JPS60113239A - Photosensitive material - Google Patents

Abstract

PURPOSE:To reduce degree of generation of unevenness of image by dispersing particles comprising specific mixture in a protective layer. CONSTITUTION:An emulsified product comprising substantially uniformly and separately disperset combined produce obtd. from a mixture of hydroquinone derivs. expressed by the formulas [ I ]-[III], or mixture of isomers thereof having <=100 deg.C freezing point, with polymer insoluble in water but soluble in org. solvent and having recurrent units contg. -(C=O)-O- bond such as polyvinyl acetate, polymethyl methacrylate, polyester of 1,4-butanediol with adipic acid, or polycaprolactone in the binder comprising hydrophilic colloid such as gelatin, is coated on a photographic layer and dried to obtain a protective layer. By this method, oxidation of developing component by the oxygen in the air during development of the treating liquid is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to photographic light-sensitive materials, and particularly to multilayer color light-sensitive materials. More specifically, the present invention relates to a color diffusion transfer photographic material having a protective layer effective for improving image unevenness, sharpening image gradation, and improving color reproducibility.

(Prior Art) The color diffusion transfer method typically uses a dye developer as a dye-donating compound (hereinafter referred to as "coloring material") (for example, U.S. Pat. II
/j, All'A issue, same 3. Hiroshi/S, 1; US No. 3.1944.111, etc.) and couplers or redox compounds that are non-diffusible even under alkaline conditions (provided that they release all of the diffusible dye as a result of development). type (e.g., U.S. Patent J, 227.110, 3
．． 21゜37.2, II, 013.3/2, etc.). The photographic light-sensitive material for this color diffusion transfer method consists of at least a photosensitive sheet and a developer storage bag (pound) that can be ruptured by pressure and is placed between this sheet and a cover sheet or image-receiving sheet. The most typical example is the "Film 22" which has a 7-ohm diameter (for example, the U.S. patent 3.3t, ♂
No. 1, 3. ≠ij.

t≠μ issue, British patent/, 330,! 2≠ etc.).

Film units with such a format are useful as instant photographic films, but in particular, film units that store a processing solution containing a highly active black-and-white developer such as Hydroquino in the casing. , there is an open circuit in that image unevenness is likely to occur in the transferred image.

As a result of repeated tests by the present inventors to investigate the cause of image unevenness, we found that this image unevenness occurs when the hydroquinone content in the processing liquid is high or when the processing liquid viscosity is high (10,000 cp).
or above), or when the processing solution development speed is slow (lθn/
It was found that this phenomenon appears conspicuously when the treatment solution is developed in an atmosphere of air (see below), and does not occur in an atmosphere of an inert gas such as nitrogen or argon.

Therefore, image unevenness occurs because the developing components in the high-viscosity processing solution are oxidized by oxygen in the air at the tip of the developing solution during the development of the processing solution. In addition, if the processing liquid has a high viscosity, the liquid is not rotated and mixed at the tip and an oxidation pattern remains, resulting in unevenness.

(Object of the Invention) Therefore, an object of the present invention is to provide a four-tone photosensitive material in which image unevenness is less likely to occur.

(Structure of the Invention) As a result of various studies, the present inventors have developed a method to reduce the amount of the silver halide emulsion layer that forms a silver image by treating it with an alkaline processing solution in the presence of a silver halide developer after exposure. In a photographic light-sensitive material having one layer on a support, during storage the layer located above the silver halide photographic emulsion layer 111+1 furthest from the support of the photographic light-sensitive material has a freezing point of too 0c or less. A certain hydroquinone derivative mixture and a water-insoluble, organic solvent-soluble homopolymer or copolymer having a repeating unit with a -〇-0-1 bond in the main chain or side chains are combined to form individual particles. It has been found that the above object can be effectively achieved by a photographic material characterized by being dispersed in a hydrophilic organic colloid.

(Effects of the Invention) By providing the protective layer of the present invention, it is possible to not only reduce image unevenness, but also to obtain a color photosensitive material with sharp image gradation9 and good color reproducibility. .

(Detailed explanation of the structure of the invention) The "protective layer" of the photosensitive material of the present invention may be composed of at least two layers, and the one in which the hydroquinone derivative and polymer used in the present invention are combined is , it is sufficient if it is contained in at least one of these layers.

Furthermore, as is clear from the provisions of the claims, the "protective layer" is clearly distinguished from the "intermediate layer" located between the two halogenated crab emulsion layers that form the image. .

In addition, the freezing point of the hydroquinone derivative mixture used in the present invention is the same as the eutectic point for a mixture that has a eutectic point (eutectic mixture), and the temperature at which this mixture begins to solidify for a mixture that does not have a eutectic point. means. Further, the term "hydroquinone derivative mixture" means a mixture of at least two kinds of hydroquinone derivatives.

As an example of the hydroquinone derivative mixture used in the present invention, λ number of tertiary alkyl groups of the carbon atom is described in JP-A-Sho Sa-Kota 637 (U.S. Pat. 2. j or λ, mixture of hydroquinone compounds substituted at position B, U.S. Patent J, 700
Examples include isomer mixtures typified by the isomer mixture of secondary dodecylhydroquinone described in No. 53.

In addition, isomer mixtures of compounds represented by general formulas (1) to (1) in F can also be used.

General formula (T) OH General formula (n) General formula (1u) OH 01 (wherein, Xl, X2 and X3 may be the same or different, a halogen atom (e.g. chlorine atom, bromine atom, etc.); (For example, an alkyl group having carbon number/-j, 2 (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-decyl group, tert -decyl group, n-dodecyl group, 5ee-dodecyl group, tert-dodecyl group, n-
Pentadecyl group, 5ec-pentadecyl group, tert-
pentadecyl &, sec-octadecyl group, ter
straight-chain or branched alkyl groups such as t-octadecyl group), substituted alkyl groups having a total number of carbon atoms of 1-22 [substituents include halogen atoms such as chlorine atoms or bromine atoms, hydroxy groups, alkoxy groups, substituted Examples include amino groups (including alkyl or arylsulfamoyl groups and alkyl or arylcarbamoyl groups), cyano groups, etc. (for example, μm chlorobutyl group, λ-hydroxyethyl group,
-methoxy7propyl M, 3-n-1-tylsulfamoylpropyl group, etc.)], carbon number 3 -. 22 alkenyl groups (e.g. allyl group, etc.), cycloalkyl groups having 3 to 2 carbon atoms (e.g. cyclohexyl group, etc.), aralkyl groups having 7 to 22 carbon atoms (e.g. benzyl group, phenethyl group, v-methylphenylethyl group) Aryl group (e.g. phenyl group, hydroxy group, phenyl group substituted with alkyl or arylsulfonyl group); Alkoxy group, e.g. optionally substituted alkoxy group having 1 to -22 carbon atoms (e.g. methoxy ethoxy group, n-methoxy group, n-dodecyloxy group); aryloxy group, for example, an optionally substituted aryloxy group having 2 to 22 carbon atoms (for example, phenoxy group, μ-n-butoxyphenyloxy group); ); alkylthio group, e.g. number of carbon atoms! -22 optionally substituted alkylthio group (
For example, methylthio group, ethylthio group, n-hentylthio group, n-dodecylthio m, n-pentadecylthio group, j
-chloropentylthio group, etc.); or arylthio group,
For example, it represents an optionally substituted arylthio group having carbon atoms a6 to a22 (eg, phenylthio group, ≠-nitrophenylthio M, etc.).

Furthermore, Xl and x2 may jointly form a condensed ring, preferably a ring having j to 7 carbon atoms (e.g., a 7-bentane ring, a cyclohexane ring, a 7-glohexadiene ring, a norbornene ring, etc.). represent something.

R is an aliphatic group 1@for example, an alkyl group having 1 to 1 carbon atoms (the list is methyl group, ethyl group, n-propyl group, n-butyl group, 4 n-octyl group, n-decyl group, n- (straight chain and branched alkyl groups such as dodecyl group and i-pentyl group), substituted alkyl groups having 1 carbon atoms and λ, and those having a halogen atom (chlorine atom or bromine atom) as a chiral group, such as λ-chloroethyl 4.2-y lomoethyl group, 3-chloropropyl group, Hiro-bromobutyl group, dichloromethyl group, etc.; those with a hydroxy group, such as co-hydroxyethyl, 3-hydroxypropyl group, Hiro-hydroxy-butyl group, t- Hydroxyhexyl group, etc.; those with a sulfonyl group, such as ethanesulfonylmethyl group, 1
-butylsulfonylethyl group, arylsulfonylbutyl group, etc.; those having an alkoxy group (e.g. methoxy group, ethoxy group, n-butoxy group, n-hexyloxy group, etc.), such as ethoxyethyl group, methoxyethyl group,
Ethoxyethyl group, n-butoxyethyl group, 3-methoxypropyl group, n-hexyloxoethyl group, etc.; alkylthio group (e.g. methylthio group, ethylthio group, n-
Hexylthio group! etc.), such as a methylthiomethyl group, methylthionyl f k M, j -enzyme-propyl-L n-hexylthioethyl group, etc.; ,
N-dimethylamino)butyl group, j-acetamidopentyl group, Hiro-methinesulfonylaminobutyl group, anilinomethyl group]; cycloalkyl group (e.g. cyclohexyl); for example, even if it has a substituent group having 7 to 2 carbon atoms Good aralkyl groups (e.g. benzyl group, hiro-methylbenzyl group, μm chlorobenzyl group, phenethyl group, ≠-
(methylphenylethyl group, etc.) 1, or aryl groups, such as phenyl groups and substituted phenyl groups, 1 having a halogen atom (e.g. chlorine atom, bromine atom) as a substituent,
For example, ≠−chlorophenylru &,! -'Romophenyl group, λ-chlorophenyl group, etc.; Those with a hydroxy group, such as Eva λ-hydroxyphenyl group, Hiro-hydroxyphenyl &, x, s-dihydroxyphenyl group; Contains an optionally substituted alkyl group Things, examples (4+-methylphenyl group, ≠-1-propylphenyl s, ti-n
-dotecylphenyl group, Cochrolowhiro-methylphenyl group, μmchloromethylphphenyl 2,3-dihydroxy-gualkylphenyl group, etc.: those with an optionally substituted alkoxy group, such as ≠-methoxyphenyl group, μ- Ethoxyphenyl group, ll-n-propoquinphenyl group, λ-methyldermethoxyphenyl group, 3-methoxyphenyl group, 4A-n-iathyloxophenyl group, a-n-dodecyloxophenyl &, 3-n- Those with an optionally substituted argylthio group such as a pentadecyloxophenyl group, examples are id'Hiro-methylthiophenyl group, gouethylthiophenyl group, ≠-n-butylthiophenyl group, 3-n-hexylthio Phenyl%, 3
．． -n-f sylthio-phenyl group, etc.; those with an alkoxy 7 carbonyl group, such as -methquincarbonylphenyl4, 't-ethoxycarbonyl=cochlorophenyl group; those with a carboxy group, such as t-carboquine Phenyl group, etc.; those having a carbamoyl group, such as l-purbamoylphenyl group, goomethylaminocarbonylphenyl-m, 1-10low 4'-(N, N
-diethylaminocarbonyl) phenyl group, etc.; substituted amine group (substituents include alkyl group, aralkyl group,
Those having a phenyl group, a carbon [or an acyl group derived from a sulfonic acid (each of these substituents may be further substituted), such as a φ-methylaminophenyl group, ≠-(N, N- Diethylaminophenyl m, 4'-
(N-ethyl-N-benzylamino) phenyl group, guacetamidophenyl group, μm methanesulfonylaminophenyl group, 3-n-heptanoylaminophenyl group,
3-Phenylsulfonylaminophenyl group, etc.; those with a nitro group, such as Hiro-nitrophenyl group, l-nitro-J-methylphenyl group, cochloro-μ-nitrophenyl group; those with a cyano group, such as ≠ - cyanophenyl group, etc.; those with annyl groups, such as gouacetylphenyl group, λ-methyl-Hiro-acetylphenyl group, goupensoylphenyl tJ, l; things with sulfonyl group, such as ≠-methanesulfonylphenyl 3
1s, 2-chloro-Hiro-ethanesulfonylphenyl group,
l-phenylsulfonylphenyl group, J-(=,j-dihydroxy-4'-tert-benalphenyl)sulfonylphenyl group lx (!: ;Those having a sulfamoyl group, such as 3-sulfamoylphenyl group, j-
(n-phthylaminosulfonyl) phenyl group, 2-chlorophenylaminosulfonylphenyl group; and those with sulfo group, such as F'i'l-sulfophenyl group, cochloro! - Represents l such as a sulfophenyl group.

(2) Preferably, it does not contain a dye residue or its precursor.

In the molecule represented by the formula ([L(n) and (III),
The total number of carbon atoms in Xl, X2, X3 and 几 is preferably at least 10 or more in order to make the compound non-diffusible, and more preferably from 1 to 30 carbon atoms.

Specific examples of compounds represented by general formulas (1) to (Ill) are listed below.

(1) H H H O)1 H H H H H H H H H H H 01-1 (JH H 1-1 H (22) 0H (23) 0H O)1 (25) OH H -Koumasu Q (32 ) This hydroquinone conductor admixture has the ability to develop halogenation, provided that the solid complex thought to be formed between it and the polymer does not substantially liberate this mixture when it comes into contact with an alkaline processing solution. Even if there is, it is not harmful because the solid complex is not affected. Essentially, it is preferable to have a remarkable ability to prevent image unevenness but no ability to develop silver halide.

In this regard, the hydroquinone derivative mixtures specifically listed above are preferred.

The hydroquinone derivative mixture used in the present invention preferably has a freezing point of lro 0C or lower. Particularly preferred are those that are liquid or waxy at room temperature.

Representative polymers useful in the present invention include, but are not limited to, the following:

(A) The 1a substituent of the substituted alkyl group of the monopolymer and copolymer R1 and R2 containing the following repeating units includes a halogen atom, an alkoxy group, an aryl group, an acyl group, a cyano group, an amino group, etc. can be mentioned. Also, R2
Examples of the substituent of the substituted aryl group include an alkyl group, a halogen atom, and an alkoxy group. Ro
The alkyl group is preferably a methyl group.

Suitable vinyl monomers that can be used to make this polymer include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl Examples include phenylacetate, vinylacetoacetate, vinyl lactate, vinyl benzoate, vinyl chlorobenzoate, vinyl naphthoate, and the like.

Suitable comonomers that can be copolymerized with these monomers include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, methyl vinyl ketone, fumarate, maleate, itaconate, α- Examples include chloroethyl vinyl ether, methylenemalonitrile, acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, butadiene, isoprene, and vinylidene.

Specific examples: l) Polyvinyl acetate, 2) Polyvinyl propionate, 3) Vinyl acetate-vinyl alcohol copolymer (LiO: 1
0) (B,) Homopolymers and copolymers containing the following repeating units. Suitable vinyl monomers that may be used to make these polymers include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl Acrylate, n-ethyl acrylate, octyl acrylate, λ-chloroethyl acrylate,! -cyanoethyl acrylate, N-(β-dimethylamine ethyl)
Examples include acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-zolopyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

Suitable comonomers that can be copolymerized with these monomers include, for example, the vinyl monomers described in (A).

Concrete example:! I] Polymethyl methacrylate j) Polyethyl acrylate t) Polyethyl methacrylate 7) Polybutyl acrylate t) Polybutyl methacrylate t) Polyisobutyl methacrylate 10) Polyisopropyl methacrylate //) Polyoctyl acrylate / 2) Butyl acrylate - Acrylamide copolymer (
5rs) /J) Stearyl methacrylate-acrylic acid copolymer (RIO: 1O) (C) Polyester resin obtained by condensing a polyhydric alcohol and a polybasic acid.As the polyhydric alcohol, HO-几- Glycols or polyalkylene glycols having a structure of 0H (R3 is a hydrocarbon chain of #1.2 to about 1 carbon atoms, especially an aliphatic hydrocarbon chain) or polyalkylene glycols are effective, and as polybasic acids, HO
OC-R'-COO) (()L' represents a simple bond or a hydrocarbon chain having 1 to about /λ carbon atoms) is effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
, J-Flopylene Gelicol, l.

3-propylene glycol, trimethylolzolopano,
/, 44-butanediol, inobutylene diol, 1
．． j-bentanediol, neopentyl glycol, /
, A-hexanediol, l.

7-hebutanediol, /, If-octanediol,
/, ternonanediol, 1llO-decanediol,
/, /l-undecanediol, /.

l2-dodecanediol, /, /3-tridecanediol, l,≠-diol, glycerin, diglycerin, triglycerin, l-methylglycerin, erythritol,
Examples include mannitol and sorbitol.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, se/macinic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. , fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimelic acid, /clopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct Things can be given.

Specific examples: /4C)/, 4'-butanediol-adipic acid polyester/j) Ethylene glycol-sebasonate polyester (D) Other polyesters obtained by ring-opening polymerization, such as the following, with the following repeating units: Polyester The following repeating unit is 1. In the formula, m represents an integer from v to 7. The -C112- chain may be branched.

Suitable monomers for use in making this polyester include .beta.-propiolactone, .delta.-caprolactone, dimethylzorobiolactone, and the like.

Specific examples: /A) Polycaprolactone /7) Polypropiolactone /J') Polydimethylzorobiolactone The properties of the polymer used in the present invention vary depending on the thickness of the protective film to be applied, but typical ones are protective It is contained in an amount of about J to about 0% by weight based on the hydrophilic binder in the layer.

A useful ratio (by weight) of hydroquinone derivative mixture to polymer in the present invention is about 0.0 parts polymer to 1 part hydroquinone derivative mixture. / or within a range of approximately 3 metropolitan areas.

Hydroquinone derivative mixture coating title I L<
uO, OJ ~0.31/m2, and the appropriate polymer coating t is 00OO~O0ri f/m,
Preferably it is 0.0/~0.3 f/m.

Hydrophilic binders in which the mixture of hydroquinone derivatives and monomers are dispersed according to the invention are, for example, gelatin, gelatin carriers modified with acylating agents etc., gelatin grafted with vinyl polymers, casein , tannin substances such as albumin; cellulose g conductors such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and methyl cellulose; =tt polymers such as vinyl alcohol, polyacrylamide, polyvinyl ethers, such as polymethyl vinyl ether Valve lysates; anionic synthetic polymers such as partially hydrolyzed polyacrylic acid and polyacrylamide can be used. These hydrophilic binders can be used alone or in combination.

In 1, the preferred method for preparing this hydroquinone derivative mixture-polymer mixture dispersion tl-
The hydroquinone derivative mixture and the relatively hydrophilic, water-insoluble polymer of the present invention are dissolved in a volatile organic solvent that is sparingly miscible with water (eg, ethyl acetate). By emulsifying the solution in a sol of a hydrophilic binder such as gelatin, small droplets of the hydroquinone derivative mixture and the polymer dissolved in the volatile bath agent are finely dispersed in the aqueous phase. A dispersed emulsion is obtained. The composition is solidified, for example, by cooling, and the solidified composition is then noodled and substantially all the solvent is removed by evaporation or washing at room temperature. Through this step, an emulsion is obtained in which the hydroquinone derivative mixture-polymer combination is substantially uniformly dispersed as separate particles in the hydrophilic colloid binder. The average size of the particles is suitably in the range of about o,i-2μ.

The protection Im can be provided by the hydroquinone derivative mixture and the polymer by applying the emulsified dispersion obtained in the above step onto Photograph 1- and then drying it. When dissolving both in a low boiling point solvent, a portion of the water-soluble low boiling point solvent (e.g. methanol etc.) (e.g. io~/4c'
may be used in combination. Further, during emulsification, it is effective to use a surfactant such as that used in emulsifying and dispersing coloring materials.

When forming the retention layer according to the present invention, the solvent used is oil (a water-insoluble organic solvent whose content does not substantially change before and after application).
It is preferable not to use .

The silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or a mixture thereof, in which halogen The composition is selected depending on the purpose of use and processing conditions of the photosensitive material, but the iodide content is 10 mole% or less and the chloride content is J
Particularly preferred is silver bromide, silver iodobromide, or silver chloroiodobromide in an amount of Omole% or less. The silver halide emulsion may be a conventional surface latent image type emulsion or an internal layer image type emulsion.

Internal RA image type halogenated emulsions advantageously used in the present invention include US Pat.
, 20t, J/J No. 3, 17. No. 27, No. 3,
No. 71/, No. 27, and No. 3 of the same. Conversion type emulsions, core/gel type emulsions, etc. described in 35.0/Hiro issue, etc.
Examples include emulsions containing different types of gold maple.

As a nucleating agent for directly obtaining a positive image using this type of emulsion, US Pat.
, 7f5; Ibid. J, 227
．． Hydrazides and Hydrazides Collection British Special Issue II'F/, λ13.13/No. 112, Equity tl[(μ
U.S. Patent No. 31/l≠, U.S. Pat. /j, quaternary chloride adduct described in No. 111: Rice Painting Patent J, 7/l, ≠7
The nucleating action described in the θ issue (nucleat
ing ) a sensitizing dye having a substituent in the dye molecule; USA! Patent 4', 030.

The acylhydrazinophenylthiourea compounds described in No. 225, &, 03/, and /j7 are representative.

The silver halide emulsions used in the invention can have color sensitivity extended by spectral sensitizing dyes, if desired. As the spectral sensitizing dye, a noanino dye, a merocyanine dye, etc. can be used as appropriate.

Although Tanimune's compounds can be used as colorants for use in the present invention, dye-releasing redox compounds are particularly useful.

Diffusible dye-releasing redox compound (hereinafter referred to as “DRl”)
(referred to as "compound") can be represented by the following general formula.

-D Specific examples of Y include U.S. Patent 3. riλr, No. 3/2, No. 3
,? ? 3. gJlt issue, TL, 07A, 329, ≠, /32. /j3, Dohiro, OSS, Hiro2, same≠
, 033.3/l issue, same issue, /9za.

No. 235, same≠, /7ri, λri No.1, rotation, /&9, r
9.2 No. 3, f444', 7za No. 5, No. 31 Hiro≠3. Rihiro No. 3, 3.7j/, +107. No. 3
, μ≠J, No. 939, 3. φHiro3.9Hiroθ No. 3
．． 621.9s No. 2, 3,910,1779, I
L, lf3.7!3, same≠, /Hiro2. g 1, q, 27g, 750, ψ, /39°37? No., same q
, λ/l, No. 361, No. 3, Hiroko I, No. 6≠, μ
,/Tade, to 3! No. r, 4 ψ.

l Tata, 31≠ issue, same gu, 27r, 7so issue, same 4A,
/33,92t No., I, 33t, 322, ≠, /3, 31, No. 33-1073, No. 53-6033, No. 34 (-13012, No. 31) 13
-/No. 10127, No. lt-72tμλ, No. 31-/
413/No., j7-san O≠3, No. 17-6jO,
No. j7-2073j, No. 53-69033, No. 5.
No. 2-1127, etc. For the dye moiety represented by D, examples of yellow dyes: US Pat. No. 97,200, 3.30.

No. 722, μ, 0/3, No. 633, 11.2'1s
, o2r issue, 44. /j7. JOri issue, same ψ.

13ri, 3/3 issue, same≠, /rij, 222, intermediary, /
≠f, A≠1, same≠llqg, 6ko 3, Disclosure /7A30 (/7F), Disclosure /A Guaj (/77).

Example of magenta dye: US Patent No. cf3,1IrJ, No. 107, 3,11111
゜J'μj, 31ri 3λ, Jro, 31ri 3
/, /ll' No. 1, No. 3,932,301, No. 3゜ri! Hiroshi, t76, Intermediate, 233.237, Intermediate, λs
r, sori issue, same≠, 2IO, 2'16 issue, same u, /
a2. ryi issue, same F, JIJ7.1017, same≠
, λt7.2 Octopus; JP-A-Shojλ-/θ&, No. 727,
Same number jλ-106727, same number j3-λj, number Aλ, same number j! -Jj, No. 1011, same jG-73. C#7,
What is described in j4-''//01.0 and jj-/J≠ of the same.

Examples of Noan colors: US nationality total 3. Sanzako, Ri7λ, same 3. riλri.

No. 740, same≠, 0/J, No. 631, same, 26g, A
2j, 4', 17/, 2jθ, rotation.

O-, Su 3/No., same μ #l Hiroko, rri No. 1, same Gu, /9
j, Tata No. 1, same≠, /l1L7. j-41, same φ,
l≠f, J Goo No.; British Patent/, 31/.

/3r issue; JP-A-Shoj Gutata-Hiroshi 31, 5.2-11
No. 27, No. 13-177123, No. 33-/≠JJ,
2J No., j4'-Tata 413/No., jA-7101
, No. 1; European Patent (EPC) jJ.

No. 037, No. j3,0110; Re5earch1
)isclosure /7,4jθ(/?7F) issue,
and same/l, ≠7! (/ri77).

The coating amount of these compounds is generally about /x10' to /X/
0 mol/tn is suitable, preferably 2X1
0-. 2×10 mol/nt.

The alkaline processing composition (developer) that can be used to process the photosensitive material of the present invention contains sodium sulfite, potassium sulfate, ascorbic acid, reductones (
For example, piperidinohexose reductone).

The developer may contain sodium hydroxide, potassium hydroxide, sodium chloride, potassium carbonate, trisodium phosphate, sodium metaborate, etc. as an alkaline agent and buffer +411. The appropriate amount of these agents is such that the p)(p) of the developer is 10 to 44 or more, preferably p
Select H/J~/4C. In addition, the developer contains a color development accelerator such as benzyl alcohol, and agents that lower the minimum density of direct positive images such as benzimidazoles such as lobenzimidazole, benzito IJ 7zole, and j-methyl- It is advantageous to include compounds used as coupled antifoggants, such as benzotriazoles such as benzotriazole.

Various known fi image agents can be used to develop the light-sensitive material of the present invention. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, comethylhydroquinone, t-butylhydroquinone, sodium methylhydroquinone sulfonate, sodium t-butyl-hydroquinone sulfonate, kaacol, pyrogallol; aminophenol 4; , such as p-aminephenol, N-
Methyl-1)-7 minophenol, 2. II-diaminophenol, etc.; 3-pyrazolidones, e.g. / -phenyl-3-pyrazolidone, +, 4A-dimethyl-/-
Phenyl-3-pyrazolidone, Hiro, ≠-dihydroxymethyl-1-phenyl-J-Hira7" IJton, Ri,
Hiro-dihydroxymethyl-/-p-tolyl-3-pyrazolidone, ≠-methyl-≠-hydroxymethyl-7-phenyl-3-virasoliton, Hiro-methyl-guhydroxymethyl-/-p=nitrile 3-pinzolidone, goomethi Rougoohydroxymethyl/-rl-tolyl-3-pyrazolidone and the like; ascorbic acid and the like can be used alone or in combination. For the first reaction, it is useful to use a combination of 3-pyrazolidones and hydroquinos.

In addition, when a dye is obtained by a dye-forming coupler,
An aromatic-grade amine developing agent, preferably a p-phenylenediamine type developer, can be used. A specific example thereof is t-amino-3-methyl-N.

N-diethylaniline hydrochloride, N.

Bediethyl-p-phenylenediamine, 3-methyl-
<1-Amino-N-ethyl-N-β-(methane-sulfamide)ethylaniline, 3-methyl-4'-7mi/
-N-ethyl-N-(β-sulfoethyl)aniline, 3
-ethoxy-V-amino-N-ethyl-N-(β-sulfoethyl)aniso/, Hiro-amino-he-ethyl-N-(
β-hydroxyethyl)aniline. Such developing agents may be included in the alkaline processing composition (processing element) or in appropriate layers of the light-sensitive material.

In the present invention, when a Dl (It compound) is used as a coloring material, any halogen-stopping developer (or electron donor) can be used as long as it can cross-oxidize it. However, 3-pyrazolidones are preferred.

When the photosensitive material of the present invention is used as a film unit for diffusion transfer method, it may be processed with a viscous developer (I
Delicious. This viscous developer is used for the development of breast wounds (
The liquid composition contains processing components necessary for (1) formation of a diffusion transfer dye image, and the main solvent is water, and may also contain other hydrophilic solvents such as methanol and methyl cellosolve.

The processing composition contains the p) necessary to cause development of the emulsion layer.
A sufficient amount of alkali is added to maintain I and to neutralize acids (e.g., hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid, etc.) generated during development (and the various processes of dye image formation). contains. Examples of alkalis include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate 1, alkali metal or alkaline earth metal salts such as diethylamine, or amines. is used, preferably about 12 or more p) ((% p
It is desirable to contain caustic alkali at a concentration that provides H/4'). More preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers provide treatment compositions with at least 1 void, preferably SOO to ioo, at room temperature.
.

It is best to use it to give a viscosity of about poise.

The processing composition may also contain light-absorbing substances such as carbon black and pH indicator dyes as light-shielding agents to prevent the silver halide emulsion from fogging due to external light during or after processing, and U.S. Pat. 3. It is advantageous to contain a desensitizer such as that described in J7 R. No. 333, especially in the case of a monosheet type film unit. Furthermore, an IJI image suppressor such as benzotriazole can be added to the processing liquid composition.

When carbon black is used in the treatment composition,
In order to inactivate the sulfur compounds contained as impurities in carbon black, Pb1ZnXCu, AI,
Metal ions such as Ag may also be contained.

The above treatment composition is described in U.S. Patent No. 2.5ψ3. /No.11,
2, tlA3.114, 2. A! 3゜732, 2.723.0j 1, 3,066.4A 7, 0!4. It is preferable to use it by filling it into a rupturable container such as those described in Getter, 31isλ, sis, and the like.

Using the photosensitive material of the present invention, color photographs can be obtained, for example, by the following steps. That is, a light-sensitive material (or light-sensitive element) on which a silver halide photographic emulsion combined with at least one colorant is coated on a support is image-wise (
image).

The brightened silver halogenide emulsion is then developed by treatment with an alkaline processing composition in the presence of the developer (electron transfer agent) described above. A dye image is then formed as a result of development of the silver halide emulsion.

When utilizing color diffusion transfer, the process involves (a) forming a distribution of diffusible dye to form an image, and then (b) diffusing (transferring) at least a portion of this dye into an image-receiving layer (or image-receiving element). ).

This results in a diffusion-transferred color image on the image-receiving layer.

Further, by the same method as above, color photographs can also be obtained by utilizing the dyes remaining in the light-sensitive material (or light-sensitive element).

That is, in step (b) of the above method, all the diffusible dyes are removed by water washing or diffusion transfer, and the remaining silver and silver halide are fixed with the white (this may be done at the same time). By removing the dye, a color image consisting of the non-diffusible dye (or coloring material) remaining in the photosensitive material can be obtained.

As stated above, the light-sensitive material of the present invention primarily consists of a light-sensitive element (1) coated with at least one layer of silver halogenide emulsion 1- on a support (provided that (on which the protective layer of the present invention is coated) is further treated with (1) and the image receiving element (or image receiving layer) (2) by a processing composition (3).
A film unit consisting of (1), (2) and (3) is most effective for the present invention.

In the embodiments including (1), (2), and (3) above, the means for supplying the processing composition may be a container (bod) that contains the processing composition and can burst under pressure. In this container, the contents (processing composition) in the container are supplied between the photosensitive layer and the cover sheet, or between the photosensitive layer and the image-receiving layer by applying pressure with a pressure member. It is arranged M as follows.

The image-receiving element described above may be placed on a separate support so that it is superimposed with the light-sensitive element after exposure.

Such embodiments are described, for example, in US Pat.
It is described in the following. Alternatively, the image receiving element may be electrically coupled to the photosensitive element throughout before, during and after exposure.

In addition, as another aspect, image reception g! The element may be provided on the same support as the photosensitive element. Such an integrated form (film unit) is described, for example, in Belgian patent 7j7.76.
A variant of this is also described in Belgian patent 7j7, 7'5. According to this embodiment, the support is transparent, and at least an image-receiving layer, a reflective layer (white layer), a light-shielding layer, and a photosensitive layer are coated thereon, and an alkaline processing composition and a light-shielding agent are coated thereon. A burst oJ capacity container containing a rupture oJ capacity is disposed between the top layer (protective layer) of the photosensitive element and a transparent cover sheet (coated with a neutralizing layer and timing In). This film unit is loaded into a camera, exposed through a transparent sheet, and then passed between a pair of pressure members in the camera when the film unit is taken out. The pressure member ruptures the container and spreads the processing composition and light blocking agent onto the photosensitive element of the film unit. Each silver halogenide emulsion is developed by the processing composition, so that the diffusible dye formed diffuses imagewise into the receiver no., thereby obtaining a transferred image thereon. In this way, a color photograph can be viewed against the background of the light-reflecting layer (white layer).

Furthermore, as a variation of the integrated configuration, a release layer may be provided between the image-receiving layer and the photosensitive element. Thereby, after forming the transferred image, the photographer can peel it off as needed and use it as a normal color print or color slide.

The invention will be explained in further detail by the following examples.

Example 1 An emulsion containing a hydroquinone isomer mixture and a polymer used in the protective layer of the present invention was prepared as described in Dingichi.

Emulsion / λ, j-T-pentadesilver droquinone isomer mixture ≠ Of and vinyl acetate polymer 20f dissolved in ethyl acetate j Occ was prepared, and this was mixed into an aqueous gelatin solution containing 10% gelatin 6o.

Sodium dodecylbenzene sulfonate was dispersed in K, sodium dodecylbenzene sulfonate, the dispersion was solidified by standing cooling, the solidified composition was noodled, and substantially all the solvent was removed by washing.

A photosensitive material (1) of the present invention and a comparative photosensitive material (II) having the structures and compositions shown below were prepared.

Each photosensitive material was exposed to light using 2rsa 0y;-tungsten light through an optical wedge with a density difference of 0.2 (maximum exposure depth at this time was IOCMS). Each exposed photosensitive material is passed between a pair of device compression rollers.
The treatment was carried out by passing the sample at a speed of .

The photosensitive material (1) of the present invention is a photosensitive element (1) prepared by coating 1111i in F on a transparent polyethylene terephthalate support in the listed order, and the following cover sheet fixedly in a face-to-face relationship. In order to spread the alkaline viscous treatment liquid over both layers, a bag-like container (this container is ruptured by pressure) is placed between the two layers at the end of each layer. A single sheet-like sensitive material (film unit) that incorporates a viscous processing liquid with the following composition.

Transparent z IJ ethylene terephthalate film support with the following layers in the listed order +! A cover sheet was made by overturning.

(1) Neutralizing layer made of polyacrylic elRc1011/m2).

(2) A timing layer consisting of acetyl cells (/Of/1n2).

Viscous treatment liquid composition (1) Copoly[styrene-N-vinylbenzyl-N
,N,N-)lyhexylammonium chloride)'
1.01/pn2 and 5 images containing Zera f741.017m2.

(2) 2 titanium dioxide f/m2 and gelatin.

White reflective layer containing 2f//m2.

(3) Carbon black 2.71//T12 and gelatin 2. ? Opaque floor containing l/p12.

(4) Cyan dye-releasing redox compound o having the following structure,
5oy72n2, H N , N-diethyl laurylamide 0.30ν/m2
and a layer containing gelatin/, Jf/m2.

(5) Red-sensitive internal m1 quadrangular bromide scissors All (gelatin l.

lv/〃z2, silver/ , 4' l/ln 2) and/
-7 cetyl-λ-[≠-(2, googe-t-pentylphenoxyacetamido)phenyl]-hydrazine [nucleating agent] (0,0/If/1n2) and sodium coventadecylhydroquinone-yo-sulfonate (0,Ot
7.77 m2) containing l-0 (6) gelatin o, lrf
/m2 of the present invention 1)2. j-di-t-pentadecylhydroquinone eutectic mixture o, try/m and vinyl acetate polymer θ, 075y/m % history, polyethylene acrylic acrylate latex O0 9/112% Chinbin 01jsl/fufu+2, hardener Tris An image unevenness prevention storage layer containing acryloyl perhydrotriazine θ, o, tAl/m 2 .

In addition, a comparative sample (TI
11 is exactly the same as the photosensitive material (1) except that the emulsion layer of the present invention is not added to the layer (6) of (I).

As a result of comparing the appearance of unevenness in the image area after development processing of the photosensitive materials ([) and (II), it was found that the color image area of the comparative photosensitive material (1) had significant step unevenness of cyan color. In the photosensitive material (1) having the film-retaining layer of the present invention, step unevenness in the image area is totally <7k<I[! II It was observed that image unevenness was prevented.

The photosensitive material of the present invention ((II) and the comparative photosensitive material (1v
) was created.

(1) Mordant layer of Example-1.

(2) White reflective layer of Example-No.

(3) Opaque layer of Example-1.

(4) No. containing the cyan dye-releasing redox compound of Example-7.

(5) Red-sensitive internal latent image type improved silver emulsion layer of Example-1.

(6) gelatin C1,097M12) and λ,j-di-t-pentadecylhydroquinone eutectic mixture (1,09
7m) and polyvinyl acetate (kCO, t9/m).

(7) Magenta dye-releasing redox compound with the following structure: 1 (0,1097m2), N,N-diethyl laurylamide (0,0Of/In2) and gelatin (/,29
7 m2).

(8) Green-sensitive internal latent image type beautifying silver emulsion (gelatin/, 19
/yn2, silver/, 4 (9/1) 12) and the same nucleating agent as jt- (0,0/39/ln), 2--F: ntadecylhydroquinone-j-sulfonic acid sodium A (
7,06797 m2).

(9) Gelatin (t, o9/m) and λ,j-G-t-pe/tadesol hydroquinone eutectic mixture C1,09
/Jn”)- and polyvinyl acetate (o, le 9/1112
) A layer containing a color mixing prevention agent.

(10) A yellow dye-releasing dox compound with the following structure (Ct, oq/m), N,N-diethyl laurylamide (0,0/Ml), gelatin (800/nl)
).

(11) P? Sensitive internally clearing type bromide edge emulsion (gelatin/
, /9/m2, @t, lq/nt2), the same nucleating agent as the fifth layer (O0θ/19/ln), and 2-be/resylhydroquinone-! - Sodium sulfonate (o
, θ1.7y/m2).

(12) Same as photosensitive element (6) of Example 1, 2°! -D-t-pentadecylhydro-quinone eutectic mixture 01.209/m2 and vinyl acetate poly-r-0°/0
A protective layer for preventing image unevenness containing 9/m2.

Comparative photosensitive material (iVl: 2. Protective layer containing neither j-di-t-bentatecylhydroquinone nor vinyl acetate polymer IJ).

The photosensitive materials (Ill) and (lv) of this example are
As a result of exposure and development processing in the same manner as above, the comparison photosensitive material (I
In V), significant yellow step unevenness occurred in the image area, whereas in the photosensitive material (IIl) having image unevenness prevention protection +fi of the present invention, no image unevenness occurred at all, and a remarkable improvement effect was achieved.

Furthermore, as is clear from the results in Table 1, when comparing the light-sensitive material of the present invention (■1) and the comparative light-sensitive material (1■) in terms of leg gradation (c gamma) and minimum density, The gradation C gamma of the photosensitive material (1) of the present invention is higher than the V4 gradation (gamma) of the comparative photosensitive material (1v), and has a lower minimum density value and sharper image gradation, which is preferable for color blindness. It can be seen that this shows the reality.

Example 3 Same as Example 3 except that the following jm (6') to C9Y and (12)' were used instead of N(6) to (9) and (12) of the photosensitive element of Example λ. Photosensitive materials (V) to (vll) were prepared by sequentially coating on a transparent polyester support.

(6) l gelatin (/, 09/n12) and co, j-
Di-1-pentadecylhydroquinone eutectic mixture (t,
oq/m ) and methyl methacrylate polymer (0,
A magenta dye-releasing redox compound (o, 2t
g/1n2), magenta dye-releasing redox compound of structural formula (0,/I7m2), tricyclohexyl phosphate (o, org/m2), λ,! - a layer containing di-t-pentadecylnohydroquinone (o, ooyq/m 2 ) and gelatin (θ, ri'I/m 2 ).

~ 0 (8) / green-sensitive internal latent image type direct reversal silver bromide emulsion (at the amount of o, r2y7m2, gelatin o, ty q/m
2) Nucleating agent with the following structure (o, o 4Lq7m2) &
lJ2~layer containing sulfoj-〇-pentadecylno-hydroquinone sodium salt (θ, /jlil/m ).

(9)' Gelatin (/, 012/ln) and 2. j-di-t-pentadecyl/%hydroquinone eutectic mixture (/
1-0 (12y Example-2) containing + Og/vt2) and methyl methacrylate polymer (0,19/ln)
A protective layer prepared in the same manner as .

However, photosensitive material (V): ko, j-t-pentadecylno-hydroquinone eutectic mixture *0, / j Q7
m2 and vinylboria acetate -0,071Q/m'
A photosensitive material having a protective layer for preventing image bugs containing ll1li.

Light-sensitive material c vi > : λ, j-t-ventaracil hydroquinone eutectic mixture 0. /j(1/ln') and methyl methacrylate polymer 〇, M optical material having an image unevenness prevention protective layer containing 7097m2.

Comparative photosensitive material (V!f): 2. A photosensitive material having a protective layer containing neither an r-di-1-1-tadecylhydroquinone eutectic mixture nor a vinyl acetate polymer nor a methyl methacrylate polymer.

The following 11 (1
)' to (3)' were applied to cover sheets.

(1)' 0 to 2 tons of acrylic acid and butyl acrylate (
weight ratio) copolymers (2J Q/tn 2) and O/, f-bis (J, J-epoxypropoxy.

-1-6 containing butane (0,ll4A9/nl)
(2)' Acetylcellulose (hydrolyzes acetyl in 1009 → lullose to produce an aceral group in 3, DaQ) C3,ry/m2) and 10 pairs of aO of styrene and maleic anhydride (weight ratio) copolymer (molecular weight approximately 50,000) (0,29'/77J2) and 1-(β
-cyanoethylthio)-nophenyltetrazole (o
, 1tsti7′ m).

'(3)' Combined combination of tg vinylidene, methyl acrylate, and acrylic acid rz pair 12 pairs/J pair J (Mine 111・Ka) Diameter l, ~Jpm
) (0,0397 m ), the above photosensitive material (
V) ~ (V*+ > *Half-exposure so that the reflected color density is about /, j, integrated with a tearable container containing the processing solution and a cover sheet, and subjected to λs'C conditions. Develop the processing liquid using the pressing member (at Acm/sec)
The unevenness of the transferred dye images was compared.

As a result, the comparison photosensitive material (vi+> had noticeable unevenness in yellow, whereas the photosensitive materials (V) and (vl) to which the protective layer for preventing image unevenness of the present invention was applied had unevenness in the color image within the screen. It did not occur.

Further, after exposing the photosensitive materials (V) to CV+*> through a wedge having a stepped density change, the container containing the processing liquid and the cover sheet are similarly integrated, and the processing liquid is spread using a suppressing member. Table 2 shows the results of measuring the reflection density of the processed and transferred dye images and comparing the 80 curves.

The photosensitive materials (V) and (vl) having the protective layer for preventing image unevenness of the present invention were 11% higher than the comparative photosensitive material (Vi+).
It can be seen that the color fA (gamma) of the image area is high, the minimum reflection density value is low, and the color reproducibility is sharp and favorable.

Example 4 Photographic layers were sequentially coated on a transparent polyester support in the same manner as in Example 3 except for protection 1- to prepare a photosensitive material (vm).
(X) was produced.

Photosensitive material (Vill) A photosensitive material was prepared in which the protective layer 1- was made into two layers instead of the protective layer of the photosensitive material (V) of Example 3 as described below.

(Lower layer): Gelatin t, 3t/m, Tinuvin O0jg
/m, 2. ! - di-t-pentadecylhydroquinone eutectic mixture (o, /y/ln”) and vinyl acetate polymer o, oje
1-0 included in /ln2 (Top M): gelatin t, 3o/m, polyethylene acrylic acrylate latex 0.2g/m2, bag film agent trisacryloylperhydrotriazine 0.0g/ln2 (protection containing 1,97m) -0 Photosensitive material (1x) A photosensitive material was prepared in which the protective layer was changed to 2IQj instead of the protective layer of the photosensitive material (V) of Example-3 as described below.

(Lower layer): Gelatin i, 3g7η12, Tinuvin 0.
A layer containing 197 m.

(Upper layer): Gelatin 7.3g/m2, λ, J-Gt
-Be/tadeflu hydroquinone eutectic mixture (0,197 m2) and vinyl acetate polymer 0. Protective layer containing OJQ/ln, latex O6 9/tn 2 of polyethylene acrylic acrylate, hardener trisacryloyl perhydrotriazi 1 0.021a9/n12f.

Photosensitive material (X) A photosensitive material (gold) of Example 3 was prepared in which a two-layer protective dΦ layer was used instead of the Vl protective layer as shown below.

(Lower layer): Gelatin/-J9/111, tinuvin o, 1-0 including ry7m2 (upper layer): Gelatin/, JIF/ν? z2, ko, j-
Di-t-pentadecylhydroquinone eutectic mixture CO,/97111'') and methyl methacrylate polymer 〇, 07 9/m 1 Latex of polyethylene acrylic acrylate 0, P 97m % Hardener Tris-acryloyl-hydrotriazine 0.02471
A protective layer containing /ln.

The above photosensitive material (vm > ~ (X)) having the 1III image unevenness prevention protective layer of the present invention is half-exposed so that the reflection density becomes about 1.j, and a cleavable container and cover containing the processing solution are prepared. The sheet was integrated with the sheet, and the processing solution was spread (at 1 c/sec) using a suppression member under 2s 0c conditions, and the unevenness of the transferred dye image was observed.

As a result, it was found that all of the photosensitive materials (Vlil) to (x) of the present invention did not cause color image unevenness within the screen.

Preferred embodiments of the present invention are listed below.

/)% In claim 1, the hydroquinone derivative mixture has substantially no ability to develop silver halide and may have a longitudinal solidification point below r o OC (more preferably liquid or wax at room temperature). A photographic light-sensitive material characterized in that it is made of

λ) A photographic light-sensitive material according to Embodiment 1), characterized in that the Notsuta hydroquinone derivative mixture is a eutectic mixture of branched alkylhydroquinones.

3) In embodiment l), the hydroquinone derivative mixture is a mixture of hydroquinone compounds having a tertiary alkyl group having a carbon number of is at the 2, 5, 6, and 6 positions of the 2nd and 6th positions of a benzene group, or a second A photographic light-sensitive material that is an isomer mixture of dodecylhydroquinone.

Hiroshi) In embodiment l), a mixture of hydroquinone derivatives f
t'l! I F, the following general formula (1), (11) or (
A photographic light-sensitive material characterized by being an isomer mixture represented by Iff).

General formula (1) General formula (It) General formula (lil) In the formula, Xl, X2, and X3 may be the same or different; group, alkylthio group or arylthio group. Furthermore, Xl and X2 may jointly form a fused ring. is an aliphatic group or an aryl group (
It is preferable that the dye does not contain a dye residue or a precursor thereof.

j) In embodiment l), the coating amount of the hydroquinone derivative mixture in the protective layer is 0.02 to 0.3'I
/7722 Photographic light-sensitive material.

6) In claim 1, the photographic X-sensitive material is characterized in that the polymer that is combined with the hydroquinone derivative mixture to exist as individual particles is a vinyl acetate polymer or a methyl methacrylate polymer.

7) The photographic material according to embodiment t), wherein the coating amount of vinyl acetate polymer or methyl methacrylate polymer in the protective layer is 0.0/-0.3 g/772.

l) At least two protective layers! - and has a freezing point of 1000C or less in at least one layer of the hydroquinone derivative mixture and a water-insoluble, organic solvent-soluble compound having a repeating unit having -〇-〇-bond 1 in its main chain or side chain. 3. The photographic light-sensitive material according to claim 2, characterized in that the polymer or copolymer is combined and dispersed as individual particles.

b) A photosensitive material is contained in a) a photosensitive sheet and a cover sheet or an image receiving sheet, and c) a container that can be ruptured by pressure (this container contains a processing solution; The photographic light-sensitive material according to claim 1, which is a color enlargement transfer photographic film unit consisting of at least a color expansion transfer photographic film unit (located between a cover sheet or between a photosensitive sheet and an image-receiving sheet) .

IO) In embodiment), the photographic light-sensitive material, wherein the processing liquid contained in a container that can be ruptured under pressure V contains at least hydroquinones.

//) Actual @Aspect lθ) A photographic light-sensitive material in which the processing liquid contains 3-pyrazolidones and hydroquinones.

Claims (1)

[Scope of Claims] l) A photographic light-sensitive material having at least one silver halide emulsion layer on a support, which forms a silver image by processing with an alkaline processing solution in the presence of a silver halide developer after exposure. In the protective layer located above the silver halide photographic milk Wl1 layer furthest from the support of the photographic light-sensitive material, an idoquinone derivative mixture and a -C-〇-bond having a freezing point of 1Oθ0C or less are present. It is characterized by the fact that water-insoluble, organic solvent-soluble polymers or copolymers having repeat alignment in the main chain or side chain are combined and dispersed as individual particles. Photographic material.