JPS62150346A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material small in color staining and color fogging, and superior in color reproductivity by incorporating a specified colorless compound. CONSTITUTION:The colorless compound to be added is represented by formula I in which each of R<1> and R<2> is independently H, halogen, or the like; R<3> is H or the like; R<4> is an optionally substituted hetero ring or the like; and the total C number of R<1>-R<4> is >=8. This compound is added, preferably, in an amount of 1X10<-5>-1X10<-3>mol/m<2> in the case of an interlayer, an antihalation layer, and a protective layer, and, preferably, in an amount of 1X10<-3>-1X10<-1>mol per mol of silver halide in the case of a silver halide emulsion layer. This compound is embodied by formula I-1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color light-sensitive material, and more particularly to a silver halide color fJ true light-sensitive material in which the occurrence of color contamination and one-color fog is improved.

(Prior art) After exposing a silver halide color photographic light-sensitive material, aromatic first
A method of forming a color image by processing with a color developer containing a grade amine developing agent is well known.

In such a color image forming method, the developing agent described in - is oxidized by oxygen in the air, and this oxidized developing agent reacts with a color coupler in an unexposed or low-exposed area of the photosensitive material to form a dye. It is well known that this causes color fog.

In addition, in ordinary color sensitive materials that have two or more emulsion layers containing color couplers with different color sensitivities and different hues, the oxidized developing agent generated by the phenomenon in one color-sensitive layer is mixed with the other. It is also known that it diffuses into the color-sensitive layer and reacts with couplers, causing color contamination (color mixing).

A method using a hydroquinone compound has been proposed as one f-stage for preventing these undesirable color capri and color contamination.

For example, U.S. Pat. No. 2,360,290, 2.41
No. 9,613, No. 2,403.721, No. 3.960
．． Kasa No. 570 contains mono-n-alkylhydroquinones, which are disclosed in U.S. Patent No. 3,700.453 and Japanese Patent Application Laid-open No. 1983-10.
6329. 50-156438. West German patent publication 214
U.S. Pat. No. 2,728,659 and U.S. Pat. No. 2,732.
No. 300, No. 3,243,294, No. 3゜700.4
53, British Patent No. 752,148, 4ν Kaisho 50-1
56438, 53-95281), 54-296
Dialkyl-substituted hydroquinones are described in No. 37 and Japanese Patent Publication No. 50-21249, and arylhydroquinones are described in U.S. Pat. No. 2,418,613.

Although these compounds do have some effect in preventing color fogging and color staining, the effect is small and there is a problem in that colored substances are produced after the preventive effect is achieved.

Therefore, acyl group, nitro group, cyano group, formyl group,
Hydroquinones nuclearally substituted with electron-withdrawing groups such as halogenated alkyl groups have been proposed in US Pat. No. 4,198,239. Although these materials are certainly excellent in their ability to prevent color staining, they have problems such as producing colored substances, deteriorating performance during the production and storage of sensitive materials, and being covered with silver halide emulsions.

In addition, hydroquinones substituted with aliphatic acylamino groups, ureido groups, urethane groups, etc. are disclosed in U.S. Pat.
No. 8,239.

It is true that these compounds have a certain degree of ability to prevent color staining.
There was also less coloring. However, its ability to prevent color staining is still insufficient, and there are also problems with storage stability, such as precipitation of crystals during the production of sensitive materials.

In addition, hydroquinones substituted with an alkyl group, an aralkyl group, or an acylamino-7-containing sulfonic acid group have been proposed in U.S. Patent No. 2,701,197, but these compounds cannot be used during production or storage of sensitive materials. It has the drawback that it diffuses into the sensitive material layer to which it is not added, and not only deteriorates the ability of the added layer to prevent color stains and fog in one color, but also changes the photographic performance of other layers during manufacturing and storage. .

In addition, JP-A-59-202465 describes hydroquinones substituted with sulfonamide groups, but their ability to prevent color staining was still insufficient. Hydroquinones having an attractive group, such as hydroquinones substituted with carbamoylno and There were problems such as a high degree of coloration.

Additionally, hydroquinone is used in U.S. Pat.
No. 66, US Pat. No. 4,277.558, etc., but US Pat. No. 3,930.886 does not specifically describe the compound of the present invention, and US Pat. , 277.558 uses hydroquinone and quinone in combination, and when the compound of the present invention is used in such a method, the ability to prevent color staining is actually reduced. Further, the compounds of the present invention are not specifically exemplified.

(Problems to be Solved by the Invention) The first objective of the present invention is to provide a photosensitive material with less color contamination and one-color fog, and the second objective is to provide a photosensitive material that generates colored substances during storage and development. The third objective is to provide a photographic material containing a color stain-preventing agent that is stable for a long period of time without changing its ability to prevent color stain, dyeing, or color fog during manufacturing and/or storage. The fourth objective is to provide a photosensitive material with excellent color reproducibility that shows performance, and the fourth purpose is to improve the emulsion layer thickness,
An object of the present invention is to provide a photosensitive material with a thin intermediate layer.

(Means for Solving the Problems) The above aspects of the present invention can be achieved by incorporating a substantially colorless compound represented by the following general formula (I) into a silver halide color photographic light-sensitive material. Ta.

(I) H (wherein R1 and R2 are each independently a hydrogen atom, a 1M halogen atom substituted or unsubstituted alkyl, acylamino,
Represents an alkoxy, aryloxy, alkylthio, arylthio, sulfonyl, acyl, hemoyl or sulfamoyl group.

Further, R1 and R2 may jointly form a carbocyclic ring. R
3 represents an atom or an alkyl group in water 2;

R4 represents a 1-substituted or unsubstituted heterocyclic ring or cycloalkyl group (the total number of carbon atoms of R1 to R4 is 8 or more). The present invention will be described in more detail.

In the general formula (I), R1 and R2 are each independently a hydrogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), a substituted or unsubstituted alkyl group (carbon number 1-40, e.g. methyl, t- Butyl, 1-octyl, cyclohexyl,
n-hexadecyl, 3-decanamidopropyl, etc.),
7 acylamino groups (2 to 40 carbon atoms, e.g. acetylamino, n-butanamide, 2-hexyldecanamide, 2
-(2',4'-di-t-amylphenoxy)butanamide, benzoylamino, etc.), alkoxy groups (1 to 40 carbon atoms, e.g. methoxy, ethoxy, butoxy, n-
octyloxy, methoxyethoxy, etc.), aryloxy groups (6 to 40 carbon atoms, e.g. phenoxy, 4-t-octylphenoxy, etc.), alkylthio groups (1 to 4 carbon atoms).
0° e.g. butylthio, hexadecylthio, etc.), arylthio group (carbon number 6-40° e.g. phenylthio, 4
-dodecyloxyphenylthio, etc.), sulfonyl 1%
(1 to 400 carbon atoms, e.g. methanesulfonyl, benzenesulfonyl, totesylbenzenesulfonyl, (etc.)
, acyl group (carbon number 2-40゜acetyl, benzoyl,
tetradecanoyl, etc.), a carbamoyl group, or a sulfamoyl group, and R1 and R2 may jointly form a carbon ring. R3 represents a hydrogen atom or alkylthio (having 1 to 20 carbon atoms, such as methyl, ethyl, etc.). R4
is a substituted or unsubstituted heterocyclic group (carbon number J 3 to 40; for example, 2,6-dihexyloxypyridin-4-yl, N-tetradecylpyrrolidin-2-yl, N-tetradecylpiperidin-3-yl) ), cycloalkyl group (carbon a
5-40° e.g. 3-decanamidocyclohexyl, 3
R1-R representing -((2',4'-di-L-amylphenoxy)butanamide)cy14chlorohexyl, etc.)
The total number of carbon atoms in 4 is 8 or more.

In general formula (I), R1 and R2 are preferably a hydrogen atom, a halogen atom, an alkyl group (, an alkoxy group, an alkylthio group), and most preferably a hydrogen atom, a halogen atom, or an alkyl group.

In general formula (I), a preferred substituent for R3 is a hydrogen atom.

Preferred substituents for R4 in general formula (I) are heterocyclic groups. (It is.

R -R' in general formula (I) can further have a substituent, and these groups include generally known organic groups, halogen atoms, hydroxyl groups, carboxyl groups, sulfo groups, etc. can be mentioned.

The compound represented by the 1r1 general formula (1) used in the present invention (hereinafter always referred to as the compound of the present invention) can be used in layers in a sensitive material, such as light-sensitive emulsion layers (It-sensitive layer, green-sensitive layer and red-sensitive layer). layers) or adjacent layers thereof (for example, intermediate layers adjacent to different color-sensitive emulsion layers and intermediate layers sandwiched between substantially the same color-sensitive emulsion layers), protective layers, antihalation +h agents, etc. However, it is preferably contained in an intermediate layer sandwiched between emulsion layers having different color sensitivities.

The amount of the compound of the present invention to be added is from 1xlO-7 to IXIO-7 in the case of intermediate layer, antihalation layer and protective layer.
-2mol/m', preferably from 1O-6 to 3
x 10'mol/m'', more preferably 1 x lO to l
Xl0'mol/rn'.

In the case of a silver halide emulsion layer, lXl0' to 1 mol, preferably 3 x 1O to 3X10' mol, more preferably lXl0 per mol of silver halide contained in the layer.
to lXl0' mole.

Specific examples of the compounds of the present invention are listed below, but the present invention is not limited thereto.

H H H H (Jti H H tt tt The compound of the present invention is generally synthesized by 2.5-
It can be obtained by an amidation reaction between dihydroxyanilines and carboxylic acid chlorides, and can also be obtained in Synthesis Example 2.
As shown in Figure 2, it is also possible to take a synthetic route in which an amidation reaction is carried out by introducing a group called a protecting group such as a furkyl group or a benzyl group into a hydroxyl group, and then deprotection is carried out.

Synthesis Example 1-1.Synthesis of 3-(α-(2,4-di(t)-amylphenoxy)butanamido)cyclohexanecarboxylic acid 3-7 8.8g of ethyl minocyclohexanecarboxylate was added to 50mu of Pyri9F. α-(2,4-di(1)-amylphenoxy)butanoyl chloride 17
．． After 0 g was gradually added dropwise with stirring, stirring was continued for an additional 15 minutes, and the system was added to 300 mL of ice water containing 60 mL of concentrated hydrochloric acid, and extracted with ethyl acetate. After drying with magnesium sulfate, it was elited to obtain 22 g of an oily substance. ' The above oil was dissolved in 200 mM ethyl alcohol, and 50 ml of an aqueous solution containing 6.5 g of potassium hydroxide was gradually added dropwise thereto. After refluxing on a hot water bath for 2 hours, the mixture was allowed to cool, poured into 300 m of ice water containing 20 m of concentrated hydrochloric acid, and extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated to obtain 20 g of 3-(α-(2,4-di(1)-amylphenoxy)butanamido)cyclohexanecarboxylic acid as an oil.

Synthesis Example 1-21 Synthesis of Exemplified Compound (5) Berichte (B
8.1 g of aminohydroquinone hydrochloride, prepared from nitrohydroquinone by the method of Henrich (Rent 1ch), 54, 2509 (1921), and 7 m9 of triethylamine. 80 m of pyridine under a nitrogen stream
1, and 3-(α-(2,4-di(
1)-Amylphenoxy)butanamido)cyclohexanecarboxylic acid chloride (21 g) was gradually added dropwise. After stirring the system at room temperature for 30 minutes, 5 ml of ice water containing 100 ml of concentrated hydrochloric acid was added.
The mixture was gradually poured into 00mu with stirring. After extraction with ethyl acetate, drying, e-condensation, and purification by column chromatography yielded light brown oily substance 2 of Exemplified Compound (5).
3g was obtained.

Calculated value as C33H48N2o5 (%) C near 1.71. H: 8.75°N:
5.07 Actual all value (%) C near 1.38. H: 8.56°N: 4.82 Synthesis Example 2-1. Synthesis of N-(2-hexyldecanoyl)isonipecotic acid lOg of ethyl inipecotate and 6 ml of pyridine were dissolved in 100 mJl of acetonitrile, and 16.5 g of 2-hexyldecanoyl chloride was gradually added dropwise thereto with stirring. After the addition was completed, stirring was continued for an additional 15 minutes, and the system was poured into 300 ml of ice water containing 10 ml of concentrated hydrochloric acid, and extracted with ethyl acetate. After drying with magnesium sulfate,
Concentration gave an oil.

The above oil was dissolved in 200 mM of ethyl alcohol, and a 50 mM aqueous solution containing 6.5 g of potassium hydroxide was gradually added dropwise thereto. After refluxing for 2 hours on a hot water bath, let it cool and add 20ml of concentrated hydrochloric acid! The mixture was poured into 300 mfL of ice water containing L and extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated to obtain 21 g of N-(2-hexyldecanoyl)inipecotic acid as an oil.

Synthesis Example 2-20 Synthesis of Exemplified Compound (6) 2.9.2 g of 5-dimethoxyaniline and 8 ml of pyridine were dissolved in 100 mJl of acetonitrile, and the carboxylic acid obtained in Synthesis Example 2-1 was added thereto by a conventional method. 23 g of N-(2-hexyldecanoyl)inipecotyl chloride was gradually added dropwise while stirring. After stirring the system for an additional 15 minutes,
The mixture was added to 300 mM ice water containing 15 molar concentrated hydrochloric acid, and extracted with ethyl acetate. After drying with magnesium sulfate, C condensation was performed to obtain 27 g of an oily substance.

Dissolve the above oil in 500 mJl of dichloromethane,
While stirring under water cooling, 12 mu of boron tribromide was gradually added. After the dropwise addition was completed, the mixture was stirred at room temperature for another hour, and then poured with ice water at 50°C.
At 0 mft, extraction with ethyl acetate, drying, and concentration were performed. After purifying the obtained crude crystals by column chromatography, a mixed solvent of n-hexane and ethyl acetate (
Recrystallization was performed from a mixture ratio of 1:3 to obtain 20 g of colorless crystals of Exemplified Compound (6).

Calculated value (%) for 028H4BN204 C near 0.89. H:9.7ON:5
．． 91 Actual value (%) C near 0.73. H:9.92N:5
．． 72 The compound of the present invention or the coupler or dye image-providing compound that can be used in combination with the present invention described below can be introduced into the light-sensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, etc. Preferably, an oil-in-water droplet dispersion method can be cited as a typical example.

In the oil-in-water dispersion method, the oil is dissolved in either a high-boiling point organic solvent of 175°C or higher and a low-boiling point so-called auxiliary solvent, either alone or in a mixture of both, and then water is added to the presence of a surfactant. Or finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
, No. 027, etc. Minute 1'f! 1. This may be accompanied by phase inversion, and depending on the cost, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl tucrate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (dioctyl azelate,
glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (
(N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and as auxiliary solvents, solvents with a boiling point of about 30°C to about 160°C can be used; typical examples include ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-nitoxyethyl acetate,
Examples include dimethylformamide.

Latex dispersion methods can be applied to the dispersion of the compounds of the invention,
The process, effects and specific examples of latex for impregnation are as follows:
U.S. Patent No. 4,199,363, OLS No. 2,541
, No. 274 and OLS No. 2,541,230.

The compounds of the present invention can preferably be used in ordinary color photographic materials using a coupler type, and color diffusion transfer photographic materials using ready-made dye-providing compounds.

When applying the compound of the present invention to color diffusion transfer photography, peel-off (beer-apart) type or
No. 16356, No. 48-33697, Japanese Unexamined Patent Publication No. 1983-1
3040 and British Patent No. 1.330,524.
It is possible to adopt the structure of an integrated type film unit as shown in Japanese Patent Laid-Open No. 57-119345, or a type that does not require peeling as described in JP-A-57-119345.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is about 2 mol%.
silver iodobromide containing up to about 25 mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of up to about 10 microns, a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution. An emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, Research 5 Disclosure +- (
RD), No. 17643 (December 1978), 2
pp. 2-23, “1. Emulsion Preparation (Emulsion Pr.
and types)” and the same, No. 8716 (November 1979), 648.
You can follow the method described on page.

The photographic emulsion used in the present invention may be prepared by any of the acid method, neutral method, ammonia method, etc. Also, the method for reacting the soluble silver salt with the soluble halogen salt is the one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used. A method in which six particles are formed under an excess of silver ions (so-called back mixing method) can also be used. As one type of the py1 mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald or double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling p, Ag and pH during the formation of one grain.

A typical monodispersed emulsion is an emulsion in which silver halide grains have an average grain diameter of more than about 0.11 microns, and at least about 95% by weight of the silver halide grains are within ±40% of the average grain diameter. The average grain diameter is about 0.25 to 2 microns, and at least about 95% by weight, or in some cases at least about 95%, of the silver halide grains have an average grain diameter of ±20 microns.
% can be used in the present invention.

A method for making such an emulsion is described in U.S. Pat. No. 3,574.8.
No. 28, No. 3,655.394 and British Patent No. 1
, No. 413,748. Also, JP-A-48
-8600, 51-39027, 51-830
No. 97, No. 53-137133, No. 54-48521
Monodisperse emulsions such as those described in Japanese Patent Application No. 54-99419, Japanese Patent No. 58-37635, and Japanese Patent No. 58-49938 can also be preferably used in the present invention.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science, and 6 Engineering.
nce and Engineering), 1st
4, pp. 248-257 (1970): U.S. Patent No. 4
, No. 434.226, No. 4,414,310, No. 433.048, No. 4,439,520, and British Patent No. 2,112,157. I can do it. When using tabular grains,
The advantages of sensitizing dyes, such as improved color sensitization efficiency, improved granularity, and increased sharpness, are detailed in US Pat. No. 4,434.226 cited above.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. Also, mixtures of particles of various crystal forms may be used.

The emulsion of the invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research, Disclosure+-Na176
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two research and disclosure documents, and the descriptions are shown in the table below.

Additive type RD 17843 RD 1871
1111 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, strong Pages 23-24 Page 648 Right column - Color sensitizers Page 648 Right column 4 Brightening agents
24 Page 5 Antifogging agent Pages 24-25 Page 649 Right column and Stabilizer 6 Light absorber, Fi Page 25-26 Page 849 Right column ~
Luther dye ultraviolet 650 left column line absorber 7 anti-stain zL agent 25 page right a eso page left to right 8 dye image stabilizer 25 page 9 hardener page 26 page 651 left column 10
Binder page 26 - Same 11 Plasticizer, lubricant Page 27 650 Right column 12 Coating aid, surface Pages 28-27 Same as above Activator 13 Static prevention Page 27 Same Laxative Various color couplers are used in combination in the present invention. Specific examples include the research and disclosure mentioned above.
(RD) Not 7643, the important 0 dye-forming power puller described in the patent described in ■-〇-G is a coupler that provides the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development through color development. Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers are R
In addition to the couplers described in the patents described in D 17643, ■-〇 and Section D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used in the present invention include hydrophobic acylacetamide couplers such as Palast) 1. Specific examples thereof include US Pat. No. 2,407,210; No. 875,057 and US Pat. No. 3,265,506. The use of two-hit jI8 yellow couplers is preferred for the present invention. US Pat. Nos. 3,408,194 and 3,447
, No. 928-1 No. 3,933,501 and No. 4
Oxygen atom separation type yellow coupler described in No. ゜022.620, etc., or Japanese Patent Publication No. 58-10739
So, U.S. Patent Nos. 4,401,752 and 4,326.
, No. 024, RD18053 (April 1979), British Patent No. 1.425.020, West German Application No. 2,2
No. 19,917, No. 2.261,361, No. 2,
Typical examples include the nitrogen atom separation type yellow couplers described in No. 329,587 and No. 2,433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include 5-pyrazolone and pyrazoloazole couplers that are hydrophobic through a palust group. Among the 5-pyrazolone couplers, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of coloring dye, hue, and coloring density.
No. 311.082, No. 2.343.703, No. 2
, 600.788 Lee, 2.908.573, 3.062.653, 3,152.896 Gin, and 3,936,015.

Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897. . Also European patent: 57
The 5-pyrazolone coupler described in No. 3.636, which has the ballast no.

As pyrazoloazole couplers, U.S. Patent i3,
369,879, preferably pyrazolo(5,1-C)(1,2,4))riazoles described in US Pat. No. 3,725.087. U.S. Patent No. 4,500,63 in terms of low yellow side absorption of the coloring dye and light fastness.
Imidazo(1,2-b)pyrazoles as described in No. 0 are preferred, and pyrazolo(1,5-b)(1,2,4)h riazoles as described in European Patent No. 119,860A are preferred. Particularly preferred.

Cyan couplers that can be used in the present invention include:

Hydrophobic, diffusion-resistant naphtholic and phenolic couplers include the naphtholic couplers described in U.S. Pat.
No. 052,212, No. 4゜146.396, No. 4
Typical examples include the oxygen atom elimination type double naphthol couplers described in No. 228,233 and No. 4,296,200. Specific examples of phenolic couplers are described in U.S. Patent Nos. 2,369,929, 2,801,171, 2,772,162, and 2,895,826. There is. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 772,002, US Pat. No. 2,772,162, US Pat.
．． No. 758,308, No. 4,126,396, No. 4.334.011, No. 4,327.173, West German Patent Publication No. 3,329,729 and European Patent No. 1
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 21,365 and U.S. Pat.
No. 6,622, No. 4.333.999, No. 4,4
51.559 and 4.427.767, etc., which have a phenylureido group at the 2-position and have a 5-
These include phenolic couplers having an acylamino group in the position.

In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with a color photosensitive material for photographing.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366.237 and British Patent No. 2,
No. 125,570 contains specific examples of magenta couplers, and European Patent No. 96,570 and West German Application No. 3,2
No. 34.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3.451.82.
No. 0 Oyo and No. 4. o80.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102.173 and US Pat. No. 4,367.2.
It is described in No. 82.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD l 7643.
The patented couplers described in Sections 1-F are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent Nos. 2,097.140 and 2,131.
It is described in No. 188. Couplers that release nucleating agents that have an adsorption effect on silver halide are particularly preferred;
and 59-170840, etc.

The color photographic material according to the present invention includes the above-mentioned RD, N
o17643, pages 28-29 and the same, No.18716
651, left column to right column.

The color photographic light-sensitive material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleaching and fixing (11') or fixing.

In the washing process, it is common to use two or more tanks for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this process, 2~
Nine countercurrent baths are required. Various compounds are added to the water stabilizing bath for the purpose of stabilizing the image. For example, membrane pH
Various buffering agents (for example, pH 3 to 8)
For example, borate, metaborate, borax, phosphate,
Typical examples include carbonate, potassium hydroxide, sodium hydroxide, ammonia water (used in combination with monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, water softeners (
(inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzisothiazolinone, irithiaturon, 4-thiazolinebenzimidazole, halogenated phenol, etc.), surfactants Various additives such as photobrighteners, optical brighteners, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

When the uninvented compound is used in a color diffusion transfer photographic light-sensitive material, the dye image-providing compound used in combination with the silver halide emulsion layer may be negative-working or positive-working and processed with an alkaline processing composition. Sometimes they are initially mobile or non-mobile within the photographic element.

Negative-working dye image-providing compounds useful in the present invention include couplers that react with oxidized color developing agents to form or release dyes, specific examples of which are U.S. Pat.
No. 550 and Canadian Patent No. 602,607. l for use in the present invention! Preferred negative-type dye image-producing compounds include dye-releasing redox compounds that release dyes by reacting with developing agents or electron transfer agents in an oxidized state; a typical example thereof is disclosed in U.S. Pat.
．． No. 928,312-1 No. 4,135,929, No. 4,055,428, No. 4,336,322,
It is described in No. 4,053,312, etc.

The immobile positive-working dye donor IF compound that can be used in the present invention is one that does not accept any electrons (i.e., is not reduced) or loses at least one electron during photographic processing under alkaline conditions. There are compounds that release diffusible dyes after being absorbed (i.e., reduced), specific examples of which are described in U.S. Pat. No. 4,199,354;
80゜479, 4,199,355, 4,13
9.379 So, 4,139,389, 4゜232
．． No. 107 and Japanese Unexamined Patent Publication No. 53-69033.

Additionally, positive-working dye image-providing compounds that are initially mobile under alkaline photographic processing conditions are also useful in the photographic elements of this invention. A typical example of this is a dye developer, typical examples of which are described in US Pat. No. 3,482,972 and US Pat. No. 3,880,658.

The dyes formed from the dye image-providing compounds used in this invention may be ready-made dyes or alternatively dye precursors that can be converted into dyes in photographic processing steps or additional processing steps, resulting in the final image dye. may or may not be metal complexed. Representative dye structures useful in the present invention include metal-complexed or non-metal-complexed dyes such as azo dyes, azomethine dyes, anthraquinone dyes, and phthalocyanine dyes.

Among these, there are 4 cyan, magenta and yellow pigments.
To ν! If necessary.

Further, as a type of dye precursor, a dye-releasing redox compound that temporarily shifts light absorption in a photosensitive element to a dye moiety can also be used in the present invention.

Processes for obtaining color diffusion transfer images using dye-releasing redox compounds are described in Photographic, Science, Endoscopy, and Engineering J.
Photographic 5science andE
ngineering) Magazine, Vol. 20, N.
o4, p, 155-164, July/August
1976.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or motion pictures, color reversal film for slides or television, color paper, color positive film, color diffusion transfer direct positive sensitive material, and color reversal paper. The present invention can also be applied to black-and-white light-sensitive materials using a three-color coupler mixture as described in Research, Disclosure 17123 (July 1978).

(Effect of the invention) The silver halide color photographic light-sensitive material of the present invention has color JrJ
Produces color images with extremely little color fog. Further, in the photographic material of the present invention, the color stain preventive agent is not easily oxidized during storage or development, and exhibits a stable ability to prevent color stains from insects. The photosensitive material of the present invention does not suffer from deterioration in its ability to prevent color contamination and one-color fogging during manufacture and/or storage, does not change its photographic performance over a long period of time, and has excellent color reproducibility. Furthermore, in the photosensitive material N'1 of the present invention, the thicknesses of the emulsion layer and the intermediate layer can be made thinner.

Example Next, the present invention will be explained in more detail based on examples.

Example 1 Triacetylcellulose film support with transparency of 1!11]
- A multilayer color photosensitive material (Sample 101) consisting of each layer having the composition shown below was prepared.

1st layer: Anti-halation 1st layer black colloidal silver ・・・・・・・・・・・・・・・ O
, 15g/m'' UV absorber U-1...0
．． 08g/rrl" Same U-2...
O, 12g/m″ gelatin ・・・・・・・・・
・・・・・・・・・・・・ 1.3g/rn” 2nd layer:
Intermediate layer 2.5-di-t-pentadecylhydroquinone...0.18g/rn' coupler C-1...0.1
1g/m″ gelatin・・・・・・・・・・・・・・・
...... 1.5g/m" 3rd layer: 1st red-sensitive emulsion layer... 1.2g/m" Sensitizing dyestuff...・・・・・・・・・・・・ 1.4X10' moles per mole of silver ■!・・・・・・・・・・・・・・・ 1.4Xlo-' mole fJl for 1 mole of silver ・・・・・・・・・・・・・・・5.6X10-' mole same ■ 4.0XIO-4 mole coupler C-2 for 1 mole of silver...0.45g /
rn' coupler C-3...0.03
5g/m'' coupler C-4...0.
025g/rn” Gelatin ・・・・・・・・・・・・
...... 1.8g/rn' 4th layer: 2nd red-sensitive emulsion layer... River... 1.0g/rn' Sensitizing dye I...・・・・・・・・・ 5, 2X 10-”%/lz for 1 mole of silver II ・・・・・・・・・・・・ 1.5×10’ mol for 1 mole of silver 1Till ・・・・・・・・・・・・・・・
2, lX10' moles per mole of silver ■...1 old... 1.5X10-5 moles per mole of tIJ Coupler C-2...old... 0.050 g/ Coupler〇-5.1 Old・-0,070g/m'Coupler C
-3・・・・・・・・・ 0.035g/rn' Seratin ・Old...Old Old Old Old... 1.0g/m"5th
Layer: Intermediate layer comparative compound A-1...0. lOg/m″
Tri-credit triphosphate...0.10g/m'Gelatin...Old..."-0, 60g 7m"
6th layer: 1st green emulsion layer・・・・・・・・・・・・ 0.80g/green sensitizing dye V・・・・・・・・・・・・・・・tM1
Sensitizing dye ■ 4, OX 10”% per mole ■ 3.0XIO-5 mole per mole of silver ■ ... ...... 1.0X10-4%/L per mole of silver.

Coupler C-6・・・・・・・・・・・・ 0.45
g/rn' coupler C-7・・・・・・・・・・・・
0.13g/ni' coupler C-8...
...0.02g/ln' coupler C-4...
・・・・・・・・・ 0.04g/m″ gelatin ・
・・・・・・・・・・・・・・・・・・・・・ 1.0
g/m'' 7th layer: 2nd green-sensitive emulsion layer 0.85 g/m
m' sensitizing dye V ・・・・・・・・・・・・・・・ 2.7×10-4 mol sensitizing dye ■ for 1 mol of silver ・・・・・・・・・・・・・・・... 1.8XIO" 5 moles per mole of silver ■ 7.5X10' mole coupler C-6 = 0.095g per mole of silver /m' Coupler C-7・・・・・・・・・ 0.015g/m″ Gelatin ・・・・・・・・・・・・・・・・・・・・・
1.0g/m' 8th layer: Yellow filter, yellow colloidal silver 0.08g
/m'2.5-di-t-pentadecylhydroquinone...0,090 g/
m' Seratin ・Old, old, old...old... 1.
0 g/rr11 9th layer: 1st blue-sensitive emulsion layer 0.37 g/rn
'Sensitizing dye■ ・・・・・・・・・・・・・・・ Silver 1
4.4X10” mole coupler 〇-9 for moles...0.71g/
m' coupler C-4...0.07
g/rn' gelatin...1 old...-1,0
g/m' 1st O layer: 2nd blue-sensitive emulsion layer 0.55 g/m"
Sensitizing dye■...Group...Old...3.0 x 10' moles per mole of silver Coupler C-9/Old---Group/0.23g/m'
Gelatin ・・・・・・・・・・・・・・・・・・・・・
・ 0.9 g/m' 11th layer: 1st protective layer ultraviolet absorber U-1... O, 14 g/m'' times
U-2-0.22g/m' gelatin...
...old old old...0.9 g/m'1st
2nd layer: 2nd protective layer・・・・・・・・・・・・ 0.25g/m'
Polymethacrylate particles (diameter 1-5JL) ・"-0,10g/m" Gelatin ・1 Old・・・・・・・・・・・・・・・ 0,9
g/m' In addition to the above composition, gelatin hardener H-1 and a surfactant were applied to each layer.

(Samples 102 to 113) Instead of comparative compound A-1 in the fifth layer of sample 101,
Comparative compounds A-2, A-3, A-4, A-5, A-
6 and A-7, compounds (1), (2), (3) of the present invention
Samples 102 to 113 were prepared in the same manner as sample 101, except that 21 equimolar amounts of (), (5), (6), and (13) were replaced.

These samples were exposed to red imagewise light and subjected to the following color development process. The density of the sample after processing is measured using a red filter and a green filter, and the value obtained by subtracting the magenta fog density from the magenta density at the exposure amount that gives the cyan density measured with the red filter a density of (fog + 1.5) is calculated as the color cloudiness. They are summarized in Table 1 as degrees.

The development used here was carried out at 38°C as described below.

Color development 3 minutes 15 seconds Deep peak 6 minutes 30 seconds Washing 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing
Stable for 3 minutes and 15 seconds 1
The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid M 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1.3mg hydroxylamine sulfate 2.4
g4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate ji! 4. Add 5 g water and 1.0 liter pH 10
, 0 bleaching liquid For ferric ammonium ethylenediaminetetraacetate 100.0g ethylenediaminetetraacetic acid disodium salt 10.0g ammonium bromide 150.0g ammonium nitrate to, 0g Add water
1.0 sentences pH 6.0 Fixer ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water
1.0 ml pH 6.6 Stabilized liquid formalin (40%) 2.0 ml polyoxyethylene-p-monononyl phenol ether (average degree of polymerization = 10) Add 0.3 g water 1.01 Also, to these samples (A ) for 7 days at 25°C and 60% relative humidity.
and (B) 71 at 40°C and 80% relative humidity.
After being exposed to white light, the color development was carried out. The density of these processed samples was set to 411, and the yellow, magenta, and cyan density was 1 each under condition (A).
．． Table 1 summarizes the respective densities of condition (B), which is a condition of forced deterioration in the exposure field that results in a density of 5.

From the results in Table 1, it can be seen that the degree of color turbidity is from sample 108 of the present invention to
113 and Comparative Example Samples 106 and 107 have small values, and it is clear that the compounds used in these samples have a high ability to prevent color staining. On the other hand, in terms of photographic performance after being placed under forced deterioration conditions, the magenta and cyan densities of Samples 106 and 107 were significantly reduced, whereas samples 108 to 113 of the present invention showed only a slight decrease in density. It can be seen that it is.

Structure of the compound used in the examples 1"114 ('11-T Average molecular weight 20,000 Compound (6)) O of Patent No. 2336327
H・・L)l-1 A-2 (Compound (8) of U.S. Pat. No. 4,198,239)
'A-3 (Compound 1-2 of U.S. Pat. No. 4,277,558
2) 0 i H 8-・1 (compound (1
)) A-5 (Compound (15) of JP-A-57-22237
)OH [Jtl A-6 (Compound (9) of U.S. Pat. No. 2,701,197)
0 mouth υh A-7 (compound (6) of U.S. Patent No. 2701197)
Example 2 Photosensitive sheet A was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate film support.

(1) Copoly[styrene-N-vinylbenzyl-
N,N,N-)lyhexylammonium chloride)3.
0 g/rn', gelatin 3, mordant layer containing 0 g/m'.

(2) Titanium dioxide 20g/rrf, gelatin 2.
A light reflecting layer containing 0 g/m'.

(3) A light-shielding layer containing 3.0 g/m'' of carbon black and 2.0 g/m'' of gelatin.

(4) A layer containing 0.65 g/rn'' of a magenta dye-releasing redox compound having the following structure and 1.2 g/rrf of gelatin.

(5) Green-sensitive internal latent image type direct reversal silver bromide emulsion (silver (7) ft 1,2 g/m''), gelatin 7 (1,2 g/m''),
3g/m'), a nucleating agent with the following structure (0.04mg/rn
) and 2-sulfo-5-n-pentadecylhydrone, sodium tli (0,12 g/rn').

(6) Compound (1) of the present invention, 0.53 g/rrf
and tricyclohexyl phosphate 0,2 g/
layer containing m'.

(7) Yellow dye-releasing Tonks compound with the following structure: 0, 75 g/rn' and tricyclohexylphos 7
Z-to 0.2g/rn' and gelatin 71.2g/m
A layer containing '.

(8) A layer containing gelatin (1, Og/m').

Photosensitive sheets C and D were prepared in the same manner as photosensitive sheets B and comparative sample 1.

・Photosensitive sheet: 2.5-di-t-pentadecylhydroquinone described in JP-A-54-2963-7 is used as a color stain preventive agent for layer (6) of photosensitive sheet A in place of the compound of the present invention. , the same photosensitive sheet as A except that 0.49 g/ba was replaced.

・Photosensitive sheet C: Color stain prevention W of layer (6) of photosensitive sheet C
A photosensitive sheet identical to A, except that the agent was replaced with the compound (22) of U.S. Pat.

Pot photosensitive sheet D = layer (7) and layer (8) of photosensitive sheet A
Same photosensitive sheet as A except that it is not coated with.

A cover sheet was prepared with the following layers applied in sequence on a transparent polyester support.

(1) Polyacrylic acid 17 g/m', N-human 0
Xisuccinimide benzene sulfonate 0.06g/
rn' and Echi L/7gri: 1-JL10.5g/m
A layer coated to a thickness of 7 microns containing '.

(2) Timing layer coated with acetic acid cellulose (acetyl acid degree 54) to a thickness of 2 microns.

8-782 shown on the back.

Timing layer coated with TENX to a thickness of 4 microns.

A treatment solution having the following composition was prepared.

After exposing the photosensitive sheets A to D with a wedge, they are integrated with the container containing the processing liquid and the cover sheet,
The processing liquid was spread to a thickness of 80 microns using a suppressing member under conditions of 35°C and 35°C to obtain a transferred color image. The transferred image was measured with a color densitometer and Dg (green filter density), Db (
The value of blue filter density) was obtained. D when Dg=2.0
Value of b In the photosensitive sheets A-C prepared here, the layer (6) containing a color stain preventive agent has a layer (5) containing a green-sensitive silver halide emulsion in which the oxidized developer generated in the layer (5) contains silver halide. When diffused through layer (6) in the direction of layer (7) containing a yellow dye-releasing redox compound not associated with emulsion layer (5), it reacts with this oxidized developer to release yellow dye. It is applied to prevent the magenta color from becoming muddy, that is, from mixing yellow with magenta and deteriorating the magenta hue.

Therefore, the ability of the layer (6) containing a color stain preventive agent in photosensitive sheets A, B, and C is the value of Db - Db (photosensitive sheet D).
In other words, it can be determined by the degree of color turbidity. It is clear that photosensitive sheet A using the compound of the present invention has significantly lower &i of color cloudiness than comparative photosensitive sheets B and C, and has high color stain prevention agent ability.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing at least one substantially colorless compound represented by the following general formula (I). (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each independently represent a hydrogen atom, a halogen atom, substituted or unsubstituted alkyl, acylamino, alkoxy, aryloxy, alkylthio, It represents an arylthio, sulfonyl, acyl, carbamoyl or sulfamoyl group, R^1 and R^2 may jointly form a carbocycle, R^3 represents a hydrogen atom or an alkyl group, and R^4 represents a hydrogen atom or an alkyl group. Represents a substituted or unsubstituted heterocycle or cycloalkyl group. The total number of carbon atoms of R^1 to R^4 is 8 or more.)