JPS62264041A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of dry-processing with simplicity and rapidly and capable of forming a colored image having a high sensitivity by a short exposure time by mounting a photosensitive layer composed of a photosensitive silver halide and a specific compd. on a substrate body. CONSTITUTION:The titled material is formed by mounting the photosensitive layer contg. at least photosensitive silver halide, a developer, a polymerizable compd., a color image forming substance and hydrazine derivatives shown by formula I and/or II on the substrate body, and is formed so as to make the color image forming substance an immobile state by heat-processing the image, after exposing it. In the formula, R1 is a substd. or an unsubstd. alkyl or cycloalkyl group, R2 and R6 are each hydrogen atom or a substd. or an unsubstd. alkyl group, R3 is a monovalent group derivated from a substd. or an unsubstd. aromatic ring or aromatic heterocyclic ring, R4 and R5 are each a substd. or an unsubstd. aryl group. Thus, the titled material capable of dry- processing with simplicity and rapidity and capable of forming the color image having the high sensitivity by the short exposure period, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Technical Field The present invention relates to photosensitive materials. More specifically, a photosensitive silver halide is used as a photosensor, an image-like latent image is formed on the silver halide by light irradiation, and then a monopolymerizable compound is combined or crosslinked, and a coexisting dye or The present invention relates to a photosensitive material that immobilizes a dye-forming substance.

Prior Art and its Problems Various types of photosensitive materials other than so-called conventional photographic materials are known that utilize photosensitive silver halide as a photosensor. For example, British Patent No. 8
No. 66.631 uses silver halide as a catalyst,
A method of directly causing photopolymerization has been disclosed, but in this method, it is thought that the product generated by photolysis of silver halide acts as a catalyst for IK synthesis, and the silver halide is reduced by normal development. The sensitivity was not as high as in the case. Furthermore, Belgian Patent No. 642,477 discloses that after exposed silver halide grains are developed with an ordinary developer, the resulting silver image or unreacted silver halide is used as a catalyst to cause a polymer compound to be formed. A method for forming images in an image-like manner has been disclosed, but this requires complicated operations. Furthermore, Special Publication No. 45-1149, No. 47-
No. 20741.

No. 49-10697, JP-A-57-138632,
No. 58-169143 discloses that when exposed silver halide is developed using a developer, the developer is oxidized and at the same time, coexisting vinyl compounds start polymerizing to form an image-like polymeric substance. Although a method for forming the film has been disclosed, this method requires a development process using a liquid, and the process requires a relatively long time.

There are various known image forming methods using such photosensitive silver halide as a photosensor, but none of them provide high sensitivity or require complicated development processes. It has disadvantages such as.

(2) Purpose of the Invention The purpose of the present invention is to provide a highly sensitive photosensitive material that can produce color images through simple and rapid dry processing and in a short exposure time.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the first invention provides at least a photosensitive silver halide, a developer, a polymerizable compound, a color image forming substance, and a hydrazine derivative represented by the following general formula (I) and/or the following general formula on a support. This photosensitive material is characterized in that it has a hydrazine derivative represented by (II) and is configured to immobilize a color image forming substance by heat development after image exposure.

General formula (I) Rt -N H-N H-C-R2 General formula (II) R3-N H-N H-C-R5 (In general formula (I), R1 is a substituted or unsubstituted Alkyl group, cycloalkyl group, aralkyl group,
Represents an aryl group, alkenyl group, alkynyl group or heterocyclic group. R2 is a hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, alkenyl group, alkynyl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, or amino salt represents.

In the above general formula (II), R3 represents a monovalent group derived from a substituted or unsubstituted aromatic ring or aromatic heterocycle. R4 and R5 each represent a substituted or unsubstituted aryl group. R6 represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkoxycarbonyl group, or carbamoyl group. ) The second invention provides a support containing at least a photosensitive silver halide, a developer, a polymerizable compound, a color image forming substance, a base and/or a base precursor, and the following general formula (I
) and/or a hydrazine derivative represented by the following general formula (■), and is configured to immobilize a color image forming substance by heat development after image exposure. It is the material.

General formula (I) II R1-N H-N H-C-R2 General formula (II) R3-N H-N H-C-Rs (In the above general formula (I), R1 is a substituted or unsubstituted Alkyl group, cycloalkyl J^, aralkyl J
^, represents an aryl group, alkenyl J^, an alkynyl group or a heterocyclic group. R2 is a hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, alkenyl group, alkynyl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, or amino represents a group.

In the above general formula (II), R3 is derived from a substituted or unsubstituted aromatic or aromatic heterocycle -
・Represents the base of valence. R4 and R5 each represent a substituted or unsubstituted aryl group. R6 represents a hydrogen atom f or a substituted or unsubstituted alkyl group, aryl group, alkoxycarbonyl group, or carbamoyl group. ) ■Specific structure of the invention From now on, the specific structure of the present invention will be explained in detail.

The photosensitive material used in the dry image forming method of the present invention includes a hydrazine derivative represented by the following general formula (I) and/or
Or it has a hydrazine derivative represented by the following general formula (■).

General formula % Formula % (1) General formula 6 In the above general formula (I), R1 is a substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, n
-butyl group, hexyl group, 2-ethylhexyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, octadecyl group, 2-methoxydiethyl group, 2-chloroethyl group, furfuryl group, etc.), cycloalkyl group (e.g. cyclopentyl group) group, cyclohexyl group, etc.), aralkyl group (e.g. diphenylmethyl group, benzyl group, furfuryl group, 1-phenylethyl group, etc.), aryl group (e.g. phenyl group, tolyl group, xylyl group, methoxyphenyl group, dimethoxyphenyl group, 2-methoxy-4-methylphenyl group, naphthyl group, 2-methoxynaphthyl group, etc.), alkenyl group (e.g. propenyl group, butenyl group, styryl group, etc.), alkynyl group (e.g. propargyl group, phenylethyl group, etc.), or Heterocyclic groups (for example, 4-ethoxyphthalazino group, benzothiazolyl group, quinolyl group, benzochromanyl group, pyridyl group, imidazolyl group, indolyl group, etc.) are preferred, and among these, substituted or unsubstituted aryl groups, An aralkyl group or a heterocyclic group is preferred.

R2 is a hydrogen atom f or a substituted or unsubstituted alkyl group (e.g. methyl group, trifluoromethyl group, trichloromethyl group, t-butyl group, heptyl group, pentadecafluoroheptyl group, 3- (2,4- t-pentylphenoxy)propyl group, etc.), cycloalkyl group (e.g., cyclohexyl group, etc.), aralkyl group (e.g., benzyl group, diphenylmethyl group, etc.), aryl group (e.g., phenyl group, dichlorophenyl group, etc.)
methoxycarbonylphenyl group, tolyl group, 4-cyanophenyl group, naphthyl group, etc.), alkenyl group (e.g. styryl group, propenyl group, butenyl group, etc.), alkynyl group (e.g. phenylethynyl group, propargyl group, etc.), heterocycle groups (e.g. pyridyl group, benzimidazolyl group, quinolyl group, chenyl group, furyl group, benzothiazolyl group, benzochromanyl group, etc.), alkoxy groups (e.g. trifluoroethoxy group, 2-methoxyethoxy group, etc.), aryloxy J^ (for example, phenoxy group, 4-cyanophenoxy group, etc.), alkylthio group (for example, n-butylthio group, n-octylthio group, dodecylthio group, etc.), arylthio group (for example, phenylthio group, etc.), or amino! ! , (for example, diethylamino group, dibutylamino group, benzylamino group, di-2-ethylhexylamino group, etc.), among which substituted or unsubstituted alkyl groups, aralkyl groups, aryl groups, alkenyl groups, alkynyl groups, etc. Alternatively, a heterocyclic group is preferable.

Preferred specific examples of the hydrazine derivative represented by the general formula (I) used in the present invention are shown below.

ON HN HCOCH3ζΣNHNHCOH(Hd-
1) (Hd-2) (Hd-
3) ()-NHNHcodiniXco2CH3()Id-4) (Hd-5) (Hd-6)
(ΣNHNHCOCH-CHO (Hd-7) (ΣNHNHCOCH-CHO (Hd-7) (> (Hd-8) (Hd-9) (Hd-10) (Hd-11) (Hd-12) (Hd-13) (Hd-14) (Hd-15) (Hd-16) (Hd-17) (Hd-18) (Hd-19) CH30()NHN HC0c7) Its(Hd-2
0) (Hd-21) (Hd-22) (Hd-23) (Hd-24) (Hd-25) (Hd-26) (Hd-27) (Hd-28) 8 (Hd-29) (Hd -30) (Hd-31) ()id-32) (Hd-33) (Hd-34) (Hd-35) ()Id-36) (Hd-37) (Hd-38) Next, the general formula ( ■) will be explained. R3 represents m groups derived from a substituted or unsubstituted aromatic ring or aromatic heterocycle.

R4 and R5 each represent a substituted or unsubstituted aryl group. R8 represents a hydrogen atom T- or a substituted or unsubstituted alkyl group, aryl group, alkoxycarbonyl group or carbamoyl group.

Examples of the aromatic ring or aromatic heterocycle constituting R3 include benzene, naphthalene, anthracene, pyridine, imidazole, benzimidazole, benztriazole, thiazole, benzthiazole, phthalazine, quinoline, and isoquinoline.

These substituents include alkyl groups (for example, methyl group, ethyl group, butyl group, t-butyl group, t-amyl group, 2-ethylhexyl group, t-octyl group, nonyl group, dodecyl group, octadecyl group, etc.). ), aryl groups (e.g. phenyl group, tolyl group, benzyl group, diphenylmethyl group, etc.), halogen atom γ- (e.g. fluorine atom r-1 chlorine atom t, bromine atom, etc.), alkyl or aryloxy group (e.g. methoxy group) , ethoxy group, 2-methoxyethoxy group, benzyloxy group, octyloxy group, octadecyloxy J^, phenyloxy group, etc.), alkyl or arylsulfonyl group (e.g. methylsulfonyl group, ethylsulfonyl group, butylsulfonyl J^, benzylsulfonyl group, octylsulfonyl group, dodecylsulfonyl group, octadecylsulfonyl group, benzenesulfonyl group, etc.), cyano group, carbamoyl group, substituted carbamoyl group, (e.g. N,N-diethylcarbamoyl J
^, N, N-dibutylcarbamoyl group, N.

N-dioctylcarbamoyl group, N-methyl-N-octadecylcarbamoyl group, N-methyl-N-benzylcarbamoyl group, etc.), sulfamoyl group, substituted sulfamoyl group (for example, N.

N-diethylsulfamoyl group, 2-ethylhexylaminosulfonyl M, N,N-dibutylsulfamoyl group, N,N-dioctylsulfamoyl group, N-methyl-
N-octadecylsulfamoyl group, etc.), alkyl or arylcarbonyl group (eg, acetyl group, benzoyl group, etc.), and the like.

Preferred examples of R3 include m groups derived from substituted or unsubstituted benzene, naphthalene, thiazole, and phthalazine. In this case, the substituent group can be chosen from an electron-attracting or electro-fondonting group, and the general formula (I
The reactivity of the compound represented by I) can be expressed in 38 sections.

Specific examples of R4 and R5 include phenyl group, p-chlorophenyl group, tolyl group, p-bromophenyl group, p-
-methoxyphenyl group, 2,6-dichlorophenyl group,
Preferred are p-cyanophenyl group, methoxycarbonyl group, and the like.

Specific examples of R6 include hydrogen atom t, alkyl groups such as methyl group, ethyl group, butyl J, c, amyl group, 2-ethylhexyl group, dodecyl group, octadecyl group, etc., and aryl group such as phenyl group and p-chlorophenyl group. , tolyl group, p-bromophenyl group, P-methoxyphenyl group,
2.6-dichlorophenyl group, p-cyanophenyl group, etc., methoxycarbonyl group as alkoxycarbonyl group,
Ethoxycarbonyl group etc., carbamoyl group, substituted carbamoyl group as N,N-diethylcarbamoyl group%N,
Examples include N-dibutylcarbamoyl group, among which methyl group, phenyl group, p-chlorophenyl group, p-bromophenyl group, methoxycarbonyl group and the like are preferred.

Preferred specific examples of the hydrazine derivative represented by the general formula (II) used in the present invention are shown below.

2 HD-1,0 D-11 D-12 D-13 HD-14 D-16 1'l17a
The synthesis of the hydrazine derivative represented by the Pn general formula (II) will be specifically explained below by giving a synthesis example.

To a mixture of 43.2 g (0.4 mol) of phenylhydrazine and 500 ml of tetrahydrofuran was added 55.7 g (0.2 mol) of trityl chloride little by little at room temperature with a stirring knife. added. After addition, when heated to 30℃, it gradually generates heat and 5
The temperature rose to 0°C. After heating and stirring at 50° C. for 5 hours, the mixture was allowed to cool to room temperature, and the crystals were filtered off. The crystals were washed with tetrahydrofuran, the washing liquid and the filtrate were combined, and the solvent was distilled off under reduced pressure F.

The residue was recrystallized twice from benzene-hexane (1:1) to obtain 38 g of almost colorless prismatic crystals (yield 54
%). mp=131-133℃ (decomposition) 1 degree decomposition Composite compound HD-2 2.4.6-Dolichlorophenylhydrazine hydrochloride 99
．． 2 g (0.40 mol) and tetrahydrofuran 750
mJI mixture at room temperature, triethylamine 55.4
+d was added dropwise.

Then, 55.7 g (0.2 mol) of trityl chloride was added little by little, and the mixture was heated to 50-60°C. After heating at the same temperature for 3 hours, the mixture was allowed to cool to room temperature, and the crystals were separated by filtration. The crystals were washed with tetrahydrofuran, the washings and filtrate were combined, and the solvent was distilled off under reduced pressure.

Recrystallize the residue from acetonitrile to obtain white crystals with 62.9%
g (yield 69%). mp=144~147℃(
Decomposition) 300 g of 4-methanesulfonylchlorobenzene (1,5
7 mol) and 300 ml of chlorosulfonic acid (4,5
3 mol) at room temperature with stirring. 1 of the mixture
The temperature was raised to 20°C and stirring was continued for 16 hours. After cooling, the reaction solution was poured into ice water, and the resulting crystals were collected by filtration and air-dried to obtain 293 g of HD-39a (yield: 64%).

Butyloctylamine 52.5g (0.28 mol),
35 g (0.34 mol) of triethylamine and N,
200 ml of N-dimethylformamide was mixed, and 81.2 g of crystals of HD-39a were added thereto while cooling with water and stirring.

Thereafter, the mixture was heated to 50°C and stirred for 3 hours.

After the reaction solution was allowed to cool, it was poured into water and extracted with ethyl acetate. The organic layer was washed several times with dilute hydrochloric acid and water and then dried over magnesium sulfate. After filtering off the magnesium sulfate and distilling off the solvent, it was purified by silica gel column chromatography to obtain 83 g of HD-39b (oil) (yield: 6
7%).

3-3.2- N-Puru N-Off Rusuru) ID-
39b 62. Ig (0.14 mol) was dissolved in ethanol and added dropwise to a mixture of 35 g (0.7 mol) of foamy hydrazine and ethanol at room temperature. 50 minutes after completion of dripping
The mixture was heated to ℃ and stirred for 10 hours. After cooling, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed several times with dilute hydrochloric acid and water, dried over magnesium sulfate, the solvent was distilled off, and purified by silica gel column chromatography to obtain HD-3.
59 g of crystals of 6c were obtained (yield 97%).

4-4. Δ of HD-39 59 g (0.136 mol) of HD-39c and 15 g (0.15 mol) of triethylamine were dissolved in tetrahydrofuran, and 40 g (0.1 mol) of triphenylmethyl chloride was dissolved in tetrahydrofuran.
, 143 mol) was added as a solid and stirred at 50°C for 6 hours. After cooling, the crystals formed were filtered, the solvent was distilled off from the filtrate, methanol was added, and the mixture was cooled to below 5°C to crystallize. The obtained crystals were purified by recrystallization from methanol to obtain 3940 g of HD-3 (yield: 43%).

mp=108-110°C The hydrazine derivative represented by the general formula (I) is dissolved in a solvent such as methanol, dichloromethane, ethyl acetate, cyclohexanone, etc., and the hydrazine derivative represented by the general formula (■) is dissolved in a solvent such as cyclohexanone, dichloromethane, ethyl acetate, It is dissolved in a solvent such as methanol and used in the oil drop method or microcapsule method.

The amount added is 0.1 to 70 mol % in the case of the acyl hydrazine derivative of general formula (I) and 0.01 to 50 mol % in the case of the hydrazine derivative of general formula (■) with respect to 1 mol of the polymerizable compound.
It is preferable to set it as mol%. Moreover, in any case, it is preferable that the content is 0.1 to tsoo mol % per 1 mol of silver. The hydrazine derivatives of general formulas (I) and (II) may be used in combination, but whether they are used alone or in combination, they are preferably used in combination with a developer.

The photosensitive material of the present invention uses a photosensitive silver halide as a photosensor, and the latent image nuclei of the silver halide generated by exposure act as a catalyst to cause an oxidation-reduction reaction between the silver salt and the dorazine conductor. A polymerization reaction is carried out using the resulting radical intermediate as an initiator, or a radical is generated by thermal decomposition of a redox reaction product between a hydrazine derivative and a silver salt, or a radical is generated by reacting this product with another compound. Perform the polymerization reaction as an initiator, or
Alternatively, if the developer coexists with the hydrazine derivative,
In the process of forming developed silver by reducing silver salt with this developing agent, the hydrazine derivative is catalytically decomposed on the developed silver or reacts with the oxidized developer to efficiently generate radicals, and these radicals act as initiators. The color image-forming substance is immobilized by 1R polymerization or crosslinking of the polymerizable compound. however,
In the present invention, the reaction mechanism has not been elucidated in detail,
The mechanism is not limited to the above mechanism.

Therefore, the photosensitive material of the present invention is composed of a photosensitive element and an image receiving element. Here, the photosensitive element includes a photosensitive silver halide, a reducing agent, a developer, a hydrazine derivative, a polymerizable compound, and a color image-forming substance, and at least the polymerizable compound and the color image-forming substance are the same microorganisms. An element encapsulated in a capsule or emulsified oil droplet is meant, while an image-receiving element is an element that fixes the color image-forming material emitted from the photosensitive element and forms a color image. The structure of these elements and the method of image formation will be described below, but embodiments using the photosensitive material of the present invention are not limited thereto.

(1) When the color image-forming substance is itself a colored dye or pigment.

(a) A light-sensitive element and an image-receiving element are coated on separate supports to form a light-sensitive material and an image-receiving material, respectively, and the light-sensitive material is imagewise exposed, heated or uniformly exposed, and then formed into an image-receiving material. The combined pressure forms a color image on the image-receiving material.

(b) A photosensitive element is coated on the support, a light reflecting layer is coated thereon, and an image receiving element is further coated thereon. This light-sensitive material is imagewise exposed from the support side, heated or uniformly exposed, and then the color image-forming substance is moved imagewise to the image-receiving element by applying pressure to form a color image on the image-receiving element.

(2) The color image-forming substance itself is colorless or light-colored, but develops color when other energy is applied. In this case, the configuration is likely to be R-like, where (a) and (b) in (1) above are the same. In either case, a step of applying energy to cause the color image-forming substance to develop color is required. However, if this color development occurs at the same time as (1) heating, exposure, or pressurization, no special process is required.

(3) Color image formation! When a color former (in this case called a color former) is colorless or light colored by itself, but develops a color when it comes into contact with another component (called a color developer).

(a) In the same manner as (a) of (1) above, if a color developer is contained in the image receiving element, the color image forming substance and the color developer come into contact with each other under pressure, and a "color image is formed". Form.

(b) In the same manner as (b) of (1) above, if a color developer is contained in the image receiving element, the color image forming substance and the color developer come into contact with each other under pressure, and a color image is formed. Form.

(C) There is an embodiment in which the photosensitive element and the image receiving element are coated adjacent to each other on the support 1, or the components of these two elements are mixed and coated. In either case, when the color developer is used as a component of the image-receiving element, the photosensitive material (which also serves as the image-receiving material) is imagewise exposed and then heated, or the oil droplets destroyed by applying pressure after uniform exposure. Alternatively, a color image forming substance and a color developer are catalyzed in the vicinity of the microcapsules to develop color and form a color image. In this case, since the color image forming material in the portion where no color develops is substantially colorless, it can be visually seen directly as a color image.

Various recording materials using oil droplets or microcapsules have been known. For example, Japanese Patent Publication No. 42-14344 (U.S. Pat. No. 3,219,44)
No. 6) involves image-wise exposing a sensitive sheet containing many fluid droplets that become non-flowing when exposed to light, superimposing this onto an image-receiving sheet and applying pressure to the entire sheet. A method for transferring an image according to exposure onto this image-receiving sheet is disclosed.

Furthermore, in JP-A No. 52-89915, one component of a two-component heat-sensitive coloring material iτ and a light marketable material are encapsulated in microcapsules, and this microcapsule is mixed with the other component of the heat-sensitive coloring material. A method is disclosed in which an image is obtained by coating the photosensitive sheet on a base sheet, exposing the photosensitive sheet imagewise to harden the microcapsules in the exposed areas, and then heating the entire surface to develop color only in the unexposed areas. .

Furthermore, Japanese Patent Application Publication Nos. 57-124343 and 57-1798
No. 36 and No. 57-197538 discloses an image forming method using microcapsules containing a vinyl compound, a photopolymerization initiator, and a dye precursor, by applying pressure to the entire surface after exposure to form a dye image that does not require heating. A method is disclosed. Further, Japanese Patent Publication No. 54-20852 (US Pat. No. 3,700,439) discloses an image forming method using Michler's ketone as a photosensitive substance in an encapsulated manner.

U.S. Pat. No. 3,072,481 also encapsulates a photosensitive material that is readily converted to a colored form in a liquid but is photoinsensitive when solid, and a layer of this encapsulation is imaged. A method of forming an image by exposing the capsule to light and then rupturing the capsule to evaporate the solvent, a so-called photosensitive and pressure sensitive image forming method, has been disclosed.

Various image forming methods using the above-mentioned microcapsules are known, but all of them have in common a low sensitivity to light, particularly a marked lack of sensitivity to green light and red light. In addition, an attempt to increase this sensitivity has the disadvantage that storage stability decreases.

That is, the present invention solves these drawbacks by using photosensitive silver halide as a photosensor.

In the present invention, depending on the type of photosensitive silver halide used, it is possible to produce a polymer compound corresponding to both exposed and unexposed areas.

Ru. Areas where polymer compounds have formed have increased pressure resistance compared to areas where they have not formed, and as a result, the color image can be transferred by applying pressure to the areas where polymer compounds have not formed. A color image can be formed using a forming substance. Therefore, in the present invention, depending on the type of photosensitive silver halide used or the color image forming process adopted, either a negative image or a positive image can be freely created for the i-image, and in some cases, both negative and positive images can be created simultaneously. You can also make one.

For example, when obtaining a color image by transferring an area where no polymer compound is formed, a normal negative-working silver halide emulsion can be used to obtain a positive-working image with respect to the original image. In order to form a negative image, U.S. Pat.
．． No. 367.778 and 3,447,927;
Mixtures of surface-imaged silver halide emulsions and internal-imaged silver halide emulsions such as those described in US Pat. No. 6,382 can be used.

In the present invention, when obtaining a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan in the subtractive color method, the light-sensitive material is at least three types of silver halide emulsions each sensitive to different spectral regions. It is necessary to have

Typical combinations of at least three light-sensitive silver halide emulsions sensitive to very different spectral regions include a combination of a blue-sensitive emulsion, a green-sensitive emulsion and a red-sensitive emulsion; a green-sensitive emulsion; a red-sensitive emulsion; Examples include combinations of infrared-sensitive emulsions, combinations of blue-sensitive emulsions, green-sensitive emulsions and infrared-sensitive emulsions, and combinations of blue-sensitive emulsions, red-sensitive emulsions and infrared-sensitive emulsions. Note that the infrared light-sensitive emulsion herein refers to an emulsion that is sensitive to light of 700 nm or more, particularly 740 nm or more.

For example, when using a combination of an n-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion, the blue-sensitive emulsion works in conjunction with the yellow imaging material, the green-sensitive emulsion works in conjunction with the magenta imaging material, and the red-sensitive emulsion works in conjunction with the magenta imaging material. The emulsion may be immobilized by light irradiation in conjunction with the cyan image forming substance.

By using oil droplets or microcapsules in this way, it is possible to separate yellow, magenta, and cyan image-forming substances and include them in the same photosensitive element, thereby forming a color image with a simple operation. be able to.

The silver halides used in the present invention include silver chloride, silver bromide,
It may be silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition within the grain f- may be uniform. It may have a multiple structure with different compositions on the surface and inside (Japanese Patent Application Laid-Open No. 154232/1983).

5B-108533, 59-48755, 5
No. 9-52237, US Patent No. 4,433.048 and European Patent No. 100984). In addition, tabular grains having a grain thickness of 0.5 microns or less, a grain size of at least 0.6 microns, and an average aspect ratio of 5 or more (U.S. Pat. Nos. 4,414,310, 4,435,499 and West German published patent (OLS) No. 3.241.646AI, etc.) or monodispersed emulsions with near uniform particle size distribution (
JP 57-178235, JP 5B-100846, JP 58-14829, International Publication No. 83102338A
1, European Patent No. 64,412A3, and European Patent No. 83
．． 377A, etc.) may also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. By mixing two or more types of monodispersed emulsions with different grain sizes, the gradation can be changed.
: You can also do AwJ. - The grain size of the silver halide used in the present invention is preferably one in which the average grain size is from o,oot microns to 10 microns, and more preferably from o,oot microns to 5 microns.

These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonia method, and the reaction method of soluble silver salt and soluble halide salt may be one-sided mixing method, simultaneous mixing method, or these methods. Any combination is acceptable. Back-mixing method to form grains under excess silver ion, or p
The Chondral double jet method, which keeps Ag constant, can also be used. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and □halogen salts may be increased by E (JP-A-55-142329, JP-A-55'-158124, U.S. Pat. No. 3.650,
757 etc.). Epitaxially bonded silver halide grains can also be used (Japanese Patent Application Laid-open No. 16124/1983,
U.S. Pat. No. 4,094,684).

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
Organic thioether derivatives described in No. 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used. In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

Further, water-soluble iridium salts such as iridium (m, IV) chloride and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used to improve high-light failure and low-light failure.

Silver halide is used as an emulsion, and the emulsion may be free of soluble salts after precipitation or physical ripening, and thus can be subjected to the Nudel water washing method or the precipitation method. The silver halide emulsion may be used as it is after heating, but it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known yellow sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used independently or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (JP-A-58-126526, JP-A-58-21564).
No. 4).

The silver halide emulsion of the present invention may be of the surface latent image type where the latent image is mainly formed on the surface of the grains, or may be of the internal latent image type where the latent image is formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. An internal latent image emulsion suitable for this purpose is disclosed in U.S. Pat.
．． No. 592.250, No. 3,761,276, Japanese Patent Publication No. 58-3534, and Japanese Patent Application Laid-open No. 57-136641.

A preferred nucleating agent for combination is U.S. Pat.
, No. 552, No. 4,245.037, No. 4,25
No. 5,511, No. 4.266.013, No. 4.2
No. 76.364 and OLS No. 2,6
No. 35,316.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to Log/m'' in terms of silver.

In the present invention, an organic silver salt that is relatively stable against photosensitive silver halide light deficiency can be used in combination as an oxidizing agent. In this case, the photosensitive silver halide and the organic silver salt need to be in contact or at a close distance.

When heated to a temperature of 80° C. or more, preferably 100° C. or more, the organic silver salt oxidizing agent is considered to participate in redox using the latent image of silver halide as a catalyst.

Organic compounds used to form such organic silver salt oxidizing agents include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having mercapto groups or α-hydrogens, and iminobase compounds. Examples include compounds.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lylunic acid, and oleic acid. Typical examples include silver salts derived from adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid, or camphoric acid.

Silver salts derived from halogen-substituted or hydroxyl-substituted fatty acids of these fatty acids, or fatty acid carboxylic acids having thioether groups can also be used.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3°5-dihydroxybenzoic acid, 0-lm- or p-methylbenzoic acid, 2.
4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid,
Representative examples include silver salts derived from terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid, or 3-carboxymethyl-4-methyl-4-thiazoline-2-thione.

As a silver salt of a compound having a thiocarbonyl group having mercapto or α-hydrogen, 3-mercapto-4-
Phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercaptobenzthiazole, S-alkylthioglycolic acid (alkyl group having 12 to 22 carbon atoms), dithioacetic acid, etc. Thiocarboxylic acids, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1 , 2,4-triazole U.S. Patent No. 4.1
Examples include silver salts derived from mercapto compounds described in No. 23,274.

As a silver salt of a compound having an imino group, Japanese Patent Publication No. 44-
30270 or 45-18416, or derivatives thereof, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, carboimides such as butylcarboimide benzotriazole Benzotriazoles, nitrobenzotriazoles described in JP-A-58-118639, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole, etc., described in JP-A-58-118638, U.S. Patent No. 4.220 .1 described in No. 709
．． Representative examples include silver salts derived from 2.4-triazole, IH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof.

Also, Research Disclosure Magazine 17029 (1
Organometallic salts other than the silver salts and copper stearate described in June 1978), patent application No. 58-22153
Silver salts of carboxylic acids having an alkynyl group such as phenylpropiolic acid described in No. 5 can also be used in the present invention.

The above organic silver salts are 0 per mole of photosensitive silver halide.
．． 0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is suitably 1 mg to 10 g/rn''.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.: Mercaptopyrimidines: mercaptotriazine thioketo compounds such as oxadolinthione; niazaindenes, such as triazaindenes, tetraazaindenes, especially 4-hydroxy substituted (1,3,3a);

7) Tetraazaindenes), pentaazaindenes, etc.: Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can. For example, U.S. Patent No. 3,954,474
No. 3,982.947, Special Publication No. 52-2866
Those described in No. 0 etc. can be used.

Silver halide emulsion of the present invention: In the 1ilIyJ method, it is advantageous to use gelatin as a protective colloid, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and 1tIR derivatives; polyvinyl Synthetic hydrophilic polymeric substances of type S such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

In addition to lime-processed gelatin, acid-processed gelatin and ``Priten of the Society of Scientific Photography of Japan: /
(Bull, Soc, Sci, PhoL.

Japan) J number (No) 16.30 pages (19
Enzyme-treated gelatin as described in 66) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The photosensitive silver halide used in the present invention may be spectrally sensitized with dyes. Dyes that may be used include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, conjugated merocyanine dyes, holopolar-cyanine dyes, 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 applied to these dyes as basic heterogeneous mIQ nuclei.
That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, and selenazole nucleus.

Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic layer hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus , indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon L'J.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl bridge, and the like can be applied.

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

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. Patent No. 2,933,390;
No. 35,721, a), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743,5
10), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,615,61
No. 3, No. 3゜635.641, No. 3.617.29
The combinations described in No. 5, No. 3,635,721 are particularly useful.

In order to incorporate these sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion, or they may be added to a welding solvent such as water, methanol, ethanol, acetone, methyl cellosolve, etc. alone or in combination. It may be added to the emulsion by dissolving it in Moreover, after dissolving them in a substantially water-immiscible solvent such as phenoxyethanol,
It may be dispersed in water or parent wood colloid, and this dispersion may be added to the emulsion. Furthermore, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. In addition, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately,
Alternatively, a mixture may be dissolved.

When added to an emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives.

It may be added to the emulsion during or immediately after chemical ripening, and may be added to the emulsion as described in U.S. Pat. No. 4,183,756;
It may be carried out after nucleation of silver halide grains according to No. 225,666.

The amount added is generally about 10@-8 to 10' mole per mole of silver halide.

There are various developing agents that can be used in the present invention, such as hydroquinones, catechols, p
-Aminophenols, p-phinidine diamines, 3
-Pyrazolidones, 3-aminopyrazoles, 4-amino-5-virazolones, 5-aminouracils, 4゜5
-dihydroxy-6-aminopyrimidines, reductones, amylreductones, O or p-sulfonamidophenols, O or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamide-5 Compounds such as -pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, and α-sulfonamide ketones can be mentioned.

Preferred developing agents include compounds represented by the following general formulas (1) to (19).

4 (1B) (19) In the formula 1, R is an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, a cycloalkyl group, an aryl group, a substituted aryl group, a halogen atom r~, a hydroxyl group,
Alkoxy group, substituted alkoxy group, aryloxy group,
Substituted aryloxy group, acylamino group, sulfonylamino group, acyl group, sulfonyl group, carbamoyl J^,
Substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl J^, cyano group, nitro group, carboxy group, sulfo group, alkenyl group, alkynyl group, amino group, substituted amino group, ureido group, substituted ureido group, alkylthio group, arylthio group, N Represents a group selected from the ring formula J&. n represents an integer from 0 to 5, and when n is plural,
R may be the same or different, and multiple R may combine with each other to form a ring, and R and R1 or R
2 may be combined to form a ring.

R1 to R6 may be the same or different, respectively,
Alkyl group, substituted alkyl group, aralkyl group, substituted aralkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, substituted aryl group, halogen element f-1
Water WR group, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryloxy group, acylamino group, sulfonylamino group, carbamoyl group, substituted carbamoyl group, cyano group, carboxy group, sulfo group, amino group, substituted amine group, It represents a group selected from a ureido group, a substituted ureido group, an alkylthio group, an arylthio group, and a heterocyclic group, and may be bonded to each other to form a ring.

Specific examples of preferred developing agents are shown below, but the present invention is not limited thereto.

(D-1) (D-2) (D-3)
(D-4) (D-5) (D-6
) (D-7) (D-8) (D-9
) (D-10) (D-11) (D-1
2) (D-13) (D-14) (D-
15) (D-16) (D-17) (
D-18) (D-19) (D-20)
(D-21) (D-22) (D-29
) ′″Ll-jUJ (L)-317(D
-32) (D-33) (D-37) (D-38) (D-39)
(D-40) (D-43)
(D-44) (D-45) (
D-46) (D-47) (D-48)
(D-49) (D-50)
(D-51) (D-52) (D-53) (D-54)
(D-55) (D-56)
(D-57) (D-58)”
n9 (D-59) (D-60
)(D-61) (D-62)(
D-63) (D-64) (D-
65) (D-66) (D-6
7) (D-68) (D-69)
(D-70) (D-71)
(D-72) (D-73) (D-78) (D-79) (D-8
0) (D-81) 'υ-62λ(
D-83) (D-84) (D-85) (D-86) Among these compounds, those that have a basic group that forms a salt with an acid can be used in the form of a salt with an appropriate acid. It can also be used as an active site that exhibits reducing properties (NH group or OH
group) with an appropriate protecting group (e.g. formyl group, acetyl group,
It can also be used in a protected form with a trifluoroacetyl group, etc.).

The amount of developer added can vary widely, but is generally 0.1 to 1500 mol%, preferably 1% by mole, based on the silver salt.
It is 0 to 300 mol%.

Examples of the polymerizable compound that can be used in the present invention include addition polymerizable monomers, oligomers, and polymers thereof. As addition polymerizable monomers, carbon-
Compounds having one or more carbon unsaturated bonds can be used.

Examples of these are acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, and styrenes. , vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers, aryl esters, and derivatives thereof.

All of these compounds are useful in the present invention, but since heat development treatment is performed in the present invention, those with a boiling point of 80° C. or higher, which are less likely to volatilize during heating, are preferred. Further, in order to increase the S/N ratio of the obtained color image, it is desirable to use a crosslinkable compound having an effect of increasing the viscosity or degree of curing of the produced polymer compound. The crosslinkable compound referred to herein is a so-called polyfunctional monomer having a plurality of vinyl groups or vinylidene groups in its molecule. Preferred examples of the polymerizable compound used in the present invention are shown below.

Acrylic acid, methacrylic acid, butyl acrylate, methoxyethyl acrylate, butyl methacrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-acryloylmorpholine, N
-acryloylpiperidine, glycidyl acrylate,
2-ethylhexyl acrylate, acrylic anilide, methacrylic anilide, styrene, vinyltoluene,
Chlorostyrene, methoxystyrene, chloromethylstyrene, 1-vinyl-2-methylimidazole, 1-vinyl-2-undecylimidazole, 1-vinyl-2-undecylimidacillin, N-vinylpyrrolidone, N-vinylcarbazole , vinyl benzyl ether, vinyl phenyl ether, methylene-bis-acrylamide, trimethylene-bis-acrylamide, hexamethylene-
Bis-acrylamide, N,N'-diacryloylpiperazine, m-phenylene-bis-acrylamide, P-
Phenylene-bis-acrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, bis(4-acryloxypolyethoxyphenyl)propane, 1,5-bentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol acrylate,
Polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, N-methylol acrylamide, diacetone acrylamide, triethylene glycol dimethacrylate, pentaerythritol tetraaryl ether.

Furthermore, the combination of a polymer compound having a vinyl group or vinylidene group, for example, a polymer compound having a hydroxyl group, amino group, epoxy group, halogen atom, or sulfonyloxy group in the side chain, with acrylic acid, methacrylic acid, or a derivative thereof. Condensates and the like can also be used in the present invention.

Furthermore, compounds in which a vinyl group or vinylidene group is bonded to the core of the developer described in 111, such as m -N, N-di(acryloyloxyethyl)aminophenol, P-acryloyloxyethoxyphenol, etc., are also used as polymerizable compounds. In this case, the developer and the polymerizable compound can be used together. Furthermore, compounds containing vinyl groups in the molecules of color image-forming substances, such as dyes or leuco dyes, can also be used as polymerizable compounds, in which case the polymerizable compounds and color image-forming substances can be combined.

The polymerizable compound of the present invention is 0.0% relative to the silver halide salt.
5 to 1200% by weight, preferably 5 to 9 sof
ili1% can be used.

There are a variety of color image-forming materials that can be used in the present invention. For example, dyes and pigments are examples of substances that are themselves colored. When these are used, a color image can be formed by destroying the portions (oil droplets or microcapsules) in which no polymer is produced and transferring them to an image-receiving material using an appropriate method. In addition to commercially available dyes and pigments, there are also publicly known dyes and pigments described in various documents (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, FIJ, 1972; "Latest Pigment Handbook" edited by Japan Pigment Technology Association, published in 1978). are available. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, non-colored color image forming substances include those that are colorless or pale in themselves but develop color when subjected to some kind of energy such as heating, pressure, or light irradiation, and those that do not develop color even when energy is applied to them; It is classified as one that develops color when it comes into contact with another component. Examples of the former include thermochromic compounds, piezochromic compounds,
Photochromic compounds and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes are known. All of these develop color upon heating, pressurization, light irradiation, or air oxidation. Examples of the latter include various systems that develop color through acid-base reactions, redox reactions, coupling reactions, chelate-forming reactions, etc. between two or more components. For example, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran used in pressure-sensitive paper, and an acidic substance (coloring agent) such as acid clay or phenols: aromatic diazonium salts, diazotates, Systems using azo coupling reactions of diazosulfonates, naphthols, anilines, active methylenes, etc.: reactions of hexamethylenetetramine with ferric ions and gallic acid, reactions of phenolphthalein-complexanes with alkaline earths, etc. Chelate-forming reactions such as reactions with similar metal ions, redox reactions such as reactions between ferric nistearate and pyrogallol, and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

Further, as another example of a system in which color is generated by a reaction between two components, a case where this reaction proceeds by heating is known. In this case, it is necessary to heat the mixture at the same time or immediately after the two components are mixed by breaking oil droplets or microcapsules during pressurization.

The color former in the color former/developer system is (l
) triarylmethane type, (2) diphenylmethane type,
They include (3) xanthine compounds, (4) thiazine compounds, and (5) spiropyran compounds, and specific examples include those described in JP-A-55-27253.

Among these, (1) triarylmethane-based coloring agents and (3) xanthine-based coloring agents are preferred because they cause less fog and provide high coloring density. Specific examples include crystal violet lactone, 3-diethylamino-6-chloro-
7-(β-ethoxyethylamino)fluoran, 3-diethylamino-6-methyl-7-anilinofluoran,
3-Triethylamino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7-
Examples include o-chloroanilinofluorane, which can be used alone or in combination.

As the color developer, phenolic compounds, organic acids or metal salts thereof, oxybenzoic acid esters, acid whites, etc. are used.

Examples of phenolic compounds include 4.4”-isopropylidene-diphenol (bisphenol A), p-Le
rt-butylphenol, 2.4-dinitrophenol, 3.4-dichlorophenol%4.4'-methylene-
Bis(2,6-LerL-butylphenol), p
-Phenylphenol, 1.1-bis(4-bitroxyphenyl)cyclohexane, 1゜1-bis(4-hydroxyphenyl)-2-ethylhexane, 2.2-bis(
4-bitroxyphenyl)butane, 2.2'-methylenebis(4-terL-butylphenol), 2.2'-
In addition to methylenebis(α-phenyl-p-cresol)thiodiphenol and 4,4′-thiobis(6-LerL-butyl-m-cresol)sulfonyldiphenol,
Examples include p-LerL-butylphenol-formalin condensate and P-phenylphenol-formalin condensate.

Examples of organic acids or metal salts thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, 0-toluic acid, P-toluic acid, salicylic acid, 3-LerL-
Butylsalicylic acid, 3゜5-diLerL-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3.5-
(α-Methylbenzyl)salicylic acid, 3-LerL-
Octylsalicylic acid and its zinc, lead, aluminum, magnesium, and nickel salts are useful. In particular, salicylic acid-induced suspensions and their zinc salts or aluminum salts are excellent in terms of color developing ability, fastness of colored images, and storage stability of recording sheets.

Examples of oxybenzoic acid esters include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, benzyl p-oxybenzoate, and the like.

Further, an oil-absorbing white pigment can also be used in combination to diffuse and fix the capsule contents.

These color developers can be added as a eutectic with a thermofusible substance with a low melting point, or a low melting point compound can be added to the surface of the color developer particles in order to melt at a desired temperature and cause a color reaction. It is preferable to add it in a fused state.

Specific examples of low melting point compounds include higher fatty acid amides,
Examples include, but are not limited to, waxes such as stearamide, erucamide, palmitic acid amide, ethylene bisstearamide, or higher fatty acid esters, phenyl benzoate derivatives, hexaaromatic ether derivatives, and urea derivatives. It's not something you can do.

Other color formers/developer systems include, for example, phenolphthalein, fluorescein, 2", 4'
, ',7'-tetrabromo-3,4,5,6-titrachlorofluorescein, tetrabromophenol blue, 4゜5.6.7-titrabromophenolphthalein, eosin, alarin cresol red, 2- Such as naphtholphenolphthalein.

Color developers include inorganic and organic ammonium salts, n-organic amines, amides, urea and thiourea and their derivatives, thiazoles, virols, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillins, Examples include nitrogen-containing compounds such as triazoles, morpholines, piperidines, amidines, formazines, and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine,
Stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidacillin, 2°4.5- Trifuryl-2-imidacillin, 1°2-diphenyl-4,4-dimethyl-2-imidacillin, 2-phenyl-2-imidacillin, 1.2.
3-1 rifhenylguanidine, 1.2-ditolylguanidine, 1.2-dicyclohexylguanidine, 1.2-
Dicyclohexyl-3-phenylguanidine, 1,2.
3-Tricyclohexylguanidine, guanidine 1-lichloroacetate, N,N''-dibenzylpiperazine, 4.4
'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, and 2-benzoylhydrazino-benzothiazole.

The color image forming substance of the present invention is preferably 0.5 to 50 parts by weight, particularly preferably 2 to 20 parts by weight, per 100 parts by weight of the monopolymerizable compound.
Used in parts by weight. The color developer is used in a ratio of about 0.3 to 80 parts by weight to 1 part by weight of the color former.

Furthermore, the storage stability can be improved by encapsulating the thermal polymerization inhibitor in oil droplets or microcapsules. The amount of the thermal polymerization inhibitor added is preferably 0.05 to 5% by weight based on the polymerizable compound.

The microcapsules used in the present invention can be produced by methods known in the art. For example, U.S. Patent No. 2.800,
No. 457, a method utilizing coacervation of a wood-loving wall-forming material as seen in No. 2.800.458, U.S. Pat. No. 3,287,154, and British Patent No. 990.
．． No. 443, Special Publication No. 38-19574, No. 42-44
No. 6, interfacial polymerization method as seen in No. 42-711,
U.S. Patent No. 3,418°250, U.S. Patent No. 3,660,3
04, methods using isocyanate-polyol wall materials as seen in U.S. Pat. No. 3,796,669, U.S. Pat. No. 3,914,
511, U.S. Pat. No. 4,001.140; U.S. Pat. No. 4,087;
Urea found in No. 376 and No. 4,089.802
Method using formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming materials, US Pat. No. 4
, 025,455, a method using wall forming materials such as melamine-formaldehyde resin, hydroxypropyl cellulose, etc., Japanese Patent Publication No. 36-9163, JP-A-51
in 5 by polymerization of monomers found in No.-9079.
itu method, British Patent No. 952,807, British Patent No. 965,
Polymerization dispersion cooling method as seen in U.S. Patent No. 074, U.S. Pat.
No. 11,407 and the spray drying method described in British Patent No. 930,422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

The microcapsule wall of the present invention is particularly effective when using a microencapsulation method by polymerizing a glue actant from inside an oil droplet. That is, it is possible to obtain capsules, which are desirable as a photosensitive material and have a uniform particle size and excellent storage stability, within a short time.

For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance that reacts with it to form the capsule wall are used. (e.g., polyol, polyamine) is mixed into an oily liquid to be encapsulated, emulsified and dispersed in water, and then the temperature is raised to cause a polymer formation reaction at the oil droplet interface to form microcapsule walls. . At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid.

In this case, regarding the polyvalent isocyanate to be used and the polyol and polyamine that react with it, US Patent No. 3,281,383, US Pat. -40347
No. 49-24159, JP-A-48-80191, and JP-A-48-84086, and these can also be used.

Examples of polyvalent isocyanates include m-phenylene diisocyanate, P-phenylene diisocyanate,
2.6-tolylene diisocyanate, 2.4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3.3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3 .3'-dimethyldiphenylmethane-
4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene Diisocyanates such as -1,2-diisocyanate and cyclohexylene-1,4-diisocyanate; triisocyanates such as 4°4',4''-triphenylmethane triisocyanate and toluene-2,4,6-triisocyanate; .4′-dimethyldiphenylmethane-2,2”, tetraisocyanates such as 5°5′-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 2
．． There are isocyanate prepolymers such as adducts of 4-tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, and adducts of tolylene diisocyanate and hexanetriol.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers.

The following polyols described in Japanese Patent Application No. 158469/1982 can also be used.

That is, ethylene glycol, 1.3-propanediol, 1.4-butanediol, 1.5-bentanediol, 1.6-hexanediol, 1.7-heptanediol, 1.8-octanediol, propylene glycol, 2.3-dihydroxybutane, 1.2-dihydroxybutane, 1.3-dihydroxybutane, 2.2-dimethyl-1,3-propanediol, 2,4-bentanediol, 2.5-hexanediol, 3- Methyl-1
, 5-bentanediol, 1,4-cyclohexane dimetatool, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-
Phenylpropylene glycol, 1.1.1-)-limethylolbroban, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin-1,4-di(2-hydroxyethoxy)benzene,
Condensation products of aromatic polyhydric alcohols such as resorcinol dihydroxyethyl ether and alkylene oxides, p-xylylene glycol, m-xylylene glycol, α.

α'-dihydroxy-P-diisopropylbenzene, 4
．． 4'-dihydroxy-diphenylmethane, 2-(p,
p”-dihydroxyphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A,
Examples include adducts of propylene oxide and bisphenol A. The polyol is preferably used in a ratio of 0.02 to 2 moles of hydroxyl groups per mole of isocyanate groups.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2-hydroxytrimethylene. Diamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminoprobylamine, tetraethylpentamine,
Examples include amine adducts of epoxy compounds.

Polyvalent isocyanates can also react with water to form polymeric materials.

When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be any of water-soluble anionic polymers, nonionic polymers, and amphoteric polymers. As the anionic polymer, both natural and synthetic polymers can be used, such as -COO-1-3O
Examples include those having 3-groups and the like.

Specific examples of anionic natural polymers include gum arabic and alginic acid, and examples of synthetic polymers include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, and lignin sulfonic acid.

In addition, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers, and co-'n1 polymers. , carboxy-modified polyvinyl alcohol, etc. Nonionic polymers include polyvinyl alcohol, poly-N-vinylpyrrolidone, hydroxyethylcellulose, methylcellulose, and the like.

Examples of amphoteric compounds include gelatin.

These water-soluble components t are used as an aqueous solution of 0.01 to 1OwL%. The particle size of microcapsules is 20μ
2!4 is arranged below.

At least a polymerizable compound and a color image-forming substance are encapsulated in such microcapsules. In this case, silver halide, RJ PII4 hydrazine conductor, etc. are also usually encapsulated in the capsule, but in that case, silver halide and a developer are first added to a polymerizable compound in which a color image-forming substance is dissolved. An oil phase is obtained by dispersing or dissolving and and a dorazine derivative, and this is mixed with an aqueous phase in which a hydrophilic polymer compound is dissolved to emulsify and disperse to form an emulsion. Simultaneously with or subsequent to this emulsifying dispersion, a wall can be formed at the oil/water interface of the emulsion particles in a known manner. The method for making microcapsules is not limited to this, and various methods can be applied.

The size of the capsule used in the present invention is 80μ or less,
In particular, from the viewpoint of storage stability and handling properties, the temperature is preferably 20μ or more. In addition, if the capsule is too small, there is a risk that it will disappear into the pores or fibers of the substrate, but this depends on the properties of the substrate or support, so it cannot be said unconditionally, but 0.1μ
The following is preferable.

It is preferable that the capsule used in the present invention does not substantially change under pressures of about 10 kg/c or less, and that rupture occurs when a greater pressure is applied to the capsule. The magnitude of the pressure at which this destruction occurs can be changed depending on the application and is not limited to a specific value, but
It is preferable to break it at a pressure of about 500 g/cd. These pressure characteristics can be adjusted depending on the particle size of the capsule, the thickness of the capsule wall, and the type of wall material used.

The photosensitive material of the present invention contains hydroxy compounds, carbamate ester compounds, aromatic methoxy compounds, and organic sulfonamide compounds described in Japanese Patent Application No. 60-25838 in microcapsules or microcapsules to change thermal reactivity. Can be used outside the capsule. These compounds appear to alter the glass transition temperature of the microcapsule wall.

Various image formation accelerators can be used in the present invention. The image forming accelerator has functions such as promoting the redox reaction between the silver salt oxidizing agent, the developer and the hydrazine derivative, and promoting the transfer of the image forming substance from the photosensitive element to the image receiving element.
From a physicochemical function, it is a base or a base precursor.

It is classified into oils, thermal solvents, surfactants, and compounds that interact with silver or silver ions.

However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound has multiple functions. There are many.

Examples of preferred bases include t#, alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolinates as basic bases.
．． Metaborate: Ammonium hydroxide: Quaternary alkylammonium hydroxide: Other metal hydroxides, etc. Organic bases include aliphatic amines (trialkylamines, hydroxylamines, fatty acids, Aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted δ group amines and bis(p-(dialkylamino)phenyl)methanes), heterocyclic amines, amidine , cyclic amidines, guanidines, and cyclic guanidines, and those in which p has a of 8 or more are particularly preferred.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heating, compounds that release amines through reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmann rearrangement. Compounds that emit bases and compounds that generate bases by electrolysis or the like are preferably used. Preferred base precursors of the former type that generate a base upon heating include trichloroacetic acid salts described in British Patent No. 998,949, etc., α-sulfonylacetic acid salts described in U.S. Patent No. 4,060.420, Salts of propiolic acids described in JP-A-59-180537, 2-carboxycarboxamide derivatives described in U.S. Pat. No. 4,088,496, and alkali metals and alkaline earth metals in addition to organic bases as the base component. salts with thermally decomposable acids (JP-A-59-195237); hydroxamic carbamates described in JP-A-59-168-440 using Rossen rearrangement; Examples include the aldoxime carbamates described above. Others: British Patent No. 998,945, U.S. Patent No. 3.220,84
No. 6, Japanese Patent Application Publication No. 50-22825, British Patent No. 2. o7
Base precursors such as those described in No. 9.480 are also useful.

The following compounds can be mentioned as compounds that generate bases by electrolysis.

For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation.

Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently.

In addition, methods using electrolytic reduction include the production of amines by the reduction of nitro and nitroso compounds; the production of amines by the reduction of nitriles; the production of p-aminophenols and p-aminophenols by the reduction of nitro compounds, azo compounds, azoxy compounds, etc. - Generation of phenylenediamines and hydrazines, etc. p-aminophenols, p
- Phenylenediamines and dorazines can not only be used as bases, but they can also be used directly as color image-forming substances. Of course, it is also possible to generate an alkaline component by electrolyzing water in the coexistence of one of various inorganic salts.

Specific examples of bases or base precursors include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium quinolate, potassium quinolate, dibasic sodium phosphate, dibasic phosphoric acid potassium, tertiary sodium phosphate, tertiary
Potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, sodium metaborate, potassium metaborate,
Borax, ammonium hydroxide, tetramethylammonium, tetrabutylammonium, ammonia, MeNH
2 (Me represents CH3. The same applies below), Me2 NH
%EtNH2 (Et stands for C2Hs. The same applies below)
, Et2 NH1 C4Hg NH2, (C4H9)2 NH1HOC28
4NH2, (HOC2H4)2NH.

(IOC2H4)3N, Et2　NCH2CH20H1 H2NC2H4NH2, M　e　N　HC2H4N　HM　e　.

Me2 NC2H4NH2, H2NC3H6NH2, 82NC4) 1a NH2, 82NC5) 1to NH2, Me2 NC2H4NMe2, Me2 NC3H6NMe2, j-1 Guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2 -Picoline trichloroacetic acid, guanidine carbonate Salt, triphenylguanidine, guanidine phenylsulfonylacetate, guanidine 4-chlorophenylsulfonylacetate, guanidine 4-methyl-sulfonylphenylsulfonylacetate, guanidine 4-acetylaminophenylpropioleate, and the like. Other bases that can be used include, for example, alkaline agents and compounds used as buffers in conventional photographic materials and processing solutions.

The base or base precursor used in the invention can be used in a wide range of amounts.

It is appropriate to use the coating Mll52 of the photosensitive element in an amount of 50% by weight or less in terms of ffi amount, more preferably 0.5% by weight or less.
A range of 01% to 40% by weight is useful.
In the present invention, the base and/or base precursor may be used as a mixture of two or more types.

The base and/or base precursor is dissolved in water or alcohol and then incorporated into the photosensitive element and/or image receiving element as a solution or dispersion. In addition, U.S. Patent No. 2.322,0 using a high boiling point organic solvent
Using the h-method described in & in No. 27, or boiling point approximately 30℃
None Organic solvents at 160°C, such as lower alkyl acetates such as ethyl acetate, butyl borate, ethyl propionate, secondary butyl alcohol, 2-tyl isobutyl ketone, β-ethoxyethyl fucetate, methyl cellosolve acetate, cydulohexane After dissolving it in a liquid, it is incorporated into an optical element and/or an image-receiving element as a dispersion.

Examples of high-boiling organic solvents include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenino 1 phosphate, tricresyl phosphate, dioctyl butyl phosphate),
benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (
For example, tributyl trimesate) is used.

The high boiling point organic solvent and the low boiling point organic solvent listed in item L may be mixed and used. Alternatively, a dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

Furthermore, the addition-polymerizable polymer described in δ of the present specification and its oligomers and polymers may be used by mixing them into the polymer.

The base and/or base precursor can be dispersed in a binder, which can be used alone or in combination. It is preferable to use a hydrophilic binder.

- As the oil, a high boiling point organic solvent used as a solvent during emulsification and dispersion of hydrophobic compounds can be used.

Thermal solvents are solid at normal temperatures, melt near the development temperature and act as a solvent, and include ureas, urethanes, amides, pyridines, sulfonamides, sulfones, sulfoxides, esters, and ketones. Compounds of the ethers and ethers which are solid at temperatures below 40°C can be used.

The thermal solvent may be included in the photosensitive material or in the image-receiving material.

Examples of the surfactant include pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, and polyalkylene oxides described in JP-A-59-57231.

Examples of compounds that interact with silver or silver ions include imides, nitrogen-containing heterocycles described in JP-A-59-177550, thiols, thioureas, and thioethers as described in JP-A-59-111636. can be mentioned.

The image formation accelerator may be incorporated into either the photosensitive material or the image-receiving material, or may be incorporated into both. The layer to be incorporated may also be incorporated in the emulsion layer, intermediate layer, protective layer, image-receiving layer, and any layer adjacent thereto. The same applies to a form in which the photosensitive layer and the image-receiving layer are provided on the same support (E).

Image formation accelerators can be used individually or in combination, but generally a greater accelerating effect can be obtained when several types are used in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper mentioned here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or interacts with silver and silver salts to stop development. It is an inhibitory compound. Specific examples include acid precursors that release acid when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305;
Examples include compounds that release acids through Rossen rearrangement as described in Japanese Patent Application No. 59-85834, and examples of electrophilic compounds that undergo a substitution reaction with bases upon heating include those described in Japanese Patent Application No. 59-858.
Examples include compounds described in No. 5836.

The image-receiving element of the present invention is an element for fixing the color image-forming substance emitted from the photosensitive element, and is coated on the same support as the photosensitive element, or coated on a separate support. .

Furthermore, the image receiving element of the present invention can have at least one layer containing a mordant, if necessary. Image reception fiJ
When A is located on the surface, a protective layer can be provided thereon. Further, if necessary, it may be constructed of two or more layers using mordants having different mordant powers.

When a mordant is used in the image-receiving layer, any mordant can be selected from among the mordants used in diffusion transfer type light-sensitive materials, and among them, polymer mordants are particularly preferred.
Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing monocyclic ring moiety, a polymer containing these quaternary cation groups, and the like.

Regarding polymers containing one vinyl unit having a -grade amino group, Japanese Patent Application No. 169012/1982;
Specific examples of polymers containing a vinyl monomer having a tertiary imidazole group include Japanese Patent Application Nos. 58-226497 and 58-2.
No. 32071, US Pat. No. 4.282.305, US Pat. No. 4,115,124, and US Pat. No. 3.148.061.

Preferred specific examples of polymers containing a quaternary imidazolium salt at the 2nd position in vinyl chloride include Kenkoku Patent i2,
No. 056,101, No. 2.093,041, No. 1
, 594.961, U.S. Patent No. 4,124.386, U.S. Patent No. 4.115,124, U.S. Patent No. 4,273,853
No. 4,450,224, Japanese Unexamined Patent Publication No. 48-2822
It is described in No. 5, etc.

Other preferred specific examples of polymers containing one vinyl chloride unit having a quaternary ammonium salt include U.S. Pat. No. 3,709,690, U.S. Pat. Patent Application No. 58-166135, No. 58-169012, No. 58-232070,
It is described in 5B-232072 and 59-91620.

In the present invention, a solvent can be used in conjunction with the encapsulation of the polymerizable compound and color image forming substance. A solvent can also be used when introducing a developer, a hydrazine derivative, a color developer, etc. into necessary elements. For example, a solution in water or a hydrophilic organic solvent can be coated directly onto the support, optionally with a binder, or by a known method such as that described in U.S. Pat. No. 2,322,027. can be introduced into elements. By using a solvent in the microcapsules, it is also possible to control the degree of destruction of the capsules upon pressurization and the amount of transfer of the color image-forming substance within the capsules to the image receiving element. of the solvent used in the capsule (It is 1 to 500 i' with respect to the amount of the compound used)
A proportion of 1q parts is preferred.

Natural oils or synthetic oils can be used alone or in combination as the solvent used in the present invention. Examples of these solvents include cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, and! - Diarylethanes such as phenyl-1-xylylethane, 1-phenyl-1-p-ethyl phenylethane, 1,1'-ditolylethane, etc., phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate) , triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. butoxyethyl succinate, dioctyl azelate), trimesates (e.g. tributyl trimesate), lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate,
Secondary butyl alcohol, methyl isobutyl ketone, β-
Examples include ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone.

The binders used in the photosensitive element and image-receiving element of the present invention can be contained alone or in combination. A hydrophilic binder can be used for t. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds, especially in the form of latexes, which increase the moderate stability of photographic materials.

The supports used in the photosensitive and image-receiving elements of the present invention are those that can withstand processing temperatures.
Common supports include glass, paper, wood-free paper, synthetic paper, metal parts and their analogues, as well as acetyl cellulose film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene film, etc. Includes terephthalate films and their associated films or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Patent No. 3,634.089, U.S. Patent No. 3.7
The polyester film described in No. 25,070 is preferably used.

The photosensitive material (image-receiving material) of the present invention may optionally include a protective layer,
Auxiliary layers such as an intermediate layer, an antistatic layer, an anticurl layer, a release layer, and a matting agent layer can be provided. In particular, it is desirable that the protective layer contain an organic or inorganic matting agent for the purpose of preventing adhesion.

In addition, antifoggants, fluorescent whitening agents, antifading agents, antihalation and irradiation dyes, pigments (including white pigments such as titanium oxide), and water release agents are added to the photosensitive element and image receiving element as necessary. , a thermal polymerization inhibitor, a surfactant, a thermal solvent, a fractional vinyl compound, and the like.

Various exposure stages can be used in the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, commonly used light sources such as sunlight, strobes, flashes, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams, and CRT light sources, plasma light sources,
Fluorescent tubes, light emitting diodes, etc. can be used as light sources. It is also possible to use an exposure stage that combines a micro-shutter array using an LCD (liquid crystal) or PLZT (lead titanium zirconate doped with lanthanum) and a linear light source or a planar light source.

The type of light source and the amount of exposure can be selected depending on the wavelength to which silver halide is sensitive by dye sensitization and the sensitivity.

The original image used in the present invention may be a black and white image or a color image.

The original image may be a line image such as a 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 may be carried out by contact printing over the original, reflection printing, or enlargement printing.

It is also possible to output images taken by a video camera or the like or image information sent from a television station directly to a CRT or FOT, and then form this image on a photosensitive material -F using a contact lens or a lens, and then print it. be.

In addition, LEDs (light emitting diodes), which have recently become popular, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively exposes light. In this case, to reproduce a color image, three types of LEDs are used that emit green, red, and infrared light, and the emulsion portions that are sensitive to these lights contain yellow, magenta, and cyan image-forming substances, respectively. It should be designed like this.

That is, the green-sensitive area may contain a yellow image-forming substance, the red-sensitive area may contain a magenta image-forming substance, and the infrared-sensitive area may contain a cyan image-forming substance. Other combinations are also possible as required.

In addition to the above-mentioned method of directly attaching or projecting the original image, the original image illuminated by a light source is read with a light receiving element such as a phototube or CCD, and then stored in the memory of a computer, etc., and this information is added as necessary. After processing, this image information may be reproduced on a CRT and used as an image-like light source, or the three types of LEDs may be directly emitted for exposure based on the processed information.

These exposure times vary depending on the type of silver halide used and the degree of sensitization.

In the present invention, a conventionally known method can be used as a heating method after imagewise exposure.

For example, the photosensitive material may be brought into direct contact with a hot plate such as a hot plate or a drum, or may be transported using a beat roller.

Heating can also be performed using air heated to a high temperature, high frequency heating, or a laser beam. Depending on the photosensitive material, it can also be heated using an infrared heater.

Furthermore, it is also possible to apply a method of heating using eddy currents generated by electromagnetic conduction.

Alternatively, the photosensitive material may be heated in a heated bath containing a liquid inert to the photosensitive material, such as a fluorine-based liquid.

Furthermore, the photosensitive material may be heated by providing a heat source separate from the heating means described above. For example, a layer of conductive particles such as carbon black or graphite may be provided in a photosensitive material, and the Joule heat generated when electricity is applied may be utilized.

The heating temperature at this time is generally 80°C to 200°C, preferably 90°C to 160°C.

Various patterns can be applied as the pattern for heating the photosensitive material. The most common method is heating at a constant temperature, but depending on the characteristics of the photosensitive material, multi-stage heating may be used, such as heating at a high temperature for a short time and then gradually lowering the temperature.
is valid. In this case, the heating time is generally 1 second to 5 seconds.
minutes, preferably 5 seconds to 1 minute.

If the photosensitive material is susceptible to air oxidation during heating, it is effective to deaerate the area around the heating section or replace it with an inert gas. Further, the surface of the photosensitive material may be brought into direct contact with a heated portion or may be exposed to air. When developing with the surface of the photosensitive material facing the air, it is also effective to attach a cover to prevent moisture and volatile components from evaporating from the photosensitive material and to keep the material warm.

■Specific effects of the invention According to the present invention, a photosensitive silver halide is used as a photosensor, and a hydrazine derivative represented by the general formula (I) and/or a hydrazine derivative represented by the general formula (II) is used. It has a developing agent and is configured to immobilize the color image-forming substance by heat development after image exposure, so it is a highly sensitive product that can form color images in a simple and quick dry process and in a short exposure time. A photosensitive material is obtained.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Example 1 Benzotriazole S L; 28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
000+nJ2. The solution was kept at 40°C and stirred. Add 17g of silver nitrate to this solution and 100ml of water!
The solution was added over 2 minutes. The pH of this benzotriazole silver emulsion is J! Trim, settle and remove excess salt. After that, the pH was adjusted to 6.30, and the yield was 40.
0 g of benzotriazole silver emulsion was obtained.

Add 600 ml of an aqueous solution containing sodium chloride and potassium bromide and fI acid to a well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in 100,100 O of water kept at 75°C) of 11°L S. Silver aqueous solution (water 60
0.59 mol of silver nitrate dissolved in 0 ml) was simultaneously added at an equal flow rate over 40 minutes. In this way, a dispersed cubic silver chlorobromide emulsion (!Q! 80 mol %) having a uniform grain size of 0.35 .mu.m was prepared.

After washing with water and desalting, 5 mg of thioV&acid sodium and 4
Chemical sensitization was carried out at 60° C. by adding 20 mg of -hydroxy-6-methyl-1,3°3a,7-chitrazaindene. The yield of emulsion was 600 g.

1.8 g of trimethylolpropane triacrylate, Burger Script Red L-6-8 (Ciba Geigy) 1
g, and 2 ml of methylene chloride were mixed and dissolved, stirred and mixed in 10 g of 10% polyvinyl alcohol (F1 degree 500) containing 0.1 g of sodium dodecylbenzenesulfonate, and then mixed with a homogenizer at 15,000 rpm for 6 minutes.
The mixture was emulsified and dispersed. In this way, the average particle size is 0
．． Thirty-one dispersions of 4 μm color imaging material were prepared.

1 piece of silver chlorobromide emulsion, 24 g of benzotriazole silver emulsion
After mixing and stirring 30 g of a dispersion of Color Image Forming Material 7't, 9 ml of a 5% aqueous solution of Emarex NP-8 (Nippon Emulsion) was added and mixed for 1 minute at 40°C.

To this was added 20 ml of water, 12 ml of a 15% methanol solution of hydrazine derivative Hd, and 2 mJZ of a 5% methanol solution of developer D-162 to prepare a coating solution. This was coated on a polyethylene terephthalate film to a wet film thickness of 50 μm and dried to obtain a photosensitive element A.

E poison to tJA! 11 g of 40% sodium hexametaphosphate aqueous solution was added to 125 g of water, and 34 g of zinc 3.5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and coarsely dispersed using a mixer. The liquid was dispersed using a Dynamyl disperser, and 6 g of 50% SBR latex and 55 g of 18% polyvinyl alcohol were added to 200 g of the obtained liquid and mixed uniformly.

This mixed solution was weighed 30 μm on a scale of 43 g/g on art paper.
After uniformly coating the film to a wet film thickness of , it was dried to form an image receiving element.

The photosensitive elements (A) to (F) obtained were imagewise exposed for 1 second at 200 lux using a tungsten bulb, and then heated for 40 seconds on a hot plate heated to 125°C. Next, this photosensitive element and the image receiving element were stacked together and weighed 350 kg1.
When passed through an 0f pressure roller, a clear magenta positive color image with gradations corresponding to the unexposed areas was obtained on the image receiving element.

Maximum density: 1.55 Minimum density: 0.30 Further, although the same process as described below was carried out using a photosensitive element to which a developing agent or a hydrazine derivative was added in East Germany, no clear image could be obtained.

Photosensitive element A' was prepared in the same manner as in photosensitive fiA, using a 5% triethanolamine aqueous solution instead of water, and was evaluated in the same manner as above with a heating time of 20 seconds. A sharp magenta positive color image was obtained on the receiving element.

Maximum density: 1.55 Minimum density: 0.22 Example 2 Photosensitive element A or A' of Example 1 was photosensitive in the same manner as in Example 1 except that the hydrazine derivative and developer were used as shown in Table 1. Photosensitive element B corresponding to element A
-G, and photosensitive elements B' to G' were prepared corresponding to photosensitive element A', and the same evaluation as in Example 1 was carried out for each.

These results are shown in Table 1.

Example 3 Photosensitive element H was prepared in the same manner as in Example 1 except that in photosensitive element A or A' of Example 1, a hydrazine derivative and a developer were used as shown in Table 2.
~K, photosensitive element H' ~ was prepared corresponding to photosensitive element A'.

The same evaluation as in Example 1 was performed corresponding to each case.

These results are shown in Table 2.

Example 4 1.8 g of trimethylolpropane triacrylate, Parker Script Red 1-6-8 (Ciba Geigy) I
g, developer D-520, 16g, hydrazine derivative Hd
-381,19 g and 2 tafL of methylene chloride were mixed and dissolved, and 0.1 g of sodium dodecylbenzenesulfonate were mixed and dissolved.
Contains 1g of 10% polyvinyl alcohol (IR degree 50
0) After stirring and mixing in 10 g, the mixture was emulsified and dispersed using a homogenizer at 15.00 Or, p, m for 6 minutes.
A dispersion of color imaging material with an average particle size of 0.4 μl was thus prepared.

In Example 1, 6 g of the silver chlorobromide emulsion prepared in A, 24 g of the benzotriazole silver emulsion, and 30 g of the dispersion of the above color image forming substance were mixed, and then Emarex NP-8 (Japan Emulsion) was mixed. ) 9 ml of 5% aqueous solution, 20 mff1 of water and 1511 iL of methanol were added and mixed for 1 minute at 40°C to obtain a coating solution.

This was applied to polyethylene terephthalate to a wet film thickness of 50 μl and dried to form a photosensitive element.

In addition, in the photosensitive element, hydrazine derivatives are used as Hd-3.
Photosensitive element M was prepared in the same manner except that 8 was changed to HD-39.
was created.

The above-mentioned photosensitive types AM and L were used and evaluated in the same manner as in Example 1, except that the heating time was changed to 60 seconds.

These results are shown below.

Photosensitive element No., maximum density minimum density L
1.50 0.60M 1.
51 0.63 In addition, photosensitive elements L' and M' were prepared using a 5% triethanolamine aqueous solution instead of water in the photosensitive types JL and M, and the same evaluation was performed with the heating time set to 35 seconds.

Photosensitive element No., maximum density minimum density L'
1.50 0.45M'
1.50 0.50 Example 5 In the photosensitive element A' of Example 1, 20IIIt of 5% triethanolamine aqueous solution was mixed with guanidine carbonate 10% water/
A photosensitive element A'' was prepared in the same manner except that the ethanol (1/1 ffi ratio) solution was changed to 15 mJZ, and evaluated in the same manner at a heating temperature of 140° C. and a heating time of 20 seconds.

Maximum concentration 1.54 Minimum concentration 0.25 Example 6 Microcapsules: and 15 g of trimethylolpropane triacrylate) 6 g of polymer P-1 with the following structure, Pergascript Red L-6- Dissolve 0.9 g of B (Ciba Geigy), 1.2 g of the silver chlorobromide emulsion prepared in Example 1, 4.8 g of benzotriazole silver, Emarex NP-8 [Nippon Emulsion Co., Ltd.] 10% aqueous solution 0 Aqueous solution 0 days, 5 Nor solution 1.2 ml, and developer D-162, 5%
Add 0.2 ml of methanol solution and mix with a homogenizer for 3
Emulsification and dispersion was carried out at 18,000 rpm for minutes. Then Millionate MR-100 [FI Hon Polyurethane Co., Ltd.] 0
．． Add 15 g, stir at 3000 rpm for 1 minute, and then add Take*-to D-x ION [Take [J1 Yakuhin Co., Ltd.]
Add 5g and heat at 3000 r.p. for 1 minute. p-m. It was stirred with

Add this solution to 30 g of 4% methyl cellulose aqueous solution and 1 part of water.
5 g was added thereto, and emulsified and dispersed using a homogenizer at 6000 rpm for 1 minute. Add this to 45g of water
was added and heated at 60° C. for 1 hour while stirring to obtain a coating liquid.

P-1 (Number: mol%) This was placed on a polyethylene terephthalate film at 30 μm.
A photosensitive element N was prepared by coating and drying to a wet film thickness of m.

When this photosensitive element N was used and the same image-receiving element as in Example 1 was used and the same operation was carried out, a clear magenta positive color image with gradation was obtained on the image-receiving element.

In photosensitive element N, triethanolamine 40
Add 0.2512% aqueous solution to make microcapsules: J
! A photosensitive element N' was prepared in the same manner except that the photosensitive element N' was evaluated using a heating time of 35 seconds, and a clear magenta positive color image with gradation was obtained on the image receiving element.

From the above, the effects of the present invention are clear.

Procedure Ne FIT official document (spontaneous) December 18, 1985 Patent Application No. 227528, 1985 2, Name of the invention Photosensitive material 3, Person making the amendment = 1 Relationship with the case Patent applicant Location Minamiashigara City, Kanagawa Prefecture 210 Nakanuma Name (520) Fuji Photo Film Co., Ltd. 4, Agent
101 Telephone 864-4498 Address 3-2-2-6 Iwamoto-cho, Chiyoda-ku, Tokyo Contents of the amendment (1) Change the "fluoryl group" on page 12, line 15 of the specification to "
9-fluorenyl group".

(2) "Phenylethyl group" on page 13, lines 7-8 is corrected to "phenylethynyl group".

(3) The structural formula rHD-22J on page 31 of the same page is ” and correct it.

(4) "r(1:1)" on line 37, 14 is corrected to "(capacity ratio 1:1)J.

(5) No. 411'It Correct "acylhydrazine" in the 4th line to "hydrazine".

(6) After "preferable." on the second line of page 42 of the same document [Note that when hydrazine derivatives of general formulas (I) and (■) are used together, (I)/(II) = 9515-5 /9
5 (molar ratio). ” is inserted.

(7) The structural formula rD-8J of No. 7300 is “ 111+ ” Add +E.

(8) The structural formula rD-45J on page 77 of the same page is ” and correct it.

(9) Replace No. 78r'L as shown in the attached sheet.

(10) "rS/N ratio" on page 85, line 8 is corrected to "S/N ratio (contrast)".

(!l) "Silver halide salt" on line 8888 is corrected to "1 part by weight of silver halide salt."

(12) ro, os or 1200 on page 88, line 9
"% by weight" is corrected to "5 to 1.2 x 105 parts by weight".

(13) "5 to 950 parts by weight" on page 88, line 10 is corrected to "12 to 1.2 x 10' parts by weight."

(14) Change “No. 42-711” on page 98, line 3 of the same to “
No. 42-771”.

(15) Same page 98! The 8th line is “Special Public Service Publication No. 36-9163
"No." is amended to "Special Publication No. 36-9188."

(16) “Mike Melo” on page 105, lines 15-16.
・・・－・－Adjusted. ” to be deleted.

(17) page 13535, line 2, R adjustment” at rpH4,
Adjust it to O.''

(18) rHd-IJ in Table 2 on page 142 of the same
Correct with IJ.

(19) rHd-2J in Table 2 on page 142 of the same
Correct it to 2J.

(D-48) (D-49) (D
-50) (D-51) (D-52) Procedural formalities (methods) 1. Indication of the case 1985 Patent Application No. 227528 2. Name of the invention Photosensitive material 3. Person making the amendment Related Patent Applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Agent
101 Telephone 864-4498 Address 3-2-2 Iwamoto-cho, Chiyoda-ku, Tokyo Address 6, Subject of amendment Procedure amendment submitted on December 18, 1986, Contents of amendment Contents of amendment Correct column (16) as follows.

(16) r micro on page 105, lines 15-16...
・・・・・・It will be adjusted. ” to be deleted.

Claims (4)

[Claims] (1) At least a photosensitive silver halide, a developer, a polymerizable compound, a color image forming substance, and a hydrazine derivative represented by the following general formula (I) and/or a hydrazine derivative represented by the following general formula (II) are disposed on a support. What is claimed is: 1. A photosensitive material comprising a hydrazine derivative containing a hydrazine derivative, which is configured to immobilize a color image forming substance by heat development after image exposure. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above general formula (I), R_1 is a substituted or unsubstituted alkyl group, Represents a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkynyl group, or a heterocyclic group.R_2 is a hydrogen atom or a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, or an alkynyl group. group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, or amino group. In the above general formula (II), R_3 is derived from a substituted or unsubstituted aromatic ring or aromatic heterocycle. R_4 and R_5 each represent a substituted or unsubstituted aryl group. R_6 represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkoxycarbonyl group, or carbamoyl group. ) (2) The photosensitive material according to claim 1, wherein at least a photosensitive silver halide, a polymerizable compound, and a color image forming substance are incorporated into oil droplets or microcapsules. (3) On a support, at least photosensitive silver halide, a developer, a polymerizable compound, a color image forming substance, a base and/or a base precursor, and a hydrazine derivative represented by the following general formula (I) and/or the following: General formula (
1. A photosensitive material comprising a hydrazine derivative represented by II) and configured to immobilize a color image forming substance by heat development after image exposure. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above general formula (I), R_1 is a substituted or unsubstituted alkyl group, Represents a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkynyl group, or a heterocyclic group.R_2 is a hydrogen atom or a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, or an alkynyl group. group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, or amino group. In the above general formula (II), R_3 is derived from a substituted or unsubstituted aromatic ring or aromatic heterocycle. R_4 and R_5 each represent a substituted or unsubstituted aryl group. R_6 represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkoxycarbonyl group, or carbamoyl group. ) (4) The photosensitive material according to claim 3, wherein at least a photosensitive silver halide, a polymerizable compound, and a color image forming substance are incorporated into oil droplets or microcapsules.