JPS6184641A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To increase the solubility or dispersibility of additives, to improve a hue and to prevent fading and stain by forming a hydrophilic org. colloidal layer contg. a photographic reagent dispersed in the presence of specified chlorinated paraffin on a support. CONSTITUTION:At least one hydrophilic org. colloidal layer contg. a photographic reagent dispersed in the presence of chlorinated paraffin having >=175 deg.C b.p. under ordinary pressure is formed on a support. The photographic reagent is slightly soluble in water. The chlorinated paraffin gives strong intermolecular force to photographic additives and solvates well the additives, so it shows superior dispersing power. Since the paraffin has moderate polarity, it can well control the hue of color developed by a coupler by making use of difference in polarity. The paraffin dissolves hardly components which damage a color image during storage such as water and a developing agent, so it can protect a dye image from fading and stain.

Description

[Detailed Description of the Invention] υ (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and in particular, the present invention relates to a silver halide photographic light-sensitive material, and in particular, the present invention relates to a silver halide photographic light-sensitive material, and in particular, a hydrophilic organic material is obtained by dispersing a photographically useful reagent that is sparingly soluble in water using chlorinated paraffin. This invention relates to a silver halide photographic material contained in a colloid layer.

(Prior Art) Conventionally, photographically useful reagents that are poorly soluble in water (for example, oil-soluble couplers, antioxidants used to prevent fading, color fogging, or color mixing (7T, for example, alkylhydroquinone) Hii,
alkylphenols, chromans, coumarons, etc.),
Hardener, oil! @Note Filter dye, oil-soluble ultraviolet absorber, DIR compound (e.g., DIR, hydroquinones, colorless DIR, compound, etc.), developer, dye developer,
DDE4. Redox compounds, DDR+ couplers, etc. 1
is dissolved in a suitable high-boiling solvent and dispersed in a solution of a hydrophilic organic colloid, especially gelatin, in the presence of a surfactant, to form a hydrophilic organic colloid layer (e.g., a light-sensitive emulsion layer, a filter layer). , back layer, antihalation layer, intermediate layer, protective layer, etc.). As the high boiling point organic solvent, heptatalytic acid ester compounds and phosphoric acid ester compounds are particularly used.

Phthalate ester compounds and phosphate ester compounds, which are high boiling point organic solvents, affect coupler dispersibility, affinity with colloid layers such as gelatin, stability of color images, and hue of color images. It has been widely used because of its excellent chemical stability in light-sensitive materials, low cost, etc.

However, these known high boiling point organic solvents (e.g. phthalate ester compounds and phosphate ester compounds) are difficult to use in recent photosensitive materials that require high performance due to the effects of light, heat and humidity on color images. The effect of preventing fading and staining was still insufficient. In some cases, these high-boiling point organic solvents are not necessarily suitable for producing a colored image with a desirable hue, and new high-boiling point organic solvents have been sought.

In particular, low polarity, high boiling point organic solvents have been proposed for the purpose of separation, ie, to prevent fading of color images and the occurrence of stays. For example, aromatic hydrocarbons such as t-butylbenzene are used in JP-A-0123, paraffin is used in JP-A-Tata 4A32, and JP-A-39-/33! ≠
J issue and 1? -737ri No. 52 has l-dodecene, t
-Unsaturated hydrocarbons such as butylbenzene are disclosed.

However, these low-polar, high-boiling organic solvents generally have polar partial structures in their molecules, such as couplers.
(Due to insufficient solubility of the drug,
It had the drawback of low dispersion stability and failures such as precipitation.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a novel high-boiling point organic solvent with excellent solubility and dispersibility for photographic additives, and a silver halide photographic light-sensitive material using the same. It is about providing.

A third object of the present invention is to provide a silver halide photographic material in which fading of color images and occurrence of staining are suppressed by using a novel high-boiling organic solvent.

A third object of the present invention is to provide a silver halide photographic light-sensitive material in which the hue of a developed color image is improved by using a novel high-boiling point organic solvent.

(Means for Solving the Problems) These objects of the present invention are directed to a hydrophilic paraffin in which at least one photographic reagent is dispersed in the following conditions: having at least 17riit-% of the organic colloid layer on the support;
Achieved by silver halide photosensitive materials with special characteristics.

The chlorinated paraffin used in the present invention is chlorinated*
Polymers obtained from quaternary, branched or cyclic paraffins or chlorine-substituted unsaturated hydrocarbons such as vinyl chloride, vinylidene chloride, allyl chloride, or copolymers of these monomers and other olefins, which do not have a single composition. or a mixture. The number of carbon atoms in the chlorinated paraffin is preferably 1 or more, and the number of carbon atoms in the chlorinated paraffin is preferably 25.
It is 0 or more and 10,000 or less. The weight ratio of chlorinated/rough-in is preferably at least the average lo coefficient, more preferably from 30% to tOs on average. Specific examples of chlorinated paraffins used in the present invention are shown below in terms of their average composition, average molecular weight, and average chlorine content.

The reason why the chlorinated paraffin of the present invention has better solubility in photographic additives than paraffins and unsaturated hydrocarbons is mainly due to the strong intermolecular force caused by so-called dispersion force.
This difference in effectiveness, which is thought to be due to good solvation, is due to the solubility of organic compounds between hydrocarbon solvents such as n-hexane and halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride. This can clearly be seen in the difference between

On the other hand, the chlorinated paraffin of the present invention has lower polarity than commonly used high boiling point solvents such as phthalates and phosphates, and is presumed to exhibit various features. For example, it is possible to control the hue of the color forming dye of the coupler to a preferable hue by utilizing the difference in polarity, and it is also possible to control the hue of the color forming dye of the coupler to a preferable hue, and it is also possible to control the hue of the color-forming dye of the coupler to a preferable hue, and the solubility of components that are not preferable and not suitable for preservation of color images in water and developing agents is poor. Therefore, it is thought that fading of the color image and occurrence of staining are suppressed. Such effects will be made clear in the examples.

The amount of the chlorinated/finishing fin used in the present invention depends on the type of photographically useful reagent coexisting and its physicochemical properties, but can be varied arbitrarily within the range of 1-200% by weight in most cases. Preferably, the chlorinated paraffin and the floating device useful reagent are used for one cycle under conditions such that they coexist and disperse uniformly in a compatible state. Furthermore, the chlorinated paraffin of the present invention can be added to the hydrophilic organic colloid layer of a photographic light-sensitive material together with a photographically useful reagent by a simple oil-in-water dispersion method or the like. In this method, a solution of a photographically useful reagent is obtained using a low-boiling auxiliary solvent, if necessary, and an oil, and then finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Phase inversion may be used for dispersion, and if necessary, auxiliary solvents may be removed or reduced by distillation, noodle washing, Fi ultrafiltration, etc. before use for coating.

The chlorinated paraffin of the present invention may be used alone or in combination, and a photographically useful reagent that is poorly soluble in water may be dissolved as a high-boiling organic solvent, or other known high-boiling organic solvents may be used as required. May be used in combination with

In the present invention, the poorly water-soluble photographically useful reagents include all photographically useful reagents which are dispersed in a hydrophilic organic colloid layer using a conventionally known high boiling point solvent.

Typical photographically useful reagents that are poorly soluble in water include photographic couplers (e.g. yellow couplers, magenta couplers,
cyan coupler, black coloring coupler, non-coloring coupler, etc.)
, antioxidants and antifading agents that prevent color fogging and fading of colored images (for example, alkylhydroquinones and their mono- or dialkyl ethers, alkylphenols, chromans, coumarans, hindered amines, transition gold complexes, etc.) etc.), hardeners, oil-soluble filter dyes, oil GTT antihalation dyes, oil-soluble ultraviolet absorbers, fluorescent brighteners, DEL compounds (e.g. DIR couplers, DI
RI Hydrokino/etc.), developer, DDB coupler, D
(, H, compounds, dye developers, development inhibitors and their precursors, development accelerators and their precursors, etc.).

In the chlorinated paraffin of the present invention, a poorly soluble photographically useful reagent can be dispersed in these water and incorporated into the hydrophilic organic colloid layer, but in particular, a photographic coupler can be dispersed,
It is very advantageously used when it is included in a photosensitive silver halide emulsion layer.

Photographic couplers that can be applied to the present invention include aromatic primary amine developers (for example, phenylenediamine derivatives, aminophenol derivatives, etc.) in color image processing.
When a silica compound undergoes a coupling reaction with an oxidant of
For example, magenta couplers include j-pyrazolone couplers, pyrazolotriazole couplers, pyrazolobenzimidazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetamide couplers, etc., and yellow couplers include acylacetamide couplers (
For example, there are benzoylacetanilide couplers, piparoylacetanilide couplers, etc.), malondiamide couplers, etc., and naphthol couplers and phenol couplers can be mainly mentioned as cyan couplers.

Specific examples of cyan, magenta and yellow couplers used in the present invention are 1 (D/76≠J (/27 is 1-
It is cited in ``Gekko ■-D'', 17/7 (January 1972) and is described in the established patent.

Preferably, these couplers contain a pallast group or are polymerized and diffusion resistant. It is preferable that the coupling position is substituted with a leaving group rather than a hydrogen atom. Couplers in which a chromophoric dye is suitably diffusible, colored couplers, colorless couplers, or couplers which release a development inhibitor or accelerator upon coupling reaction can also be used in tfC.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Pat.
1AO7, 210, same No., Ir7j, 0! I7 and 3.2t! , No. 106, etc. In the present invention, a two-way yellow coupler can be preferably used, and US Patent No. 3. Hiro01, / Pu No. J, 1
Iu7. 'ri Jt, same flood 3. It is described in JJ, No. 601 and 1fi, No. 440/, No. 75, etc., and is a yellow coupler of the oxygen atom separation type. l-1
07J issue, rice lj! I special iN No. Hiro, O Coco, No. 620, No. 620, No. 3 Koro, o2u No., uD/Ir01.3 (
1979), British Patent No. 1. fλj, No. 020, West German Application Publication No. 2,2/RI, No. 17, No. 2. Col.
, /, No. 361, same! ig2,329. ! No. 17 and Co.

A typical example thereof is the fC crab atom dissociation type yellow coupler described in Kou No. 33,112. α−
Pivaloylacetanilide thread couplers are characterized by their fastness, while α-be/diylacetanilide couplers are characterized by good coloring properties.

The magenta takashi 2- that can be used in the present invention is preferably an oil-protected indacylon type or cyanoacetyl type! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. The j-pyrazolo/type couplers are preferably substituted with an arylamino group or an acylamino group at the 3-position from the viewpoint of the hue and color development speed of the chromophore, and typical examples thereof include U.S. Pat. No. 2,31/, No. 0112, same No. J, 34c
J, No. 703, same No. 2. too, Zrr issue, same issue J
, No. 901.173, No. J, O6J, No. 413, No. 3. /1, rP4 and rP3. 36.0t! It is written in the number etc. 2 equivalents! - Pyrazolone-based cazolas are preferred, as leaving groups, U.S. Pat.
．． No. 41P, or the nitrogen atom leaving group described in US Patent No. V, izi.

The arylthio group described in IF5 is preferred.

Also, European Patent No. 73. It has a pallast group as described in AJ&'iyK! -Pyrazolone couplers have high color reactivity.

Examples of pyrazoloazole couplers include pyrazolo [l, 2
-b) (/, J, ≠] triazoles, US Patent g3,
Pyrazolobenzimidazoles described in No. 367, r97, preferably R, D 1o (lyr Kounen Otsuzuki) Vζkisen pyrazolotetrazoles, P and 1 (DJ44JJ
O (April 19114) VC and Ripyrazolobirazoles are retired. Imidazopyrazoles described in the patent application Shojl-23μJIAVc and the pyrazo'mouth of the shearing plate [/,
r-b] (l, j, ≠) triazole song yu, brother various elemental yellow with little sub-absorption and Genken 2Il: the
Most preferable for use in combination with

Cyan couplers that can be used in the VCIj2 of the present invention include oil-protected naphthol-based and phenol-based couplers, preferably naphthol-based cazolers described in U.S. Pat. 012, 2/Co No. 1t, llA&, No. 396,
Same number 4! , JJ, r, JJJ issue and same@Hiroshi, Kota t,
A typical example is the highly active 2-equivalent naphthol coupler of the oxygen atom elimination type described in No. 200. Specific examples of phenolic couplers are given in U.S. Pat.
Kota No.-0, No. 73 (No. 7, No. 2.77, No. 132, No.-, rot, i7 and No. 2.
It is written in ryz, rkotsu issue, etc.

Cyan couplers that are robust to heat, humidity and temperature are preferably used in the present invention, typical examples being the phenolic cyan couplers described in U.S. Pat. No. 3,772,00J, U.S. Pat. No. 2,77J, 161 No. J,
7! I, No. 301, W, 4c, / Coro, No. 3 Ribu,
Same No. 1I, 3J4A, No. 0/1, Same No. Hiroshi, J, 27. /
No. 7J, West German Patent Publication No. J, J Kota, 7 Ko? No. 71c, J-
Diacylamino-substituted phenolic couplers and U.S. Pat. ! ! , 2nd issue, same issue ≠, ≠j/ ,! ! ri issue and the same number Hiro, Hiro core.

No. 747, etc., there is a phenylthaleide group at the co-position. These include phenolic couplers having an acylamino group at the -position.

In order to correct the unpleasant absorption in the short wavelength region of the magenta and cyan coupler color pigments, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. U.S. Patent No. Hiroshi, /4J, A70 and Special Publication No. 1983
Yellow-colored magenta couplers described in U.S. Pat.
Typical examples include magenta-colored cyan couplers described in Japanese Patent No. JSR and Japanese Patent No. GGI, 14TT, IT.

These color couplers may form a stack of -2- or more. Typical examples of polymerized couplers are described in U.S. Patent No. 3. ≠j/, rkoo and ≠.

oro, No. 211. Specific examples of polymerized magenta couplers are given in British Patent Nos. 2,10, 173 and US Patent @Hiroshi, 347. It is described in Kot No.2.

In addition, chromophoric diffusive couplers can be used in combination to improve graininess, and such couplers are described in US Pat.
Examples of magenta couplers are given in European Patent No. 21.4J, Co. 37 and British Patent No. 2.1.170. ．．
No. 173 and West German Patent Publication (OLS) J, JJII
,j! Specific examples of yellow, maze/red, and cyan are listed in the section.

One or more of these couplers can be used in the same layer in order to satisfy the custom requirements for optical materials, and the same compound can of course be added to different layers. .

These couplers may be dispersed using the chlorinated paraffin of the present invention, or, if desired, may be dispersed using a combination of chlorinated paraffin and a known high-boiling organic solvent. It may also be emulsified separately using a known high boiling point organic solvent and used in combination with the present invention.

Specific examples of high-boiling organic solvents that can be used in combination with the chlorinated paraffin of the present invention include phthalic acid esters (dibutyl tucrate, dicyclohexyl phthalate, dicoethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid, Phosphonic acid esters v4 (triphenyl phosphate, tricresyl phosphate, coethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, driftoxyethyl phosphate, trichloropropyl phosphate, coethylhexylphenylphosphonate, etc.)
, benzoic acid esters (λ-ethylhexylbenzoate, dodecylbenzoate, no-ethylhexyl-p-
hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, co,≠-')-tert-7-milphenol, etc.)
, aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-butoxyj-tert-octylaniline, etc.), carbonization Examples include hydrogens (paraffin, dodecylbenzene, diisozolopyrnaphthalene, etc.).

Couplers that are particularly preferably used in combination with the chlorinated paraffin of the present invention will be described in detail below. In other words, the following general formula (
1), ([), [■], (IV), (V) and (Vl)
The chlorinated paraffin of the present invention in the coupler D dispersion represented by ? Most preferably, it is used.

General formula CI) In general formula CI), R1 is a tertiary alkyl group or an aryl group, and R2 is a hydrogen atom, a nitrogen atom, an amino group, an alkoxy group, or an alkyl group.

R3 represents a halogen atom, an alkoxy group, an alkyl group, a carbonamide group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a cyano group. m is an integer from 0 to 3, and when m is a plurality of numbers, R3 of the flj numbers may be the same or different. X is a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer (for example, a halogen atom, an acyloxy group, an aryloxy group, a heterooxy group, an arylthio group, a heterocyclic thio group) Examples of R8 include t-butyl group, no-ethyl-! -Methylpropyl group, cochrochlore/,/-dilf ethyl group, adamantyl group, phenyl group, methoxyphenyl group, no-methylphenyl group, etc., and examples of R+2 include chlorine atom, bromine atom, fluorine atom, methoxy group. , methyl group, dimethylamino group, etc., R
Examples of +3 are chlorine atom, methoxy group, dodecyloxy7
Carbonyl group, hexadecane sulfonamide group, no (
J, 4L-di-tert-amylphenoxy)butanamide group, μm(,2, Hiro-dini-tert-amylphenoxy)butanamide group, tetradecyloxy group, etc. Examples of X include acetyloxy group, μm dodecyloxycarboerphenoxy group , Hiro-(≠-benzyloxyphenylsulfonyl) phenoxy &,! -(4cmhydroxyphenylsulfonyl)phenoxy group, pyrazolyl group, imidazolyl group, chlorotriazolyl group, -1pyridyloxy group, l-benzyl-3-hydantoynyl group, l-benzyl-j-ethoxy-3-hydantoynyl group l group, l-penzyl-nophenylurazol-3-yl group, μ,! −
dimethoxycarbonylimidazol-7-yl group, l-
Examples include carboxyphenoxy groups and the like. The couplers represented by the general formula [1] may be linked to each other via lu, 2, lu, or X to form a multimer or polymeric coupler.

General formula [2] In the general formula [■], R1 is a carbo/amide group, anilino group, or ureido group, R2 is a phenyl group, and X is a coupling with an oxidized aromatic primary amine developer. reaction V
This represents a group that can leave from this (hereinafter referred to as a leaving group).

X is a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or an aliphatic group with an activated carbon coupled via a hydrogen atom,
Aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic/aromatic or foamy carbonyl groups, carbamoyl groups, alkoxycarbonyl groups, and groups that bond with aryloxycarbonyl groups; Halogen atoms, aromatic ano groups, heterocyclic groups, etc. Aliphatic, aromatic or heterocyclic groups referred to in X, Ro and 1L2
may be further substituted with 11″f, examples of which include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (for example, methyl, [-octyl, dodecyl, trifluoromethyl) groups), alkenyl groups (e.g. allyl group, octadecenyl group), aryl groups (e.g. phenyl group, p-)lyl group, octyl group, etc.), alkoxy groups (e.g. methoxy group, be/zyloxy group, methoxyethoxy group, etc.) ), aryloxy groups (e.g. phenoxy group, co,≠-di-tert-amylphenoxy group, J-tert-butyl-μmmhydrofodiphenoxy group), acyl groups (e.g. acetyl group, benzoyl ml), sulfonyl groups (e.g. methane sulfonyl group, toluenesulfonyl group, etc.), calsequi7 group, sulfo group, cyano group, hydroxy group, amino group (e.g. amino group, dimethylamino group, etc.), carbonamide group (e.g. 7adoamide group, trifluoroacetamide group, Tetradecanamide group, benzamide group ring, sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfo/amide group, p-1 luenesulfonamide group, etc.), acyloxy group (e.g., aceto Φ7, etc.), sulfonyloxy group (
(e.g., methanesulfonyl group, etc.), alkoxycarbonyl group (e.g., dodecyl group, etc.), aryl carbonyl group (e.g., phenoxycarbonyl group, etc.), carbamoyl group (e.g., dimethylcarbamoyl group, tetrazosol group, etc.), sulfamoyl group. groups (e.g., methylsulfamoyl group, hexadecylsulfamoyl group, etc.), imide groups (e.g., suffunimide group, phthalimide group, octadecenyl suffunimide group, etc.), compound repeating groups (nopyridyl group, λ-furyl group, etc.) , nochenyl group, etc.), alkylthio group (inverted is methylthio group, etc.), arylthio group (e.g. phenylthio, 41e
etc.). Examples of methoxy group, etc.), afuroxy group (e.g. acetoxy group,
(tetrazokayloxy group, penzoyloxy group, etc.),
Aliphatic or aromatic sulfonyloxy T5 (e.g. methanesulfonyloxy group, toluenesulfonyloxy group 1), carbonamide group (e.g. dichloroacetamide group, trifluoroacetamide group, etc.), aliphatic or aromatic sulfonamide group (e.g. methanesulfone) Amide M, p-toluenesulfonamide 41.7-lkoxycarponyloxy group (e.g.
Eg, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic/aromatic or heterocyclic thio group (e.g., ethelthio group, hexadecylthio group, Hiro-dodecylphenylthio group, pyridylthio group, etc.), ureido group (e.g. methylureido group, phenylureido group, etc.)
,! membered or double-membered nitrogen-containing heterocyclic groups (e.g., imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1.nodihydrochooxo-7-pyridyl group, etc.), imide group (if kept, suffunimide group, phthalimide group) , hydantoinyl group, etc.), aromatic azo groups (eg, phenylazo group, etc.), and the like. Well, there is a so-called bis-type coupler obtained by condensing a ≠ equivalent Kutzler with an aldehyde 17tFi ketone gradient as a leaving group bonded via a carbon atom.

Either R2 or Additionally, a molecular coupler may be formed.

In addition, the coupler represented by the general formula [11] is the following keto-
It is known in the art to have tautomeric compounds in the enol form.

Examples of the compound represented by the general formula ([1)] and synthesis method are, for example, published in JP-A-Kokai Akihiro Day 1//l, J/, Ibid! Hiro - Hiro rs Hiro 0, same month - 4λ Hiroj Hiro, same! j-//103'/
-1 same j4-Jrol AJ, same jl.

-roaus, same j/s-/2t133, same j7-ao
aa, same j7-izrzl, same j7-2≠7! Ko, same!
t-77 Hiroμ01 Jr-403; 37, 11-#j
4AJ2, same 1 (-tt7rp&, ItJjr-/14
130. same! r-/u! 9174. Same j1-ko011!
/, Tokukai Akira! ≠-770, same! ≠-IO4Lri/, same!
μm co/J j rX same jJ-1ijλ, same! 3-
(eye j3, same!7-JA!77, special application Showa 5r-ttOs
Y&, same jlr-/3, Ko IJII, same jter 2bu7ko2, US patent 3λ27jj4A, same JIA32j2
/, 'fiJ104/'% Dohiro Jj/I 7, etc.

General formula (Ill) In general formula (III), R represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an aromatic primary amine developer intoxicant. represent. Za, Zb, l and Zc are methine, substituted methi/,
=N- or -N) l-represents gold.

A compound represented by the general formula CIll) is a j-membered-j-membered condensed @nitrogen:A? 3j is an elemental coupler, whose coloring nucleus exhibits isoelectronic aromaticity with naphthalene, and whose chemical structure is generally referred to as azapentalene. , preferred compounds (t H-imidazo(/,, 2=b:1 pyrazole river, /) i-pyrazolo(/, j-b) pyrazole term, i [-1-pyrazolo(j,/- c) [/.

[Co, μ] Triazole Isamu, /1-1-Pyrazolo (/.

j-b) (/, co, l] triazoles and /H-pyrazolo (/, j-d) tetrazoles, which have the general formula C111a), (lllb), (IIIc), (l), respectively.
tld) and (111C).

[River a) (Iub)Clilc,
l (ill (1) Substituents R, R in the general formula (tlla) to (file)
and EL4 will be explained in detail. R2,2~
3 R3 and R represent an aliphatic group, an aromatic group, or a ring group, and these represent substituents commonly used for these substituents (e.g., halogen atom, alkyl group, alkynyl group, group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, sulfonyloxy group, acyl group, sulfonyl group, carboxy group, sulfo group, hydroxy group, amino group, carbonamide group, sulfonamide group, carbamoyl group , sulfamoyl group, alkoxycarbonyl group, aryloxybenzenyl group, ureido, sulfinyl group, alkylthio group, arylthio group,
/ano group, etc.)
In addition to the leaf atom, t and R4 may be a substituent having 2% or less of the halogen atoms in () above. X represents a water atom or a group that can be removed by a coupling reaction (hereinafter referred to as a detachment), and X represents a leaving group υT ( !:difference,
X is an oxygen atom, a nitrogen atom, a sulfur atom, or a sulfur atom mediated by a coupling active carbon and a flylJ rib group), an aromatic group, a complex, an aliphatic group, an aromatic group, an aliphatic group, an aromatic group, or a sulfonyl group. , aliphatic, aromatic, or halogen atoms, aromatic azo atoms, etc. that bond with carbonyl groups, and aliphatic, aromatic, or il ( y J , "zl group is I'llJ
Ite k may also be substituted with the same substituents as R and R, and when there is one or more of these substituents, they may be the same or different. Specific examples of leaving groups include: ), Rogge/Kyoko (4 fluorine atoms, chlorine atoms, 4 bromine atoms), alkoxy groups (e.g. ethoxy group, 7 dodecyloxy groups, methoxyethercarbamoylmethoxy group, carboquinepropyloxy group) group, methanesulfonyl ethoxy group, aryloxy group (for example, Hiro-chlorophenoxy group, ≠-methoxyphenoxy group, Hiro-carboxyphenoxy group, etc.), acyloxy group (for example, acetyl group,
7 tetradecanoyl groups, penzoyl group, etc.),
Aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy &'
:? ), azolamino h (e.g. dichloroacetylamino group, trifluoroacetylamino group, heptafluorophthyrylamino group, etc.), aliphatic or aromatic sulfo/amide groups (e.g. methanesulfonamide group, p-toluenesulfone) Amide J) 5%), alkoxycarbonyloxy group (e.g. ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group), aliphatic, aromatic or a heterodanthio group (e.g., ethylthio group, phenylthio group, etc.), a carbamoylamino group (e.g., N-methylcarbamoylamino group, N-methylcarbamoylamino group,
-phenylcarbamoylamino group, etc.), 7M4 and 6
membered 9-membered heterocyclic group (e.g. imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, !, 2-dihydro-oxo l-pyridyl ￥1F), imide group (e.g. succinimide group, fold/toynyl group) groups), aromatic azo groups (e.g. phenylazo groups), and these groups may be further substituted with substituents allowed as substituents for 1L2, 3 and 1.Also, There are bis-type cazoles obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a fc leaving group via a carbon atom.

Any of R2, Ru3, R4, or may be formed.

Compound examples, synthesis methods, etc. of couplers represented by the general formulas (Ia) to cme] are described in the documents listed below. The compound triIFF of the general formula (ill a)
Gansho j r-, 2J #J! etc., the general formula (Ill
b) The compound of formula (IIIc) is applicable to Japanese Patent Application No. 5r-isii≠V, and the compound of general formula (IIIc) is applicable to Japanese Patent Application No. 4C7-co7sl/
The compound of general formula (lllld) is patent application Shoj? −μ
5jl- and the same jter277≠j′! ? Also, the compound of the general formula [Exe] is a patent application! lr-/41co10/, etc., respectively.

Tokukai Akira again! r-IA20uj, % Gansho 5r-rr9'
IO1 same I! -42123, same jlr-jJ taco≠ and same ta I-! The highly color-forming and 9-last groups arranged in the 2 octopus 7 etc. are compounds J) of the general formula [...a] ~ (tile)
It can be applied to both.

General formula [1v] General formula (■1, Ru, fi alkyl group, aryυ
On the group °;i', on the heterocyclic group, 1 mo2 is a hydrogen atom, halogen; , +(,3 represents an alkyl, aryl, anilino group or a heterocyclic group,
4) React with the latex test jr missing condolence/yamin earth sacrifice with the drug j1 conversion body! 1 Cursed Chaotic Foundation ((I・
For example, 1j represents a halogen group, an alkoxy group, an aryloxy group, an argyldina group, an arylthio group, a carbamoyl group, a sulfonamide group, a heterodanoxy group, a hetero group, etc.). ratio 0, le 2, [t3 and
/ζ Among the groups listed above, the substitutable groups are as follows! 1 Functional device 1 function group (e.g. Halogen 7P
C-molecule, hydroxyl group, carboxy group, cyano group, nitro layer, alkyl group, aryl group, heterofilling, alkoxy group, aryloxy group, heterocyclic group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbamoyl group, sulfamoyl group, ureido group, alphky/carbonyl group, carbonamide group, sulfonamide group, sulfamoylamino group, etc.). Ru and Ru2 may be combined to form a j to 7-membered ring.

As an example of t-butyl group, ! -(Ko, Hiro-Gee
rt-amylphenoxy)propyl group, /-(2,g-
Di-tert-amylphenogyshi)amyl group, /-(J
-tert-butyl-guhydroquinophenoki 7) Tria'/"LL/(≠-tert-amyl-chlorophenoxy)heptyl group, examples of R2 include fluorine atom, chlorine atom, methyl group, etc.'? , "30 examples include trifluoromethyl group, hezotafluoroprobyl &,t
,i.

Co, --Tedrafluoroethyl group, phenyl group, 2-chlorophenyl group, 2-methanesulfonamidophenyl group, Co14'7chlorophenyl group, ≠-77nophenyl group, λ-Cucoro≠-cyanophenyl group, Pe/ Tafluorophenyl group, coptanosulfonoidephenyl group, ≠-7anoanilino group, ≠-methanesulfonylanilino group, ≠-buta/sulfonylanilino group, (A-N,N
-diethylsulfamoylphenyl group, j, #-diqualoanilino group, 3-methanesulfonamidoanilino group, λ-chlorohiro-cyanoanilino l & etc. Examples of X include fluorine atom, salt atom, bromine atom, Methoxy turnip,
Methoxyethoxy group, no-hydroxyethoxy group, carpoquinmethoxy group, N-(-monomethoxyethyl)carbamoylmethoxy'4s3-carpoki7propyloki/group,
λ-carboxymethylthioethoxy group, phenoxy group,
≠-methoginophenoxy group, Hiro-chlorophenoxy7k,
``-tert-octylphenoxy7 groups'' and 3-pentadecylphenoxy groups can be mentioned, respectively.

General formula CV) In the general formula (V), R is an alkyl group r1R2 is a halogen atom or an alkyl group, 1 (+3 is an alkyl group,
The aryl group is a hetero-field group, and , arylthio group, carno (moyloxy group, sulfo/amide group, heterooxylic group, heterocyclic thio group, etc.).

Examples of R+2 include methyl group, ethyl group, propyl group, isozolobyl group, n-butyl group, t-butyl group, be/tadecyl group, etc. Examples of R+2 include fluorine atom, chlorine atom,
Methyl group, ethyl group, etc., 'am30 Examples include 1-(co, ≠-di-tert-amylphenoxy oligopropyl group,
/-(λ, 4cm sheet tcrl-alphaenoquino)amyl&, /-(2, Hiro-di-tert-amylphenoxy)hebutyl group, 1-(tA-tert-amyl-λ-
chlorophenoquine) heptyl lk,'-(noter
t-amyl≠-chlorophenoxy・7) Heptyl group, etc., are listed as X in the general formula [■] as an example f
I can list each of them.

Couplers of general formulas (IV) and (V) may be used in combination.

General formula CVI) In the general formula LVI), ru is a hydrogen atom, hydroxy group, amino group, carbonamide group, sulfo/amide group, ureido group, sulfamoylamino group, alkoxy/carbonylamino group -1, fc is alkoxy Sulfonylamino"5lfzl (2 is an alkyl group, aryl group, or heterofj1 group, X is a hydrogen atom, or atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carbamoyloxy group, a sulfo/amide group, a heterozygote group, a heterozygote group, etc.).

Examples of R1 include hydroxy group, amino group, ethylamino group, anilino group, acetamide group, trifluoroacetamide group, methanesulfonamide group, toluenesulfonamide i, and J-phenylureido group, and examples of R2 include n-dodecyl. group, n-hexadecyl group, n-dodecyloxypropyl group, 3-(co,goo-tart-amylphenoxy7)propyl group, Hiro-(2,≠-ter
t-amylphenol)butyl group, 2-tetradecyloxyphenyl group, -one roll! -Dodecyloxycarbonylphenoxy group etc. General formula (IV) as an example of tXX
In X, fcfe and substituents can be mentioned, respectively.

The casolers represented by the general formulas [■], [■] and [■] are respectively R1, L2, R3 or Xl of the general formula ((V)).
R of general formula (V), ru 2, ru.

or X, any one of Ro, R2 or X in general formula (Vl) is a covalent or higher polyvalent group, -
It is possible to form a 2-coupled substance or a multi-wave substance of more than 2 ions, or a polymeric coupler may be formed by connecting a polymeric raw button and a cassoler core.

Examples of force solers preferably used in the present invention are shown below. (Y-Otsu) (J)l (yr-r) α υH (Y-ta) (Y-//) (Y-to) (Y-tko) (M-/1 α α (M-J) (M-J) α (M-″)(.

(M-j) (M-
1) (M-4)
(M-ta) (M-7) (M-to) α (M-77) α (81-/ri) (M-1t) (M-koO) (M-col) α (M- ko3) (M-21) α (llil-Jda) (M-koj) α (M-27) (M-J4) α (M-kot) (ht-ichita) Ct (M-J /J (M-JO) α α (M-32) (M.-33) (J-(CH2) α (M-3 Hiroshi)
(Il'α 0-(OH,), -υ-( (M-J7) α Cl,), -QC2H.

α (M-4'co) α (M-4'/) α α (M-≠3) (8(-ffi41 (M-jfl ・(M-BuO) H3 C1(.

(M-sri) (M-7da) (A4-74) H3 CIG'21 (M-77) x/y=zO/jo(wt), C13 (M-C13 (/y=≠0/bu) 0(wl) (M-J'/1 yc/y"=j O/j O(W t 1(M-10)
, x/y-Jj/≠j(Wtl (M-1) x/y==!0.'jO(wt) (M-4J) (M-rj) C,u■(t) (M- 141) sHi□(1) (C-/l υH (t)C8H1゜(C,H,), NSO□NH CN (C-/0) p
F*C61(□3 (C-/1) (JC4H.

UCH.

(C-Kohiro) α (C-kot) rcSH,.

(C-coj) F α (C-17) (t) L: 8[(1゜ (tic 811 l.

(5H1l (1) C5H, □ (t) C, H, 1 (1) (:, +117 (C-364 (JH QC) 13 (C-') .H (tic 5H, □ (CJ 7) 0H (C-dal) (C-Hiroshi J) α (C-μm) V (C-sant) (C-da3) α (C-sanj) c! (C-jO) (C-jJI F toesn1□ (C-zt) ft)C,H11 (t)C, 口,□ (t)C@ )117 (tK八へ1□□ (t)C8)11゜(C-jFl (C-A o ) (C-4Jl (C
-47)ocH2C(JNHCH20H2(JCH3(
JCH2CH2802(C-41(C-44) yoCH25υ C( (C-bl) α (C-4寥) (:++3-UCH2C00H (C-47) C* zHzs 0Ck-12CH,N
H+:l(J2CH3(C-A I) (C-70) OC)13 C,Hl,(t) (C-77) CH3SO,N)i (C-7JI CH80NH0CH2CH2CH2e(JUHC81-
11, (tJ :C-7a) 5H1 (C-7J) ()C)i, CH25C)12CO(JH, (1) (C-77) α (C-7,P).

(C-7F) The chlorinated paraffin of the present invention can be used as a photographically useful reagent for emulsifying and dispersing ultraviolet 1 absorption. For example, US patent @J,! 33.7 reference, same No. ≠lko 34,0/
No. 3, Tokko Akira! /=6, j Hiro O, 9 and 1 European Patent No. 17. Benzotriazole substituted with an aryl group described in /10 etc., US Pat.
No. 22 and μ, /9! ,the law of nature? U.S. Patent No. 3,701,10j and U.S. Pat. and British Patent Nos. 1 and 3, Jjtj, U.S. Patent No. 76/, 27 and
4', μJ/, 7Ji, 6 U.S. Pat.
00, '/-! ! The fluorescent brightener 'if-+' of ultraviolet absorption injection described in No. 1' is also suitable for historical use.

An example of a standard for ultraviolet absorbers is described in 1 (1993), D Koko 23 (year 791).

The present invention is also applicable to various organic and metal complex fading inhibitors used to improve the storage stability of color-forming images, especially yellow and magenta images. Hydroquinones, 6- and dorocyclomanes,! - Hydroxycoumarans, spirochromans, spiroinodanes, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and each of these compounds Typical examples include ether or ester sieve conductors in which the phenolic hydroxyl group of 1 is silylated, acylated, or alkylated, and Kananishi complexes are also known.

Specific examples of these compounds are described in the patent specifications below.

Hydroquinones are US patented! 40, 2ri No. 0, same, air, tt No. 3, same, 7oo.

Reference No. 53, same, 2,711)/, /ri No. 7, same, 7-
r, ts9, same, 73, JOO, same.

731.7≦j, same 3. Ritko, 5'4L≠No., Dohiro,≠30. Thank you! No. 1, British patent no.

1/l, 0j1, etc., bu-hydroxychromans,
! -Hydroxycoumarans and spirochromans are covered by U.S. Patent No. 3. ≠J Co, No. 300, J8j No. 77.010, J,! 74', No. 427, same J.

art, Ri0ri No. 3.76, No. 337, Tokukai Shoj
J-/! Spiroinodans are covered by U.S. Patent No. 340.1112, and p-alkoxyphenols are covered by U.S. Patent No. 73! , No. 7/l, British Patent Co., Ltd.
ott, ri7j (B), JP-A-Shojter/0/l2,
Special public Akira! For reference, Hifdartophenols are disclosed in U.S. Patent J, 700, Hiromu! ! No., Tokukai Shoj
Coke No. 2223, US Special Itf Dream, Coco 1. λJ! No. Tokko Akira! No. 4J Co. No. 3, etc., contains gallic acid g4, metele/dioxybe/zenes, and aminophenols.
U.S. Patent J, 4cj7.079, fFfJ4, respectively.
A, JJ Co., art, Japanese Patent Publication No. Shojj-J//444C, etc., and Hifdate amines are described in U.S. Patent J, JJ4. I
J! No., same reference, CoAt, No. 193, British Patent/, JCot
, rr issue, same/, J! Reference, No. 313, Ibid.

ulo, 1st issue, Tokuko Show 11-/Hiroshi JO issue, Tokukai Show 5
r-ttg No. 034, same! Issue 131, same! Day 7riaa etc., phenol injection hydroxyl group o ether,
The ester visiting conductor is a US patent.

/11. No. m, same person, 77th person, coco No. 0, same person, co! −
1Jlt issue, Douyuu, Kobusan, 7koo issue, Tokukaisho! Goo 7
three! ! JO issue, same 7l-4JJ/ issue, same! l-1011
No. 07, same jter 10!32, special public show j7-j7tj
No. rd, US Patent No. rd.

Metal complexes are described in U.S. Pat.
/, 11! No., British Patent J, 027.

7J/(A) etc., respectively.

Examples of these antifading agents are shown below.

A-/ -j C4U, (t) A-≠ -t Ut-1(:H3 A-1 ct-i an3 -1t A-/ Co) The present invention is applicable to many color and black and white photosensitive materials. Color negative film for general use or motion pictures, color reversal film for slides or television, color paper, color positive film) and color reversal, color expansion IPt transfer type photosensitive materials and heat developable type. Typical examples include color photosensitive materials. aD/7/coJ (/P71 July), etc., or by using the tricolor cassoler mixture described in U.S. Pat.
102. The present invention can also be applied to black-and-white photosensitive materials for X-rays and the like by using the black color-forming coupler described in No. 34. Films for plate making such as scanner film, X-ray film for indirect medical use or industrial use, negative black and white film for photography, black and white stamp 1-paper, 00M or FiS regular micro film,
The present invention can also be applied to silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

(D precedent) The above magenta coupler (M-/)! f, chlorinated paraffin of the present invention y (4) j ml and ethyl acetate 1 ml
Add e and heat the resulting solution containing gelatin lOf and dodet/rubet/ze/sulfonic acid soda o, zt.
Add to an aqueous solution tOxl of c and stir, then stir at high speed with a homogenizer to obtain a fine coupler dispersion. 1 to the glass plate”
It was coated and dried to prepare a sample <tot).

Similarly, the yellow coupler (Y-2), cyan coupler (C-cot) and carbon a/J-
Emulsified dispersion WJ of the coupler was prepared using normal paraffin of tu in the combinations shown in Table 1. Sample (/17 pieces) ~
(104). The film surfaces of samples (10/) to (200) were observed under a microscope, and the results are shown in Table 1.
) When preparing vI4, the coupler did not photodissolve when dissolved in cyan coupler (C-cof) t-normal paraffin and ethyl arsenate.

As is clear from Table 1, the chlorinated paraffin of the present invention is superior to paraffin in coupler solubility and dispersion stability.

The cause of the coarsening phenomenon of oil droplets in sample <102) is not clear, but even if the coupler (IVI, /) and normal paraffin are heated above the melting point of the coupler, the two do not mix and have poor compatibility. Therefore, it is presumed that this is caused by poor compatibility.

(Example 1) A sample was prepared by coating an emulsion layer and a protective layer on a polyethylene laminate paper support in the following order.

Add 2.2 liters of the chlorinated paraffin (1) of the present invention to the coupler (M-/), 4Lf, then add ethyl acetate,
Add 4ml and heat to dissolve with gooc. Add 2 to this solution
Sodium 0-dodecylbenzenesulfonate aqueous solution 0.
After adding 6xlf, aqueous solution containing 10% gelatin and 1% sodium dodecylbenzenesulfonate/29
A fine coupler emulsion dispersion was obtained by stirring at high speed with a homogenizer.

To the obtained emulsified dispersion, a salt having a silver content of 4 J per kq and a molar ratio of silver bromide and silver chloride of 4t1 to 70:30 was added to the emulsified dispersion.
4CI, 1Lf, 1A% Zera f71-3-0Of, water j
Occ and! An aqueous solution of sodium tidodecylbenozene sulfonate/cc was added and mixed, and the amount of coupler coated on the support was 4, (FX/o mol/, 2).
It was applied so that it became K.

On top of this layer, a gelatin protective layer with a dry film thickness of lμ was applied to prepare a sample.

Similarly, the chlorinated paraffins ('), (s) of the present invention
For comparison, samples were prepared using normal paraffin, l-dodecene, tricresyl phosphate, trioctyl phosphate, and dibutyl phthalate with carbon a/co~lμ, and samples (co02), (co03), and (co03), respectively, were prepared for comparison. kooIA), (JOj), (ko04), (-〇7) and (
Cor) Toshitomo.

One of these samples was exposed to light using a 9-edge for sensitometry, and then developed using the following processing steps.

Processing process temperature Time Developing solution 33°0 3 minutes 30 seconds White fixer
Wash with water at 33°C for 30 seconds.
0c 3 revolutions Dried developer nitrilotriic acid salt JNa 2. Of benzyl alcohol ljgodiethylene glycol ・ ・ IO, lNa2SO3i,
oy KBr -o,zy Hydroxylamide/Wc acid salt 3.02≠-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-p-fuunicine diamine-sulfur 9jlL j , Of
Na3CO3 (/water salt) 3゛o y
Add water to make tl (pH 10,/) - bleach-fix ammonium thiosulfate (70wt%) t 50w
1Na2803 /sfN
Ha (F e (EDTA))
j j fEDTA-JNa
II Add water to make /l (pH 4, li)
Result of measuring d1 degree of treated sample with green light lr
Shown in the table. In addition, the maximum absorption wavelength (λmaX)-'2 in the spectroscopic spectrum of the sample is also shown.

Further, the treated sample was stored at -100°C for 74 days, and the contact with Tomoki Stay/ was measured using blue light, and the results are shown in Table 1.

From Table λ, in the following samples (J17/) to (KOJ) in which the coupler was dispersed using the chlorinated paraffin of the present invention, the hue of the developed color image was favorable, and furthermore, staining occurred due to heat. It can be seen that the chlorinated paraffin of the present invention is an excellent high boiling point organic solvent. It can be seen that chromophore, gamma, and color-forming compounds are crystalline, and in particular, saturated molecules such as normal paraffin and l-dodecene are included in unsaturated hydrocarbon compounds and have excellent color-forming properties.

(Example 2) In place of the coupler (M-/) in Example 1, coupler (Y
-7) Gold 2. j! Using f, chlorinated paraffin (1) was added to 2
．． Using 1cc, a sample was prepared in the same manner as sample (20/), and sample (30/) was used.

Chlorinated paraffin (4), (5) instead of chlorinated zero rough fin (1) of sample (317/) and tricresyl phosphate, trioctyl phosphate,
The samples were exploded using dibutyl phthalate, and the samples were (30), (JOJ), (30 Hiroshi), (3Ot) and (30≦), respectively. Obtained friend sample (JO/) ~ (JO
Example 1
The same development process was performed. Next, the obtained nine colored samples were used in a quinanone light irradiation device at an illuminance of 30,000 lux.

Testing the light fastness of color images.

The test results were measured using sickle H color light on days φ, r, and 16 of light irradiation, and are shown in Table 3 as a ratio of friendliness to fresh concentration before irradiation. Tomodashi Fresh Thick HJi
/ , test results at 0.

From Table 3, samples using the chlorinated paraffin of the present invention (30
/) to (JOJ), it can be seen that the color fastness of the developed color images to light is superior to that of samples using known high-boiling point organic solvents, such as tricresyl phosphate, trioctyl phosphate, dibutyl phthalate, etc.

(Example 3) A sample was prepared by coating an emulsion layer and a protective layer on a cellulose triacetate film support in the following order.

Cyan coupler (C-Jr) r, at chlorinated/rough-in (4) r, 4Ccc and ethyl acetate 1
Add tcc, heat and dissolve with tooc, and add gelatin 101 and dodecylbenzenesulfonic acid f to this solution tube! J
Ram/f': Contains trj OoCo water mmi 00
ml and stirred at high speed with a homogenizer to obtain a fine coupler emulsified dispersion.
A silver iodobromide emulsion containing ay of silver and having a molar ratio of silver iodide to silver bromide of t to F hiro / 00 ff is added, mixed and deposited on the above support - coupler coating amount is 7X to 'mol / m
So that it becomes (befu).

On top of this layer is a gelatin retention layer with a dry film thickness of lμ? Apply sample <4! ot) was produced.

Instead of chlorinated paraffin (4) in sample (Reference 01), (
5) For comparison, tricresyl phosphate, trioctyl phosphate, dibutyl phthalate and N,N-
Samples were prepared in the same manner as the sample ($07) using diethylroughrinamide, and samples (4COJ) and ($t7) were prepared using diethylroughrinamide.
7), (4!044), (4I0!) and (aot).

These samples were exposed to 9-edge light for sensitometry and then developed with Jr''C in the following processing steps.

1 Color development ・・・・・・・・・・・・・・・ 3
Minutes/j seconds 2 Uba White ・・・・・・・・・・・・・・・
・6 minutes 30 seconds 3 wash with water・・・・・・・・・・・・
... 3 minutes! Second 4 Fixation ・・・・・・・・・
・・・・・・ 6 minutes 30 seconds 5 Wash with water ・・・・・・
・・・・・・・・・ 3 minutes! Excerpt 6 Stability...
3 minutes/j seconds The specific treatment liquid composition used in each step is as follows.

Color developer sodium nitrilotriacetate /, Of sodium sulfite u, at sodium carbonate! 0. Of potassium bromide
/, 44? Hydroxyclamine/sulfate 2-(N-Ether-N-β-hydroxyethylamino) 1 No methylaniline sulfur! ! Add 1 salt, j2 water /1 bleach solution, ammonium bromide, 0. Of ammonia water (it fight), Occ ethylenediamine-tetraacetic acid sodium iron salt /30. Of glacial acetic acid
1a, add occ water
/1 Fixer Sodium tetrapolyphosphate 2.02 Sodium sulfite Hiroshi, Of ammonium thiosulfate (yochi) /7! , Occ City 1N! , sodium sulfate ≠, add tf water
171 stabilizer formalin t, occ water was added /1 Spectral spectral spectral at a given time was measured for the developed sample obtained, and the maximum absorption wavelength (1 m ax ) is shown in the table. In addition, the treated sample was stored in ioo"c for It days, and the chlorinated paraffin of the present invention was sample (≠0
1) and (4c02), the hue of the developed color image is preferable, the change in hue due to the color density is small, and it can be seen that they have excellent custom-made T-.

In addition, the generation of stay due to heat is less than that of the table specimen, which indicates that the untreated paraffin of the present invention is superior.

(Example 4) Write on cloth j and screen on polyethylene laminated paper VC
The 1st/ji (bottom layer) to the 7th layer (top layer) were all coated to prepare a color photographic material sample (rot).

Senior self? The middle cloth of the first bar is prepared as follows. That is, the yellow coupler (Y-7) shown in Table 1
100f was dissolved in dibutyl phthalate (DBPn/J≦, 7 rinses and ethyl acetate 2001!11, and this H solution 2
t@dodecylbenzene sulfo/acid sodium aqueous solution 10
This emulsified dispersion was emulsified and dispersed in a lO tizelatin aqueous solution r00mt containing m1, and then this emulsified dispersion was converted into a sand-sensitive silver bromide emulsion (Br
lO mole)iaz.

A coating solution was prepared by mixing with Ag fat 57f (containing Ag fat 57f).

The other layers were prepared using a coating solution 1r by a four-ball method.

The hardening agent for each I1m is ko, 4I--dichloro4-
Hydroxy-5-)riazine sodium salt was used.

The following methods were used for the spectral tfI sensitization of each emulsion.

Sensitizing emulsion layer: J, J'-G (r-sulfopropyl)
-Selenacya di/sodium salt (10 moles of CoX per 441 moles of halide) Green-sensitive emulsion layer: 3,3'-di(γ-sulfopropyl)
-j, j'-diphenyl-terethyloxacarbo7anine sodium salt (co,!X10 mol per mol of silver halide) Red-sensitive emulsion layer; J, J'-di(r-sulfozolopyl)
- Termethyl-thiadicarbocyani/sodium salt (per 7 moles of silver halide, !

Edge-sensitive emulsion l emotion; Red-sensitive emulsion'@; Table! Inner thigh color inhibitors A and B and ultraviolet absorber UV-/
, UV-J, UV-J No Seizo n and the following.

B; (↑Anti-fading agent) UV-t C,H9(t) UV-J C4H,(This invention instead of the coupler solvent trioctyl phosphate in the third layer of the sample (rot) Chlorinated paraffin (seasonal,
Samples (10/) of the same chlorinated paraffin (4) were used in place of the coupler solvent dibutyl phthalate in the first layer.
A sample was prepared in the same manner as above and designated as sample '#+CJ-02).

After exposing the wiping materials (jtO/) and (jOko) with brown light for sensitometry, they were not subjected to the same development process as in Example 1, and then irradiated with a fluorescent lamp for 4 weeks. Perform a light fastness test of the color image.

? )) tQ D s =/ , o? Light irradiation between the hexagons17)? &, trial #-+ (0.t6 at jO/l
, the sample (jO) was 00j2.

Next, the samples (60/) and (jOλ) were subjected to an unexposed atomic test and exposed to i4 for 3 weeks at 1000C.
1.15 minute test on a white background.
/ ) at θ, /j, sample (tocon at 0°l/).

As described above, it is clear that the light fastness of color images is improved and the occurrence of staining is suppressed by using the chlorinated rough-in as described above.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 9. νDear Director General °ゝ゛・１、＝Jt、Display Showa! 2nd year patent application No. 06R3 Hiroshi No. 2, Title of invention: Silver halide photographic light-sensitive material; U, Relationship with 111 cases of persons applying t+11+E Patent applicant l◆? ! dsj 1-1-4, the subject of the amendment 5, the revised statement of the contents of the amendment (no changes to the contents) will be submitted.

Procedural amendment dated December 1, 1985, 1, “Indication of the matter 1939, 1985, patent application No. 20613
4c No. 2, Title of invention Silver halide photographic light-sensitive material 3
, Relationship with correction stand °IGr'l- Patent applicant appointment
Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Subject of amendment: 5 of the “Detailed Description of the Invention” in the description, Contents of the amendment The description in the “Detailed Description of the Invention” section of the description will be amended as follows. .

/) Page 17, line l- "amide" "Amides" and correct it.

2) Change the chemical structural formula on page ≠4 (M-//) to “(M-/r
＞ ” is corrected.

3) The chemical structural formula on page 13 A-1/ 'A-ii ” and correct it.

Claims (1)

[Claims] A halogen characterized by having on a support at least one hydrophilic organic colloid layer in which at least one photographic reagent is dispersed in coexistence with chlorinated paraffin having a boiling point of 175° C. or higher at normal pressure. Silver chemical photographic material.