JPH02187753A - Color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a compd. having strong light absorption in a near IR region and forming a diffusion transfer type color image having superior photographic properties such as transferability and fastness by incorporating an IR-absorbing image-forming compd. represented by a specified general formula into a silver halide color photosensitive material. CONSTITUTION:Silver halide and an IR-absorbing image-forming compd. represented by general formula I are held on the support of a silver halide color photosensitive material. In the formula I, Dye is an IR-absorbing dye group or dye precursor group represented by formula II, X is a single bond or a combining group and Y is a group producing a difference in the diffusibility of a dye component before and after a reaction with a photosensitive silver salt having a latent image in proportion or inverse proportion to the silver salt. A compd. having strong light absorption in a near IR region and forming a diffusion transfer type color image having superior photographic properties such as transferability and fastness is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel infrared light-absorbing image-forming compound and a color photosensitive material containing the same.

[Conventional technology]

Color diffusion transfer photography is well known in the art using dye-imaging compounds which, upon development of silver halide under basic conditions, provide dyes with diffusivity different from that of the imaging compound itself.

These systems typically form color images using three color pigments: yellow, magenta, and cyan, and have almost no absorption in the wavelength range longer than the visible range, that is, in the infrared range. Generally, the absorption tail of cyan dyes on the long wavelength side extends to 700 nm or more, but no cyan dyes having large absorption in the infrared region are known at all. On the other hand, in recent years, optical character reading devices and label barcode reading devices have been developed, and their use is increasing.
It is gaining importance. Most of these devices use a light emitting diode or semiconductor laser that emits light with a wavelength of 700 nm or more as a reading light source.They also use a tungsten lamp as a light source and a 900 nm light receiving element.
The light receiving sensitivity peak is around 700 to 1200 nm.
Those with a sensitivity range in m are widely used. However,
Images using the above dyes have almost no light absorption in the near-infrared region of 700 nm or more, so it is impossible or very difficult for these reading devices to read the image information. Therefore, the light absorption wavelength is 700 nm, preferably 700 nm.
There has been a strong desire to develop a diffusion transfer type color image forming compound having a wavelength of 50 nm or more.

[Purpose of the invention]

An object of the present invention is to provide a diffusion transfer type color image forming compound that has strong light absorption in the near-infrared region (700 nm or more) and has excellent photographic properties such as transferability and fastness.

Another object of the present invention is to provide a color photosensitive material whose image information can be read using an image reading device equipped with an easily available light source such as a semiconductor laser.

[Means for solving problems]

The above object of the present invention has been achieved by incorporating an infrared light-absorbing image-forming compound represented by the following general formula (1) into a silver halide color light-sensitive material.

(Dye-X)q -Y (I) [wherein, Dy
e represents an infrared light-absorbing dye group or a dye precursor group represented by the following formula (If), X represents a simple bond or a connecting group, and Y represents a photosensitive silver salt having a latent image on the image. It represents a group having the property of producing a difference in the diffusivity of the dye component before and after the reaction with the silver salt in correspondence or inverse correspondence.

In the formula, R1 is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an acylamino group. group, sulfonylamino group, acyl group, sulfonyl group, carbamoyl group, sulfamoyl group, ureido group, urethane group, alkylthio group, nitro group, alkoxycarbonyl group, and R2 is an alkyl group, aryl group, heterocyclic group, alkoxy R3 represents a halogen atom, an alkoxy group, an amino group, an alkylthio group, an aryloxy group, an acylamino group, an aryl group, or a heterocyclic group. Moreover, these substituents may be further substituted with other substituents. n represents an integer from 0 to 4, and from 2 to
4 may be the same or different.

Dye and X may be bonded from any position in formula (II). q is 1 or 2, and when q is 2, Dye-X
may be the same or different.

The present invention will be explained in more detail below.

R1 is a hydrogen atom, a halogen atom (chlorine atom, fluorine atom, etc.), an alkyl group (alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, fluoromethyl group, etc.), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group, etc.), aralkyl group (benzyl group, 2-phenethyl group, etc.), aryl group (e.g. phenyl group, p~tolyl group, p-methoxyphenyl group, 0 -methoxygenyl group, etc.), alkoxy group (alkoxy group having 1 to 8 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, 2-methoxyethoxy group, 2-hydroxyethoxy group, etc.), aryloxy group (e.g. phenoxy group, p-methoxyphenoxy group, 0-carboxyphenoxy group, etc.), cyano group, acylamino group (e.g. acetylamino group, propionylamino group, 0-carboxybenzoylamino group, etc.), sulfonylamino group (e.g. methanesulfonylamino group) , benzenesulfonylamino L
p-methoxybenzenesulfonylamino group, etc.), ureido group (3-methylureido group, 3.3-dimethylureido group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), arylthio group (phenylthio group, 0-carboxyphenyl group) thio group, etc.), alkoxycarbonyl group (
methoxycarbonyl group, ethoxycarbonyl group, etc.), carbamoyl group (methylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (methylsulfamoyl group, dimethylsulfamoyl group, etc.), sulfonyl group (
methanesulfonyl group, ethanesulfonyl group, 2-methoxyethylsulfonyl group, etc.), acyl group (acetyl group, propionyl group, cyanoacetyl group, acetoacetyl group, etc.), urethane group (methylurethane group, ethylurethane group, etc.), amino groups (amino group, methylamino group, dimethylamino group, carboxymethylamino group, 0-carboxyanilino group, P-hydroxyanilino group, etc.), hydroxyl group, carboxyl group, heterocyclic group (α-pyridyl group, T-pyridyl group, 2-furyl group, etc.). Among these, particularly preferred are alkyl groups having 6 or less carbon atoms, alkoxy groups having 6 or less carbon atoms, chlorine atoms, acylamino groups having 7 or less carbon atoms, sulfonylamino groups having 7 or less carbon atoms,
Examples include an aryloxy group having 8 or less carbon atoms, a hydroxyl group, a carboxyl group, a carbamoyl group having 7 or less carbon atoms, and a sulfamoyl group having 7 or less carbon atoms.

R2 is an alkyl group (up to 6 carbon atoms, e.g. methyl group, ethyl group, etc.), an aryl group (up to 8 carbon atoms, 2-carboxyphenyl group, 4-methanesulfonamidophenyl group, etc.), a heterocyclic group (e.g. α represents a pyridyl group, 2-thienyl group, 2-furyl group, morpholino group, etc.), an alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), and an amino group (methylamino group, dimethylamino group, etc.).

Among these, particularly preferred are alkyl groups having 3 or less carbon atoms, aryl groups having a hydrophilic group, hydrophilic heterocyclic groups (pyridyl group, furyl group, morpholino group, etc.), and alkoxy groups having 3 or less carbon atoms. It is.

R2 is a halogen atom (chlorine atom, fluorine atom, etc.), alkoxy group (methoxy group, methoxyethyl group, etc.), amino group (methylamino group, dimethylamino group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), aryloxy groups (2-carboxyphenoxy group, 4-carboxyphenoxy group, etc.), acylamino groups (acetylamino group,
2-carpoxybropionylamino group, etc.), aryl group (2-carboxyphenyl group, 4-carboxyphenyl group, etc.), heterocyclic group (4-pyridyl group, 2-pyridyl group,
morpholino group, etc.), and particularly preferred among these are a halogen atom, an alkoxy group, an acylamino group, and a heterocyclic group.

It is necessary that the dye part has no hydrophobic group that suppresses the diffusion of the dye, and on the contrary, it is desirable that the dye part has a water-soluble group that promotes the diffusion.

Basically, X is an elementary atom that is bonded to which part of the Dye moiety,
alkyl group or substituted alkyl group), ~502--C〇-, alkylene group, zta alkylene group, phenylene group, substituted phenylene group, naphthylene group, substituted naphthylene group, -〇--3o-, and Groups obtained by combining two or more of these divalent residues are representative examples, and preferred among them are -NRs -3Ox -
NRs Go-ya-R6-(L)*-(R?)J
-, R7 and R1 each represent an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group, and L is 10--CO-3O-3Ox Soz N
H N HS Oz CON HN HCO-, k represents O or l, l represents 1, and when k = 0, it represents 1 or 0.

Also -NRs -3Ow - and NRs Co- and R
A combination of b (L) k (R? L- is also preferred.

The bonding pattern between Dye part and Y part is Dye 5OzNH-Y
Particularly preferred are those of the form .

Next, Y will be explained in detail.

Y is first selected such that the compound of formula (1) is oxidized and self-cleaved upon development to become a non-diffusible image-forming compound to provide a diffusible dye.

An example of Y useful in this type of compound is an N-substituted sulfamoyl group. For example, Y can include a group represented by the following formula (Yl).

α N)ISO□ In the formula, β represents a group of nonmetallic atoms necessary to form a benzene ring, and a carbon ring or a hetero ring is fused to this benzene ring to form, for example, a naphthalene ring, a quinoline ring, 5, 6, .
7.8-Tetrahydronaphthalene ring, chroman ring, etc. may be formed.

α represents a group represented by 10011 or -NHG". Here, G" represents a hydrogen atom or a group that produces a hydroxyl group when hydrolyzed, and G1 is a hydrogen atom, having a carbon number of 1 to 22.
represents an alkyl group or a group that allows NHGI2 to be hydrolyzed. Ba1l serves as a ballast group. b is 0
．． 1 or 2.

Specific examples of this type of Y are described in JP-A-48-33826 and JP-A-53-50736.

Another example of Y suitable for this type of compound is the formula (Y
Examples include groups represented by ll).

It is described in JP-A-57-4043, JP-A-57-650 and US Pat. No. 4,053,312.

Furthermore, another example of Y suitable for this type of compound is a group represented by the following formula (YI[I).

In the formula, Ba1l, α, and b have the same meanings as in the formula (Yl), and β' represents an atomic group necessary to form a carbocyclic ring, for example, a benzene ring, and a carbocyclic or heterocyclic ring is further added to this benzene ring. Rings are fused to form naphthalene ring, quinoline ring, 5,6
, 7.8-tetrahydronaphthalene ring, chroman ring, etc. may be formed.

A specific example of this type of Y is disclosed in U.S. Patent No. 4.055°428.
No., JP-A-56-12642, JP-A No. 56-16130, U.S. Pat. No. 4,336,322, where Ba1l,
cr and b have the same meanings as in formula (YI), and β'' represents an atomic group necessary to form a heterocycle, such as a hylazole ring or a pyridine ring, and if this heterocycle has a carbocycle or a heterocycle, A specific example of this type of Y is described in JP-A-51-104343.

Further, as Y effective for this type of compound, there is one represented by the formula (Y part).

n In the formula, T preferably represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, or -Co-G"1; G21 is -QGIZ3-Gtt or a group, represents a cycloalkyl group or an aryl group, G23 represents the same group as the above G'' group, or G'' represents an acyl group derived from an aliphatic or aromatic carboxylic acid or sulfonic acid, Q24 is hydrogen or a (represents a substituted or substituted alkyl group); δ represents a residue necessary to complete the fused benzene ring.

An example of this type of Y is U.S. Pat. No. 4,198°235.
No. 4,179,291, No. 4゜273.85
No. 5, British Patent No. 2,090,991 and OA No.

Furthermore, examples of Y suitable for this type of compound include a group represented by formula (YV).

G'' NH5 (h In the formula, Ba1l has the same meaning as in the formula (Yl), ε is an oxygen atom or =N032 group (G32 represents a hydroxyl group or an amino group which may have a substituent), In this case, examples of H,N-G'' compounds include hydroxylamine, hydrazines, semicarbazides, thiosemicarbazides, etc., and β'' in the formula is a saturated 5-, 6-, or 7-membered ring. or a group of atoms necessary to form an unsaturated, non-aromatic hydrocarbon ring.

G'' represents a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, etc. Specific examples of this type of Y include U.S. Patent No. 4.1.
No. 49,892 and JP-A-54-48534.

In addition, examples of Y in this type of compound include, for example, U.S. Pat. No. 3,493.939, U.S. Pat.
U.S. Patent No. 3,443.934, U.S. Patent No. 3,844,7
Examples include those listed in No. 85.

Furthermore, Y in the present invention includes a group represented by formula (YVI).

In the formula, α is 0R41 or NHR'', R41 is hydrogen or a hydrolyzable component, and R4t is hydrogen or an alkyl group having 1 to 50 carbon atoms or NH
It is a group that enables R42 to be hydrolyzed, A'' represents an atomic group necessary to form an aromatic ring, Ba1l is an organic immobilization group preserved on the aromatic ring, and Ba1l may be the same or different. , m is an integer of 1 or 2.

X is a divalent organic group having 1 to 8 atoms, and the nucleophilic group (Nu) and the electrophilic center (carbon atom) generated by oxidation form a 5- to 12-membered ring. Nu represents a nucleophilic group. n is an integer of 1 or 2. α is the above formula (
It has the same meaning as Y I ). A specific example of this type of Y is described in JP-A-57-20735.

Furthermore, another type of compound represented by formula (I) releases a diffusible dye by self-ring closure in the presence of a base, but when it reacts with an oxidized developer, the dye release does not substantially occur. There are non-diffusible imaging compounds.

Y that is effective for this type of compound is, for example, the formula % formula % where α' is an oxidizable nucleophile such as a hydroxyl group, a primary or secondary amino group, a hydroxyamino group, a sulfonamide group, etc. group or its precursor, α
" is a dialkylamino group or any group defined for α', G" is an alkylene group having 1 to 3 carbon atoms, a represents O or 1, and G1 is 1 to 40 carbon atoms. a substituted or unsubstituted alkyl group containing
or a substituted or unsubstituted aryl group containing 6 to 40 carbon atoms, QSI is an electrophilic group such as -co--cs, and cs4 is an oxygen atom, sulfur atom, selenium atom, nitrogen atom, etc. Yes, if it is a nitrogen atom, a hydrogen atom,
It may be substituted with an alkyl group or substituted alkyl group containing 1 to 10 carbon atoms, or an aromatic residue containing 6 to 20 carbon atoms.

G"% G" and G" each have the same meaning as a hydrogen atom, a halogen atom, a carbonyl group, a sulfamyl group, a sulfonamide group, an alkyloxy group containing 1 to 40 carbon atoms, or "G", and GSs and G" may together form a 5- to 7-membered ring.

Further, G'' may be G'' (QSI), NG53 G54. However, at least one of G'', G'', G'' and cs7 represents a ballast group.

Examples of this type of Y are described in US Pat. No. 4,108,850.

Further examples of Y suitable for this type of compound include formulas (Y■) and (YIX).

\ RAS Nu" and Nu" may be the same or different and represent a nucleophilic group or its precursor, Z61 is R
h4 and R'' represent a divalent atomic group that is electronegative with respect to the substituted carbon atom, and each of R61R'' and R'' is hydrogen, a halogen, an alkyl group, an alkoxy group, or an acylamino group, or RAS and Rai forms a fused ring with the rest of the molecule when in adjacent positions on the ring,
Alternatively, Ro and R'' form a fused ring with the remainder of the molecule, each of R'' and RAS, which may be the same or different, represents hydrogen, a hydrocarbon group, or a substituted hydrocarbon group, and the substituent R61 , R1, R'', R&4 or RAS of sufficient size (B
all) are present to render the compound immobile.

Specific examples of this type of Y are described in British Patent No. 1,593,669 and US Patent No. 4,232,107.

Another suitable Y for this type of compound is a group represented by formula (YX).

G? 1 In the formula, Na l l and β' are the same as those in formula (YII), and G7I represents an alkyl group (including a substituted alkyl group). Specific examples of this type of Y are described in U.S. Pat. No. 3,928,678 and U.S. Pat. No. 4,199,355.

Another type of compound represented by formula (1) includes non-diffusible imaging compounds that do not release dye by themselves, but do release dye when reacted with a reducing agent. In this case, it is preferable to use a compound that mediates the redox reaction (so-called electron donor).

Y that is effective for this type of compound is, for example, the formula (YXI
) are mentioned.

NO□ Compounds of this type are also suitable for Y as formula (YX[A)
and (YXIB).

In the formula, Ba1l and β' are the same as those in formula (yn), and G'' is an alkali group (including a substituted alkyl group). Specific examples of this type of Y are described in U.S. Pat.
No. 2,891, No. 4,139.379, No. 4.2
It is described in No. 18.368.

Further examples of Y suitable for this type of compound include a group represented by (YXO).

A specific example of Y is given in U.S. Patent No. 4,139°379.
No. 4.356.249, No. 4.358.52
It is stated in No. 5.

(Nu ox)' and (Nu ox)2
may be the same or different, respectively (, represents the oxidized nucleophilic group, the other symbols represent the formula, (Y■) and (YIX
). ) For specific examples of this type of Y, see U.S. Pat.
．． It is described in No. 604.

The patent specifications listed in YX[, YXI, YX[A and YXIB describe electron donors used in combination.

Also, more preferably, European Patent Box 220.7
No. 46A2, US Pat.
-201654 etc., N-X bond (
A compound having So, -X (where X is the same as the above) and an electron-withdrawing group in one molecule, as described in Japanese Patent Application No. 106885/1985. A compound having a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-63-271344, JP-A-61-271341
Examples include compounds having a CX' bond (x' is synonymous with X or represents -502-) and an electron-withdrawing group in one molecule.

Particularly preferred compounds represented by formula (I) include formula (
YXIV). Specific examples of Y are described in JP-A No. 62-215,270, but compounds represented by formula (YXV) are particularly preferably used in the present invention.

In the formula, EAG represents a group that accepts or takes electrons from a reducing substance. N and O represent a nitrogen atom and an oxygen atom, respectively. R81, Rew represents a substituent other than a hydrogen atom. R
When 11+ or R'' is bonded to +Time+v, it represents a simple bond or a substituent other than a hydrogen atom.R'' and R112 may be bonded to each other to form a ring.

is the same as the above). -0- is particularly preferred.

Time represents a group that releases Dye through a subsequent reaction by causing cleavage of the nitrogen-oxygen single bond in the formula, and t represents 0 or 1. In the formula, a solid line represents a bond, and a broken line represents at least one bond.

In the formula, R113 and R114 are each a simple bond, a hydrogen atom, or a group capable of substituting this, and may be bonded to each other to form a saturated or unsaturated carbocyclic ring or a heterocyclic ring. General formula (Y)IV), (YXll) is R1
It is preferred to have a ballast group at the 11% R'' or EAG position.

The ballast group in general formulas (Y I ) to (YXV) renders the dye image-forming compound of general formula (1) non-diffusible and is preferably an organic ballast group, which has 8 to 32 carbon atoms.
Preferably, it is a group containing a hydrophobic group up to . Such an organic ballast group is attached directly to the dye image-forming compound or as a linking group (for example, an imino bond, an ether bond, a thioether bond, a carbonamide bond, a sulfonamide bond,
They are bonded via a ureido bond, an ester bond, a carbamoyl bond, a sulfamoyl bond, etc. alone or in combination).

Specific examples of the compound of general formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

0■ shi4t1w5ノ137- rishi+bn3x Next, the method for synthesizing the compound of general formula (1) of the present invention will be explained from a specific synthesis example G.

Synthetic intermediate (22-a) of self-intermediate (22-a) is disclosed in JP-A-60-93434, JP-A-60-257579 and Japanese Patent Application JP-A-61-18330.
It was synthesized according to the synthesis method described in No. 0.

Synthesis of intermediate (22-d) First, intermediate (22-b) is synthesized by the following method.
22-c) (diazonium salt of 2-chloro-4-nitroaniline) was synthesized. 9.5 g of intermediate (22-b),
36% hydrochloric acid 80ai! While stirring the suspension, an aqueous sodium nitrite solution (sodium nitrite/water = 4.3 g/8 d) was added dropwise to the suspension at an internal temperature of 5°C or lower. After reacting for an additional 3 hours at below 5°C, 1 g of sulfamic acid
was added to decompose excess nitrite.

23.6 g of the intermediate (22-a), 120 methanol
11i! While stirring the solution, the diazonium salt was gradually added at an internal temperature of 5°C or less. 1 below 5°C
After reacting for an hour, the reaction was continued for an additional hour at room temperature. The precipitated crystals were collected by filtration, washed with methanol, thoroughly dried, and then used in the next step. Yield 6g Synthesis of intermediate (22-e) 26g of the above intermediate 5N,N-dimethylacetamide 13
111. 26 parts of phosphorus oxychloride was added dropwise to a suspension consisting of 150 parts of acetonitrile and 150 parts of acetonitrile while stirring. After reacting at 60°C for 2 hours, the reaction solution was cooled to room temperature and poured into ice water II! , while stirring. After stirring this suspension at 10°C or less for 1 hour, the precipitated crystals were collected by filtration, washed with water, and air-dried.

Yield 22g Synthesis of compound (22) 22g of intermediate (22-e) was added to a suspension containing 23g of intermediate (22-f), 70yd of N,N-dimethylacetamide, and 8.2d of pyridine at an internal temperature of 5°C or less. I added it little by little while maintaining it. After 1 hour, acetone 137d and methanol 137W1 were added to the reaction solution, and 67% of water was added dropwise at 55-60°C to precipitate an oily substance, which crystallized when stirring was continued for an additional 2 hours. The crystals were collected by filtration and diluted with methanol.
It was thoroughly washed at 00sdi. These crystals were collected by flash column chromatography (silica gel: chloroform/
It was purified using methanol = v/v = 60/1).

Yield 29g Yield 70χ Melting point 133-5℃ λIIM' 672.5nmε11
M^9.77X 10' The dimethylformamide solution of compound (22) is 800
It had absorption down to nm.

Compound (21) was synthesized in substantially the same manner as compound (22) according to the above synthetic route.

Melting point 128-130°C1λ”’689.4nm.

εDK' 6.83 XIQ4 The dimethylformamide solution of compound (21) is 800n
It had absorption up to a wavelength range longer than m.

Synthesis Example (3) Synthesis of Compound (2) 6.34 g of p-toluenesulfonate of 2-amino-4-hexadecyloxy-5-toctylphenol was dissolved in a mixture of 30 d of dimethylacetamide and 10 d of pyridine, and then cooled with water. , intermediate (21-
e) 7.15g was added in small portions. After stirring at room temperature for 1 hour, the reaction solution was poured into cold dilute hydrochloric acid and extracted with ethyl acetate.

After washing the extract with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (eluent: n-hexane/ethyl acetate-1/2) to obtain the orange compound (2). 4.6 g of brown crystals were obtained. Melting point 15
7-162°c0 In the light-sensitive material of the present invention, the compound represented by formula (1) can be used alone, but it is usually used together with yellow, magenta, and cyan image-forming compounds to form a full-color image. Provided to the system. In this case, the image-forming compound of the present invention can be added together with any of the yellow, magenta, and cyan image-forming compounds, or can be added separately from them. Note that the yellow, magenta, and cyan image forming substances here are the same as those of the general formula (1) except that the Dye portion of the general formula (1) is a yellow, magenta, or cyan dye or a precursor thereof, They are known.

Generally, the infrared light-absorbing image-forming compound of the present invention has a short wavelength region of absorption in the cyan dye region (600 to 700 nm).
Since they often overlap with m), it is advantageous for color reproduction to add them together with the cyan image forming compound.

The infrared light-absorbing image-forming compound of the present invention can be added to the light-sensitive material in exactly the same manner as other image-forming compounds. In many cases, the substrate Y in general formula (1) contains a hydrophobic ballast group that makes the image-forming compound itself diffusible, so an addition method is often adopted in which the image-forming compound itself is emulsified and dispersed in a state dissolved in a non-volatile oil. be done.

The amount of the infrared light-absorbing image-forming compound of the present invention added varies depending on the type and purpose of the photosensitive material or the physical properties of the compound itself, but is generally 0.05-1.0 g/n (
is within the range of

The image-forming compound in the present invention can be used alone, but a reducing substance that reduces exposed silver halide and cross-oxidizes with the compound of the present invention can be used in combination. Various reducing substances can be used, but preferably hydroquinones, 3-pyrazolidones, aminophenols, catechols, p-phenylenediamines, aminonaphthols, catechols, p-
-Phenylenediamines, aminonaphthols, reductones, etc.

It is also possible to use a precursor that is hydrolyzed under alkaline conditions to produce the above-mentioned reducing compounds.

For example, Japanese Patent Publication No. 55-52055, Japanese Patent Publication No. 54-39
No. 727, Japanese Unexamined Patent Publication No. 57-135949, etc.

More preferable reducing compounds include the following compounds.

3-pyrazolidones, such as 1-phenyl 3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl 4-methyl-1-phenyl-3-pyrazolidone, 1-m-1- Dyl-3-pyrazolidone, 1-p-tolyl-3-viratritone, 1-ferul-4-methyl-3-pyrazolidone, l-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-4,4
-bis-(hydroxymethyl)-3-pyrazolidone, 1
．． 4-di-methyl-3-pyrazolidone, 4-methyl-3-
Pyrazolidone, 4,4-dimethyl 3-pyrazolidone, 1
-(3-chlorophenyl)4-methyl-3-pyrazolidone, 1-(4-lylorophenyl)-4-methyl-3-pyrazolidone, 1-(4-)lyl)-4-methyl-3-pyrazolidone, 1- (2-)lyl)-4-methyl-3-pyrazolidone, 1-(4-)lyl)-3-pyrazolidone,
1-(3-tolyl)-3-pyrazolidone, 1-(1
-) Lyle 14,4-dimethyl-3-pyrazolidone, ■-
(2-trifluoroethyl)-4,4-dimethyl-3-
Pyrazolidone, 5-methyl-3-pyrazolidone, 1.5
-diphenyl-3-pyrazolidone, ■-phenyl-4-methyl-4-stearoyloxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-lauroyloxymethyl-3-virapritone, 1-phenyl-4゜4-bis-( lauroyloxymethyl)-3-pyrazolidone, 1
-Phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-3-acetoxypyrazolidone; Hydroquinones, such as hydroquinone, toluhydroquinone, 2.6
-dimethylhydroquinone, t-butylhydroquinone, 2゜5-di-t-butyl-hydroquinone, t-octylhydroquinone, 2.5-di-octylhydroquinone, pentadecylhydroquinone, 5-peitadecylhydroquinone-2-sulfone acid sodium, p-
Benzoyloxyphenol, 2-methyl-4-benzoyloxyphenol, 2-t-butyl-4-(4-chlorobenzoyloxy)phenol, etc.; aminophenols, such as 4-amino-2,6-dichlorophenol, 4-t-butyl-4-(4-chlorobenzoyloxy)phenol; Amino-2,6-dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3
-Methylphenol sulfate, 4-amino-2,6
-dichlorophenol hydrochloride, p-aminophenol, p-methylaminophenol, p-dimethylaminophenol, p-dimethylaminophenol,
p-dibutylaminophenol, p-piperidinoaminophenol, 4-dimethylamino-2,6-simethoxyphenol, etc.; phenylenediamines such as N-methyl-p-phenylenediamine, N, N-dimethyl-p-
Phenylene diamine, N, N diethyl-p-phenylene diamine, N, N.

N',N'-tetramethyl-p-phenylenediamine, 4-diethylamino-2,6-simethoxyaniline, etc.; reductones, such as piperidinohexose reductone, pyrodinohexose reductone, etc.

Furthermore, Research Disclosure Magazine No. 151,
1510B, U.S. Pat. No. 4,021,240, 2
．． 6-dichloro-4-substituted sulfonamidophenol,
2,6-dipromo-4-substituted sulfonamidophenol, p-(N,N-dialkylaminophenol)sulfamine, etc. are described in JP-A-59-116740, and are useful. In addition to the phenolic reducing agents described above, naphthol reducing agents such as 4-aminonaphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful.

These reducing substances or their precursors alone can
They can be used in combination of more than one type.

Silver halides that can be 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 inside the particle may be uniform, or it may have a multiple structure with different compositions on the surface and inside (Japanese Patent Application Laid-open No. 154232/1983,
B-108533, 5!14B755, 59-
52237, US Patent No. 4,433,048 and European Patent No. 100.984). In addition, the thickness of the particles is
Tabular grains of 0.5 μm or less, with a diameter of at least 0.6 μm and an average aspect ratio of 5 or more (U.S. Pat. No. 4,414
, No. 310, No. 4.435499 and OLS No. 3241.646A1, etc.), or monodispersed emulsions with a nearly uniform grain size distribution (JP-A-57-17
No. 8235, No. 5B-100846, No. 58-148
29, International Publication No. 83102338A1, European Patent No. 64,412A3 and European Patent No. 83.377A1, etc.) can also be used in the present invention. growth habit, halogen composition, particle size,
Two or more types of silver halides having different grain size distributions may be used together.

By mixing two or more types of monodispersed emulsions with different particle sizes,
You can also adjust the gradation.

The grain size of the silver halide used in the present invention preferably has an average grain size of 0.001 μm to 10 μm.
More preferably, the thickness is from 0.001 μm to 5 μm. These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonia method, and the reaction method of the soluble silver salt and soluble halide salt may be one-sided mixing method, simultaneous mixing method, or any of these methods. Any combination of these may be used. Back-mixing method where particles are formed under silver ion excess, or PAg
The Chondral double-jet method, which maintains a constant value, 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 (JP-A-55-142329, JP-A-55-142329;
-158124, U.S. Patent No. 3,650,757, etc.).

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Patent No. 4
, No. 094, 648).

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, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (■, ■) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Tardel water washing method or precipitation method can be applied.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526, JP-A-58-215644).
.

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions with nucleating agents and/or optical fogging may also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. No. 2,592,250, U.S. Pat. . Preferred nucleating agents for combination in the present invention are U.S. Pat.
OLS No. 4,155.511, OLS No. 4,266.031, OLS No. 4,276.364 and OLS No. 2.635
, No. 316, etc. For optical fogging, see Japanese Patent Publication No. 45-12710, Japanese Patent Publication No. 159641/1983.
A publicly known method can be used.

The silver halide used in the present invention may be spectrally sensitized with methyl dyes and others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex 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 used as the basic heterocyclic nucleus for these dyes. i.e. vilorin nucleus,
Oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and aromatic in these nuclei Nuclei in which hydrocarbon rings are fused, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus etc. can be applied. These nuclei may be substituted on carbon atoms.

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

These sensitizing dyes may be used alone or in combination (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 a sensitizing dye may be included in the emulsion. for example,
Aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. Nos. 2,933,390 and 3,63)
5.721, etc.), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. No. 3,743,51),
0 etc.), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,615.61
No. 3, No. 3,615,641, No. 3,617,2
The combination described in No. 95, No. 3,635,721 is particularly advantageous.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

A surfactant may be added alone or in combination to the photographic emulsion used in the present invention.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, improving sensitized photographic properties, antistatic, and antiadhesion. These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactants such as sulfoniums, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric ester groups, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols It is divided into amphoteric active agents such as

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. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. -mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triaza Tetraazakindenes (especially 4-hydroxy-substituted (1,3,3a, 7-tetraazakindenes), pentaazaindenes, etc.; benzenethiosulfones, benzenesulfinic acid, benzenesulfonic acid amide, etc.) A number of compounds known as antifoggants or stabilizers can be added.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, thioether compounds, thiomorpholines A, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain 3-pyrazolidones and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)
Acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used.

Various other additives may be used in the silver halide photographic material of the present invention. For example, hardeners, brighteners, dyes, desensitizers, coating aids, antistatic agents, plasticizers, slip agents,
Matting agents, development accelerators, mordants, ultraviolet absorbers, anti-fading agents, anti-fogging agents, etc.

Regarding these additives, specifically, Research Disclosure (RESEARC) I DISCLO3U
RE ) No. 176, pages 22-31 (RD-17643)
(Dec, 197 B) etc. can be used.

The compound of the general formula (1) of the present invention capable of releasing a diffusible dye is disclosed in, for example, JP-A-58-149046 and JP-A-59-1.
No. 54445, No. 59-165054, No. 59-18
No. 0548, No. 59-218443, No. 60-133
No. 449, U.S. Patent No. 4.503.137, U.S. Patent No. 4.
No. 474,867, No. 4,483.914, No. 4
, No. 455,363, No. 4,500,626, No. 4,740.445, JP-A No. 61-238056, etc., to form a mobile dye. It is preferably used in heat-developable photosensitive materials that utilize silver halide to be transferred to the dye fixing layer. Note that hereinafter, the heat-developable photosensitive material may be referred to as a photosensitive element.

When applied to a heat-developable photosensitive element, an organic metal salt can be used in combination with the photosensitive silver halide as an oxide. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in J.K. Koi No. 60-113235, and acetylene silver described in JP-A No. 61-249044. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50cm or Log/r in terms of silver.
rr is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1000) pages 24-25, the nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or the mercapto compounds and mercapto compounds described in JP-A-59-111636. Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive element and the dye fixing element. Examples include those described on pages (26) to (28) of JP-A-62-253159.

Specifically, a transparent or translucent hydrophilic binder is preferred, for example, a protein compound such as gelatin, a gelatin derivative, or a natural compound such as a cellulose derivative, a starch, a polysaccharide such as gum arabic, dextran, pullulan, etc.
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, the super absorbent polymer described in JP-A-62-245260 etc., namely -〇〇〇M or -3O3M (
M is a hydrogen atom or an alkali metal) homopolymers of vinyl monomers or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Jujutsu Chemical (
Sumikagel L-5H) manufactured by Co., Ltd. is also used. Two or more of these binders can be used in combination.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. Furthermore, when a highly water-absorbing polymer is used in the dye-fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye-fixing element to another object after transfer.

In the present invention, the amount of binder applied is 20 per 1M.
The amount is preferably 10 g or less, more preferably 7 g or less.

The constituent layers (including the back layer) of the photosensitive element or dye fixing element contain various polymers for the purpose of dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and improvement of the physical properties of the pressure sensitization prevention layer. It can contain latex. Specifically, Japanese Patent Publication Nos. 62245258 and 62-1366
Any of the polymer latexes described in No. 48, No. 62-110066, etc. can be used. In particular, if a polymer latex with a low glass transition point (40°C or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used for the back layer, curling can be prevented. is obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. It also includes image-forming substances (dye-providing compounds) having reducing properties (in this case, other reducing agents can also be used in combination). Further, a reducing agent precursor which does not itself have reducing properties but which discovers reducing properties by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in the present invention include those mentioned above, as well as US Pat.
, No. 4,483.914, columns 30-31, No. 4 of the same
, No. 330,617, No. 4.590,152, pages (17) to (18) of JP-A-60-140335, No. 47-40245, No. 56-138736, No. 5!
No. 11-178458, No. 59-53831, No. 59
-182449, 59-182450, 601
No. 19555, No. 60-128436 to No. 60-1
Up to No. 28439, No. 60-198540, No. 60-
No. 181742, No. 61-259253, No. 62-2
No. 44'044, No. 62-131253 to No. 62-
There are reducing agents and reducing agent precursors described in pages 78 to 96 of European Patent No. 220,746A2.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent is optionally added to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of precursors can be used.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).

Particularly useful electron transfer agents are 1-phenyl-3-virazolides or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive element, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below.

In the present invention, the amount of reducing agent added is o per mole of silver.
, 0.01 to 20 mol, particularly preferably 0.01 to 10 mol.

In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. 4.50.
No. 0,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, a dye-fixing element is used in conjunction with the photosensitive element. The dye fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. Regarding the relationship between the photosensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

Auxiliary layers such as a protective layer, a release layer, and an anti-curl layer can be provided on the dye fixing element as necessary.

In particular, it is useful to provide a protective layer.

In the constituent layers of the photosensitive element and the dye fixing element, a high boiling point organic solvent can be used as a plasticizer, a slippery agent, or a peelability improving agent between the photosensitive element and the dye fixing element. Specifically, pages (25) and 61 of JP-A-62-253159.
-245253, etc.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into dimethylsiloxane. Examples include various modified silicone oils described in the "Modified Silicone Oil" technical data P61BB published by Shin-Etsu Silicone Co., Ltd.
In particular, carboxy-modified silicone (product name X-22-37)
10) etc. are effective.

Also, Japanese Patent Application Publication No. 62-215953, Japanese Patent Application No. 622368
The silicone oil described in No. 7 is also effective.

Antifading agents may be used in the photosensitive element and the dye fixing element. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A-46-2784, etc.), and other JP-A-54-48535 and JP-A-62-13
There are compounds described in No. 6641, No. 61-88256, and the like.

Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, U.S. Pat. No. 4,241,155;
No. 4,245,018, columns 3 to 36, No. 4,25
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1983-234103, JP-A No. 62-31096, Japanese Patent Application No. 1983 There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The antifading agent for preventing fading of the dye transferred to the dye fixing element may be contained in the dye fixing element in advance, or may be supplied to the dye fixing element from outside such as a photosensitive element. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Optical brighteners may be used in the photosensitive element and the dye fixing element. In particular, it is preferable to incorporate the fluorescent whitening agent into the dye-fixing element or to supply it from outside the photosensitive element. Examples include K, Veenkataramang'Th
e Chemistry of 5ynthetic
Dyes J Volume V Chapter 8, JP-A-61-143752
Examples include compounds described in No.

More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, hendioxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in the constituent layers of light-sensitive elements and dye-fixing elements include U.S. Pat.
Examples include hardeners described in Japanese Patent No. 61-18942.

More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene bis(
(vinylsulfonylacephmide) etannat), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

Various surfactants can be used in the constituent layers of the photosensitive element and the dye fixing element for the purposes of coating aids, improving peelability, improving slipperiness, preventing static electricity, accelerating development, and the like. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of the photosensitive element and dye fixing element are coated with improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photosensitive element and the dye fixing element. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc. are used.
In addition to the compounds described on page 29 of No. 6, patent applications No. 110064/1982 and No. 62/11 of 1982 include benzoguanamine resin beads, polycarbonate resin beads, and AS resin pieces.
There is a compound described in No. 0065.

In addition, the constituent layers of the sensitivity element and the dye fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A-61-
No. 88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing element. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. It has functions such as promoting the movement of the dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it has a base or base precursor, a nucleophilic compound, a high boiling point solvent (oil), a thermal solvent, a surfactant, It is classified as a compound that interacts with silver or silver oil. However, these physical groups generally have complex functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,678.
, 739, No. 38-404111.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing element in order to improve the storage stability of the photosensitive element.

In addition to the above, combinations of poorly soluble metal compounds and compounds capable of complexing reaction with metal ions constituting this poorly soluble metal compound (referred to as complex-forming compounds), as described in European Patent Publication No. 210,660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis as described in this issue can be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.

Various development stoppers can be used in the photosensitive element and/or dye fixing element of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that quickly neutralizes or reacts with the base to lower the base concentration in the film and stop development after proper development, or a compound that interacts with silver and silver salts to stop development. It is an inhibitory compound.

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
It is described on page 32).

As the support for the photosensitive element or dye-fixing element of the present invention, one that can withstand processing temperatures is used. -For boat fishing, paper and synthetic polymers (films) can be used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose (e.g. triacetyl cellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, synthetic resin pulp such as polyethylene, and natural pulp. Mixed paper, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, glass, etc. are used.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used.

A hydrophilic binder, alumina sol, a semiconductor metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods of exposing and recording images on a photosensitive element include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method in which the original image is scanned and exposed through a slit using an exposure device, etc. A method in which image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure; There are methods of outputting the image to an image display device such as a spray display or a plasma display, and exposing the light directly or through an optical system.

Light sources for recording images on the photosensitive element include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., as mentioned above, such as U.S. Pat. No. 4,500,6.
The light source described in No. 26, column 56 can be used.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. signal, CG, C
Image signals created using a computer such as AD can be used.

The color photosensitive material of the present invention may be designed to be processed by a so-called normal wet color diffusion transfer method. In this case, the above-mentioned photosensitive material and dye fixing material can be used, except for additives specific to heat development (eg, organic silver salt).

The base and electron transfer agent may be supplied from the processing solution in a rupturable container. A viscosity imparting agent and the like can be added to this treatment solution as is well known. Color diffusion transfer methods are well known in the art, and the present invention is applicable to any of these known means.

(Effects of the Invention) According to the present invention, since it contains the image-forming compound represented by the general formula (1), it is possible to obtain a color photosensitive material that provides a color image that can be read by an infrared light reader. can.

(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 The method of making the emulsion for the first layer will be described.

A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 d of water and keeping it warm at 75°C) contains an aqueous solution containing sodium chloride and potassium bromide (600 -) and a silver nitrate aqueous solution (600 - of water). 0.59 mol of silver nitrate dissolved in the solution) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 8
0 mol%) was prepared.

After washing with water and desalting, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was carried out at 60°C by adding 0■. The yield of emulsion was 600 g.

Next, I will talk about how to make the emulsion for the third layer.

An aqueous solution containing sodium chloride and potassium bromide in a well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water and keeping it warm at 75°C) 600 #li! and silver nitrate aqueous vi, <water 6
A solution prepared by dissolving 0.59 mol of silver nitrate in 0.00 mol of silver nitrate) and the following dye solution (1) were simultaneously added at equal flow rates over 40 minutes. In this way, the average particle size is 0.35
A monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) on which a μ dye was adsorbed was prepared.

After washing with water and desalting, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was carried out at 60°C by adding 0■. The yield of emulsion was 600 g.

Dye solution (1) Next, a method for preparing a silver halide emulsion for the fifth layer will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin and ammonia dissolved in 1000 d of water and kept at 50°C) was mixed with an aqueous solution IQQQa containing potassium iodide and potassium bromide (and a silver nitrate aqueous solution (in 1000 d of water)). A monodispersed silver iodobromide octahedral emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was added at the same time while keeping p and Ag constant. was prepared.

After washing with water and desalting, 5 iIg of chloroauric acid (tetrahydrate) and 2 μg of sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion is 1. It was 0 kg.

I will explain how to make organic silver salt.

Organic silver salt (1) This article describes how to make benzotriazole silver emulsion.

28g of gelatin and 13.2g of benzotriazole to 33g of water
Dissolved in 00d. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

R The pH of this benzotriazole silver emulsion was adjusted, precipitated, and excess salt was removed. Thereafter, p was adjusted to 6.30 to obtain a benzotriazole silver emulsion with a yield of 400 g.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were mixed with 10 g of 1% aqueous sodium hydroxide solution.
It was dissolved in 00ml and 2oolle of ethanol.

This solution was kept at 40°C and stirred.

A solution prepared by dissolving 14.5 g of nitric acid in 200 id of water was added to this solution over a period of 5 minutes.

The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of organic silver salt (2) in a yield of 300 g.

Next, a method for preparing a gelatin dispersion of an image-forming compound will be described.

4 g of the image forming compound (2) of the present invention, 4 g of the cyan image forming compound described below, and 0.2 g of the antifoggant having the following structure.
g.) 3.5 g of lysononyl phosphate was weighed out, 40 ae of ethyl acetate was added thereto, and the mixture was heated and dissolved at about 60° C. to form a uniform solution. This solution, 0.5 g of soda dodecylbenzenesulfonic acid and 100 g of a 10% solution of lime-treated gelatin were mixed with stirring, and then dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a cyan image-forming compound dispersion. Dispersions of image-forming compounds were prepared in a similar manner by using the following yellow and magenta image-forming compounds, respectively.

With these, a color photosensitive material 101 having a multilayer structure as shown in Table 1 was produced. For comparison, the same color photosensitive material 102 (comparison 1) was prepared without the image forming compound of the present invention.
made.

yellow imaging compound Cyan image forming compound (C-1) 0 ■ magenta imaging compound Next, we will discuss how to make the dye fixing material.

63 g of gelatin, 130 g of a mordant having the following structure, and 80 g of guanidine picolinate were dissolved in 1300 m of water, coated on a paper support laminated with polyethylene to a wet film thickness of 45 μm, and then dried.

Water as a mordant was supplied with a wire bar, and then the dye fixing material and the membrane were stacked so that they were in contact with each other. The temperature of the membrane that absorbed water was 9
It was heated for 20 seconds using a heat roller whose temperature was adjusted to 5°C. Next, when the dye-fixing material was peeled off, a black character image with excellent contrast was obtained on the dye-fixing material.

The obtained image was scanned using the optical character reader MS-OC manufactured by Judenko.
When a reading test was conducted using R, the following results were obtained.

Furthermore, on top of this, 35 g of gelatin and 1.05 g of 1,2-bis(vinylsulfonylacetamidoethane) were added to 800 m
A dye fixing material D-1 was prepared by coating and drying a solution dissolved in water to a wet film thickness of 17 μm.

Using a tungsten light bulb, the multilayered color photosensitive material was exposed to a character image pattern at 20 lux for 1 second through a transparent test chart for exposure. 15d/nf101 on the emulsion surface of the light-sensitive material of this exposure method.
(2) 100% 102 (Comparison 1) 0% OCR by incorporating the image forming compound of the present invention
It can be seen that reading aptitude can be imparted.

Comparative Example A photosensitive material was prepared in the same manner as in Example 1 except that the image forming compound of the present invention was omitted from Example 1 and the cyan image forming compounds were replaced with C-2 and C3 shown below.

Exposure and development were carried out in the same manner as in Example 1, and an OCR reading test was conducted on the obtained image. The results are shown below.

Photosensitive material comparison 2 Comparison 3 Cyan image-forming compound normal succession rate 0% 10% C-3: C-2: Example 2 The image-forming compound of the present invention of Example 1 was (2) or (1)
, (5), (6), (9), and (15) were used in the same manner as in Example 1 to prepare color photosensitive materials 201, 202, 203, 204, and 205 each having a multilayer structure.

A dye fixing material was prepared in the same manner as in Example 1, and exposed under the same conditions.
Development was performed, and the resulting image was subjected to an OCR reading test. The results are shown below.

(2) 100% (6) 100% (10) 100% (11) 100% It can be seen that all the image forming compounds of the present invention have excellent OCR reading ability.

Example 3 A method of preparing silver halide emulsions for the fifth layer and the first layer will be described.

Add 600 d of an aqueous solution containing sodium chloride and potassium bromide to a well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 d of water, kept at 75°C) and a silver nitrate aqueous solution (in 600 d of water). 0.59 mol of silver nitrate dissolved therein) was simultaneously added at an equal flow rate over a period of 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (50 mol % of bromine) with an average grain size of 0.40 μm was prepared.

After washing with water and silver salt, sodium thiosulfate 5■ and 4hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was carried out at 60°C by adding 0■. The yield of emulsion was 600 g.

Next, we will explain how to make a silver halide emulsion for the third layer.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water, kept at 75°C), 600 ml of an aqueous solution containing sodium chloride and potassium bromide, and an aqueous silver nitrate solution (600 ml of water)
(0.59 mol of silver nitrate dissolved in
Added at equal flow rates over a period of minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene were added to perform chemical sensitization at 60°C.

The yield of emulsion was 600 g.

Next, how to make a gelatin dispersion of an image-forming compound will be described.

4 g of the infrared light-absorbing image forming compound (2) of the present invention, 4 g of the cyan image forming compound, 0.3 g of the antifoggant of Example 1, and sodium succinate 2-ethylhexyl ester sulfonate as a surfactant. 0.5g of triisononyl phosphate and 20g of triisononyl phosphate were weighed out, 60d of ethyl acetate was added thereto, and the mixture was heated and dissolved at about 60°C to form a homogeneous solution. This solution and a 10% solution of lime-processed gelatin 15
After stirring and mixing with 0g, use a homogenizer for 10 minutes,
Dispersion was performed at 110,000 rpm. This dispersion is called a dispersion of cyan image forming compound.

Dispersions of yellow and magenta image-forming compounds were prepared using yellow and magenta image-forming compounds in a manner similar to that described above.

The organic silver salts (1) and (2) used in Example 1 were used. From these, a color photosensitive material 301 having a multilayer structure as shown in Table 4 was prepared. For comparison, color photosensitive material 302 (comparison 4) was prepared in the same manner except that the image forming compound of the present invention was omitted.
made.

10〇- (D-1) Cyan image forming substance (D-2) (D-3) SO3■N(CzHs)s SO3θ Magenta image forming substance u UL; IJs3jnj Yellow image forming substance The dye fixing material was the same as in Example 1. A material having the same composition as D-1 except that guanidine picolinate was removed was prepared and used as dye fixing material D-2.

A tungsten light bulb was used in the above-mentioned multilayered color photosensitive material, and 15
Exposure was made for 1 second using Lux.

After that, it was placed on a heat block heated to 140 °C for 30 minutes.
Heat evenly for seconds.

Next, after supplying 20 d of water per layer to the film side of the dye fixing material, the heat-treated photosensitive coatings were stacked on the fixing material so that the film surfaces were in contact with each other.

After heating on a heat block at 80° C. for 6 seconds, the dye fixing material was peeled off from the photosensitive material, and a black character image with excellent contrast was obtained on the fixing material.

The obtained image was subjected to an OCR reading test, and the following results were obtained.

Photosensitive material Infrared light absorbing image forming compound Regular continuity rate 301
(7) 100%302(
Comparison 4) 0% It can be seen that the image-forming compound of the present invention is effective even in a high-temperature development system of 100° C. or higher.

Patent Applicant: Fuji Photo Film Co., Ltd. 1999 Year-Month-Day-4, Subject of amendment: “Claims” column of the specification,
“Detailed description of the invention” column

Claims (1)

[Claims] At least silver halide and the following general formula (
A silver halide color photosensitive material comprising an infrared light-absorbing image-forming compound represented by I). (Dye-X)q-Y(I) [In the formula, Dye represents an infrared light-absorbing dye group or dye precursor group represented by the following formula (II), and X represents a simple bond or linking group. In the formula, Y represents a group having a property of producing a difference in the diffusivity of the dye component before and after reaction with the photosensitive silver salt, corresponding to or inversely corresponding to the photosensitive silver salt having a latent image. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) In the formula, R^1 is a hydrogen atom, halogen atom, hydroxyl group, cyano group, carboxyl group, sulfo group, alkyl group, cycloalkyl group, aralkyl group, aryl group, hetero cyclic group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, acyl group, sulfonyl group,
Represents a carbamoyl group, sulfamoyl group, ureido group, urethane group, alkylthio group, nitro group, alkoxycarbonyl group, R^2 represents an alkyl group, aryl group, heterocyclic group, alkoxy group, amino group, R^3 is a halogen atom, an alkoxy group, an amino group, an alkylthio group,
Represents an aryloxy group, an acylamino group, an aryl group, or a heterocyclic group. Moreover, these substituents may be further substituted with other substituents. n represents an integer from 0 to 4, and when it is 2 to 4, it may be the same or different. Dye and X may be bonded from any position in formula (II). q is 1 or 2, and when q is 2, Dye-X may be the same or different.