JPH02123350A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material permitting rapid processing and having improved stability of performance, and improved whiteness of edge area, by incorporating silver halide emulsion into an emulsion layer, and incorporating also a specified compd. into one layer on a base body. CONSTITUTION:Spectrally sensitized silver halide emulsion sensitized by a kind of compd. expressed by formula I is incorporated into a red-sensitive emulsion layer, and a kind of compd. expressed by the formula II is incorporated into one of photosensitive layers or non-photosensitive layers on the base body. Further, a total amt. of the silver halide emulsion layers on the base body is regulated to <=0.65g/m<2> expressed in terms of Ag. In the formula I, Z is O atom or S atom; each R1 and R2 is alkyl group; each V1-V8 is H atom, halogen, acyl group, etc.; X is a charge balancing counter ion; n is a number necessary for neutralizing the charge. In formula II, R is alkyl group, alkenyl group, etc.; X is H atom, alkali metal atom, etc. Thus, a silver halide color photographic sensitive material permitting rapid processing, having improved stability of prepn., improved preservation stability of product, and improved whiteness of edge area, is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent manufacturing stability and product storage stability, and is resistant to temperature fluctuations during exposure. There is little variation in performance against
This invention relates to a silver halide color photographic material for printing that has excellent whiteness in edge areas.

(Prior Art) In recent years, higher efficiency and higher productivity have been required for processing color photographic materials. This trend is especially noticeable for color print production.
In order to respond to finishing delivery deadlines and price competition, the so-called color lab format is simultaneously being concentrated into large-scale laboratories with high production efficiency, and decentralized into mini-labs that are suitable for short-term finishing. is the current situation. Although these two types of laboratories are contrasting in form, they both have strong demands for increasing the yield rate during printing, especially in the current situation where it is difficult to have skilled operators. In this case, the stability of the performance of the photosensitive material for color printing (hereinafter referred to as color photographic paper) used is an important factor that influences yield. In other words, if the photographic performance changes between production lots of color photographic paper, or changes during storage in the laboratory, the condition settings must be re-set when printing the prints. Production is not possible.

On the other hand, as a result of research conducted by the present inventors, it has been found that variations in temperature conditions during exposure also have a large effect on variations in the performance of color photographic paper. If the sensitivity changes depending on the temperature at the time of exposure, for example, even if you set the printing conditions at the beginning of printing, if the temperature of the color photographic paper rises due to the heat of the lamp as printing continues,
If the set conditions remain unchanged, the print density and color balance will change, making it impossible to obtain good prints. Therefore, a photosensitive material that is highly dependent on temperature during exposure cannot be efficiently produced.

Now, in addition to the stability of performance as already mentioned, shortening of printing processing time is also desired in order to accommodate short delivery times.

From the viewpoint of speeding up the processing time, silver bromide, silver chlorobromide, and silver chloride, which do not substantially contain silver iodide, have been used as silver halide emulsions applied to color photographic papers. It is known that silver halide emulsions with a high silver chloride content have a high development speed and are advantageous for rapid processing. However, it is also known that the higher the silver chloride content, the more likely it is to cause fogging and the more difficult it is to obtain high sensitivity. It has been reported that various compounds called photographic stabilizers are useful for compensating for these drawbacks. In particular, mercapto compounds such as those represented by compounds (n), (III), or (IV) of the present invention are excellent in improving the fog of silver halide emulsions with a high silver chloride content. No. 62-269957.

However, it is also known that the adsorption power of spectral sensitizing dyes decreases as the silver chloride content increases, leading to the aforementioned performance fluctuations during the production of color photographic paper and performance fluctuations during product storage. It was also a factor that made it more likely to occur. In particular, pentamethine cyanine dye, which is commonly used for the purpose of spectral sensitization in the red light region in color photographic paper, etc., changes the degree of adsorption depending on the aging of the coating solution prepared during manufacture, resulting in changes in photographic sensitivity. It is known that there are problems such as sensitivity fluctuations when the product is stored for a long period of time. It has also been revealed that mercapto compounds such as those represented by compounds (II), (III), or (IV) of the present invention promote changes in sensitivity (especially desensitization) of the former coating solution over time. .

Techniques for improving the sensitivity fluctuation due to aging of the coating solution when red-sensitive spectral sensitizing dyes are used are already known. Sensitizing dyes are disclosed. However, even with these spectral sensitizing dyes, the effect is not sufficient when using the mercapto compound of the present invention, and in addition, sensitivity fluctuations during storage of the product cannot be sufficiently improved, and temperature changes during exposure It was found that it was not possible to improve the sensitivity change caused by the change in sensitivity. It has also been found that these drawbacks become more noticeable as the silver chloride content of the silver halide emulsion increases.

Further, US Pat. No. 4,513,081 also discloses a spectral sensitizing dye that can improve the desensitization that occurs with aging of a coating solution. However, even the dye described in this patent was not sufficient to improve sensitivity changes during product storage or sensitivity changes due to temperature changes during exposure.

As a result of research conducted by the present inventors in order to solve the above problems, we have developed a spectroscopy system that has excellent stability of the coating liquid over time, excellent performance stability during product storage, and less temperature dependence during exposure. We have discovered a group of compounds represented by general formula (I) as sensitizing dyes. However, when light-sensitive materials were constructed using these sensitizing dyes and practical tests were conducted, it was revealed that they had serious defects. That is, it has been found that the edge portions of the photosensitive material that have been processed and cut develop color during development, resulting in undesirable coloring. Kono'lfr@
zobMthi→-]mi'-kiyol-pigo*;shiro)taino-7;1-go11 nt significantly deteriorates its quality, making it impossible to provide it to the market.

Therefore, there has been a strong desire to develop a silver halide photographic material that is suitable for improving the production efficiency of color prints, is capable of rapid processing, has excellent performance stability, and has excellent edge whiteness. .

(Problems to be Solved by the Invention) As is clear from what has already been stated, the purpose of the present invention is to enable rapid processing, to have excellent manufacturing stability and product storage stability, and to reduce the temperature during exposure. An object of the present invention is to provide a silver halide color photographic light-sensitive material for printing, which exhibits little performance fluctuation due to fluctuations and has excellent whiteness in edge areas.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material comprising at least three types of silver halide emulsion layers having different color sensitivities on a support. The emulsion layer is represented by the following general formula (I): AsJM/++I/1%
Contains a silver halide emulsion, and at least one of the photosensitive emulsion layer or non-photosensitive layer on the support has the following: General formula (n), (III) or (I
Contains at least one compound represented by V), and further has a total silver halide emulsion coating amount of 0.65 g/rr on the support? This is achieved by a silver halide color photographic material having the following characteristics.

In general formula (I), Z represents an oxygen atom or a sulfur atom.

R1 and R2 represent substituted or unsubstituted alkyl groups.

vl, ■2, ■3, v4, V5, ■8, v7 and v8
are hydrogen atom, halogen atom, alkyl group, acyl group, acyloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group, cyano group, hydroxy group, amino group, acylamino group, alkoxy group, alkylthio group, alkylsulfonyl group, respectively. group, a sulfonic acid group, or an aryl group, and v1 to V.

Two that are bonded to adjacent carbon atoms cannot form a fused ring with each other, and each Hammett's σ value is σp+ (t=1 to 8), and Y=σ, 1+σ, 2+σ
, 3+σp4+σ, 5+σ, 6+σ, 7+σ2. When Z is an oxygen atom, Y≦-0,08, and on the other hand, if Z is a sulfur atom, Y≦-0,15.

X represents the charge-balancing counterion and n represents the value required to neutralize the charge.

The alkyl groups, alkyl moieties, carbamoyl groups, sulfamoyl groups, amino groups, aryl groups, and aryl residues listed above or below are all used to include those further substituted.

General Formula (II) In the formula, R represents an alkyl group, an alkenyl group or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor.

The alkali metal atom is, for example, a sodium atom, a potassium atom, etc., and the ammonium group is, for example, a tetramethylammonium group, a trimethylbenzylammonium group, etc. In addition, the precursor is X= under alkaline conditions.
A group formed with H or an alkali metal, such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups.

Substituents for substituted alkyl groups include halogen atoms, nitro groups, cyano groups, hydroxyl groups, alkoxy groups, aryl groups, acylamino groups, alkoxycarbonylamino groups, ureido groups, amino groups, heterocyclic groups, acyl groups, and sulfamoyl groups. , sulfonamide group, thioureido group,
Examples include a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and further a carboxylic acid group, a sulfonic acid group, or salts thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and the substituents of the alkyl group listed above.

General Formula (m) In the formula, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. The alkyl group, alkenyl group and X of R have the same meanings as those in general formula (n).

Specific examples of the divalent linking group represented above are: can be mentioned.

n represents 0 or 1, and R', R', and R1 each represent a hydrogen atom, an alkyl group, or an aralkyl group.

R'' In the formula, R and X have the same meanings as in general formula (IF), and L has the same meaning as in general formula (III).

R' has the same meaning as R, and may be the same or different.

Next, general formula (I) will be explained in detail.

In general formula (I), Z represents an oxygen atom or a sulfur atom.

Preferred alkyl groups for R1 and R2 include unsubstituted alkyl groups having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl, decyl, dodecyl, octadecyl) and substituted alkyl groups [substituents such as carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy groups having 8 or less carbon atoms (e.g., methoxy, ethoxy, benzyloxyphenethyloxy)
, a monocyclic aryloxy group having 15 or less carbon atoms (for example,
phenoxy, P-tolyloxy), acyloxy groups having 8 or less carbon atoms (e.g. acetyloxy, propionyloxy), acyl groups having 8 or less carbon atoms (e.g. acetyl, propionyl, benzoyl), carbamoyl groups (e.g.
carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group having 15 or less carbon atoms (For example, phenyl, 4-chlorophenyl, 4-methylphenyl, α
-naphthyl) and the like).

More preferably unsubstituted alkyl groups (e.g. methyl,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl), sulfoalkyl groups (e.g. 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl)
It is.

Among these, at least one of R and R2 is an unsubstituted alkyl group having 5 to 8 carbon atoms.

Vl, V2, ■8, v4, V5, ■2, ■, and V,
are hydrogen atom, halogen atom -7, (chemical formula 1), respectively.
Unsubstituted alkyl group with a total of 10 or less (e.g. methyl, ethyl), carbon number 18
The following substituted alkyl groups (e.g., benzyl, α-naphthylmethyl, 2-phenylethyl, trifluoromethyl)
, an acyl group having 8 or less carbon atoms (e.g. acetyl, benzoyl), an acyloxy group having 8 or less carbon atoms (e.g. acetyloxy), an alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) , carbamoyl group (e.g.
carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), carboxy group, cyano group, hydroxy basis,
Amino group, acylamino group having 8 or less carbon atoms (e.g. acetylamino), alkoxy group having 10 or less carbon atoms (e.g. methoxy, ethoxy, benzyloxy), 1 carbon number
Alkylthio group of 0 or less (e.g.
A sulfonyl group (eg, methylsulfonyl), a sulfonic acid group, and an aryl group having 15 or less carbon atoms (eg, phenyl, tolyl) are preferred.

Furthermore, preferably a hydrogen atom, an unsubstituted alkyl group (e.g. methyl group), an alkoxy group (e.g. methoxy group)
It is.

The two bonded to adjacent carbon atoms in V and -V cannot form a condensed ring with each other, and each Hammett stretches, and the value is σp+ (t=x~8), and Y=σ3. +
σ, 2+σ, 3+σ, 4+σ, 5+σp6+σ, 7+σ
1. When Z is an oxygen atom, Y≦-0,08, and on the other hand, if Z is a sulfur atom, Y≦-0,15. More preferably, the value of Y is Y≦−0,15 if Z is an oxygen atom.
If Z is a sulfur atom, Y≦−0,30. A particularly preferable value of Y is -0,90≦Y≦- if Z is an oxygen atom
0,17, and if Z is a sulfur atom, -1,05≦Y≦-0
, 34.

Here, σ is "Structure-Activity Relationships of Drugs - Guidelines for Drug Design and Mechanism Research", published by Nankodosha Publishing Co., Ltd., Colvin Hansch (Corwin-Hansch
), by Albert-Leo, “
Substituent Constance Book for Correlation Analysis in Chemistry and Biology J
n5tants for CorrelationAn
Analysis in Chemistry and B
John Wiley and Sons, pp. 69-161
ons) represents the value shown in the company's publication. The method for measuring σ is described in "Chemical Rev"
iews), Vol. 17, pp. 125-136 (1935
year).

According to them, the value of σ is O in the case of a hydrogen atom, -0,17 in the case of a methyl group, and -0,27 in the case of a methoxy group.

Xn is included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye.

Therefore, n can take an appropriate value of 0 or more.

Typical cations are inorganic or organic ammonium ions and alkali metal ions, while anions can be specifically either inorganic or organic anions, such as halogen ions (e.g., fluoride, etc.). ions, chloride ions, bromide ions, iodine ions), substituted arylsulfonate ions (e.g. p-toluenesulfonate ions, p-chlorobenzenesulfonate ions), aryldisulfonate ions (e.g. 1.3-
benzenedisulfonic acid ion, ■, 5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (e.g. methyl sulfate ion)
, sulfate ion, thiocyanate ion, perchlorate ion,
Examples include tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion.

Preferably it is an iodine ion.

Specific examples of the dye represented by general formula (I) of the present invention are shown below. However, it is not limited to these.

(ShiH2hashiri.

The compound represented by the general formula (1) used in the present invention is described by F.M. Hamer [Heterocyclic Compound Cyanine Gui and Related Compounder (Heter)
ocyclic Compounds - Cyani
ne dyesand related Compo
unds-) j Chapter ■, pages 270-287 (John
Willie & Thump John Wiley &amp;
5ons Inc. - New York, London - 1194
6 years), D.M. Star? -(D, M, S
turmer) [Heterocyclic Compounds Special Tobits In Heterocyclic
Chemistry□(Heterocyclic Com
pounds -3special topicsin
heterocyclic chemistry
-) J Chapter 8, Section 4, pp. 482-515 (John Wiley
& 5ons Inc. - New York, London - 11
It can be synthesized based on the method described in, eg.

Jet, a method well known in this field, can be used to add the compound (I) according to the present invention to a silver halide emulsion. Usually, it is dissolved in a water-soluble solvent such as methanol, ethanol, pyridine, methyl cellosolve, acetone, etc. alone or in combination, and added to the silver halide emulsion. It can also be added to a silver halide emulsion by dissolving it in a mixed solvent of the above organic solvent and water.

It may be added at any time during the silver halide emulsion manufacturing process, but it is added either during chemical ripening of the emulsion or after chemical ripening, before or after adding stabilizers and fog suppressants. is preferable.

The amount of compound (1) according to the present invention added is not particularly limited, but is in the range of 1X10-' to 1X10-'' mol per 1 mol of silver halide, preferably 1X10
-' to 5XlO-' moles can be selected.

Additionally, supersensitizers can be used.

Regarding supersensitization, please refer to "Photographic Science φ and Engineering" (Photograph
hic 5science and engineering
ng), Vol. 13, 13-17 (1969), Vol. 18
Volume 418-430 (1974), "The Theory of the Photographic Process", edited by James.
It is known that high sensitivity can be obtained by selecting an appropriate sensitizing dye and supersensitizer.

Although any supersensitizer can be used, compounds of general formula (V) are particularly preferred.

General formula (V) In the formula, D represents a divalent aromatic residue, R3, R4, R
s and Rs are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic group,
It represents a mercapto group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, an alkylamino group, a cyclohexylamino group, an arylamino group, a heterocyclylamino group, an aralkylamino group, or an aryl group.

Yl and Z represent -N= or -CH=, and at least one of them is -N=.

Y! and Z4 have the same meaning as Y, and Z4 have the same meaning.

Next, general formula (V) will be explained in more detail.

D is a divalent aromatic residue (e.g., a single aromatic nucleus residue, a residue of a condensation of at least two aromatic nuclei, a residue of at least two aromatic nuclei directly or an atom or atomic group) Residues of substances bonded via; further specific examples include those having biphenyl, naphthylene, stilbene, and bibenzyl skeletons, and in particular, the following: 2. Those represented by Di are preferred.

Here, M represents a hydrogen atom or a cation (eg, alkali metal ion (Na, etc.), ammonium ion, etc.) that provides water solubility.

D2; However, in the case of D2, at least one of R*, R4, Rs, and R6 has a substituent containing SO+M. M
is the same as before.

R,,R,,R,,R,respectively represent a hydrogen atom, a hydroxy group, an alkoxy group (e.g., methoxy group, ethoxy group, etc.), an aryloxy group (e.g., phenoxy group, naphthoxy group, 0-troxy group, p- sulfophenoxy group, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.)
, heterocyclic groups (e.g., morpholinyl group, piperidyl group, etc.), mercapto group, alkylthio group (e.g., methylthio group, ethylthio group, etc.), arylthio group (e.g., phenylthio group, tolylthio group, etc.), heterocyclylthio group (e.g., benzylthio group, etc.). thiazoylthio group, benzimidazoylthio group, phenyltetrazolylthio group, etc.)
, amino group, alkylamino group (e.g., methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, β-hydroxyethylamino group, di-β-hydroxyethylamino group, β -sulfoethylamino group, etc.), cyclohexylamino group, arylamino group (e.g. anilino group,
o, m- or p-sulfoanilino group, o -, m-,
or p-chloroanilino group, o-, m+, or p-anindino group, 0-1m or p-t-luidino group, o-, m-, or p-carboxyanilino group, hydroxyanilino group, sulfonaphthyl Amino group, o-
, m-, or p-aminoanilino group, 0-acetaminoanilino group, etc.), heterocyclylamino group (e.g., 2-benzothiazolylamino group, 2-pyridylamino group, etc.), aralkylamino group (e.g., benzyl amino group, etc.), aryl group (e.g., phenyl group, etc.)
represents.

In the compound represented by general formula (V), at least one of R8-R6 is an aryloxy group, a heterocyclylthio group,
or a heterocyclylamino group is particularly preferred.

Typical examples of the compound represented by the general formula (V) are listed below, but the invention is not limited thereto.

(V-1)4.4'-bis(2,6-di(benzo(V-
2) Thiazolyl-2-thio)pyrimidine-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt 4,4'-bis[2,6-di(benzo(V-3) (V-4) ) (V-5) (V-6) Thiazolyl-2-amine)pyrimidin-4-ylaminocostilbene-2゜2'-disulfonic acid disodium salt 4.4'-bis[2,6-di(1 -Phenyltetrazolyl-5-thio)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt 4,4'-bis[2,6-di(benzimidazolyl-2-thio)pyrimidine- 4-ylaminocostilbene-2゜2'-disulfonic acid disodium salt 4.4'-bis[2-chloro-6= (2-naphthyloxy)pyrimidine-4-ylamino] biphenyl-2,2'-disulfone Acid disodium salt 4.4'-bis[2,6-di(naphthyl-2-oxy)pyrimidin-4-ylaminocostilbene-2,2'-disulfonic acid disodium salt fV-7) (V-8 ) (V-9) (V-10) (V-11) 4.4'-bis[2,6-di(naphthyl-2-oxy)pyrimidin-4-ylamino] bibenzyl-2,2'-disulfonic acid di Sodium salt 4.4'-bis(2,6-diphenoxypyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.4'-bis(2,6-cyphenylthiopyrimidine- 4-ylamino)stilbene-2,2'-disulfonic acid catrium salt 4.4'-bis(2,6-cyclopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.4'-bis(2,6-dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (V-13) (V-15) (V-16) 4.4'-bis[4 ,6-di(naphthyl-2-oxy)triazin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt 4,4'-bis(4,6-dianilinotriazin-2-ylamino)stilbene -2,2'-disulfonic acid disodium salt 4.4'-bis(2,6-dimercabutopyrimidin-4-ylamino)biphenyl-2,2'-disulfonic acid disodium salt 4.4'-bis[ 4,6-di(naphthyl-2-oxy)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt 4,4'-bis[4,6-di(benzothiazolyl-2-thio) Pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (V-17) (V-18) 4,4'-bis[4,6-di(l-phenyltetrazolyl-2-amino) ) Pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino] bibenzyl-2,2' - Disulfonic acid disodium salt The compound (I) and the compound (V) may be added first or may be added simultaneously. Moreover, compound (1) and compound (V) can also be added in the form of a mixed solution.

Compound (V) is added in a range of 1X10-' to 1X10-' mol, preferably in a range of 5X10-' to 1X10-' mol, per 1 mol of silver halide.Compound (1) A preferable addition molar ratio of (V) can be selected within the range of 1150 to 1O/1.

General formula (■), general formula (III) and general formula (
Specific examples of compounds of LV) are listed below, but the invention is not limited thereto.

(II-1) (n-2) "-3 "-ri [[-7 ■-ta] ■-Hiroshi "-4 -r "-1 II-/ / [-/j) [-/J-) 11-/7) U-/ko) E-7 Hiro) f(-/ 11-7r) ■-/ri ``-ko/ ■-23 ■-2yo) ■-20 E-Koko J-2 Hiro) Ir-, zA Jiang-27) "-Kota [[-31 [-JJ [[-21 "-30 fi-JJ 11-j Hiroshi] [[-31) ■-J7) rl-32) 1 [-17 [-jJ [-Jr ■-4LO ■-≠2 II-a3 "-≠yo) II-4C4i! ■-4L4 1-rt "-!3 ■-yo!) ■-!7) (■-!ko ) [-J'4C) 17-jj) 1-Jr) fl-rri) O-Otsu0) ■-Otsul [-12) X-J H3 1-≦3) [[-jj) [-47 ) ■-≦ri■-Otohiro) ■-Ototsu) ■-+, r) [)-70) ■-ta[-/ top-73) [[-/yo) [-77) [1-10 ) @-12 [-/Hiroshi) [-/ Bu[[-/r) 2H5 III-/ Rikatsu-ko/ π-23 ]-2j @-27) π-20 ■-Kokoishi-Kohiro) Stone -2≦ [-2Ir [-22 [-37 π-33 1[[-3j] llI-37) [1-3゜1])-jko[-3≠) flI-J Otsu@-31 F7' −/ (F-j) (W-j) (W-7) (v-2 (W-≠) (V-+ (w-r (?7-P) (71-// (W-/j ) (W-/r) (V-10) (W-/ko) (+7-/≠) (W-/j) (T7-/7) (17-/ ri) (7F-/r) (IV --〇) (W-2!) (TV-27) (v-22) (W-J/ (17-Kobu (V-2r) (Tv-3o) (T7-33) ←77-j ) General formula (II) used in the present invention, ([[) or (
The compound represented by IV) can be contained in at least one of the light-sensitive emulsion layer or non-light-sensitive emulsion layer constituting the silver halide color photographic light-sensitive material. The amount of these compounds added is i, oxt per mole of silver halide.
o-'~5.0XIO mol is preferable, more preferably 1.0
X10-' to 1.0XIO-2 moles are preferred.

If the amount added is less than the above, the prevention of fogging will not be sufficient, whereas if it is more than the above, it may cause a decrease in sensitivity or a decrease in density due to inhibition of development, which is not preferable.

In the present invention, the total amount of silver halide emulsion on the support is 0.65 glr! Must be below. If a non-light-sensitive emulsion is used in addition to a light-sensitive silver halide emulsion such as a blue-sensitive, green-sensitive or red-sensitive emulsion, it is also included in the total silver halide emulsion.

If the total amount of silver halide emulsion is greater than the above, the edges of the processed and cut photosensitive material will develop unnecessary color during development.
The whiteness of the edges worsens. There is no particular restriction on the lower limit of the total silver halide emulsion, but it can be selected so as to obtain the required maximum color density.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. These light-sensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the light to which the light is exposed - yellow for blue, magenta for green, and cyan for red. By incorporating a so-called color coupler to form, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] Particles with a so-called layered structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, parts with different compositions are joined on the edge, corner, or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
The boundaries may be clear, or may be unclear due to the formation of mixed crystals due to compositional differences, or may have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is present inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized phases can be located inside the particle or on the edges, corners, or faces of the particle surface. One preferred example is one in which part of the corner of the particle is epitaxially grown.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably O, 1μ to 2μ.

The particle size distribution thereof is preferably so-called monodisperse, with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The silver halide grains contained in photographic emulsions are formed in regular shapes such as cubes, tetradecahedrons, or octahedrons.
lar), irregular crystal shapes such as spherical or plate-like, or a combination of these shapes can be used. Moreover, it may be made of a mixture of crystals having various crystal forms.

In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chemie et Ph1sique Ph
otographique (Paul Montel
Publishing, 1967) G, F, Duufin
Author Photographic Emulsion Ch
emistry (published by Focal Press, 19
66), V. L., Zelikman et a.
Making and Coating Photo
graphic emulsion (Focal P
It can be prepared using the method described in (Published by Res Inc., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondral 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.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10<-9> to 1O<-2> mol relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

In the present invention, it is essential that the red-sensitive emulsion layer contains a silver halide emulsion spectrally sensitized with at least one compound represented by the general formula (r). Mixing and using an emulsion spectrally sensitized using a sensitizing dye other than the compound represented by formula (1) in the red-sensitive emulsion layer, or
Compound of general formula (1) and general formula (1) during spectral sensitization
Although other compounds may be used in combination, as the ratio of the compound of general formula (I) that contributes to sensitivity decreases, the effect of the present invention also decreases by that amount.

In the present invention, the emulsions used in layers other than the red-sensitive emulsion layer are also subjected to spectral sensitization for the purpose of imparting sensitivity to the desired wavelength range of light. It is preferable to use a dye that absorbs light in a wavelength range corresponding to the distribution as the spectral sensitizing dye. Spectral sensitizing dyes used at this time include, for example, F, H, Har
mer'Heterocyclic compound
ds -Cyanine dies andrelat
John Wiley
& 5ons [New York, London Co., Ltd., 1964]. Specific examples of compounds are described in the above-mentioned JP-A-62-
Those described in the upper right column of page 22 to page 38 of the specification of JP 215272 are preferably used.

In the present invention, in addition to the compound represented by the general formula (n), (III) or (EV), various compounds or precursors thereof may be added for the purpose of stabilizing photographic performance. Specific examples of these compounds can be found on pages 39 to 7 of the specification of JP-A-62-215272 mentioned above.
Those described on page 2 are preferably used.

The silver halide emulsion used in the present invention is either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grains. It may be something.

The coupler used in the present invention will be described.

The light-sensitive material of the present invention can contain various color couplers. The term "color coupler" as used herein refers to a compound capable of forming a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer.

Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds;
Specific examples of macenta and yellow couplers can be found in Research Disclosure (RD) 17643 (1978
1871.7 (November 1979).

The color coupler used in the present invention preferably has a ballast group or is polymerized so as to be diffusion resistant. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler whose coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

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. No. 2,407.
No. 10, No. 2,875゜057 and No. 3,26
No. 5,506, etc. The use of two-equivalent yellow couplers is preferred for the present invention, and US Pat.
08゜194, No. 3,447,928, No. 3゜933.501, No. 4,022,620, etc., or the oxygen atom separation type yellow couplers, or Japanese Patent Publication No. 10739/1983. , U.S. Pat. No. 4,401.
No. 752, No. 4,326°024, RD18053
(April 1979) British Patent No. 1,425,020, West German Application No. 2.219,917, West German Application No. 2.26
No. 1,361, No. 2,329,587, No. 2.4
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Application Laid-open No. 33812 and Japanese Patent Application Laid-Open No. 62-240965. 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 oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same No. 2゜343
．． No. 703, No. 2,600,788, No. 2,90
No. 8,573, No. 3. 062. No. 653, same No. 3,
No. 152,896 and No. 3936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat. ．． Nitrogen leaving group described in No. 310,619 or No. 4,351,89
Arylthio groups described in No. 7 and WO (PCT) No. 88104795 are preferred. Also European Patent No. 73
．． The 5-pyrazolone coupler having a ballast group described in No. 636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369.879, preferably the pyrazolo[5,1-c]-1,2,4-triazoles described in U.S. Pat. No. 3,725.067, Research Disclosure 24220 ( 1
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
The imidazo [1,2
-b] Pyrazoles are preferred, as described in European Patent No. 119.
Pyrazolo [1°5-b Co. 1.2.4 described in No. 860
-) Riazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat.
No. 212, No. 4゜146.396, No. 4,228
, 233 and 4,296,200 are typical examples. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,80.
No. 1,171, same No. 2. 772. No. 162, No. 2
, No. 895, 826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,77
2,002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, U.S. Pat. No. 2,772,162, U.S. Pat.
No. 58,308, No. 4.126,396, No. 4,
No. 334,011, No. 4.327173, West German Patent Publication No. 3.329,729 and U.S. Pat. No. 4,50
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 0,635 and U.S. Pat.
, No. 622, No. 4,333,999, No. 4,45
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in US Pat. No. 1.559 and No. 4,427,767.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention are represented by the following general formulas (VT), (■), (■), (IX) and (X).

General formula (Vl) General formula (■) General formula (■) Zτ−−Z.

General formula (X) [However, in general formulas (VI) and (■), RIR
2 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, R5 and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R3 together with R2 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring. Yl
, Y2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent. When Yl and Y2 represent a coupling-off group (hereinafter referred to as a leaving group), the leaving group is a coupling-active carbon via oxygen, nitrogen, sulfur or a carbon atom, an aliphatic group, an aromatic group, a heterocyclic group. groups, aliphatic/aromatic or heterocyclic sulfonyl groups, groups that bond with aliphatic/aromatic or heterocyclic carbonyl groups, halogen atoms, aromatic azo groups, etc., and the fatty acids contained in these leaving groups. A group, aromatic or heterocyclic group may be substituted with a substituent permissible in R, and when two or more of these substituents are present, they may be the same or different; Furthermore, R1 may have a permissible substituent.

Examples of aliphatic groups having 1 to 32 carbon atoms for R, R2 and R6 in the cyan couplers of general formula (VI) and general formula (■) include methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-pyridyl group.
-imidazolyl group, 2-furyl group, 6-quinolyl group, etc. These groups can further include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (for example, methoxy groups, 2-methoxyethoxy groups, etc.), aryloxy groups (
For example, 2,4-di-tert-amylphenoxy group,
2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g., 2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g. acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (e.g. dimethyl carbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (e.g., butylsulfamoyl group, etc.), imide group, (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.) , aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, cyan group, carboxy group, nitro group , a sulfo group, a halogen atom, and the like.

In general formula (VI), when R1 and R5 are substitutable substituents, they may be substituted with the optional substituents described for R.

R5 in general formula (■) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group. group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, and the like.

In general formula (VI) and general formula (■), Y and Y
2 each represents a hydrogen atom or a coupling-off group (including a coupling-off atom; the same applies hereinafter), examples of which include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g. , ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4
-chlorophenoxy group, 4-methoxyphenoxy group, 4
-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocallyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g.,
(methanesulfonylamino group, toluenesulfonylamino group, etc.), amide group (e.g. dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g. ethoxycarbonyl (oxy group, benzyloxycarbonyloxy group, etc.)
, aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy groups, etc.), aliphatic or aromatic thio groups (e.g., ethylthio groups, phenylthio groups, tetrazolylthio groups, etc.), imide groups (e.g., succinimide groups, hydantoinyl groups, etc.), Examples include aromatic azo groups (for example, phenylazo groups). These leaving groups may include photographically useful groups.

Preferred examples of the cyan coupler represented by the general formula (VI) or (■) are as follows.

In general formula (VI), R5 is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group.

When R8 and R2 do not form a ring in general formula (VI), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R1 is preferably It is a hydrogen atom.

In the general formula (■), R1 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (■), R5 is preferably an alkyl group having 2 to 15 carbon atoms or a methyl group having a substituent having 1 or more carbon atoms, and examples of the substituent include an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, and an alkyl group. An oxy group is preferred.

In the general formula (■), R3 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In the general formula (■), preferred Ro is a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Yl and Y2 in general formulas (VI) and (■) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (■), Y2 is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom. When n=o in the general formula (VI), Yl is more preferably a norogen atom, and particularly preferably a chlorine atom or a fluorine atom.

In the general formula (■), R7 and R9 represent an aryl group, R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y3
represents a hydrogen atom or a leaving group. The substituents allowed for the aryl group (preferably the phenyl group) of R7 and R9 are the same as the substituents allowed for the substituent R1,
When there are two or more substituents, they may be the same or different. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. Preferred Y3 is a type that leaves off with a sulfur, oxygen, or nitrogen atom, and a sulfur-leaving type is particularly preferred.

In the general formula (■), RIO represents a hydrogen atom or a substituent, and Y4 represents a hydrogen atom or a leaving group. Za, Z
b and Zc are methine, substituted methine N- or -N I
(Represents -, one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond.Zb-Zc
When the bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. This includes the case where a dimer or more multimer is formed with RIO or Y4, and when Za, Zb or Zc is a substituted methine, the case where a dimer or more multimer is formed with the substituted methine.

Among the couplers represented by the general formula (IX), preferred couplers are the following general formulas (]Xa), (IXb), (IXc
), (IXd) and (rXe).

General formula (IXa) General formula (IXb) General formula (IXc) General formula (IXd) General formula (DCe) In general formula (IXa) to (IXe), R16 and R18 are an aliphatic group, an aromatic group, or a hetero Represents a cyclic group, and these groups may be substituted with a permissible substituent for R1. R16, R, 17 and R18 are further RO-1R, C-1RCO-1R8R8O2-1
R3O2NH-1RCNHRNH-1ROCN H-1
A hydrogen atom, a halogen atom, a cyano group, or an imide group may be included. (R represents an alkyl group, an aryl group, and a heterocyclic group) R16, R17, and RlB may further be a carbamoyl group, a sulfamoyl group, a ureido group, or a sulfamoyl group, and the nitrogen atom of these groups is R1
may be substituted with permissible substituents. Also, any one of R16, R17, R18 or Y4 is 2
It may serve as a valent group to form a dimer, or it may serve as a divalent group that connects the polymer main chain and the coupler chromophore.

Preferred R16, R1,7 and R18 are hydrogen atoms,
Halogen atom, aliphatic group, aromatic group, heterocyclic group RO-1
RCONH-1R802NH-1RNH1R8- or ROCONH- group, and preferred Y4 is a halogen atom, an acylamino group, an imide group, an aliphatic or aromatic sulfonamide group, or a 5- or 6-membered group bonded to the coupling active position via a nitrogen atom. nitrogen-containing heterocyclic groups, aryloxy groups, alkoxy groups, arylthio groups, and alkylthio groups.

In general formula (X), R11 represents a halogen atom or an alkoxy group, and R12 represents a hydrogen atom, a halogen atom or an alkoxy group. A is -NHCOR13, -N)I
SO2-R13, -8o2NHR13, C00R13,
-502N-R13.

However, R13 and R14 each represent an alkyl group.

Y5 represents a leaving group. The substituents for R12, R13, and R14 are the same as the substituents allowed for R1, and the leaving group Y5 is preferably represented by the general formula (Xa) to
It is a group represented by (Xg).

General formula (Xa) -0R20 R20 represents an optionally substituted aryl group or heterocyclic group.

General formula (Xb) General formula (Xc) R21,R
22 is a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or Represents a heterocyclic group, and these groups may be the same or different.

General formula (Xd) 0.7N\70 Wl represents a group of nonmetallic atoms necessary to form a 4-, 5-, or 6-membered ring.

In general formula (Xd), preferably (Xe) to (X
g).

General formula (Xe) General formula (Xf) General formula (X g) In the formula, R23 and R24 are each a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, R25, R26 and R27 each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group, and W2 represents an oxygen or sulfur atom.

Specific examples of these couplers include Japanese Patent Application Laid-Open No. 63-11
Although it is described in the specification of No. 939, the following compounds can be more preferably mentioned.

(C-1) (C-4) l (C-5) Ct (C-7) OCH2CH2CH2COOH (C-U) (C-9) (t)c5H,.

(C-10) Ct (C-1 (C-12) (C-13) (tJC, H, 3 (C- (C-15) Ct (C-16) (C-18) (C-In t OCH2CHC4H9 ■ 2H5 (C-20) (C-21) (C-22) OCR.

(M-:S) α Hs (M-7) (Ni-0) (M-!l) C1(.

CH.

(M-10) (M-11) (M-12) ShiH3 C@H, □(1) C8H1+(t) bond (M-14) (M-15) CH3 \ CH3 \ Bond-16) Bond-17) bond (Y-1) CH.

(Y-3) (Jl-1 (Y-4) (Y-5) (Y (Y-7) (Y-8) Couplers represented by the above general formulas (VI), (■) and (■) is usually 0.1 to 1.0 mole per mole of silver halide in the 710 silver germide emulsion constituting the photosensitive layer.
Preferably it is contained in an amount of 0.1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
) 2 to 20 and a high boiling point organic solvent and/or water-insoluble polymer compound having a refractive index (25° C.) of 1.3 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) W w2-o-p=.

W.

General formula (B) -Coo-W2 General formula (E) w, -o-W.

(In the formula, W, W, and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W is W, , O
represents W or S-W, n is an integer from ■ to 5, and when n is 2 or more, W4 may be the same or different from each other, and in the general formula (E), Wl and W2 are may form a fused ring).

The high boiling point organic solvent used in the present invention has a melting point of 100°C or less and a boiling point of 140°C, even if other than those of general formula (A) or E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), phenols (e.g. 2,4-di(1)amylphenol), etc. Examples include high-boiling organic solvents with a boiling point of 160°C or higher.

In addition, as a water-insoluble polymer compound, for example,
Examples include compounds described in Columns 18 to 21 of No. 18978, vinyl polymers (including homopolymers and copolymers) containing acrylamides and methacrylamides as one heptamer component.

More specifically, for example, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate,
Examples include polycyclohexyl methacrylate and poly t-butylacrylamide. In addition to these high boiling point organic solvents and/or water-insoluble polymer compounds, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, and methyl cellosolve acetate. boiling point 30℃~15
Organic solvents with a low boiling point of 0° C. can be used alone or in combination as required.

In the present invention, an ultraviolet absorber can be added to any layer. Preferably, an ultraviolet absorber is contained in the layer containing the compound represented by formula (VI) or (■) or in an adjacent layer. The ultraviolet absorber that can be used in the present invention is a compound listed in Item 0 of Research Disclosure No. 17643, preferably the following general formula (
It is a benzotriazole derivative represented by XI).

In the formula R2,, R, 1R,. , R11 and R+2 are the same -
or may be different: hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, acyloxy group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group , represents a 5- or 6-membered heterocyclic group containing an oxygen atom or a nitrogen atom, and Rs + and R3
2 may be ring-closed to form a 5- or 6-membered aromatic ring consisting of carbon atoms. Among these groups, those having a substituent may be further substituted with a substituent permissible for R1.

The compounds represented by the above general formula (XI) can be used alone or in combination of two or more.

The method of synthesizing the compound represented by the general formula (XI) and other examples of compounds are described in Japanese Patent Publication No. 44-29620, Japanese Patent Application Laid-open No. 151149-1982, Japanese Patent Application Laid-open No. 95233-1989, and U.S. Patent No. 3,766° No. 205, EPOO5716
No. 0, Research Disclosure
Disclosure) No. 22519 (1983,
Nα225) is described in JP-A No. 61-190537. Also, Japanese Patent Application Publication No. 58-111942, Japanese Patent Application No. 1983
No. 7-61937, No. 57-63602, No. 57-1
It is also possible to use the high molecular weight ultraviolet absorbers described in No. 29780 and No. 57-133371. It is also possible to use a combination of low-molecular and high-molecular ultraviolet absorbers.

The above-mentioned ultraviolet absorber, like the coupler, is dissolved in a single or mixed solvent of a high-boiling point organic solvent and a low-boiling point organic solvent, and is dispersed in a hydrophilic colloid.

Although there are no particular limitations on the amounts of the high-boiling organic solvent and the ultraviolet absorber, the high-boiling organic solvent is usually used in an amount of 0% to 300% based on the weight of the ultraviolet absorber.

It is preferable to use compounds that are liquid at room temperature alone or in combination.

In the coupler combination of the present invention, the general formula (XI)
When used in combination with an ultraviolet absorber, it is possible to improve the storage stability, especially the light fastness, of colored dye images, especially cyan images. This ultraviolet absorber and cyan coupler may be co-emulsified.

The amount of ultraviolet absorber applied may be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably 1XIO-' mol/n (~2
It is set in the range of 1.5 x 10-'' mol/d.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In order to improve the storage stability of chromogenic dye images, especially yellow and magenta images, various organic and metal complex fading inhibitors can be used in combination. Organic anti-fading agents include hydroquinones, gallic acid derivatives, p~
There are alkoxyphenols, p-oxyphenols, etc., and patents for dye image stabilizers, stain inhibitors, and antioxidants are cited in Research Disclosure No. 17643, Items I to 5. Further, metal complex type antifading agents are described in Research Disclosure No. 15162 and the like.

In order to improve the heat and light fastness of yellow images, a number of compounds belonging to the group of phenols, hydroquinones, hydroxychromans, hydroquine coumarans, hindered amines and their alkyl ether, silyl ether or hydrolyzable precursor derivatives are used. However, the compounds represented by the following general formulas (X■) and (XIX) can be used to simultaneously improve the light fastness and heat fastness for the yellow image obtained from the coupler of the general formula (■). It is valid.

[In the above general formula (X■) or (XIX), Rto is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a substituted silyl group, and RI2 may be the same or different, and each is an aliphatic group. group, aromatic group, aliphatic oxy group, or aromatic oxy group, and these groups may have a permissible substituent for R1. R40, R+2, R45, R41 and R1
1 can be the same or different (respectively, hydrogen atom,
It represents an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a mono- or dialkylamino group, an imino group and an acylamino group. R46, R17, Rt1 and R49 may be the same or different (represent a hydrogen atom and an alkyl group, respectively. or represents an aromatic sulfinyl group, an oxy radical group, or a hydroxyl group. A represents a nonmetallic atomic group necessary to form a 5-, 6-, or 7-membered ring.] General formula (X■) or ( XIX) or examples of compounds other than those listed above are described in British Patent No. 13268.
No. 89, No. 1354313, No. 1410846, U.S. Pat. No. 3,336,135, U.S. Pat.
No. 114036 and No. 59-5246.

Two or more of the compounds represented by formulas (X■) and (XIX) may be used in combination, and may also be used in combination with a conventionally known antifading agent.

The amount of the compound represented by the general formulas (X■) and (XIX) varies depending on the type of yellow coupler used in combination, but is 0.5 to 200% by weight based on the yellow coupler.
, preferably in the range of 2 to 150 weight 96 to achieve the desired purpose. Preferably, it is co-emulsified with a yellow coupler of general formula (X).

The various dye image stabilizers, stain inhibitors, or antioxidants described above are also effective in improving the storage stability of the magenta color-forming dyes of the couplers represented by formulas (■) and (IX) of the present invention. , the following general formula % Formula %) The compound groups represented by (XXIV) and (XXV) are particularly preferred because they greatly improve light fastness.

General formula (X In the general formulas (XX) to (XXV), R6
゜ has the same meaning as R40 in general formula (X■), Re +,
R02, R61 and Ras may be the same or different (respectively hydrogen atom, aliphatic group, aromatic group, acylamino group, mono- or dialkylamino group, aliphatic or aromatic, aromatic thio group, acyl .

Represents an amino group, an aliphatic or aromatic oxycarbonyl group, or -OR=o. Rho and Rat may be bonded to each other to form a 5- or 6-membered ring.

Furthermore, R81 and R'62 may form a 5- or 6-membered ring. X represents a divalent linking group. R68 and Rs t may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a hydroxyl group. R6,
represents a hydrogen atom, an aliphatic group or an aromatic group. Rs a
and R47 may form a 5- or 6-membered ring together. M is CuSCo, Ni.

Represents Pd or pt. When the substituents from Rat to Ram are aliphatic groups or aromatic groups, R may be substituted with the permissible substituents. n represents an integer from zero to 3, m represents an integer from zero to 4, and R
It means the number of substitutions of 62 or Rs +, and when these are 2 or more, Ra or Rs + may be the same or different. ] In general formula (XXIV), preferable X is -CH-
CH.

Rt.

-CHCH2 Rt.

-CH.

CH2 -CH-CH2 Rt.

are listed as representative examples, where R7° represents a hydrogen atom or an alkyl group.

In general formula (XXV), preferable Rat is a hydrogen-bonded vine group. Compounds in which at least one of the groups represented by Rs 2, Rs s and R84 is a hydrogen atom, hydroxyl group, alkyl group or alkoxy group are preferred, and the substituents R61 to R6I each have a total carbon atom content of It is preferable that it has 4 or more substituents.

These compounds are described in US Pat. Nos. 3,336,135 and 343.
No. 2300, No. 3573050, No. 3574627, No. 3700455, No. 3764337, No. 3935
No. 016, No. 3982944, No. 4254216,
British Patent No. 4279990, British Patent No. 1347556, British Patent No. 2062888, British Patent No. 206 '6975, British Patent No. 207
No. 7455, JP-A-60-97353, JP-A-52-
No. 152225, No. 53-17729, No. 53-20
No. 327, No. 54-145530, No. 55-6321
No. 55-21004, No. 5B-24141, No. 59-10539, Japanese Patent Publication No. 48-31625 and Japanese Patent Publication No. 54-12337 also describe synthetic methods and compounds other than the above.

Among the antifading agents advantageously used in the present invention, (XX)
The compounds represented by the general formulas (XXIV) to (XXIV) have a molecular weight of 10 to 200 relative to the magenta coupler used in the present invention
It is added in an amount of mol %, preferably 30 to 100 mol %. On the other hand, the compound represented by the general formula (XXV) is added in an amount of 1 to 100 mol %, preferably 5 to 40 mol %, based on the magenta coupler used in the present invention. Preferably, these compounds are co-emulsified with magenta couplers.

To prevent fading, for example, JP-A-49-11330,
JP-A No. 50-57223 discloses a technique of surrounding a dye image with an enzyme blocking layer made of a substance with low oxygen permeability, and JP-A No. 56-85747 discloses a technique for enclosing a dye image on the support side of a color image forming layer of a color photographic light-sensitive material. Oxygen permeability is 20i/rr?・hr-a
It is disclosed that a layer below .tom is provided and is applicable to the present invention.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (Q) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (R) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (Q) has a second-order reaction rate constant with p-anilidine of 2 (in trioctyl phosphate at 80°C) of 1. O1/mol・sec N1xlo-
This is a compound that reacts in the range of J/mol 5 seconds.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (Q) can be represented by the following general formula (QI) or (QII).

General formula (QI) R1-(A), -X General formula (Qn) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents the addition of an aromatic amine developing agent to the compound of general formula (QI[). Represents a promoting group. Here R1 and X1Y
and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (QI) and (Qn), see JP-A-63-158545 and JP-A-62-28.
No. 3338, Patent Application No. 158342-1982, Patent Application No. 1983
Those described in specifications such as No.-18439 are preferred.

On the other hand, a more preferable compound (R) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (R1 ).

General formula (RI) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (Gl), Z is Pearson's nucleophile 'CH3I
Value (R,G,Pearson,eta 1,,
J, Am, Chem, Soc,,90. 31
9 (1968)) is preferably 5 or more, or a group derived therefrom.

Specific examples of the compound represented by the general formula (R1) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-Open No. 1430-1982.
No. 48, No. 62-229145, patent application No. 63-184
No. 39, No. 63-136724, No. 62-21468
1, No. 62-158342, etc. are preferred.

Further, details of the combination with the above-mentioned compounds (R) and (Q) are described in European Patent Publication No. 277589.

The photosensitive material produced according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

The dye preferably applied to the present invention has the general formula (
DI) to (DI[I).

General formula (DI) In the formula, Zl and Z2 may be the same or different from each other and represent a group of nonmetallic atoms necessary to form a heterocycle,
L represents a methine group, and n represents 0.1.2 or 2.

The heterocycle formed by Zl and the nonmetallic atom group represented by Zl is preferably a 5- or 6-membered ring, and may be a single ring or a fused ring, such as a 5-pyrazolone ring, barbylic acid, isoxacilone, thiobarbylic acid, rhodanine,
Examples include heterocycles such as imidazopyridine, pyrazolopyrimidine, and pyrrolidone. These rings may be further substituted.

The heterocycle formed by Zl or Z2 is preferably a 5-pyrazolone ring or barbylic acid having at least one sulfonic or carboxylic acid group.

For example, British Patent No. 506°385, British Patent No. 1,177.4
No. 29, No. 1,311.884, No. 1,338,79
No. 9, No. 1゜385.371, No. 1,467.214
No. 1.433,102, No. 1,553,516, JP-A-48-85.130, No. 49-114゜42
No. 0, No. 55-161.233, No. 59-111.6
No. 40, U.S. Patent No. 3. 247. No. 127, 3,
Nos. 469,985 and 4,078°933, etc., describe oxonol dyes having pyrazolone nuclei or barbyl nuclei.

The methine group represented by L includes embodiments having a substituent (for example, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, or a halogen atom such as a chloro atom), and also includes embodiments in which L is bonded to each other. may form a ring (for example, 4,4-dimethyl-1-cyclohexene).

General formula (DII) In the formula, Rsl, R84, R"5 and R8g may be the same or different from each other, and each represents a hydrogen atom, a hydroxy group,
The alkoxy group, aryloxy group, and carba R' may be the same or different and represent an alkyl group or aryl group having a hydrogen atom and at least one sulfonic acid group or carboxyl group.

R82, R13, R''o, J: and R17 may be the same or different and each represents a hydrogen atom, a sulfonic acid group, a carboxyl group, and an alkyl group or aryl group having at least one sulfonic acid group or carboxyl group. represents a group.

General formula (D) CA ) or general formula (D I[I) (B) In the formula, RQ Q and R'' may be the same or different and represent a substituted or unsubstituted alkyl group.

I-XL2 and L1 may be the same or different (represent a substituted or unsubstituted methine group as described above, and m represents 0, ■, 2 or 3).

z and z' may be the same or different and represent a nonmetallic group necessary to form a substituted or unsubstituted 5-membered or 6-membered hetero ring, and! and n is 0 or 1.

Xe represents an anion. P represents 1 or 2, and P is 1 when the compound forms an inner salt.

U.S. Patent No. 2,843.486 and U.S. Patent No. 3,294.53
No. 9 etc., details of the above cyanine dyes are described.

Seratin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

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

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (R,). The coefficient of variation of the occupied area ratio (%) is the standard deviation S of R+ with respect to the average value ('R) of R1.
It can be determined by the ratio S/decay. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform".

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. For example, British Patent No. 685475, U.S. Patent No. 2675316, U.S. Patent No. 2839401, U.S. Patent No. 2882156, U.S. Patent No. 304
No. 8487, No. 3184309, No. 3445231, West German Patent Application (OLS) No. 1914362, JP-A-5
Polymers described in 0=47624, 50-71332, etc. can be used.

The photosensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include U.S. Pat.
No. 7, No. 2403721, No. 2418613, No. 2
No. 675314, No. 2701197, No. 270471
No. 3, No. 2728659, No. 2732300, No. 2
No. 735765, JP-A-50-92988, JP-A No. 50-
No. 92989, No. 50-93928, No. 50-110
No. 337, No. 52-146235, Special Publication No. 50-23
It is described in No. 813, etc.

Furthermore, depending on the case, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, or chloride with an average grain size of 0.20 μm or less) may be included in the silver halide emulsion layer or other hydrophilic colloid layer. A silver oxide emulsion) may also be added.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline. , 3-methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium polon hydride. , auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1
, l-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N.

Representative examples include N-tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The amount of replenishment of these color developing solutions and black and white developer depends on the color photographic light-sensitive material to be processed, but is generally 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 500ml. You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the opening area of the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment or may be carried out separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Further, a fixing treatment can be performed before the bleach-fixing treatment, or a bleaching treatment can be performed after the bleach-fixing treatment depending on the purpose. Examples of bleaching agents include iron (■), cobalt (IV), and chromium (
IV) Compounds of polyvalent metals such as M (II), peracids,
Quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide, dichromate, and iron (III).
) or organic complex salts of cobalt(III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l
, Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts and persulfates of citric acid, tartaric acid, and malic acid,
Bromates, permanganates, nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (I[[) salts and persulfates, including iron(III) ethylenediaminetetraacetate salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron aminopolycarboxylate (
III) Complex salts are particularly useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, West German Patent Box 1
, No. 290,812, No. 2,059°988, JP-A No. 53-32,736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72,623, No. 53
-95,630, 53-95.631, 53-
No. 104,232, No. 53-124,424, No. 53
-141.623, 53-28.426, Research Disclosure Nα17,129 (1978
Compounds having a mercapto group or disulfide group as described in JP-A-50-140.129; Japanese Patent Publication No. 45-8,506;
Thiourea derivatives described in JP-A No. 52-20.832, JP-A No. 53-32,735, and U.S. Pat.
Iodide salts described in West German Patent Box No. 16゜235; polyoxyethylene compounds described in West German Patent Box No. 966゜410 and West German Patent Box No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 8,836/1983: Other patents Kaisho 49-42.434,
No. 49-59,644, No. 53-94,927, No. 54-35,727, No. 55-26,506, No. 5
Compounds described in No. 8-163,940; bromide ions, etc. can be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent No. 1,290,81.
No. 2, JP-A No. 53-95,630 is preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Volume 64, P, 248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photographic light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131,632/1988 can be used very effectively. Also, JP-A-57-8゜5
Chlorinated disinfectants such as isothiazolone compounds and cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in No. 42, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microorganisms" by Hygiene Technology sterilization, sterilization,
It is also possible to use the fungicides described in "Anti-fungal Technology" and "Encyclopedia of Antibacterial and Antifungal Agents" published by Japan Antibacterial and Antifungal Science.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40°C. A range is selected. Further, the photosensitive material of the present invention can be directly processed with a stabilizing solution instead of the above-mentioned washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 58-14
．． All known methods described in No. 834, No. 60-220,345 can be used.

Furthermore, subsequent to the water washing treatment, a further stabilization treatment may be performed. A chelating agent or a fungicide can also be added to this stabilizing bath. The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can be reused in a process such as a desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may contain various types of l-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. A typical compound is disclosed in JP-A-56-64. ．． No. 339, 57-144, 54
No. 7 and No. 58-115,438.

Various treatment liquids in the present invention are used at 10 to 50°C. Normally, the standard temperature is 33-38℃,
It is possible to increase the temperature to accelerate the processing and shorten the processing time, or conversely to improve the image quality and stability of the processing solution by increasing the temperature to a lower temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2226.770 or U.S. Patent No. 3,6
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 74°499 may also be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary (Examples) The present invention will be specifically described below according to Examples. However, the present invention is not limited to these.

Example 1 32 g of lime-treated gelatin was added to 1000 ml of distilled water and dissolved at 40°C, then 11.6 g of sodium chloride was added and the temperature was raised to 70°C.

To this solution was added 2,000 ions of N,N'-dimethylimidazolidine (1% aqueous solution). 2r+l was added.

Next, a solution prepared by dissolving 32 Og of silver nitrate in 200 ml of distilled water, 21.7 g of potassium bromide and 0 sodium chloride were added.
．． Dissolve 32g in 200ml of distilled water and heat at 70°C.
The mixture was added to the above solution and mixed over 40 minutes while maintaining the temperature.

Furthermore, a solution of 128.0 g of silver nitrate dissolved in 560 ml of distilled water, 66.4 g of potassium bromide, and 11 g of sodium chloride were added.
．． 5 g and potassium hexachloride iridium(IV) 0.
03■ dissolved in 560 ml of distilled water at 70°C.
The mixture was added and mixed for 25 minutes while maintaining the temperature. Five minutes after the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed, the temperature was lowered to 40°C, and desalination and water washing were performed.

Furthermore, after adding lime-treated gelatin to adjust the pH and pAg, thylethylthiourea was added to perform optimal chemical sensitization.
was added to perform spectral sensitization. The resulting emulsion had an average grain size of 0.88μ and a coefficient of variation of grain size distribution of 0.06.
of cubic silver chlorobromide grains. This was designated as emulsion (A).

Emulsion (A) can be prepared by changing the amount of added chemicals, addition time and reaction temperature from (B) to (
Emulsions up to F) were obtained. However, emulsion (B) is emulsion (A
) was spectrally sensitized using the same < (Dye-1), and both were used as a blue-sensitive emulsion. In addition, emulsion (C) and emulsion (D) are spectral sensitizing dye (Dye-2-1) and (Dy
e-2-2) and used as a green-sensitive emulsion. Furthermore, emulsion (E) and emulsion (F) were spectrally sensitized using a spectral sensitizing dye (Dye-3), and both were used as red-sensitive emulsions.

The shape, average halogen composition, average grain size, and coefficient of variation of grain size distribution of emulsions (A) to (F) are as follows:
Shown in the table.

Table 1: For blue-sensitive emulsions (Dye O1 (3°X10 4 mol per mol of silver halide) For green-sensitive emulsions (Dye-2-1) (2°Xl0-' mol per mol of silver halide) (Halogenated For red-sensitive emulsions (Dye-3 groupings 2) (6.1X10-' moles per mole of silver halide), for red-sensitive emulsions the following The compound was added at 2.3 x 10-'' moles/% silver halide.

In addition, 4-hydroxy-6 is added as a stabilizer to each emulsion.
-Methyl-1,3,3a,7-titrazaindene was used.

A first shoe coating solution was prepared as follows.

Yellow coupler (Ex-Y) 19. 1 g, anti-fogging agent (Cpd-1) 0.17 g and color image stabilizer (
Cpd-2) 1.91g, ethyl acetate 30°0ml, solvent (Solv-1) 3.8ml and solvent (Solv-1)
2) Add and dissolve 3.8 ml of 10% sodium dodecylbenzene sulfonate.
It was added to 135 ml of 0% gelatin aqueous solution and stirred vigorously to emulsify and disperse.

The thus obtained emulsified dispersion of yellow coupler and the previously obtained silver halide emulsions (A) and (B) were mixed and dissolved to prepare a coating solution.

Coating solutions for the second to seventh layers were also prepared in the same manner. These coating solutions were coated on a paper support laminated on both sides with polyethylene in the layer structure and composition shown below to produce multilayer color photographic paper.

The composition of each layer is shown below.

The numbers represent the coating amount (g/rt?), and the silver halide emulsion represents the coating amount in terms of silver.

(Layer structure) Paper support laminated on both sides with polyethylene support [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) Silver halide emulsion ( A) 0.09 silver halide emulsion (B) 0.21 gelatin
1.28 yellow coupler (E
xY) 0.68 antifoggant (Cpd-1
) 0.006 color image stabilizer (Cpd-2)
o, 07 solvent (So 1 v-, 1)
0. 12 solvent (So 1v-2)
0. 12 Second layer (color mixture prevention layer) Gelatin 1.34 Color mixture prevention agent (Cpd-3) Solvent (Solv-3) Solvent (So'1v-4) Third layer (green-sensitive layer) Silver halide emulsion (C) Silver halide emulsion (D) Gelatin magenta coupler (ExM-1) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7 ) Solvent (Solv-3) Solvent (Solv-5) Fourth layer (ultraviolet absorption layer) Ceratin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-3) Solvent (Solv-6) Fifth layer (red feeling layer) 0, 04 o, i.

0, 10 0.075 0,05 1,47 0, 32 0,　l　0 0,08 0,03 0, OO4 0, 25 0,40 Silver halide emulsion (E) Silver halide emulsion (F) gelatin Cyan coupler (ExC-1) Cyan coupler (ExC-2) Color image stabilizer (Cpd-2) Antifoggant (Cpd-1) Color image stabilizer (Cpd-5) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-8) Solvent (Solv-1) Sixth layer (ultraviolet absorption layer) gelatin Ultraviolet absorber (UV-1) Solvent (Solv-6) Seventh layer (protective layer) gelatin polyvinyl alcohol acrylic Modified copolymer (degree of modification 17%) liquid paraffin 0,06 0, 14 0,85 0, I3 0, 15 0, 25 0,008 0,004 0,007 0,067 0, 16 0, 38 0, 13 0,06 1, 25 0,05 0,02 (ExY) Yellow coupler (ExM-1) Magenta coupler (ExC-1) cyan coupler (Cpd-1) Antifoggant (Cpd-2) color image stabilizer 11i CH, -C field 1 CONHC, Hs(t) Average molecular weight: 60° (Cpd-3) Color mixing prevention agent (Cpd-4) color image stabilizer (Cpd-5) color image stabilizer (cpa-e) color image stabilizer (Cpd-7) color image stabilizer (Cpd-8) color image stabilizer C* Hs (j) C*He(I) 4:2:5 mixture (weight ratio) of (UV-1) UV absorber 12: 10:3 mixture (weight ratio) (Solv-1) Solv. Medium (Solv-2) Solv. Medium (Solv-3) Solv. Medium (Solv 4) Melt Medium (Solv-5) Solv. Medium (Solv-6) Medium C00CH,CHC,H.

2H5 As a gelatin hardening agent for each layer, 1-oxydi-3,5-
Dichloro-5-triazine sodium salt and 1,2-
Bis(vinylsulfonyl)ethane was used in combination.

Further, the following dyes were used as dyes for preventing irradiation.

The sample thus obtained is designated as 101. In contrast to sample 101, 12 types of color photographic papers up to sample 112 were prepared by changing the compositions of the spectral sensitizing dye for red-sensitive emulsion, the stabilizer, and the third layer as shown in Table 2.

Red-sensitive spectral sensitizing dye comparison = 1 Red-sensitive spectral sensitizing dye comparison-2 (ExM-2) Magenta coupler! (ExM-3) Magenta coupler (Cpd-10) Color image stabilizer (Cpd-11) Color image stabilizer (Solv-7) Solvent The following tests were conducted to investigate the photographic properties of these coated samples.

Gradation exposure for sensitometry was applied to each sample through a red filter and an optical wedge using a photosensitive needle (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of the light source: 3200 K). The exposure amount at this time was 250 CMS, and the exposure time was 1/10 seconds.

The exposed sample was subjected to color development using an automatic processor using the processing steps and processing solution shown below, and the cyan color density was measured using a densitometer to obtain a so-called characteristic curve. From this result, the overlap density and relative sensitivity were determined. However, the relative sensitivity is defined as the reciprocal of the exposure amount that gives a density 0.5 higher than the overlap density, and is expressed as a relative value.

In addition, for the purpose of testing stability during manufacturing, the temperature was 40°C after preparation.
A sample was also prepared using the coating solution for the fifth layer, which had been aged for 8 hours, and the decrease in sensitivity was investigated.

Furthermore, in order to investigate changes in photographic performance when the samples were stored for a long period of time, similar tests were conducted on samples that had been stored for 4 months at 25° C. and 60% RH.

Next, in order to investigate the change in sensitivity due to temperature fluctuations during exposure, we investigated the difference between the sensitivity of the sample exposed under the conditions of 15°C and 60% RH and the sensitivity of the sample exposed under the condition of 35°C and 60% RH. I asked for

Then, in order to examine the whiteness of the edges of the cut samples, each sample was cut using a DOI ROLL PAPER CUTTER 210.
After cutting 20 sheets at a time and processing them in an unexposed state, they were bundled and visually observed. The evaluation was based on the following criteria.

Edge whiteness observation results evaluation ◎ Almost no coloration is observed. ○ Recognized by observation with a magnifying glass △　Clearly visible to the naked eye × Significantly recognized These results are shown in Table 3.

The treatment process and treatment solution are as follows.

Processing process Hoshi-Sho Gakuen color development 38°CI min 40 seconds Bleach-fixing 35°C 60-second rinse■ 33-35°0 20-second rinse■
Rinse for 20 seconds at 33~35°C Dry for 20 seconds at 33~35°C 70~
80°C for 50 seconds The composition of each treatment solution is as follows.

Tate Nijiya image liquid water diethylene triamine pentaacetic acid nitrilotriacetic acid ■-Hydroxyethylidene-1゜1-diphosphonic acid benzyl alcohol diethylene glycol Sodium sulfite Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline/sulfate Hydroxylamine/sulfate optical brightener (manufactured by WHITEX 4B) Add water to pH (25℃) 800ml 1.0g 2.0g 2.0g 6ml 10mj! 2,0g 0,5g 0g 5,5g 2,0g 1.5 1000m1 10.20 Weekly Kotoyokasui 400rr
l Ammonium thiosulfate (70%) 80ml Sodium sulfite 24g Iron ethylenediaminetetraacetate (■) Ammonium 30g Disodium ethylenediaminetetraacetate 5 Add water
1000ml pH (25°C)
6.50 Rinse liquid ion exchange water (calcium, magnesium each 3ppm
(below) As is clear from the results, in samples 106 and 107 that used the sensitizing dye (comparison-2), there was little decrease in sensitivity due to aging of the coating solution even when the stabilizer lll-1 was used in combination, but when the samples were kept for a long time. The sensitivity decreases significantly when stored for a period of time, and the sensitivity fluctuates greatly when the exposure temperature changes. On the other hand, sample 104 and sample 105 using sensitizing dye (comparison-1)
When stabilizer 1-1 is used in combination, the decrease in sensitivity when the sample is stored for a long period of time is small, but the decrease in sensitivity due to aging of the coating solution is large, and the change in sensitivity is also large when the exposure temperature changes. By using the spectral sensitizing dye of the general formula (I) of the present invention in combination with the stabilizer of the general formula (II), (I[I) or (IV), it is possible to reduce fogging and improve the stability of the coating solution over time. It is possible to obtain an excellent color photographic paper which exhibits little decrease in sensitivity, has little decrease in sensitivity even after long-term storage, and has little change in sensitivity due to temperature changes during exposure. However, unless the total amount of coated silver halide emulsion is less than 0.65 g/rrr, the whiteness of the edge portion will be poor and it will not be practical.

Sample 102, Sample 103, Sample 109 and Sample 111 in which the total amount of coated silver halide emulsion is 0.65 g/d or less
showed excellent results across all performance categories. However, the maximum color density of sample 111 was slightly lower than that of the other samples.

Example 2 32 g of lime-treated gelatin was added to 1000 ml of distilled water and dissolved at 40°C, then 5.8 g of sodium chloride was added and the temperature was raised to 75°C. In this solution, N, N'-
3.8 ml of dimethylimidazolidine-2-thione (1% aqueous solution) was added. Next, add 6.4 g of silver nitrate to 1 part of distilled water.
A solution of 80 ml of sodium chloride and a solution of 2.2 g of sodium chloride dissolved in 180 m of distilled water were mixed together at 75°C.
The mixture was added to the above solution and mixed for 0 minutes. Furthermore, silver nitrate 1
A solution obtained by dissolving 53.6 g of sodium chloride in 410 ml of distilled water and a solution of 52.8 g of sodium chloride dissolved in 410 ml of distilled water were added and mixed over 35 minutes while maintaining the temperature at 75°C.

After the addition of silver nitrate aqueous solution and sodium chloride aqueous solution, 5
After being maintained at 75°C for a minute, the temperature was lowered to 40°C, followed by desalting and washing with water. Furthermore, lime-treated Seratin was added to adjust the pH and pAg, and then the spectral sensitizing dye (Dye
-1) and (Dye-4), average particle size 0.05
A fine-grain silver bromide emulsion of μ was ripened by adding 0.7 mol equivalent of 4-hydroxy-6-methyl-L 3+ 3a, 7-titrazaindene and triethylthiourea to obtain emulsion (G). The resulting emulsion had an average grain size of l, 12
It contained cubic silver chlorobromide (containing 0.7 mol of silver bromide) grains with a particle size distribution coefficient of variation of 0.07.

For emulsion (G), the following emulsions (H) and (I) were obtained by changing the amount of added chemicals, addition time, and reaction temperature. However, emulsion (H) was spectrally sensitized using spectral sensitizing dyes (Dye-2-1) and (Dye-2-2) and used as a green-sensitive emulsion. And emulsion (
1) was spectrally sensitized using a spectral sensitizing dye (Dye-3) and used as a red-sensitive emulsion.

The shapes, average halogen compositions, average grain sizes, and coefficients of variation of grain size distributions of emulsions (G) to (I) were determined using the following fourth formula.
Shown in the table.

When examining the X-ray diffraction patterns of these emulsion grains, we found that
In addition to the main peak corresponding to 100 mol% silver chloride, the emulsion (
G) has a weak sub-peak corresponding to 80 mol% silver chloride (20 mol% silver bromide), while emulsion (H) has a subpeak of 72 mol% silver chloride.
A weak sub-peak corresponding to mol % (silver bromide 28 mol %) was observed, and in emulsion (1) a weak sub-peak corresponding to silver chloride 61 mol % (silver bromide 39 mol %) was observed. Ta.

For blue-sensitive emulsions (Dye-1) (CH2)4 (CH2), SO,H-N (C,Ha)s ■ per mole of silver halide.

6×10 4 moles (Dye-4) SO; SOa　H”N　(C2H6)- per mole of silver halide 1゜ 6×10 4 moles For green-sensitive emulsion (Dye-2-1) (Dye-2 per mole of silver halide 7゜ 0x10 5 moles For red-sensitive emulsion (Dye-3) For red-sensitive emulsions, Halogenate the following compounds 2° per mole of silver oxide 5X1O'' moles were added.

Using the thus obtained silver halide emulsions (G), ()I) and (I), an emulsified dispersion of a color coupler prepared in the same manner as in Example 1 was mixed and dissolved to prepare a coating solution. These coating solutions were coated on a paper support laminated on both sides with polyethylene in the layer structure and composition shown below to produce multilayer color photographic paper.

The composition of each layer is shown below.

The numbers represent the coating amount (g/rrr), and the silver halide emulsion represents the coating amount in terms of silver.

(Layer structure) Paper support laminated on both sides with polyethylene support [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) Silver halide emulsion ( G) 0.25 gelatin 1.0 yellow coupler (ExY) 0.63 color image stabilizer (C
pd-2) 0. 01 Solvent (Solv-4) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-3) Solvent (Solv-3) Solvent (Solv-4) Third layer (green-sensitive layer) Silver halide emulsion (H ) Gelatin magenta coupler (ExM-4) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Solvent (Solv-3 ) Solvent (Solv-5) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-3) 0, 26 0, 12 1, 24 0, 20 0, 08 0, 06 0,02 0,003 0,20 0,32 1,42 0,47 0,05 Solvent (Solv-6) Fifth layer (red-sensitive layer) Silver halide emulsion (I) Gelatin cyan coupler (ExC-3) Cyan coupler (ExC-4) Cyan coupler (ExC-5) Cyan coupler (ExC-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-12) Color image stabilizer (Cpd, -8) Solvent (Solv-8) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Solvent (Solv-6) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin 0° (ExM-4) magenta coupler (Cpd-12) Color image stabilizer Gelatin hardeners in each layer include 1-oxy-3°5-dichloro-s-triazine sodium salt and 1,
2-bis(vinylsulfonyl)ethane was used in combination.

Further, the following dyes were used as dyes for preventing irradiation.

The sample thus obtained is designated as 201. In contrast to sample 201, 12 types of color photographic papers up to sample 212 were prepared by changing the compositions of the spectral sensitizing dye for red-sensitive emulsion, the stabilizer, and the third layer as shown in Table 5.

(ExM-5) Magenta coupler In order to examine the photographic properties of these coated samples, the following tests were conducted.

The same tests as in Example 1 were conducted for sensitometry, stability of the coating solution over time, stability during product storage, temperature dependence during exposure, and whiteness of the edge of the cut portion. However, color development was performed using the processing steps and processing solution shown below.

These results are shown in Table 6.

Processing process Hoshi-time Yutaka-dish color development
38℃ 45 seconds bleach fixing 30-36℃
Rinse for 45 seconds ■ Rinse for 30 seconds at 30-37℃ ■ Rinse for 30 seconds at 30-37℃ ■ 30-
Dry at 37°0 for 30 seconds 70-80°C for 60 seconds The composition of each treatment solution is as follows.

800ml Ethylenediamine = N, N, 3.0gN, N
-tetramethylenephosphonic acid N, N-di(carboxyme)hydrazine 4.5g Sodium chloride 3.5g Potassium bromide 0.025 g Potassium carbonate
25.0 gN-ethyl-N-(β-
Methane 5.0g sulfonamidoethyl)-3 Monomethyl-4-aminoaniline sulfate fluorescent brightener (WHITEX-41, 2g Sumitomo (manufactured by Kiki) Add water to 1000ml pH (2
5°C) 10.05 weeks constant 1 liquid water 400ml ammonium thiosulfate (55%) 100mj7 sodium sulfite 17g iron ethylenediaminetetraacetate 55g (III) ammonium ethylenediaminetetraacetic acid diacetate 5g sodium 5g ammonium bromide
40g acetic acid
9 Add water to make 1000ml 1p
H (25℃) 5.80 animals 2 sections Liquid ion exchange water (3p each of calcium and magnesium
As is clear from the results, the effect of the present invention was remarkable even in color photographic paper for rapid processing with a high silver chloride content. Example 1 shows the effect of improving the stability of the coating solution over time and sensitivity fluctuations due to temperature changes during exposure.
It was rather larger than in the case of .

(Effects of the Invention) As is clear from the results shown in the Examples, rapid processing is possible only by using the color photosensitive material of the present invention, and excellent manufacturing stability and product storage stability are achieved. It is possible to provide a silver halide color photographic light-sensitive material for printing, which exhibits little performance fluctuation due to temperature fluctuations during exposure and has excellent edge whiteness.

Patent applicant: Fuji Photo Film Co., Ltd. Heisei/ October / Day

Claims (3)

[Claims] (1) In a silver halide color photographic light-sensitive material comprising at least three types of emulsion layers having different color sensitivities on a support, at least one of the light-sensitive emulsion layers has the following general formula (
It contains a silver halide emulsion spectrally sensitized with at least one compound represented by I), and at least one of the light-sensitive emulsion layer or non-light-sensitive layer on the support has the following general formula: Contains at least one compound represented by (II), (III) or (IV), and furthermore, the total amount of silver halide emulsion on the support is 0.65 g as a silver equivalent coating amount.
/m^2 or less. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the general formula (I), Z represents an oxygen atom or a sulfur atom. R_1 and R_2 represent substituted or unsubstituted alkyl groups. V_1, V_2 , V_3, V_4, V_5, V_6, V
_7 and V_8 are hydrogen atom, halogen atom, alkyl group, acyl group, acyloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group, cyano group, hydroxy group, amino group, acyl, amino group, alkoxy group, respectively , an alkylthio group, an alkylsulfonyl group, a sulfonic acid group, or an aryl group, and the two bonded to adjacent carbon atoms in V_1-V_8 cannot form a condensed ring with each other, and σ_p value is σ_p_i (i=1 to 8)
As, Y=σ_p_1+σ_p_2+σ_p_3+σ
_p_4+σ_p_5+σ_p_6+σ_p_7+σ_
When p_8, if Z is an oxygen atom, Y≦-0.08, and on the other hand, if Z is a sulfur atom, Y≦-0.15. X represents the charge-balancing counterion and n represents the value required to neutralize the charge. ) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ In the formula, R represents an alkyl group, an alkenyl group, or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. X has the same meaning as in general formula (II). n represents 1 or 0. General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R and X have the same meaning as those in general formula (II),
L has the same meaning as that in general formula (III). R^3 is synonymous with R, and may be the same or different. (2) The silver halide color photographic material according to claim (1), wherein the green-sensitive emulsion layer contains a two-equivalent magenta coupler. (3) At least one of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer contains silver chlorobromide or a silver chloride emulsion with a silver chloride content of 90 mol%.
2) The silver halide color photographic light-sensitive material described above.