found at positions corresponding to the mixing ratio.

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

Such silver halide, such as silver iodobromide, can be obtained by adding a silver nitrate foil solution to an odor-hypotassium solution to form silver bromide grains without stirring, and then adding iodo-hypotassium. .

Haloken [silver arsenal] may be used in combination of two or more types having different sizes and/or halogen compositions.

The size of the halogen [arsenic] particles used in the present invention preferably has an average particle diameter of 0.007 μm to 10 μm,
More preferably from 0.00/μm! , u m.

The silver halide used in the present invention may be used as it is, or may further be used as a compound such as sulfur, cerene, tellurium, etc., gold,
[Hg-sensitized] by the use of reducing agents such as platinum, rose/rum, concum, or arsenic compounds such as a) nodium, or a combination of these. For more information, please refer to “The Theory of
tho Photographic Process”
4' edition, written by T. H. James, Chapter J/lI-T-Pg.

A preferred embodiment of the present invention for 2 JC% is organic silver hydrochloride r.
It is a combination of arsenic drugs, but it is exposed to light/・Rodan 1
In the presence of arsenic, the temperature is 00C or higher, preferably 1000C.
When heated above C, it reacts with the image-forming substance 1 or, if necessary, a reducing agent coexisting with the image-forming substance, thereby forming a complete silver image. By coexisting with organic silver hydrochloric acid (arsenic agent), it is possible to obtain a photosensitive material that develops color at a higher density.

The silver halide used in this case does not necessarily have the characteristic of containing pure silver iodide crystals when silver halide is used alone; can do.

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, silver salts of lauric acid,
Silver salt of capric acid, silver salt of myristic acid, silver salt 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 oleic acid. Examples include silver salts, adipic acid silver salts, sebacic acid silver salts, succinic acid silver salts, acetic acid silver salts, J-butyric acid silver salts, and camphoric acid silver salts. Furthermore, silver salts substituted with halide 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゜j-dihydroxy7benzoic acid, silver salts of O-methylbenzoic acid, m
- silver salt of methylbenzoic acid, silver salt of p-methylbenzoic acid,
Silver salts of substituted benzoic acids such as y, silver salts of ψ-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. silver salt, silver salt of terephthalic acid, silver salt of salicylic acid,
Silver salts of phenylacetic acid, silver salts of pyromellitic acid, silver salts of 3-carboxymethyl-hiro-methyl-≠-thiacyly/-2-thione described in U.S. Pat. No. 3.715°, 130; Examples include silver salts of aliphatic carboxylic acids having a thioether group as described in US Pat. No. 3,330°ttJ.

Other examples include silver salts of compounds having mercapto groups or thio/groups and derivatives thereof.

For example, Fi3-merkafto≠-phenyl-7,2゜≠-
Silver salt of triazole, silver salt of 2-mercapto(nzimidazole), silver salt of 2-mercapto-y-aminothiadiazole, silver salt of λ-mercaptobenzthiazole, silver salt of -1(S-ethylglycolamido)benzthiazole Salt, S-alkyl (alkyl group having 12 to 22 carbon atoms)
Silver salts of thioglycol acids such as thioglycol acetic acid, silver salts of thioamides, silver salts of thioamides such as silver salts of dithioacetic acid, etc. Silver salt of carboxyni/-methyl-cophenyl-hiro-thiopyridine, silver salt of mercaptolyazine, silver salt of 2-mercaptobenzoxazole, silver salt of mercaptooxadiazole, US patent≠.

/23,2717, for example, /.

λ, 3′, which is a Hiro-mercaptotriazole derivative;
7 amino! -benodylthiol, 2. ≠-Silver salt of triazole, 3 described in U.S. Pat. No. 3.3oi, No. 671
It is a silver salt of a thione compound such as a silver salt of -(2carboxyethyl)-≠·-methyl-4L-theacylinophthion.

In addition, there are silver salts of compounds having imino groups. For example, Tokusho≠4L-30270. Silver salts of pe/zol-IJ thiazole and its derivatives described in the same publication ≠5-/r≠76, such as pe/zo) IJ thiazole silver salts, silver salts of alkyl-substituted benzotriazoles such as methylbenztriazole silver salts , silver salts of rogen-substituted benzitriazoles, such as silver salts of j-chlorobensito1 noazole, silver salts of carboimidobenzotriazoles, such as silver salts of butylcarboimidobenzotriazole, U.S. Pat.
20゜702 specification l, 2. ≠-triazole or /-H-tetrazole silver salt, carbazole silver salt,
Examples include silver salts of saccharin and silver salts of imidazole and imidazole derivatives.

Also, Research Disclosure Vol/70°797
Organometallic salts such as silver salts and copper stearate, which are described in June 1, 1999, No. 1, No. 7027, are also organometallic salt oxidizing agents that can be used in the present invention.

Two or more types of organic silver hydrochloride arsenic agents can be used.

Although the thermal development process during heating of the present invention has not been fully elucidated, it can be considered as follows.

When a photosensitive material is irradiated with light, a latent image is formed on Rodin 1 silver, which has photosensitivity. Regarding this, T.

'The Theory of
, the Phatographic Processes
s” 3rd Edition, page 103~/!
It is described on page J.

By heating the photosensitive material, the reducing agent, in the case of the present invention, the dye-donating substance, uses the latent image nuclei as a catalyst to reduce silver halide or silver halogen and the organic silver salt oxidizing agent to produce silver. However, it itself is oxidized. This oxidized dye-donating substance is cleaved to release the dye.

For details on how to make these silver halides and organic silver salt oxidizing agents and how to mix both, please refer to Research Disclosure No. 17θ2, JP-A Shojθ-3292g, JP-A Shojl
-≠232, U.S. Pat.

In the present invention, the coating amount of photosensitive silver halide and organic silver salt oxidizing agent is 50 to iog7ni in total in terms of silver.
is appropriate.

The photosensitive silver halide, organic silver salt oxidizing agent of the present invention is prepared in the following binder. 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. A hydrophilic material can be used for this ingu. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as gelatin, gelatin derivatives, cellulose derivatives, and natural colloids such as starch, gum arabic, and other polysaccharides. and synthetic polymeric materials such as polyvinylpyrrolide/water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric compounds include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring in these nuclei A fused nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus,
Henzoselenazole nucleus, penzimidazole nucleus, quinoline nucleus, etc. are applicable.

These nuclei may be substituted on carbon atoms,
Cyanine dyes or complex merocyanine dyes include a birapurin-5-one nucleus as a nucleus having a ketomethylene structure,
Thiohydantoin core, 2-thioxazolidine-2,4
-Dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei, thioparpylic acid nuclei, and other 5- to 6-membered heterocyclic nuclei can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231.658, U.S. Patent No. 2,493
, No. 748, No. 2.503.116, No. 2,519,
No. 001, No. 2,912゜329, No. 3,656,9
No. 59, No. 3,672.897, No. 3,694.21
No. 7, No. 4゜025.349, No. 4,046,572
No., British Patent No. 1,2.42,588, Special Publication No. 1977-1
Examples include those described in No. 4030 and No. 52-24844.

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

A typical example is US Patent 2. '688,545, 2.
No. 977.229, No. 3,397.060, No. 3,5
No. 22,052, 3. '527,641, 3,6
No. 17,293, 3. 6128゜964, same 3,
No. 666.480, No. 3,672.898, No. 3,6
No. 79,428, No. 3゜703.377, No. 3,76
9,301, 3.814,609, s., 133
No. 7.862, No. 4,026,707, British Patent No. 1.
No. 344.281, No. 1,507,803, Japanese Patent Publication No. 43-4936, No. 53-12,375, Japanese Patent Publication No. 53-1973
No. 2-110,618 and No. 52-109,925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3,6
No. 15,641, 3. 617. No. 295, 3,
The combinations described in No. 635,721 are particularly useful.

There are seven supports used in the present invention that can withstand processing temperatures. A common support is glass 9
Not only are paper, metals and their analogs used;
Included are acetyl cellulose film, T-cellulose ester film, polyvinyl acecool film, polystyrene film, polycarbonate film, polyethylene terreslate film, and films or resin materials related thereto. U.S. Patent 3,634,089
No. 3,725.070 is preferably used. Particularly preferably, a polyethylene terrestrial film is used.

Various dye release aids can be used in the present invention. A dye release aid is an acid-releasing agent that promotes the acid ratio reduction reaction between photosensitive silver halide and/or organic silver hydrochloride and a dye-donating substance, or is used in the subsequent dye-releasing reaction.
A base or a base precursor is used as a substance that can act nucleophilically on a dye-donating substance to promote dye release.

In the present invention, it is particularly advantageous to use these dye release aids to accelerate the reaction.

Examples of preferable bases include amines, including trialkylamines, hydroxyl/minos,
Examples include aliphatic polyamides 7, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines, and bis[p-(dialkylamino)phenylcomethanes. Also, U.S. Patent No. z, pio, t≠
The ≠ number includes tetramethylammonium betainoiodide,
Diaminobutane dihydrochloride is useful as organic compounds containing amino acids such as urea and t-aminocapronoic acid are described in US Pat. No. 3, 4L4TLA. The base precursor releases a basic component when heated. Examples of typical base precursors are described in British Patent No. Tata R, Rihiro. Preferred base precursors are salts of carboxylic acids and organic bases; useful carboxylic acids include trichloroacetic acid, trifluoroacetic acid; useful bases include guanidino, piperi')/, mopoly/, [
)-1 Luigino, Supicoline, etc. Guanidine trifluoroacetic acid, described in US Pat. No. 3,220, g≠6, is particularly useful. Aldonamides described in JP-A-3O-22T and 2J are preferably used because they decompose at high temperatures to produce bases.

These dye release aids can be used in a wide variety of ways. A useful range is 50 weight/g-cents or less, more preferably 0.5 g-cents, calculated by weight of the coated film of the light-sensitive material.
They range from 0.07 weight percent to 110 weight percent.

In the heat-developable color light-sensitive material of the present invention, it is advantageous to use a compound represented by the following general formula because development is accelerated and dye release is also promoted.

[General formula]

In the above formula, A1 "2" 3 "4 may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkylaralkyl group, an aryl group, a substituted aryl group, and a heterocyclic residue. It represents a mixed substituent, and A1 and A2 or A3 and A4 may be linked to form a ring.

A specific example is H2NS02NH2.

H2NS02N(CH3)2, H2NS02N(C2H
5)2.

H2NSO2NHCH3, H2NS02N (C2H40
H)2.

CH3NHSO□Nu (CH3.

The f-hybrid compounds mentioned above can be used in a wide range of applications.

A useful range is 200 g-cents by weight or less, more preferably 0.5 g-cents, based on the weight of the coated film of the light-sensitive material. /
From /j weight ξ − cents.

In the present invention, it is advantageous to use a water-releasing 18 compound because the dye-releasing reaction is accelerated.

A water-releasing compound is a compound that decomposes and releases water during thermal development. These compounds are particularly known in the transfer printing of fibers, and NH4Fe(S04)2./2H20 described in Japanese Patent Publication No. 31, No. 4, 1983 is useful.

In addition, in the present invention, a compound can be used to ensure the stability of the image at the same time as the development activity.

Among them, 2.
- Intiuroniums represented by hydroquinoethylinothiuronium trichloroacetate, U.S. Patent No. 3
．． Bisinothiuroniums such as /,f-(3,O-dioxaoctane)bis(intiuronium trifluoroacetate) described in No. A70, West German Patent No. 2
．． //; 2,7/Thiol compounds disclosed in Ko No. 1, US Pat. No. 11,0/2. ．． 2-amino-2 described in No. 2IQ
-thiazolium trichloroacetate, -monoamino-
1-70 Thiazolium arsenic compounds such as moethyl-1-thiazolium trichloroacetate, U.S. Pat.
Bis(2-amino-,2-thiazolium)methylenebis(sulbonyl acetate)) described in OtO, No. 1120,
, 2-amino-λ-thiazolium phenylsulfonylacetate and other compounds having α-sulfonylacetate as the acidic moiety, US Pat.
As the acidic moiety, non-carboxycarboxyamide compounds described in No. 4t9+ are preferably used.

In the present invention, a hot solvent can be contained.

The term "thermosolvent" herein refers to 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 can serve as solvents for developing agents, and compounds with high dielectric constants that are known to accelerate the physical development of silver salts.2 Useful thermal solvents include: The polyglycols described in U.S. Pat.
derivatives such as zooo, polyethylene glycol, oleic acid ester of polyethylene oxide, beeswax, monostearin, high dielectric constant compound having -5O2-1-〇〇- group, such as acetamide, succinimide, ethyl Power, Rubamate, Urea, Methylsulfonamide, Ethylene Carbonate, U.S. Patent No. 3
, AA7, Polar substances described in issue 2, lactone of t-hydroquine butanoic acid, methylsulfinylmethane, tetrahydrothiophene-t, i-9 oxide, Research Disclosure magazine/Research Disclosure magazine/2017/February issue 2t-
/, 10-decanediol, methyl anisate, biphenyl perate, etc. described on page 2r are preferably used.

In the case of the present invention, the dye-donating substance is colored, and further,
Although it is not so necessary to incorporate anti-irradiation or anti-halation substances or dyes into light-sensitive materials, in order to further improve the sharpness, Japanese Patent Publication No. 1 Al-317λ and U.S. Pat. , same 2. Filter dyes and absorbent substances described in the specifications of J-core, J-za No. 3, J-za No. 2, Rij-Otsu, Do-7ri, etc. can be contained. Preferably, these dyes are thermally decolorizable dyes, such as those described in US Patent No. 3.
7 Otori, 0/ri issue, same No. 3.74L! ; , 00ri issue,
Dyes such as those described in the same No. j', &/t, ≠32 are preferred.

The photosensitive material used in 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 conductive layer, a protective layer, an intermediate layer, an AH layer, and a peel-off layer. It can contain layers and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers) , polyalkylene glycol alkylamine or amides, silicone polyethylene/
Nonionic surfactants such as oxide adducts, ), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates , alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates L N-anru N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, such as ethers, polyoxyethylene alkyl phosphates, etc.
Aniono surfactants containing acidic groups such as phosphate groups;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaias,
Ampholytic surfactants such as amine oxides; alkyl amide/salts, aliphatic or aromatic cylindrical φ-class ammonium salts, heterocyclic bronchial ammonium salts such as pyridinium and imidazolium, and phosphonium or aliphatic or heterocyclic-containing phosphonium or Cationic surfactants such as sulfonium salts can be used.

Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those in which the number of repeating units of ethylene oxide is j or more.

Nonionic surfactants that meet the above conditions are widely used outside the field, and their structures, properties, and synthesis methods are well known. Representative known documents include 5urf
actant 5science seriesvolu
me 1. Non1onic 5urfactan
ts(Edited by Martin J,
5chick.

Marcel Dekker 'Inc, /ri Otsu 7)
, 5urface AcLive Ethylene
QxideAdducLs(Schoufeldt
, N., Pergamonpress/R6.), and nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention.

These nonionic surfactants may be used alone or as a mixture of two or more.

The polyethylene glycol type nonionic surfactant is used in an amount equal to or less than the weight of the hydrophilic binder, preferably 10% or less.

The light-sensitive material of the present invention can contain a cationic compound having a pyridinium salt. An example of a cationic compound with a pyridinium group is PSA Journal.
l, 5ection B 31r (/rij3)
, USP 2. ttar, 1q4L, USP 3.
It is described in t7/, 2 Ko 7, Tokko Sho till-3007"l, Tokko Sho≠Hir-2303, etc.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glucuraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) etc.), activated vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6
-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

For various additives, see “l'1esearchDiscl.
osure” Vol / 7o, June 197
Additives such as plasticizers, sharpness-improving dyes, AH dyes, sensitizing dyes, matting agents, fluorescent whitening agents, and antifading agents are listed in No. 1/702.

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

Further, if necessary, U.S. Patent No. 2,71. /, 79/ specification and British patent ♂37. It is also possible to apply two or more layers simultaneously by the method described in No. 5.

Various exposure means can be used in the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing include tanogsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources,
Also, CR, T4 sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources.

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 done by overlaying the original drawing by contact printing, reflection printing, or enlargement printing.

In addition, images taken with a video camera or the like or image information sent from a television station are sent directly to a CRT or FOT, and this image is formed on a heat-developable material using a contact lens 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. It is difficult to make an LED that effectively emits blue light. In this case, to reproduce a color image, green light, red light,
Three types of dyes that emit infrared light may be used, and the parts of the sensitive material that are sensitive to these lights may be designed to emit yellow maze/red and cyan dyes, respectively.

That is, if the green-sensitive portion (layer) contains a yellow dye-donating substance, the red-sensitive portion (C layer) contains a magenta dye-donating substance, and the infrared-sensitive portion (layer) contains a shea/dye-donating substance. good. Other combinations are also possible as required.

In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source is read with a light receiving element such as a phototube or CCD, and this information is stored in the memory of a computer etc. After performing so-called image processing, this image information is reproduced by the CR'T and used as an image-like light source, or based on the processed information, the three types of LEDs are directly emitted and exposed. There is also.

In the present invention, after exposure of the photosensitive material, the obtained latent image is, for example, approximately 0.6 cm to approximately 2 JO 0 °C. The element can be developed by heating the element at a moderately elevated temperature, such as from jt seconds to about 300 seconds. If the temperature is within the above range, the heating time can be increased or shortened (therefore, both high and low temperatures can be used. Especially about 1/1
Temperature ranges from 0°C to about /lo 0c are useful.

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

In the present invention, a specific method for forming a yellowish image by heat development is to transfer a hydrophilic mobile dye. For this purpose, the photosensitive material of the present invention has a photosensitive layer (on a support) containing at least silver halide, optionally an organic silver hydrochloride arsenic and a dye-donating substance which is also its reducing agent, and a binder. I) and a dye fixing layer (n) that can receive the hydrophilic and diffusible dye formed by layer (I).

The above-mentioned photosensitive layer (1) and dye fixing layer (If) may be formed on the same support, or may be formed on separate supports. The dye fixing layer ('II) and the photosensitive layer CI) can also be peeled off. For example, it is possible to carry out uniform heat development after imagewise exposure, and then peel off the dye fixing layer (I[) or the photosensitive layer. In addition, the photosensitive layer (I
) coated on a support, and a fixed layer (I[)v
When the fixing material and the fixing material coated on the support are formed separately, the light-sensitive material can be imagewise exposed and heated uniformly, and then the fixing material can be overlapped to transfer the mobile dye to the fixing layer (II).

There is also a method in which only the photosensitive material (I) is imagewise exposed, and then the dye fixing layer (n) is superimposed and uniformly heated.

The dye fixing layer (n) can contain, for example, a dye mordant for dye fixation. Various mordants can be used as the mordant, and polymer mordants are particularly useful. In addition to the mordant, a base, a base precursor, etc., and a hot solvent may be included. In particular, when the photosensitive layer (1,) and the dye fixing layer (II) are formed on different supports, it is particularly useful to include a base or a base precursor in the fixing layer (II).

The polymer mordants used in the present invention are polymers containing secondary and tertiary amine groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and having a molecular weight of 3,000-20o, ooo , especially yo,,o
These are from oo to so and boo.

For example, US Patent 2. jlAza, j7≠ issue, same 2゜4J'
Hiroshi, '/-30 issue, same 3.1 trttr, o6i issue, same 3.7! t, vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat. No. 3, t2! , &rihiro issue, same 3.
1! ri, 091. No., Dohiro, 72g.

5.3r, British Patent/, 277, ≠j3, etc. Polymer mordant crosslinkable with gelatin etc.; US Patent 3. rij♂, No. 775, 2.7.2/,
Zama No. 2, same λ, 72! , No. 01, 3, JP Akihiro
//No. 6221, same Tata≠-/≠Tata No. 22, same Yuhiro-/
Aqueous sol type mordant disclosed in US Pat. No. 21027, etc.; US Pat. No. 3. A water-insoluble mordant disclosed in the Ore specification; capable of forming a covalent bond with a dye disclosed in the U.S. Patent No. Reactive mordants; further U.S. Pat. No. 3,709. t90 issue, 3.71#, 163 issue,
Same 3, 1, 4t2. Ko♂ No. 2, same 3. Hirogg.

No. 70, 3. ! tj7IOtt issue, 3, 27/,
/≠7 issue, 3,277', /≠g issue, Tokukai Sho! 0-7
/332, j3-30321, j2-/taj,
Same as f21! The mordant disclosed in the specifications of 3-/2 Yu issue and 3-102 Hiro issue of the same publication can be mentioned.

Other US Patents 2. t, 7j, 3/4 issue, same co.

The mordants described in tryλ, No. 756 can also be mentioned.

Among these mordants, for example, those that crosslink with polymers such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used.

Particularly preferred polymer mordants are shown below.

(1) A group having a j-class ammonium group and capable of covalently bonding to gelatin (e.g., an aldehyde group, a chloroalkanoyl group, a chloroalkyl group, a vinylsulfonyl group, a gyridinium propionyl group, a vinyl sulfonyl group, an alkylsulfonokine group) For example, (-CH2-CH0-m-÷CH-CI-1101C=OC=01:2) a repeating position of a monomer represented by the following general formula and other ethylenic polymers. A reaction product of a copolymer consisting of repeating units of an unsaturated monomer and a crosslinking agent (e.g. bisalkanesulfonate, hisalene sulfite).

At least two of Blue-XeRb3, Bb, "5'7 alkyl group, aryl group, or bR3-R5 may combine to form a hetero term.

X: anion (the above alkyl groups and aryl groups include substituted ones) 3) Polymer X represented by the following general formula: about 0.25 to about J molar ratio y: about O to about 70 mole 2: About 10 to about 100% A: Monomer having at least λ ethylenically unsaturated bonds B: Copolymerizable ethylenically unsaturated monomer Q: N, PbbR, R2, R3: alkyl group, cyclic hydrocarbon group, Furthermore, at least two of Rb1 to Rb1 may be combined to form a ring. (These groups and rings may be substituted.) (4) Copolymer X consisting of (a), (b) and (C): hydrogen atom, alkyl group or halogen atom (
Alkyl groups may be substituted. ) (b) Acrylic acid ester (C) Acrylic nitrile (5) Water-insoluble polymer b, bb R, R2, R3: Each represents an alkyl group, having 3 or more repeating units represented by the following general formula. However, the total number of carbon atoms in ~R3 is /, 2 or more. (
Alkyl groups may be substituted. ) X: As the gelatin used for the anion mordant layer, various known gelatins may be used. For example, gelatin with different 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.

Mixing ratio of polymer mordant and gelatin of the present invention and
The amount of J-mer mordant applied is the amount of dye to be mordanted, 4
A person skilled in the art can easily determine the mordant/gelatin ratio depending on the type and composition of the remer mordant, the image forming process used, etc. The amount used is preferably 00j-♂fI/m2.

The dye fixing layer (■°) may have a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided over a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained.

The typical fixative material used in the present invention is obtained by mixing a polymer containing an ammonium salt with gelatin and coating the mixture on a transparent support.

For dye transfer from the photosensitive layer to the dye fixed layer.

Dye transfer aids can be used. As the dye transfer aid, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used.

Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used. The dye transfer aid may be used by moistening the image-receiving layer with a solvent, or may be incorporated into the dye in the form of crystal water or microcapsules.

Example 1 Gelatin ttot and KBrJ6? Dissolve in 3000ml of water. This solution was kept at 2zo0C and stirred.

Next, a solution of 200 g of silver nitrate and 0.0 g of water was added to the above solution over a period of 70 minutes.

After that, (2) a solution of 3.3 yt dissolved in 1 oo of water was added over 2 minutes.

The pH of the silver iodobromide emulsion thus prepared is adjusted, and the excess salt is removed by precipitation.

Thereafter, pHff1J was adjusted to 0 to obtain a silver iodobromide emulsion with a yield of ≠001.

Next, a method of preparing a gelatin dispersion of a dye-donating substance will be described.

Dye-donating substance α ■ Gota, as a surfactant, Koba /
Acid-2-ethyl-hexyl ester sulfoheptaic acid 7-:f
i”θ, tf, )!J-kresilfosphny) (T
Weigh CP) lof, add ethyl acetate 30- and add about t
After stirring and mixing the miko solution and 100 f of a 10 qb solution of lime-treated gelatin, the solution was heated and dissolved in O0C to make a uniform solution, and then mixed with a homogenizer for 10 minutes. OOORP
Disperse at M.

This dispersion liquid is called a dispersion of a dye-providing substance.

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

(a) Photosensitive silver iodobromide emulsion 2!1 (
b) Dispersion of dye-donating substance J3f(C
) Guanidine trichloroacetic acid/, solution dissolved in jtf ethanol Ij1Rt 10ml (e) * Methanol 0o4, a sensitizing dye that imparts green sensitivity! multi-solution
Hirogo (f) IO-containing aqueous solution of dimethyl sulfamide (a) to (f) of Kogo 8 green sensitizing dye or above are mixed, heated and dissolved, and then a polyethylene terephthalate film Al-
It was applied to a wet film thickness of 30 μm.

A protective layer was provided by applying a ≠tizelatin solution to a wet film thickness of 30 μm on top of this.

This sample is called a sample person.

Next, a high boiling point solvent dispersion in which only a high boiling point solvent is dispersed,
The dispersion was prepared in exactly the same manner as the non-color imparting dispersion, except that the dye imparting substance was added only once.

This is called a high boiling point solvent dispersion.

Next, the method for preparing the sample of the present invention will be described.Thickness/I
The following coating was applied as a first layer on a polyethylene terephthalate film of Iμ to a wet film thickness of 3θμ.

(a) 10 gelatin aqueous solution in iot) Dispersion of trap dye-donating substance used in sample A
30? (C) 1O chetanol solution of guanidine trichloroacetic acid
13ml liquid
(e) 104 aqueous solution of dimethyl sulfamide A second layer was coated on this layer with a wet film thickness of 30μ.

(a) Photosensitive silver iodobromide emulsion used in sample A
y Φ) High boiling point solvent dispersion (C)
104 ethanol solution of (guanidine) dichloroacetic acid
6 Gojiri
j+d(e) 0.0 h methanol solution of the above green-sensitive sensitizing dye
A protective layer was formed by applying a 4C gelatin solution to a wet film thickness of 2Jμ on top of the coating. This sample is called sample B.

Furthermore, as another sample of the present invention, sample B' having the following composition was prepared.

1st layer (wet film thickness 20μ) (a)/θ% gelatin aqueous solution l0f (b)
Dispersion of skin pigment-providing substances used in sample humans
30f 2nd layer (wet film thickness 2
0μ) (a) Photosensitive iodobromide pot emulsion used in sample 0f Φ) 104 ethanol solution of guanidine trichloroacetic acid 14! Go solution
6-(d) 0.0% of the green-sensitive sensitizing dye.
0 μ methanol solution - 1 protective layer (wet film thickness 30 μ) ≠ Gelatin solution samples A, B, B' Using a t-tungsten bulb, pass through a green filter from the protective layer side,
Exposure was performed at ooo lux for 10 seconds through a step wedge with a density difference of 0.3. It was then heated uniformly for 30 seconds on a heat block heated to /JO°C.

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

Poly(acrylic acid methyl-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (acrylic i!!;! Ratio of acrylic acid and vinylbenzylammonium chloride is i:1) iot+, tood, dissolved in water, Mixed homogeneously with loTo lime treated gelatin toot. This mixed solution was uniformly applied to a wet film thickness of 20 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample was used as an image-receiving VJ material.

After soaking the image-receiving material in water, add the heated photosensitive resist described above.
A superimposed trap where the membrane surfaces touch. After 30 seconds, the receiving material was peeled off from the photosensitive material, leaving a negative magenta color image on the receiving material. The density of this negative image was measured using a Macbeth reflection densitometer (RD-JL).

The results are shown below.

* The first stage is set at the point where the density of the wedge is zero, that is, the plain glass, and as the number of stages increases, the density increases by (7, J). The number of steps with the highest concentration.If there is a difference of one step, it will be a shoulder-to-nosed guide.

The results xl) It can be seen that in the present invention, the sensitivity is approximately 76 times higher.

It can also be seen that when the samples A, B, and B' were left for 3 days, the variation in sensitivity of the present invention was smaller and superior.

Example 2 A dispersion of a dye-providing substance was prepared by changing the dye-providing substance io in Example 1 to 33.

Comparative Sample C was prepared in the same manner as Sample A of Example 1, except that a dispersion was used in which the dye-donating substance No. 33 was changed, and a green-sensitive dye was not added.

Samples of the present invention, D%D't-, Sample B, Sample B, except that a dispersion of the dye-donating substance fi-(jJ) used in preparing B' is used and no green-sensitive dye is added;
Each was made in the same manner as B'.

Samples C and D were manufactured using a tungsten bulb and were exposed through a step wedge with a density difference of 0.3 in steps at 1000 lux from the side of the protective layer.

Thereafter, it was heated uniformly for 30 seconds on a heat block heated to iso'c.

Next, using the image receiving dye of Example 1, dye transfer was carried out in the same manner as in Example 1.

The results are shown in the table below.

In this case as well, it can be seen that the sensitivity of / is twice as high in the present invention.

Example 3 Benzotriazole t, jf and gelatin 109 parts water 10 parts
Dissolves in 00-. This solution f! Keep at O0C and stir. Next is Nitsu IIP Gin Jr! ff water io.

Add the solution dissolved in water to the above solution in minutes. The pH of the benzotriazole silver emulsion thus prepared is adjusted and the excess salt is removed by sedimentation. Thereafter, the pH was adjusted to t and o to obtain a benzotriazole silver emulsion with a yield of λooy.

Next, a method of preparing a gelatin dispersion of a dye-donating substance will be described.

Dye-donating substance (4AO) fj? , as a surfactant,
Sodium succinate-λ-ethylhexyl ester sulfonate O, JP,) leak resyl phosphate (TCP
)10r? Weigh it, add ethyl acetate JOtdf, and heat to dissolve at about 0°C to make a homogeneous solution. After stirring and mixing this solution and 1 oot of a 70% solution of lime-treated gelatin, io, oooRpM was mixed with a homogenizer for 10 minutes.
Disperse at. This dispersion liquid is called a dispersion of a dye-providing substance.

A method for preparing the photosensitive coating of Comparative Sample E will be described.

(a) Photosensitive silver iodobromide emulsion /jf(
b) Benzotriazole silver emulsion -2Of(
C) Dispersion of dye-donating substance JJf/(
d) Solution of guanidine trichloroacetic acid ylii, zt with ethanol tZW< 10N
(f) *Methanol Qo4, a sensitizing dye that gives green sensitivity
A% solution 4L of dimethyl sulfamide IQ aqueous solution was coated on a 2-8 green sensitized troμ polyethylene terephthalate film to a wet film thickness of 30 μm.

Wet the gelatin solution on top of this to a thickness of 3.

A protective layer was provided.

This sample is called sample (　E　) t-f.

Next, the method of adjusting the sample of the present invention will be described.Thickness 1
The following coatings were applied to a wet film thickness of 30μ on a 10μ polyethylene terephthalate film.

(a)/(＞Aqueous gelatin solution iotΦ)
Dispersion of dye-donating substance used in sample A
JOf(C) Ethanol solution of guanidine trichloroacetic acid in 109
IJtd liquid
! -(e) 4 lQ ice water solution of dimethyl sulfamide Apply 3 coats of the following on top of this layer.
It was coated with a wet film thickness of 0μ.

(a) Photosensitive silver iodobromide emulsion l used in sample A
! t Φ) Benzotriazole chain emulsion 10t(C)
High boiling point solvent dispersion used in sample B (d) Low coefficient ethanol solution of guanidine trichloroacetic acid trnt solution
Yo (f)
O0Q≠methanol solution of the above green-sensitive sensitizing dye
2-A protective layer was provided on this by coating a gold wet film thickness of 30A with a gold gelatin solution. This sample is called sample (F).

Sample E was used on an Ft-tungsten bulb and exposed for io seconds at 500 lux from the protective layer side through a step wedge with a density difference of 0.3 and a green filter. Thereafter, the mixture was heated uniformly for 30 seconds on a heat block heated to 13°C.

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

Poly(methyl acrylate-N,N',N-trimethyl-N-vinylbenzylammonium chloride) (acrylic acid) Ratio of methyl acrylate to vinylbenzylammonium chloride td/:I)IOftl-100d. of water and mixed homogeneously with 104 lime processed gelatin tooy. This mixed solution t-2 titanium oxide was uniformly applied to a wet film thickness of 0 μm onto a paper support laminated with polyethylene dispersed therein. After this sample was completely dried, it was used as an image receiving material.

After soaking the image-receiving material in water, heat it as described above and heat it.
Lay tiles together so that the membrane surfaces are in contact. After 30 seconds, when the image-receiving material is peeled off from the photosensitive feather, a negative magenta color image is obtained on the image-receiving material. Also applied samples E and Ffj
A sample left at O'C for 3 days was exposed, developed and transferred in the same manner.

The density of these negative images was measured using a Macbeth reflection densitometer (RD-t
It was measured with The full results are shown below.

As a result, even when all organic silver salt oxidizing agents were used together,
It can be seen that Sample F of the present invention has high sensitivity and little deterioration in sensitivity due to forced aging, which is excellent.

Example 4 Sample G-L was prepared in the same manner as in Example 1, except that the first and second layers of Sample B in Example/ were changed to the first and second layers with the following thread handles. was created.

In this embodiment, the film thickness and oil amount of the first layer and the first layer are kept constant, and the effect of the present invention is fully realized.

Exposure, development, and density measurement were performed in the same manner as in Example 1.

The results are shown in the table below.

(The method of measuring sensitivity is the same as in Example 1.) There is no difference in sensitivity between Sample L and Comparative Sample A in Comparative Example 1 of Example 1, and the effect of the present invention is obvious. It is effective for

It can be seen that the presence of the silver halide emulsion in the second layer is effective in achieving the effects of the present invention.

Preferred embodiments are as follows.

1. IF used in % claims! , an image forming method characterized in that the optical material contains an organic silver salt and gold.

2. An image forming method characterized in that the claimed WIc source material contains a reducing agent for organic silver salt.

λ Organic silver salt oxidizing agent A dye-donating substance that can be totally reduced and releases a hydrophilic mobile dye has the following general formula (
1) An image forming method according to the claims.

R-802-D (I 1 where R represents a reducible substrate that can be oxidized by an organic silver salt oxidizing agent and D represents an imaging dye Il-ara).

4. The reducing substrate R in the dye-donating substance R-8o□-D in item 3 has a redox potential of 7 with respect to a saturated calomel electrode.
．． An image forming method characterized in that the image forming temperature is λV or less.

& An image forming method characterized in that the reducing substrate R in the dye-donating substance R-802-D of item 3 is represented by the following general formula (Ill~([1).

0) 1 H N) 1- N) I- B 2 2 2 Here, R and R each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, Acylamino group, alkylsulfonylamino group, arylsulfonylamino group, iri-ruoxyalkyl group, alkoxyalkyl i, N-
carbamoyl i, N-fli substituted sulfamoyl group,
It represents a substituent selected from a halogen atom, an alkylthio group, and an arylthio group, and the alkyl group and aryl group moiety in these substituents further includes an alkoxy group, a halogen atom, a hydroxyl group, a cyano group, an acyl group, an acylamino group, It may be substituted with a substituted carbamoyl group, a substituted sulfamoyl group, an alkylsulfonylamine group, an arylsulfonylamino group, a substituted ureido group, or a carbalkoxy group.

6. D in the dye-donating substance R-80□-R of Section 3
Hydrophilic azo, azomethine, anthraquinone, naphthoquinone, styryl, nitro, quinoline carbonyl,
An image forming method as claimed in the claims, characterized in that it is a phthalocyanine dye.

7. An image forming method according to the claims, characterized in that the light-sensitive material further contains a dye release aid.

& An image forming method characterized in that the dye release aid according to item 7 is a base or a base precursor.

9. An image forming method, wherein the organic silver salt oxidizing agent of item 1 is a silver salt of a carboxylic acid derivative or a nitrogen-containing heterocyclic compound.

10, 41ij. An image forming method characterized in that the hydrophilic binder according to claim 1 is gelatin or a gelatin derivative.

11.'FF An image forming method in the claims, characterized in that the released mobile dye is transferred to a dye fixing layer using water or a basic aqueous solution.

12. An image forming method characterized by using a dye mordant in the dye fixing layer of item 1/.

13L An image forming method characterized in that the 21st organic silver salt oxidizing agent is a silver salt of a nitrogen-containing heterocyclic compound.

14L An image forming method characterized in that the dye fixing layer of item 1I is provided on a fixing material.

Heel: An image forming method characterized in that the dye fixing layer of item 1/ is provided on a light-sensitive material.

1a Sensitive silver halide, a dye-donating substance that is reducible to photosensitive silver halide and reacts with photosensitive silver halide to release all of the hydrophilic dye upon heating, and binder gold are provided on the support. , and the dye-providing substance and the photosensitive silver halide are present singly or both together in a binder layer group consisting of at least λ adjoining binder layers, in which Heat development characterized in that there exists a relationship between any one of the adjacent λ binder layers, in which the coating amount of the dye-providing substance in the binder layer on the side from which the source enters is smaller than that in the other binder layer. Color photosensitive material.

Claims (1)

[Claims] Contains a KMA photosensitive silver halide film on the support and/or a dye-donating substance that is reducing to the photosensitive silver halide and reacts with the photosensitive silver halide upon heating to release a hydrophilic dye. It has two binder layers adjacent to each other, and of the λ binder layers, the coating molar amount of the dye-donating substance of binder #(A) on the side into which exposure light enters is equal to that of the other binder. A method of forming a movable dye in the form of an image by heating a photosensitive material characterized in that the layer (B) has a small amount of deviation at the same time as exposure or after exposure in a substantially water-free state.