JPH0338639A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the fading property of a cyan dyestuff image in the dark without deteriorating the light fastness by incorporating a specified anionic surfactant and a homo- or copolymer insoluble in water but soluble in an org. solvent together with an oil-soluble coupler for photography. CONSTITUTION:This sensitive material contains at least one of anionic surfactants (A), (B) and at least one kind of homo- or copolymer insoluble in water but soluble in an org. solvent together with an oil-soluble coupler for photography. The surfactant A has at least 15c aliphatic hydrocarbon group or at least two aliphatic hydrocarbon groups having at least 17 total carbon atoms as a hydrophobic moiety in the molecule. The surfactant B has at least >=4C fluorine substd. aliphatic hydrocarbon group as a hydrophobic moiety in the molecule. By the combination of the anionic surfactant with the homo- or copolymer, the fading property of a dyestuff image in the dark is peculiarly improved.

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 particularly to a silver halide color photographic light-sensitive material in which the storage stability of dye images is improved.

(Prior art) Photographic couplers used in silver halide color light-sensitive materials have an oil-soluble group in their molecules, and are dissolved in a substantially water-insoluble high-boiling solvent, which is usually used as an anionic surfactant as an emulsifier. Many types are used, which are emulsified and dispersed in a hydrophilic colloid aqueous solution using a hydrophilic colloid.

Regarding the emulsification and dispersion of these photographic oil-soluble couplers,
Many emulsification and dispersion methods have been proposed in the past.

To give an example of a method using an anionic surfactant, for example, in U.S. Pat. No. 2,332,027, Garginol H
A (Sulfonated coconut fatt)
y alcohol (trade name of DuPont) and triisopropylnaphthalene sulfonate, Japanese Patent Publication No. 39-4293 describes a method using a water-soluble coupler having both a sulfone group or a carboxyl group and a long-chain aliphatic group as an emulsifier. Japanese Patent Publication No. 48-9979 describes a method in which an anionic surfactant having a sulfonic acid group and a fatty acid ester type nonionic surfactant of anhydrohexitol are used in combination. Also, special public service 1986-3168
No. 8 proposes a method using an anionic surfactant polymer obtained by sulfobutylating a formalin condensate of alkylphenol. However, although these emulsification and dispersion methods provide fine dispersed particles and a dispersion with excellent stability, they may not necessarily be sufficient depending on the type of coupler that is the emulsified substance. It wasn't something.

On the other hand, dye images of silver halide color photographic materials are
It is known that when stored by being exposed to light for a long time, or stored in a dark place for a long time even if exposed to light for a short period of time, the color may fade significantly depending on the storage conditions. In general, fading in the former case is called photofading, and fading in the latter case is called dark fading, and when preserving color photographs semi-permanently for recording purposes, the extent of such light fading and dark fading should be minimized. It is desired to keep the overall three-color fading color balance of the yellow, magenta, and cyan dye images in the initial state by keeping it small. However, the degree of light and dark fading of each of the yellow, magenta, and cyan dye images differs among these dye images, and after long-term storage, the overall fading color balance of the former three colors will be disrupted. There was an inconvenience that the quality of the dye image deteriorated.

The degree of photofading and dark fading naturally varies depending on the coupler used and other factors, but in most cases, dark fading is most likely to occur in cyan dye images, followed by yellow dye images, and then magenta dye images. In particular, the degree of fading of cyan dye images is greater than that of other dye images. Regarding photofading, particularly in a light source rich in ultraviolet rays, there is a tendency for photofading to occur in the order of cyan dye images, yellow dye images, and magenta dye images.

Therefore, in order to maintain a good fading color balance of the three colors yellow-magenta and cyan over a long period of time, it is necessary to suppress light and dark fading of the cyan dye image as much as possible. Various attempts have been made to improve fading. These efforts can be broadly divided into two areas: one is to develop new couplers that can produce dye images with less fading, and the other is to develop new couplers that can prevent fading. The goal is to develop additives. One example of the latter is the development of surfactants for emulsifying and dispersing oil-soluble dye image-forming couplers.

An example of this is the use of lipophilic anionic surfactants as disclosed in US Pat. No. 4,766.061.

In addition, there is also a method of incorporating a single or copolymer consisting of a repeating unit having 10-condensed 1 in the main chain or side chain into the coupler emulsion, as disclosed in International Patent Application Publication No. 088100723. Are known.

However, although these methods are certainly effective in suppressing implicit fading of cyan images, they are not completely sufficient.
It was desired to develop a better color image stabilization method.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to stably disperse fine particles of a photographic oil-soluble coupler in a photographic element that incorporates a silver halide color photographic light-sensitive material, and to disperse cyan, magenta and Yellow fading has been improved in a well-balanced manner, especially at high temperatures,
The object of the present invention is to provide a silver halide photographic material capable of forming a dye image exhibiting excellent image storage stability even at high temperatures.

In particular, it is an object of the present invention to provide a silver halide photographic material that has improved dark fading properties without deteriorating photofading properties among the fastness properties of cyan dye images.

(Means for Solving Problem R) These objects of the present invention include at least one selected from the following anionic surfactants (A) and CB), and a water-insoluble and organic solvent-soluble individual or copolymer. What is claimed is: 1. A silver halide color photographic light-sensitive material, characterized in that it contains at least one type of silver halide color photographic coupler and a photographic oil-soluble coupler.

(A) At least 15 carbon atoms as a hydrophobic part in the molecule
or at least two aliphatic hydrocarbon groups having a total carbon number of at least 17.

(B) An anionic surfactant having at least a fluorine-substituted aliphatic hydrocarbon group having 4 or more carbon atoms as a hydrophobic portion in the molecule.

achieved by.

Alion surfactant (A) preferably used in the present invention
Examples include those represented by the following general formulas (13 to (XIV)).

303M (II) C8,C00R CIl□C00R (na) (I[b) (III) +1sO3M R1-CIl(C1h)llS0,712 (I[Ia) (I[1b) (IV) RO(CIICHO)ll SO State O503M R.

(n l~50) (rVa) (rVb) (Vla) (Vlb) [■] ROC)IiCHCHtSOJ H (Xa) (Xb) ()la) (X[Ib) In the formula, R1 and R3 are aliphatic carbonization It represents a hydrogen group having a total of at least 17 carbon atoms, R is a single aliphatic hydrocarbon group having at least 15 carbon atoms, and M is a cation (H, alkali metal ion, etc.).

The anionic surfactants represented by the above (1) to (XIV) used in the present invention are preferably lipophilic ones, and although specific examples are shown below, the present invention is not limited thereto.

(A l ) CHzCOOC+Jzt(oxo
)CIl C00CIJzt(0 in O) SO,Na CToCOOC+Jzt(n) CI C00C+Jzt(n) 0Ja (A-4) CHICOOC)IzCHzOC+ Jis (n)C
HC00CHzCHzOC+t) Its(n)0Ja (A-5) C11zCOOC+J33(oxo) co cooc :+Hz(oxo) CIIzSOJa (A 6) C+ zLsclIcIlzo(C1lz) a sOJ
aCl. 11□.

(A 7) C211□.

CIIC) IzO5OJa c, n, □ p+q=32~36 (A-9) C+ stl:+J (CIlxCHO) C in 3803
H3 CHCOOC+Jsz(iso) 03Na On the other hand, an example of the fluorine-containing anionic surfactant (B) can be represented by the following general formula (XV).

General formula (XV) (Rf), (B), -X Here, Rf represents a fluorinated IA alkyl or alkenyl having 4 to 18 carbon atoms, and X is -301M.

-03O,M.

1000M1 (M is a hydrogen atom or a cation), B is 2
˜represents a trivalent linking group, n is an integer of 1 or 2, and m is an integer of 0 or 1, respectively.

A specific example of B is shown below.

-5OxN-(CHth e, 11 Ro 1l -CON-(C)I.

)-2 1l -CON-C1lt(:HxO(CIbCH-0T→
C11, ←.

RIIR mouth →CH□　←2, →CHzh-→0CIItCHth-→C1+1 ←, 0(CHt.

←.

→Ch →C118 ←, 0OCCI+□ h, 0OCCH-Cl Here, R11 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R18 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

p is 1=IO, a is 0 representing a number from 1 to 50, respectively
Next, specific examples of the fluorine-containing anionic surfactant used in the present invention will be given.

(B-1) CF3 (CFt) tsOzNcHtcIItChs
OJa Kaoru C3H? (B-2) CFi(Ch)tsO! N(CHt)ssOJillS (B-3) H(CFt)hcHtQ(Cllz)ssOsNa(B
-4) H(CFt)scHzo(CHx)g50*Na(B-
5) H(CFRIl@CH!0(CIRI4SOsll・N(C
Iria (B-6) CFs (CFi) tsOtNcHtcHto (CHt
CHtO)-(CH,) 4sOJaC,lI,
n = 1(B-7) CF3(CFz)tsOJcTocHto(CHtCH
zO), (C1lx) +5OsN8C5 old
n-3 (B-8) n=5 (B-9) -10 (B-10) CFs (CFi) hcONHcHxcH*o(CHt
) isOJa (B-11) H (CFg) * C0N (CHt) ssOJa parable Jw (B-12) CIisCOOCHg (Ch) sH Kaoru ClIC0OCR wealth (CF snow) Zeng H 3O,Na (B-13) CHiCOOCHi (CF Ri &CF5CIlCO
OCtl* (CFt) hCFs03Na 0Ja (B-16) (B-17) (B-18) CHgCl1xO(CI(*)isOsNa(B-19
) C3H? CHiCOOCHtCHJSO* (CFz)? Ch
0Ja CFi1゜(B-20) (B-21) CFi(CFi)tsOsN(CtHs)4(B-22
) CFs(CFt)++CHtO5OJa(B-23) CFi(CFx)hcOo(CHi)3sOaNa(B
-24) C+Jii-CHCOOCHt (CF O) 4H Ward 02Na (B-25) C+J! 3-CHCOOCHg (CFi) & CFcoSO
, Na (B-26) (B-27) CFs-CC-C-5OJa C*Fs (B-28) CFs-CCI-CFSOJa ■ C*ps (B-29) CPs-C-CCFSOsNa C*Fs ( B-30) 0 (B-31) 0 1 CaF+ySOJC)IxCII□OP・(Oll)I
CcoHfu (B-32) RfCOONIIa Rf-CsF+y ~c+ipgs (B-33).

j (CsF+vSOtNCHzCHxO)zP-ONH4
CcoH7 (B-34) (B-35) (B-36) OCHxR40H x/)'-50150 These compounds used in the present invention are described, for example, in U.S. Pat. No. .567.011,
No. 2,732,398, No. 2,764,602, No. 2,806,866, No. 2,809.998
No. 2,915゜376, No. 2.915,52
No. 8, No. 2934.450, No. 2.937.0
No. 98, No. 2,957,031, No. 3,472,
No. 894, No. 3,555,089 and Special Publication No. 1973
-37304, the specifications of JP-A No. 47-9613,
Journal of the British Chemical Society (J, Chem, 5oc) 1950 No. 2
789 pages, 1957, pages 2574 and 2640
Page, Journal of the American Chemical Society (J.

Amer, Chem, Soc, Vol. 79, p. 2549 (1957) and Oil Chemistry, (J.

Japan 011 Chem1st' 5Soc
), Vol. 12, p. 653.

Among these fluorinated carbon compounds used in the present invention, some are commercially available from Dainippon Ink & Chemicals Ltd.
Product name F (e.g. F-109, F-110%F
-115), and also under the trade name Monflor from Imperialke 2 Cal Industries (for example, Manflor).
r31).

The fluorocarbon-containing anionic surfactant used in the present invention can be added to either the oil-soluble coupler solution or the colloidal aqueous solution, or both, within the range allowed by solubility.

The homopolymer or copolymer used together with the anionic surfactant in the present invention may be any polymer as long as it is insoluble in water and soluble in an organic solvent. It is preferable in terms of color development and color image fastness. The polymer used in the present invention will be explained below by giving specific examples, but the polymer of the present invention is not limited to these.

(A) Vinyl Polymer Monomers forming the vinyl polymer of the present invention include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isopyl acrylate, $5 IC-budel acrylate, te4t-budel acrylate, amyl acrylate, hexyl acrylate, 1-ethylhexyl acrylate, octyl acrylate), tcrt-octyl acryle), U-/roloethyl 7 acrylate, Cope o% ethyl acrylate, φ-chlorophthyl acrylate, cyanonyl acrylate, diacetoxy ether acrylate, dimethylamino ether acrylate,
Benzyl acrylate, methoxybenzyl acrylate, coke c10 cyclohexyl acrylate, cyclohexyl acrylate.

Furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate,! -Hydroxy, cypentyl acrylate, co, codimedel-3-hydroxypropyl acrylate, nimethoxyethyl acrylate, J-methoxybdel acrylate, coethoxycetera/IJ acrylate, 2-fso-propoxy acrylate, nibutoxyethyl acrylate, ni( (nimethoxyethoxy) nibble acrylate), a-(coptoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n
-Y) /-: y-lomocomethoxedel acrylate, 1. /-dichlorocoethyl-7-edel acrylate and the like. In addition, polymers polymerized using the following monomers can be used for α.

Methacrylate esters: Specific examples include ethyl methacrylate and ethyl methacrylate.

n-propyl hexamethacrylate, isonorobyl methacrylate, n-butyl methacrylate, inbutyl methacrylate), 5ea-butyl methacrylate, [ert-butyl methacrylate, amyl meth/V1/-), hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, offder methacrylate, stearyl methacrylate, sulfobyl methacrylate, N-ethyl-N-
722 amino edel methacrylate, di(J-phenylpropyloxy) ethyl methacrylate, dimethylamino 7 edoxyethyl methacrylate, fur 7 lyl methacrylate, tetrahuman CI fur 7 lyl methacrylate, phenyl methacrylate-cresyl methacrylate, na 7 del methacrylate, 2-hydroxyethyl methacrylate),! -Hydroxypudel methacrylate, triedelene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, J-methoxybutyl methacrylate, λ-7 setoxyethyl methacrylate, 2-7cetoacetoxyethyl methacrylate, coethoxy Ete Akane Methacrylate J Co! so-propoxyethyl methacrylate, 2-butoxyethyl methacrylate), 2-(
Nimethoxyethoxy) ether methacrylate, Ni(
Coretoxie) * 4/ ) x Dermethacrylate
),! -(u-phthoxyethoxy)ethyl methacrylate, ω-methoxypolyedelene glycol methacrylate (number of moles added), allyl methacrylate, methacrylic acid dimedelaminoedelmedel chloride salt, and the like.

Vinyl esters: Specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl imbutyrate, vinyl caproate, vinyl
2 acetate, vinyl methoxy acetate, vinyl phenylacetate), vinyl benzoate, vinyl salicylate, etc.; Acrylamides: For example, acrylamide, methyl acrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide Ad, hydroxy mesol acrylamide,
Methoxyethyl acrylamide, dimethylaminoblyacrylamide, phenylacrylamide, dimedelacrylamide, diederacrylamide, β-cyanoethyl acrylamide, N-(coacetoacetoxyedel)acrylamide, diacetone acrylamide, etc.; Methacrylamides: e.g. methacrylamide, methyl methacrylamide, edel methacrylamide, propyl methacrylamide, butyl methacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylamino nibblemethacrylamide, phenylmethacrylamide, dimedelmethacrylamide, diedermethacrylamide, β-cyanoethylmethacrylamide, N-(coacetoacetoxyether) methacrylamide, etc.; Olefins: for example, dicyclopentadiene, ethylene, propylene, t-7'tene/-hentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene,
butadiene, 2. J-dimethylbutadiene, etc.; Styrenes: For example, styrene, methylsulfone, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chloroprene, dichlorostyrene, bromostyrene, vinyl benzoyl 8R me? Vinyl ethers: For example, methyl vinyl ether, 7
-f Rubinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimedelaminoethyl vinyl ether nato; Others include budel crotonate, hexyl crotonate, dibutyl itaconate, dibutyl itaconate siedel maleate, cymedel maleate.

Dibdel maleate, diethyl 7-malate, dimedel 7-malate, dibdel fumarate, mesol vinyl ketone, phenyl vinyl ketone, methoxyethyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyloxazolidone.

Examples include N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinylidene chloride, methylenemalonitrile, and vinylidene.

The monomers used in the polymers of the present invention (e.g., the monomers listed above) may also be used as polymerized co-51 polymers (using more than one species) depending on the purpose of the ER in the coupler solubility improvement section. Ru. ! In addition, in order to improve color development and solubility, monomers having acid groups such as those listed below may be used as comonomers, provided that the copolymer is water-bathable.

Acrylic acid; Methacrylic acid; Itaconic acid; Maleic acid:
Monoalkyl itaconate, such as monomethyl itaconate, monomethyl itaconate, monobudel itaconate; heptanoalkyl maleate.

For example, monomethyl maleate, monoethyl maleate, monobutyl maleate; citraconic acid; sderene sulfonic acid; vinylbenzyl sulfonate; vinyl sulfonic acid; Sulfonic acid, acryloyloxypropylsulfonic acid, etc.; Methacryloyloxyalkylsulfonic acid 1 For example, methacryloyloxymethylsulfone is methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc. Niacrylic acid alkylsulfonic acid, for example co-acrylamido-umethyl ethanesulfonic acid, co-acrylamide-co-methylpropanesulfonic acid, co-acrylamide-nimethylbutanesulfone, etc.; methacrylamide alkyl sulfonic acid, such as co-methacrylamido-co-methylethanesulfonic acid, co-methacrylamide)'-J-
meso-propane sulfone, 2-methacrylamido-co-metal butane sulfonic acid, etc.; these acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions.

Among the vinyl monomers listed here and other vinyl monomers used in the present invention, hydrophilic monomers (
Here, it refers to a material that becomes water bathable when made into a homopolymer. ) is used as a comonomer, there is no particular restriction on the proportion of the hydrophilic monomer in the copolymer, as long as the copolymer does not become water-soluble. Shikuke 4L
The amount is not more than 0,000 mol, preferably not more than 1.20 mol, and even more preferably not more than 10 mol. Furthermore, when the hydrophilic comonomer to be copolymerized with the monomer of the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually adjusted from the viewpoint of image storage stability as described above. The number of moles is 0 or less, preferably 10 or less, and i& is also preferably not containing such a comonomer.

The monomers of the invention in the polymer are preferably methacrylate, acrylamide and methacrylamide.

(B) Polyester resin obtained by condensation of polyhydric alcohol and polybasic acid The polyhydric alcohol is HO-R1-OH (Rt is a hydrocarbon chain with a carbon number of about 1/2, especially an aliphatic hydrocarbon chain) )
Glycols have the following structure.

Alternatively, polyalkylene glycol is effective, and as the polybasic acid, those having HOOC-R2-COOH (R2Fi represents a simple bond or a hydrocarbon chain of about 7.2 carbon atoms) are effective. It is.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, l
, 2-propylene glycol, /.

J-propylene glycol, trimesololpropane,
114t-butanediol, isobutylenediol, /
,! -bentanediol, neopentyl glycol, l
1 hexanediol, 1.

7-hebutanediol, i, r-octanediol, l
, 2-nonanediol, /, 10-decanediol, /
, //-undecanediol, l.

/2-dodecanediol, /, /J-)lysocandiol, /, 44-diol, glycerin, diglycerin,
Examples include triglycerin, /-methylglycerin, erythritol, mannitol, nruvit, and the like.

Specific examples of polybasic acids include cidiaic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarbo/acid 1. Dodecanedicarboxylic acid, 7-malic acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, dichlorophthalic acid, methaconic acid, inhimelic acid, cyclopentadiene-maleic anhydride adduct, rosin-anhydride Examples include maleic acid adducts.

(C) Other polyesters obtained by ring-opening polymerization, such as those shown below.In the formula, m represents an integer from I/- to 7. -〇H,- chain may be branched.

Suitable monomers that can be used with this polyester include .beta.-propiolactone, .epsilon.-caprolactone, dimethylfirobiolactone, and the like.

The molecular weight and degree of polymerization of the polymer of the present invention have no substantial effect on the effects of the present invention as long as they exceed a certain level.
If the molecular weight is too high, it will take time to dissolve in a high-boiling organic solvent or auxiliary solvent, and the solution viscosity will be high, making it difficult to emulsify and disperse, creating coarse particles and reducing color development. It becomes easier. Therefore, the molecular weight of the polymer that can be used in the present invention is preferably 1,000,000 or less.
1,000 or more, more preferably 400,000 or less and 5,000 or more, still more preferably 150,000 or less and 10,000 or more.

The ratio of polymer to auxiliary solvent when preparing an emulsified dispersion containing the polymer of the present invention varies depending on the type of polymer used, and depends on the solubility in the auxiliary solvent, the degree of polymerization, etc., or the solubility of the coupler. 6 Generally, at least the coupler, high-boiling organic solvent, and polymer are dissolved in the auxiliary organic solvent, and the solution is easily dispersed in water or an aqueous hydrophilic colloid solution. The amount of auxiliary organic solvent required to obtain a sufficiently low viscosity is used.The higher the degree of polymerization of the polymer, the higher the viscosity of the solution. Although it is difficult to uniformly determine the ratio regardless of the coupler or high-boiling point organic solvent to be used together, it is usually about 1:
A range of 0.2 to 1:50 (weight ratio) is preferred.

The polymers or copolymers of the present invention may be used alone, or in combination of two or more, and even with polymers other than the present invention, as long as the effects of the present invention are not lost. Different polymers may be used in different layers in the photosensitive material.

Specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto.

P-1> Poly(vinyl acetate) P-2) Poly(vinyl propionate) P-3> Poly(
Methyl methacrylate) P-4> Poly(ethyl methacrylate) P-5) Poly(ethyl acrylate) P-6) Poly(heptyl acrylate) P-7) Poly(
butyl acrylate) P-8) poly(butyl methacrylate) P-9) poly(
iso-butyl methacrylate) P-10) poly(is
o-propyl methacrylate) P-11) Poly(octyl acrylate) P-12) Poly(hexadecyl acrylate) P-13>Poly(hexyl acrylate) P-14) Poly(iso-butyl acrylate) P-15>Poly( iso-propyl acrylate) P-16) Poly(3-methoxyethyl acrylate) P-1F) Poly(2-methoxycarbonylphenyl acrylate) P-18) Poly(3-methoxycarbonylphenyl acrylate) P-19) Poly( 4-methoxycarbonylphenyl acrylate) P-20) Poly(2-methoxyethyl acrylate) P-21) Poly(4-methoxyphenylacrylate) P-22) Poly(3-methoxypropyl acrylate) P-23) Poly(methyl Acrylate) P-24) Poly(3,5-dimethyladamantyl acrylate) P-25) Poly(3-dimethylaminophenyl acrylate) P-26) Poly(2-cyanomethylphenyl methacrylate) P-27) Poly(4- Cyanophenyl methacrylate) P-28) Poly(decyl methacrylate) P-29')
Poly(dodecyl methacrylate) P-30) Poly(diethylaminoethyl methacrylate) P-31) Poly(ethyl methacrylate) P-32) Poly(2-ethylsulfinylethyl methacrylate) P-33) Poly(hexadecyl methacrylate) P-3
4) Poly(hexyl methacrylate>P-35) poly(
2-Hydroxypropyl methacrylate) P-36) Poly(4-methoxycarbonylphenyl methacrylate) P-37) Poly(3,5-dimethyladamantyl methacrylate) P-38) Poly(dimethylaminoethyl methacrylate) P-39) Poly( 3,3-dimethylbutylmethacrylate) P-40) Poly(3,3-dimethyl-2-butyl methacrylate) P-41) Poly(3,5,5-trimethylhexyl methacrylate) P-42>Poly( Octadecyl methacrylate) P-4
3) Poly(tetradecyl methacrylate) P-44> Poly(pentyl acrylate) P-45) Poly(4-butoxycarbonylphenyl methacrylamide) P-46) Poly(pentyl methacrylate) P-47)
Poly(4-carboxyphenylmethacrylamiton) P-48) Poly(4-ethoxycarbonylphenylmethacrylamide) P-49') Poly(4-methoxycarbonylphenylmethacrylamide) P-50) Poly(butylbutoxycarbonylmethacrylate) P -51) Poly(butyl chloroacrylate) P-52
) Poly(butyl cyanoacrylate) P 53) Poly(cyclohexyl chloroacrylate) P-54) Poly(ethyl chloroacrylate) p-55
) Poly(ethyl ethoxycarbonyl methacrylate) P-56') Poly(N-sec-butylacrylamide) P-57) Poly(N-ter-butylacrylamide) P-58) Poly(ethyl ethacrylate) p- 59) Poly(cyclohexyl methacrylate) P-60) Poly(
Ethylfluoromethacrylate) P-61 > Poly(hexylhexyloxycarbonyl methacrylate) P-62) Poly(ter-butyl methacrylate) P-
63) Poly(iso-butyl chloroacrylate) P-64) Poly(N-ter-butyl methacrylamide) P-65) Poly(iso-propyl chloroacrylate) P-66>Poly(methyl chloroacrylate) P-67
) Poly(methylfluoroacrylate) P-68> Poly(methylfluoromethacrylate) P-69) Poly(methylphenylacrylate) P-70) Poly(benzyl acrylate) P-71) Poly(4″-biphenylacrylate) P- 72) Poly(4-butoxycarbonylphenyl acrylate) P-73) Poly(sec-butyl acrylate) P-7
4) Poly(ter-butyl acrylate) P-75) Poly(2-ter-butylphenyl acrylate) P-76) Poly(4-ter-butylphenyl acrylate) P-77) Poly[3-chloro-2,2 -Bis(chloromethyl)propyl acrylate] P-78) Poly(2-chlorophenylacrylate-P-7
9) Poly(4-chlorophenylacrylate) P-80) Poly(pentachlorophenylacrylate) P-81>Poly(4-cyanobenzyl acrylate) P-82) Poly(cyanoethyl acrylate) P-83
) Poly(4-cyanophenyl acrylate) P-84) Poly(4-cyano-3-butyl acrylate) P-85) Poly(cyclohexyl acrylate) P-8
6') Poly(2-ethoxycarbonylphenyl acrylate) P-87> Poly(3-ethoxycarbonylphenyl acrylate) P-88) Poly(4-ethoxycarbonylphenyl acrylate) P-89) Poly(2-ethoxyethyl acrylate) P-9
0) Poly(3-ethoxypropyl acrylate) P-91) Poly(LH,LH,5H-octafluoropentyl acrylate) P-92) Poly(propylchloroacrylate) P-9
3) Poly(2-methylbutyl acrylate>P-94)
Poly(3-methylbutyl acrylate) P-95) Poly(l,3-dimethylbutyl acrylate) P-96) Poly(2-methylpentyl acrylate) P-97) Poly(2-naphthyl acrylate) P-98
>Poly(phenyla, acrylate) P-99) Poly(propyl acrylate) P-100) Poly(m-tolyl acrylate) P-101) Poly(0-tolyl acrylate) P-102) Poly(p-tolyl acrylate) P −
103) Poly(N-butylacrylamide) P-104
) Poly(N,N-dibutylacrylamide) P-105 Poly(N-iso-hexylacrylamide) P-106) Poly(N-iso-octylacrylamide) P-107) Poly(N-methyl-N-phenylacrylamide) P-108) Poly(adamantyl methacrylate) P-
109>Poly(benzyl methacrylate) P-110)
Poly(2-bromoethyl methacrylate) P-111) Poly(2-N-ter-butylaminoethyl methacrylate) P-112) Poly(sea-butyl methacrylate) P-113) Poly(2-chloroethyl methacrylate) P- 114) Poly(2-cyanoethyl methacrylate) P-115) 1,4-butanediol-adipic acid polyester P-116) Ethylene glycol-sebacic acid polyester P-117) Polycaphyrolactone P-118) Polypropiolactone P-119 ) Polydimethylpropion lactone P-12
0) Vinyl acetate-vinyl alcohol copolymer (95:
5) P-12,,1) Butyl acrylate-acrylamide copolymer (95:5) P-122) Stearyl methacrylate-acrylic acid copolymer (90:10) P-123) Butyl methacrylate-N-vinyl-2 −
Pyrrolidone copolymer (90: 10) P-124) Methyl methacrylate-vinyl chloride copolymer (70: 30) P-125) Methyl methacrylate-styrene copolymer (90:10) P-126> Methyl methacrylate-ethyl Acrylate copolymer (50: 50) P-127) Butyl methacrylate-methyl methacrylate-styrene copolymer (5 0: 30: 20) P-128) Vinyl acetate-acrylamide copolymer (8
5:15) P-129) Vinyl chloride-vinyl acetate copolymer (65:
35) P-130) Methyl methacrylate-acrylonitrile copolymer (65: 35) P-131) Diacetone acrylamide-methyl methacrylate copolymer* (50:50) P-132) Methyl vinyl ketone-1so-butyl methacrylate Copolymer (55: 45) P-133) Ethyl methacrylate-butyl acrylate
) (70: 30) P-134) Diacetone acrylamide-butyl acrylate copolymer (60: 40) P-135) Methyl methacrylate-styrene methyl methacrylate-diacetone acrylamide copolymer (40:40:20> P- 136) Butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:10) P-137) Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-138) Methyl methacrylate- Styrene-vinyl sulfonamide copolymer (70:20:10) P-139) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-140>Butyl acrylate-methyl methacrylate-butyl methacrylate copolymer ( 35: 35: 30) P-141>Butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38:38:2 4) P-142) Methyl methacrylate-butyl methacrylate-1so-butyl methacrylate-acrylic Acid copolymer (3 7: 29: 25 + 9) P-143>Butyl methacrylate-acrylic copolymer wood (95:5) P-144) Methyl methacrylate-acrylic acid copolymer (95:5) P-145 ) Benzyl methacrylate-acrylic acid copolymer (90:10) P-146) Butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer <35:3 5:25:5) P-147) Butyl methacrylate-methyl Methacrylate-benzyl methacrylate copolymer (35:30:35)P-148)
Cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate copolymer (37:29:34) P-149) Methyl methacrylate-butyl methacrylate copolymer (65:35) P-150> Vinyl acetate vinyl probionate copolymer ( 75: 25) P-151) Butyl methacrylate-3-acryloxybutane-1-sulfonic acid P-152) Butyl methacrylate-methyl methacrylate-acrylamide copolymer <35: 35: 30) P-153) Butyl methacrylate- Methyl methacrylate-salt f-vinyl copolymer (37: 36: 27) P-154) Butyl methacrylate-styrene copolymer (90:10) P-155) Methyl methacrylate-N-vinyl-2-
Pyrrolidone copolymer (90: 10) P-156) Butyl methacrylate-salt "vinyl copolymer (90+10) P-1 57) Butyl methacrylate-styrene copolymer (70: 30) P-158) Diacetone acrylamide- Methyl methacrylate copolymer (62:38) P-159) N-ter-butylacrylamide-methyl methacrylate copolymer (40:60) P-160) ter-butyl methacrylate-methyl methacrylate copolymer (70:30 ) P-161) N-ter-butylacrylamide-methylphenyl methacrylate copolymer (60: 40) P-162) Methyl methacrylate-acrylonitrile P-163) Methyl methacrylate-methyl vinyl ketone copolymer (38: 72) P-164> Methyl methacrylate-styrene copolymer (75: 25> P-165) Methyl methacrylate-hexyl methacrylate copolymer (70: 30) P-166) N-methyl-N-benzylacrylamide-butyl acrylate- Dibutyl fumarate copolymer (55:35 2 10) P-=167) Poly(N-(1,1-dimethyl-3-oxobutyl)acrylamide) P-168) Poly(N-octylmethacrylamide) P-169 ) N,N-diethylacrylamide-butylacrylate copolymer #(40:60) P-170) N,N-diethylacrylamide-2-butoxyethyl acrylate copolymer (65:35) P-171) N-ter- Butylacrylamide-butylacrylate copolymer 60:40) P-172) N-ter-octylacrylamide-2-ethylhexylacrylate copolymer (65:35) P-173) N,N-dibutylacrylamide -Dibutyl maleate copolymer (75:25) P-174)N-(1,1-dimethyl-3-oxobutyl)acrylamide-butyl acrylate copolymer (55:45)P-175)N
-(1,1-dimethyl-3-oxobutyl)acrylamide-butyl acrylate copolymer (70:30)P-176)N
-ter-butylacrylamide-butylacrylate copolymer (4 5: 55) P-177) N-octyl-N-ethylacrylamide-ethyl acrylate copolymer (45: 55) P-178) N-butylmethacrylamide- 2-ethylhexyl acrylate copolymer (90:10) P-179) N,N-dibutylmethacrylamide-propylacrylate copolymer (80:20) P-180) N-(2-phenylethyl)acrylamide -Butyl acrylate copolymer (25:75) P-181) N-acry'loylmorpholine-2-'
Ethoxyethyl acrylate copolymer (40:60) P-182) N-methyl-N1-acryloylpiperazine-butyl acrylate copolymer (15:85) P-183) N-acryloylpiperidine-2-butoxyethyl acrylate copolymer Combined (40:60) P-184) N=(1,1-dimethyl-3-hydroxybutyl)acrylamido-2-ethylhexyl methacrylate copolymer (75:25) P-185) N-acryloylpiperidine-butyl Acrylate copolymer (50: 50) P-186) N-(P-hydroxyphenyl)acrylamide-butyl acrylate copolymer (25: 75) P-187) N-(3-(dimethylamino)propylcoacrylamide -Butyl acrylate copolymer (35:65) P-188) N-methyl-No-methacryloylpiperazine-2-ethoxyethyl acrylate copolymer (40:60) P-189) 2,6-dimethyl-4-methacryloyl Morpholine-butylacrylate copolymer (55:45) P-190) N-ter-butylacrylamide-butylacrylate-2-ethoxyethyl acrylate copolymer (55:25:20) p-191) N-(1, 1-dimethyl-3-oxobutyl>acrylamide-butyl acrylate-N,N-diethylacrylamide copolymer (30: 50:20> P-192) N-methyl-N゛-methacryloylpiperazine-2-ethoxybutyl acrylate-ethyl Acrylate copolymer (30:40:30) P-193) 1,6-hexanethiol-ascorbic acid-sebacic acid polyester P-194) Diethylene glycol'-adipate polyester P-195)) Limethylolproban-azivin Acid-phthalic acid polyester P-196) Diethylene glycol-trimethylolpropane-adipate polyester P-197) Ethylene glycol-adipate polyester P-198) Ethylene glycol-1,4-butanediol-adipate polyester P-199>1 .4-Bis-(β-hydroxyethoxy)benzene-sebacic acid polyester P-200>Ethylene glycol-azelaic acid polyester Next, the diffusion-resistant oil-soluble coupler used in the present invention will be described in detail.

What is the diffusion-resistant oil-soluble coupler mentioned here?

It refers to a coupler that is soluble in the high-boiling point organic solvent described below and has a high expansion resistance so as to make it difficult for the coupler to diffuse in photographic light-sensitive materials.

Cyan couplers, magenta couplers, and yellow couplers preferably used in the present invention have the following general formulas (C-1), (C-11), (M-1), and (M-11).
and (Y).

General formula (C-1) H 1 General formula (C-n) H General formula (M-1) General formula (M-11) General formula (Y) In general formulas (C-1) and (C-11) , Rls
R and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R5, R1 and Rh represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R1 is R1 It may also represent a group of nonmetallic atoms that together form a nitrogen-containing 5- or 6-membered ring. Y
I and 'It represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent. n is 0 or 1
represents.

R2 in -M formula (C-11) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclo-xyl group, cyclohexylmethyl group,
Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butane acutomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-11) are as follows.

In general formula (C-1), preferable R1 is an aryl group,
A heterocyclic group, including a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an azilagino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonagodo group, a sulfamoyl group, a sulfole group, a sulfayodo group, an oxycarbonyl group, or a cyano group.

When R1 and R2 do not form a ring in general formula (C-1), Rt is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R8 is Preferably it is a hydrogen atom.

In general formula (C-11), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-n), R6 preferably has 2 to 1 carbon atoms.
It is a methyl group having an alkyl group of 5 and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an azila-kuno group, an aryloxy group, or an alkyloxy group.

In general formula (C-11), R2 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 (C-n), R6 is preferably a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred vl and V in general formulas (C-1) and (C-11) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In general formula (M-1), R? and R9 represents an aryl group, R represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
v3 represents a hydrogen atom or a leaving group.

Aryl group (preferably phenyl group) of R1 and R9
The substituents allowed for substituent R1 are the same as the substituents allowed for substituent R1, and when there are two or more substituents, they may be the same or different. R6 is preferably a hydrogen atom, an aliphatic It is an acyl group or a sulfonyl group of the above group, and particularly preferably a hydrogen atom.

Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
Particularly preferred are sulfur atom dissociative types as described in No. 51,897 and International Publication No. W088104795.

In the general formula (M-■), R1° represents a hydrogen atom or a substituent, and v4 represents a hydrogen atom or a leaving group, preferably a halogen atom or an arylthio group. Za, Z
b and Zc are methine, substituted methine, =N- or -NH
-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R2° or Y4 forms a multimer of 2I or more, Za.

When zb or Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-■), U.S. Pat.

The imidazo(1,2-b)pyrazoles described in U.S. Pat. .

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring, and the pyrazolotriazole coupler 1 is described in JP-A-61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position, such as those described in No. 849 and No. 294.785.

In general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and R4 represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NHCORl 3, Nt(S(lx-R+
3.-5Q! N) lR+2, -COOLs, -5O
represents tNR+i14. However, R11 and 1114 each represent an alkyl group, an aryl group, or an acyl group. Y represents a leaving group. As substituents for R1□, R13, and RI4, R1
The leaving group V is preferably of the type leaving off at either an oxygen atom or a nitrogen atom, with the leaving group V leaving at a nitrogen atom being particularly preferred.

General formula (C-1, (C-11), (M-1), (M-
Specific examples of couplers represented by 11) and (Y) are listed below.

(C-1) Js C, R9 (C 4) H (C-6) C, R5 (C 7) (C-8) C,l(.

(C-9) (C-10) (C-12) O1+ (C-13) (C 14) (C-15) (C-17) (C 18) (C-19) ■ (C-20) (C 21) (C-22) υshin3 (M-1) CZ (M-2) I (M-3) I (M 4) (M-6) lls (M-7) (M-8) CHl I CH3 (Y-1) (Y-2) (Y-3) ul'! (Y-4) (Y-5) (Y-6) (Y 7> (Y 8) (Y-9) The couplers represented by the above general formulas (C-1) to (Y) are:
In the silver halide emulsion layer constituting the photosensitive layer, usually 0.1 to 1.0 mol per mol of silver halide, preferably o
, i − o, s mol.

In the present invention, the oil-soluble coupler is prepared by mixing the oil-soluble coupler maintained in a solution state by any of the following methods with an aqueous hydrophilic colloid solution in the presence of the surfactant and polymer of the present invention. Fine dispersions can be prepared.

In addition, in order to further increase the stability of the resulting dispersion, the water-immiscible low-boiling organic solvent or water-miscible organic solvent used to bring the oil-soluble coupler into solution may be distilled or Preferably, it may be removed by distillation under reduced pressure, ultrafiltration, or other known methods.

When finely dispersing an oil-soluble coupler in an aqueous medium,
High boiling point organic substance used to suppress crystal precipitation (
That is, as the so-called oil component, those that are practically insoluble in water and have a boiling point of 190° C. or higher at normal pressure are useful. This type of organic substance includes carboxylic acid esters, phosphoric acid esters,
It can be selected from carboxylic acid amides, ethers, fers, anilines, substituted hydrocarbons, and surface-inactive hydrophobic organic polymers. Specific examples include di-n-butyl fucuric acid ester, di-isooctyl fural ester, dicyclohexyl phthalate, dimethoxychetyl fural ester, di-n-butyl adipate, di-isooctyl azelene. acid ester, tri-butyl citrate, butyl laurate, di-n-sebacate, triphenyl phosphate, tricresyl phosphate, tricyclohexyl phosphate, tri-n-butyl phosphate, tolylisooctyl phosphate, 4N-diethylcaprylic acid amide, N,N-dimethylpargotic acid amide, n-butyl m-pentadecyl phenyl ether, ethyl-2,4ter t-butylphenyl ether, 2.5-di-amylphenol, N, N-di-n-butyl, 2-n-butoxy, 5-t
-octylaniline, chlorinated paraffin, polyethyl acrylate and diethylene glycol-adipate polyester.

Depending on the type of coupler, the above-mentioned high-boiling point organic substance may not be used, and the coupler may be dissolved only in the following low-boiling point organic solvent or only in a water-miscible organic solvent for emulsification dispersion or precipitation dispersion.

In the present invention, in order to dissolve the oil-soluble coupler,
In addition to the high-boiling substances mentioned above, it is often advantageous to use low-boiling organic solvents that are immiscible with water (boiling points below 130° C. at 1 atm) or water-miscible organic solvents. Examples of these III solvents include propylene carbonate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, 5ec-butyl alcohol, methyl ethyl ketone, 2-pentanone,
- Pentanone, cyclohexanone, dimethylformamide, dimethylsulfoxide are examples. The preferred amount of the organic solvent used is 0.1 to 100 times the weight of the oil-soluble coupler to be dispersed.

Examples of emulsifying equipment used to carry out the present invention include a high-speed stirring type dispersion machine having a large shearing force, a dispersion machine applying high-intensity ultrasonic energy, and the like. Specifically, there are colloid mills, homogenizers, capillary emulsifiers, liquid sirens, electric iR distortion ultrasonic generators, emulsifiers having a Ballmann whistle, and the like. Preferred high-speed agitation type dispersing machines for use in the present invention include Daysilver, Polytron, Homomixer, Homofinender, Kedimill, Diendo Agitter, etc., in which the main part that performs the dispersing action rotates at high speed (50°C) in the liquid.
0-15. OOOrpm, preferably 2,000-4
, 000 rpm) 9 The high-speed stirring type dispersion machine used in the present invention is also called a day silver or high-speed impeller dispersion machine, and is disclosed in Japanese Patent Application Laid-open No. 55-1291.
As described in No. 36, it is also a preferable example to install an impeller in which pongee-like tooth-shaped blades rotating at high speed are bent vertically alternately.

Various processes can be followed in preparing oil-in-water dispersions (hereinafter referred to as "aqueous dispersions") of oil-soluble couplers in accordance with the present invention. When the coupler and the polymer of the present invention are dissolved in an organic solvent, one or two of the above-mentioned high-boiling organic substances, water-immiscible low-boiling organic solvents, and water-miscible organic solvents may be used. Dissolved in any of the above multi-component mixtures and then dispersed in an aqueous hydrophilic colloid solution in the presence of the anionic surfactant used in the present invention. In this case, the anionic surfactant of the present invention is allowed to coexist in at least one of the solution containing the coupler and the polymer of the present invention, or the aqueous hydrophilic colloid solution.

The method of mixing an oily liquid containing an oil-soluble coupler with an aqueous liquid may be the so-called "concentration method" in which the oily liquid is added into the aqueous liquid under stirring, or the reverse mixing method, but among the back-mixing methods, A phase inversion method, which is one type of method, is preferred in that it provides a finer aqueous dispersion.

It is preferable that the anionic surfactant, polymer, and oil-soluble coupler used in the present invention coexist in the silver halide emulsion layer.
Silver bromide, silver bromide, silver iodobromide, etc. can be used.

The amount of anionic surfactant used in the present invention depends on the type and amount of the oil-soluble coupler used, the polymer of the present invention, the high-boiling point organic substance, the low-boiling point WIfJ medium or the water-miscible organic solvent, and in some cases, The optimal amount will vary depending on the type and amount of other surfactants used in combination, but the usable range is 0 for the total of the substances to be dispersed, such as the coupler, the polymer of the present invention, and the high-boiling organic solvent. .5-100 heavy view%
and preferably 1 to 50% by weight. When anionic surfactant (^) and (B) are used together, (A)/
The ratio of (B) is 30/70 to 90/10, more preferably 50,150 to 90/10.

In addition, the anionic surfactant used in the present invention may be used in combination with a hydrophilic surfactant, but the amount used is the same as that of the anionic surfactant (A) and/or (B) used in the present invention.
It is necessary that the amount used is less than that of .

Further, the amount of the polymer of the present invention used is 5 to 5 to
300% by weight, preferably 50 to 200% by weight.

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, nine copies are coated on the support in the above order, but the order may be different from this. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, 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 concentration 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 those surrounding it. Shell (-layer or multiple layers)
Particles with a so-called layered structure that have different halogen compositions, or structures that have parts with different halogen compositions in a non-layered manner inside or on the surface of the particle (if they are on the surface of the particle, there are parts with different compositions on the edges, corners, or surfaces of the particle). Particles having a structure in which parts are joined can be appropriately selected and used. 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 silver halide grains have the above structure, even if the boundaries between parts with different halogen compositions are clear boundaries, they may be boundaries with unknown values due to the formation of mixed crystals due to compositional differences. It is also possible to actively 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 localized silver bromide layer is provided 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 layer is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. , a corner or a surface, and one preferable example is one in which the grain is epitaxially grown on a part of the corner of the grain.

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 the case of this birch, its 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 0.1 μ to 2 μ.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a content of 15% or less is preferable. 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 shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
It is possible to use a material having an irregular (irregu jar) crystal shape such as a spherical shape or a plate shape, or a material having a composite shape thereof. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these, 50% or more of particles having the above-mentioned regular crystal shape,
The content is preferably 70% or more, more preferably 90% or more.

In addition to these, emulsions in which tabular grains having an average aspect ratio (circular diameter/thickness) of 5 or more, preferably 8 or more, account for more than 50% of the total grains as a projected area can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Written by es Chigis et Ph1sique
Photographique (Pau1Mon
te1 Publishing, 1967), G, F, Duffin
Written by Phot.

graphic emulsion chemist
y (published by Focal Press, 1966),
Written by Maki V, L, Zelilvan et al.
ng and Coating Photography
c Emuldion (Focal Press, 1964) and the like. 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. It is also possible to use a method (so-called back mixing method) in which zero particles, which may be used, are formed in an atmosphere containing excess silver ions. 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 Chondrald 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 in the form of emulsion grains or in the process of 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 10@4 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.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F, M, ) He, written by I'arser.
terocyclic compounds-Cyan
ins dies and related cos+
pounds (John Wiley & 5ons
(New 'fork, London 3, 196
4) can be mentioned. As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272 specification, page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be 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 grain. Also good.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation of the phenolic water M group of each of these compounds. Representative examples include alkylated ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360.290,
Same No. 2,418,613, Same No. 2. Too, No. 453, No. 2.701, No. 197, No. 2,728,65
No. 9, No. 2,732,300, No. 2,735,7
No. 65, No. 3,982,944, No. 4,430.
425, British Patent No. 1,363,921, U.S. Patent No. 2,710,801, U.S. Pat. U.S. Patent No. 3,432,3
No. 00, No. 3,573,050, No. 3.514.
No. 621, No. 3.698゜909, No. 3,764
．． No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360.589, P.
-Alkoxyphenols are U.S. Patent No. 2.735.7
No. 65, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 1983
Hindered phenols are disclosed in U.S. Patent No. 3,700.455, etc.
No. 52-72224, U.S. Patent No. 4,228,
No. 235 and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat.
, 332,886, and Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Patent No. 3,336.135.
No. 4,268,593, British Patent No. 1,326
, No. 889, No. 1.354, 313, No. 1.41
No. 0.846, JP 51-1'420, JP 58
-'114036, same No. 59-53846, same No. 5
No. 9-78344, etc., metal complexes are disclosed in U.S. Patent No. 4,0
50,938, British Patent No. 4.241155, British Patent No. 2,027,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705°805)
No. 3,707,395), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070). 3,677.672, 4, 271, and 307) can be used. UV-absorbing couplers (e.g. α-
Naphthol-based cyan dye-forming couplers), ultraviolet absorbing polymers, etc. may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

That is, a compound (F) 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 (G) 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 (F) has a second-order reaction rate constant kt (in trioctyl phosphate at 80°C) with p-anisidine of 1.OjMs+ol ・see ~l
It is a compound that reacts in the range of X10-'l/mol-see.

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

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, k! If it is smaller than this range, the reaction with the remaining aromatic acholine 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.

A more preferable compound (F) can be represented by the following general formula (Fr) or (F[).

General formula (Fl) R+(A)ll-X General formula (Flu) Rx C snow V In the formula, R, and Rg each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n is 1 or Represents O.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, and X represents a group that reacts with an 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,
Y represents a group that promotes the addition of an aromatic amine developing crude drug to the compound of general formula (Fir), where R +
and X, Y and RX 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 (Fl) and (FII), see JP-A-63-158545 and JP-A-62-
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 are preferred.

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

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z is a nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. A compound represented by the general formula (Gl), which represents a group, has Z as Pearson's nucleophile "CHsl (!
! (R.G. Pearson, at al.
J, Am.

Chell, Soc, 90.319 (1968
)) is preferably 5 or more, or a group derived therefrom.

Specific examples of the compound represented by -M formula (Gl) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-Open No. 1430-1983.
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-414681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive materials produced using the present invention contain water-soluble dyes or dyes that become water-soluble through photographic processing as filter dyes in the wood-philic colloid layer or for various purposes such as preventing irradiation and halation. Such dyes which may be used 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.

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

In the present invention, the gelatin may be either lime-treated or acid-treated.Details of the gelatin manufacturing method can be found in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis. Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

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. Includes 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-based 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,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to provide a layer of water-resistant resin, especially a thermoplastic resin, on the metal surface, which is preferably obtained by vapor-depositing the metal on another substrate. It is preferable to provide an antistatic layer on the side opposite to the metal surface of the support of the present invention.For details of such a support, see, for example, JP-A No. 61-210.
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

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 most typically calculated by dividing the observed area into 6-×6- adjacent unit areas and projecting them onto that unit area. It can be determined by measuring the occupied area ratio (%) (R+) of the fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of R1 to the average value (R) of R1. The number of target unit areas (n) is preferably 6 or more, and therefore the coefficient of variation s/R can be determined by s/R.

In the present invention, the occupied area ratio of #1114 fine particles (
%) is preferably 0.15 or less, particularly 0.12 or less. When O,OS or less, the dispersibility of the particles can be said to be substantially "uniform."

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-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-anoN, N-diethylaniline, -methyl-4-amino-N-ethyl-N
-β-Hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonadoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Mention may be made of β-methoxyethylaniline and its sulfates, hydrochlorides or p-)luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain a phi buffer such as an alkali metal carbonate or phosphate, a development inhibitor or antifoggant such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole, or a mercapto compound. It is common to include In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N
- hydrazines such as biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine,
Various preservatives such as catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers 1-phenyl- Auxiliary developing agents such as 3-virapritone, viscosity imparting agents, various calcinates such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids,
For example, ethylenecyyonetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N
, N-)rimethylenephosphonic acid, ethylenediamine-N
, N,N'N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, color development is usually performed after black and white development and reversal processing. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virapritones such as 1-phenyl-3-virapritone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, the aperture ratio - the contact area between the processing liquid and the air (cm")/the capacity of the processing liquid (cn'+'
) The aperture ratio is preferably 0.1 or less, more preferably 0.00 to 0.05.

As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, methods using a movable lid as described in Japanese Patent Application No. 62-241342, Examples include the slit development method described in Japanese Patent No. 63-216050.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include compounds of polyvalent metals such as iron (III). Typical bleaching agents include organic complex salts of iron (Ill), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, Aminopolycarboxylic acids such as methyliminodiacetic acid, 13-diaminopropanetetraacetic acid, glycol ether cyanotetraacetic acid, and complex salts such as citric acid, tartaric acid, and malic acid can be used. Of these, iron ethylenecyaminetetranolate (Il[)i! Aminopolycarboxylic acid iron(III) Il salts, including aminopolycarboxylic acid iron(III) salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron(III) Il salts are particularly useful in both bleaching solutions and bleach-fixing solutions. Useful. The pll of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (IIIHff salts) is usually 4.0 to 8.0, but in order to speed up the processing, it may be processed at an even lower pH. can.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, JP-A-53-95630, Research Disclosure No. 17,129 (1978
Compounds having a mercapto group or disulfide bond as described in J.P. 1987-140129; thiazolidine derivatives as described in JP-A-50-140129: U.S. Patent No. 3,706,56
Thiourea derivative described in No. 1: JP-A-58-16235
Iodide salts described in West German Patent No. 2.748.430; polyoxyethylene compounds described in West German Patent No. 2.748.430;
Polyamine compounds described in No. 836; 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 U.S. Pat. No. 3,893,858 and West German Patent No. 1.
．． No. 290,812 and JP-A No. 53-95630 are preferable, and moreover, compounds described in U.S. Pat.
The compounds described in No. 34 are also preferred. These bleach accelerators may be added to light-sensitive materials. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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 Preservatives for bleach-fix solutions include sulfite, bisilicate, p-
) Sulfine #IM or carbonyl bisulfite adducts such as luenesulfinic acid 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 Te1eν1si
on Engineers Vol. 64, p. 248-2
53 (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 photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal J (1986), Sankyo Publishing, complete edition of sanitary technology, "sterilization of microorganisms, sterilization, antifungal technology J (1982), Society of Industrial Technology, Japan antibacterial and antifungal “Encyclopedia of antibacterial and antifungal agents” edited by the academic society (198
The fungicides described in 6) can also be used.

The pl+ 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.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40'C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the 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 a color developing agent, it is preferable to use various precursors of the color developing agent. 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. 9
, 719,492, JP-A-53-13
Examples include urethane compounds described in No. 5628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
It is also possible to incorporate birapritons. Typical compounds are described in JP-A Nos. 56-64339, 57144547, and 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50'C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

〔Example〕

Next, the present invention will be specifically explained using examples.

(Example 1) 3.0 g of the coupler represented by the following formula, 2.0 g of di-n-butyl fucury, and the surfactants and polymers shown in Table 1 were added to 8-ethyl acetate and heated to about 40°C. and completely dissolved. (Liquid A) 6g gelatin
was dissolved in 30 ttrl of water, maintained at 40°C, and the previously prepared solution A was gradually added thereto, followed by stirring for 30 minutes using a high-speed stirring homogenizer (manufactured by Nippon'jR Machine) to prepare an emulsified dispersion. The average particle size of this emulsified dispersion is 0.1 to 0.2μ
Met. On the other hand, silver chlorobromide emulsion (AgBr70wolX
, cubic, average particle size 0.49 m, variation coefficient 0.0
8, AgBr70molX, cube, average particle size 0.34μ, coefficient of variation 0. 1:2 with that of lO
(Mixed at a ratio of (Ag molar ratio)) sulfur-sensitized,
The following red-sensitizing dyes were added at 5.5% per mole of roots. OX
A 10-' mole addition was prepared. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution having the composition shown below, and it was applied to an undercoated polyethylene Ukunate Gi (containing titanium oxide as a reflective material) support. .

(Red-sensitive sensitizing dye) (0.9 x 10 4 mol per mol of halogenated i) First, each sample was tested with a sensitometer (manufactured by Fuji Photo Film Co., Ltd.),
FIIH type, light source color temperature 3200 K) is used,
gave exposure. The exposure at this time was 2 with an exposure time of 0.1 seconds.
The exposure amount was set to 50 CMS.

The exposed sample was processed using an automatic processor using the following processing steps and processing solution composition.

Nobuhi L Cheng gain - once ship - one plate color development
Bleach and fix at 37℃ for 3 minutes and 30 seconds 33
Wash with water for 30 seconds at °Ct Dry for 3 minutes at 24-34℃
Drying at 70-80°C for 1 minute &I for each treatment solution
l or as follows.

Imperial Second Return Statue Naomizu 8
00 Diethylenetrianepentaacetic acid 1.0 Nitrilotriacetic acid 2.0 Hensyl alcohol 15 Diethylene glycol
10 Sodium sulfite
2.0 potassium bromide
1.0 Potassium carbonate 3ON-
Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoanilide sulfate Hydroxylamine sulfate HHITEX B 4.5g 3.0g, 0 iooo - 10,25 Add water to pH (25" C) Kanji-44 liquid water 40
0 dAmmonium thiosulfate (70%) 15
0 d Sodium sulfite 18
g ethylenediaminetetraacetate iron (Ill) ammonium 55 g ethylenedimine 1 um 5 add water
1000 dpH (25℃)
6.70 The cyan dye density of each sample obtained was measured using a transmission densitometer through a red filter.

Next, the sample was kept in an oven at 80° C. and 70% RH, and the change in cyan concentration over time was measured. The results are shown in Table 1.

This result shows that when an oil-soluble surfactant and/or a fluorine-containing surfactant is used in combination with a polymer as in the sample of the present invention, the thermal storage stability of the colored cyan dye is specifically improved.

Chest 1 Back Example 2 A multilayer color photographic paper having the following layers 111i was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (RxY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cp
d-7) 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) were added to 0.7 g and dissolved. 8
10% sodium dodecylbenzenesulfonate 8c
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing c. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.
A 3:7 mixture of 88pa and 0.70μ (
151 molar ratio) 0 The coefficient of variation of the particle size distribution is 0.08
and 0.10, each emulsion contains 0.2 mol% of silver bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below! ! 2.0X10 for large size emulsions per mole, respectively.
-' moles were added, and for small size emulsions, sulfur sensitization was prepared after adding 2.5 x 10 -' moles, respectively.

The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.The coating solutions for the second to seventh layers were also prepared in the same manner as the Nth coating solution. Prepared. However, in preparing the emulsification liquid for the fifth layer,
Similar to j41, the surfactant and polymer were added as shown in Table 2.

The surfactant, polymer species, and amounts added are shown in Table 2. The gelatin hardening agent for each layer is l-oxy-3,5
-dichloro-5-) riazine sodium salt was used.

The blue-sensitive emulsion layer 0xe SOJH(CJs)s using the following as the spectral sensitizing dye in each layer (per 1 mole of halogenide, 2 for large emulsions, OX 10-' mole, and small size emulsions [2.5xlO-' mol each for the green-sensitive emulsion layer (4.0x10-' mol per mole of silver halide for large size emulsions, 5.0x10-' mol for small size emulsions). 6X10-' mol) and (7.0XIO-' mol for large emulsions and 1.0 (0.9 x 10-' mol for large size emulsions and 1.1 x 10-' mol for small size emulsions) for the red-sensitive emulsion layer. Halogenated I
2.6 x 10-' moles were added per mole.

In addition, 1-(5-methylureidophenyl)5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively, per mole of silver halide.
5 X 10-' mol, 7.7XIO-' mol, 2.5
X 10-' moles were added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mole of silver halide, respectively, at t x 10-
'mol and 2XlO-'mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (Layer configuration) The composition of each layer is shown below, and the numbers represent the coating amount (g/%). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper (the polyethylene on the first layer side contains a white pigment (Tilt) and a bluish dye (ulmarine blue))] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35
Color image stabilizer (Cpd-ma) 0.
06 Second N (color mixing prevention layer) Gelatin 0199 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6 solvent (Solv-4)”
"Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55 m and one with an average grain size of 0.397 jll (48
molar ratio) 0 The coefficient of variation of the particle size distribution is 0, IO and 0.
08, each emulsion contained 8 mol% of AgBr O locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (
Ext) 0.20 color image stabilizer (Cp
d-2) 0.03 color image stabilizer (
Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02
Solvent (Solv-2) 0.
40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (Cpd-5) 0.0
5 Solvent (Solv-5) 0
．． 24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 134 mixture of one with an average grain size of 0.58a and one with an average grain size of 0.45-(Ag molar ratio) 0 The coefficient of variation of the grain size distribution is 0.09 and 0.11,
(Each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23 gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-
6) 0.17 color image stabilizer (Cp
d-8) 0.04 solvent (So
lv-6) 0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (υV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.02
Solvent (Solv-5) 0.
08 Seventh layer (protective layer) Gelatin 1.3 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.17 liquid paraffin 0.03 ([!xY) 1:1 mixture (molar ratio) with yellow coupler (ExM) 1:l mixture (molar ratio) of magenta coupler (1!xC) with cyan coupler R”CJs Mixture of 2:4:4 by weight of C, ) 1% and H (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-6) Color image stabilizer C4Hq(t) 2:4:4 mixture (weight ratio) (Cpd-7) Color image stabilizer 1+:CO , -Cold T- (Cpd-8) Color image stabilizer 0■ (Cpd-9) Color image stabilizer (UV-1) 4:2:4 mixture (weight ratio) of ultraviolet absorber (Sol Sea 1) Solvent (Solv-2) 2:1 mixture of solvents (volume ratio) (Solv-4) Solvent (Solv-5) Solvent C00CIHI? (CH*)a C00CsH+t (Solv-6) Solvent The exposure of each sample was Gradation exposure was given using a three-color separation filter for measurement.After exposure, the sample was
Continuous processing (running test) was carried out using a paper processing machine until twice the capacity of the color development tank was replenished in the next processing step. ” Quantity color development 35℃ 45 seconds 1
611d l? ffi bleach fixing 30-35°C
45 seconds 215 minutes 171 rinse■ 30-35℃
20 seconds □ 1ON rinse■ 30-35℃ 20
seconds □ 101 rinse■ 30-35°C 20 seconds
350m 10N drying 70~80℃ 60
The amount of replenishment in the refill was per 1 rrf of the photosensitive material (a 3-tank countercurrent flow system was used from rinsing ■ to ■). The composition of each processing solution was as follows.

Standing two miles east trace LZL and place light blood water
800 d 80
0 af ethylenediamine-N, N N, N-tetramethylenephosphonic acid 1.5 g 2.0 g
Potassium bromide 0.015 g Triethanolamine 8.0 g 12.0 g Sodium chloride 164 g Potassium carbonate
25 g 25 gN-ethyl-N
-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g
N,N-bis(carboxymethyl)hydrazine 5.5 g 7.0 g
Fluorescent brightener (WHITBX 4B.

Sumitomo Chemical) Add 1.0g2.0g water 1000af 1000dp
i (25°C) 10.05 10
．． 45 minutes fixed amount of water (tank fluid and refill fluid are the same)
400 d
Ammonium thiosulfate (70%) 100 a
! Sodium sulfite 17 g Ethylenecyaminetetranodic acid iron (■) Ammonium 5g Ethylenediaminetetraacetic acid disodium 5g Add water to 1000 dpH (25°
C) 6.0-center z≦9 panic (
Tank fluid and refill fluid are the same) Ion exchange water (calcium,
The cyan dye concentration of each obtained sample was measured using a reflection densitometer through a red filter.

Next, when the sample was stored at 80°C under 70% IJH for 15 days and when it was stored under sunlight for 10 days, the rate of decrease in density from the initial density of 1.0 for cyan, magenta, and yellow was measured. It is shown in Table 3.

Table 3 shows that when the oil-soluble surfactant and polymer of the present invention are used in combination, thermal fading of cyan is specifically improved, and photofading is not worsened.

201 (For comparison) Triisopropylnaphthalene sulfonate 0.5 (For comparison) (P-57) 03 (For comparison) 1.0 04 (For comparison) Compound example (P-57) 3.0 (For comparison) (A 1) 06 (present invention) 0.5 Compound example (P-57) 3.0 (present invention) (P-65) (for comparison) (B-1) Table 3 (continued) Note) A negative value for layer B means an increase in apparent concentration.

In addition, in the above examples, P~57 and P-
P-103 to P-107, P-159 instead of 65,
Alternatively, similar results were obtained when P171 was used in combination with ^-17 instead of ^-1 and A-2 as the anionic surfactants used in the present invention.

(Effects of the Invention) The combination of an anionic surfactant and a polymer according to the present invention specifically improves the fading of dye images. This effect is especially noticeable from cyan couplers.

Claims (1)

[Scope of Claims] At least one selected from the following anionic surfactants (A) and (B) and at least one water-insoluble and organic solvent-soluble individual or copolymer for photographic use. A silver halide color photographic material characterized by containing an oil-soluble coupler. (A) At least 15 carbon atoms as a hydrophobic part in the molecule
or at least two aliphatic hydrocarbon groups having a total carbon number of at least 17. (B) An anionic surfactant having at least a fluorine-substituted aliphatic hydrocarbon group having 4 or more carbon atoms as a hydrophobic portion in the molecule.