CA1338101C - Silver halide color photographic material - Google Patents

Abstract

A silver halide color photographic material comprising a support having thereon at least one silver halide photographic emulsion layer containing a dispersion of oleophilic fine particles obtained by emulsifing and/or dispersing a mixture solution containing at least one oil-soluble coupler which is capable of forming a dye upon coupling with on oxidation product of an aromatic amine developing agent and represented by the general formula (I) described below and at least one non-color forming oil-soluble polymer.

(I) wherein Q1 represents an atomic group necessary to form a 5-membered or more nitrogen-containing heterocyclic ring containing at least one nitrogen atom together with the carbon atoms; Z1 represents a hydrogen atom or a group capable of being released upon a coupling reaction with an oxidation product of a color developing agent;
R1 represents an acyl group or a sulfonyl group; R2 represents a hydrogen atom or an aliphatic group having from 1 to 8 carbon atoms, or R1 and R2 may combine with each other to form a ring; and the coupler may form a dimer or polymer coupler by a substituent for R1, R2, Z1 or Q1.
The silver halide color photographic material can provide dye images, the prevention from light fading and dark fading of which is well balanced, and which exhibits image preservability under condition of high temperature and high humidity.

Description

~ ~ 1338101 SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL

FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic material, and more particularly relates to a silver halide color photographic material which can form dye images having excellent image preservability.
BACKGROUND OF THE INVENTION
It is known that dye images formed from silver halide color photographic materials are sometimes permitted to be exposed to irradiation by light for a long period of time or are left in a dark place for a long time with only a short period of irradiation to light. These conditions can cause severe fading of the dye image. In general, fading under the first circum-stance is known as light fading and fading under the second circumstance is called dark fading. When records formed from color photographic light-sensitive material are semipermanéntly stored, control over such light fading and dark fading to as great an extent as possible and maintenance of three color balance in the fading of yellow, magenta and cyan dye images are necessary so that the initial state of color balance is maintained.
However, the degree of light fading and dark fading of .. ......

t ~ 1338101 yellow, magenta and cyan dye images are different from each other and, thus, the three color balance in fading of yellow, magenta and cyan dye images is destroyed, resulting in degradation of image quality after the preservation for a long period of time.
Although the degree of light fading and dark fading is naturally different depending on the particular color couplers employed and other factors, in many cases dark fading is apt to occur in the order of cyan dye images, yellow dye images and magenta dye images, and the degree of dark fading in cyan dye images is particularly great compared with that of other dye images. Light fading also tends to occur in the order of cyan dye images, yellow dye images and magenta dye images, particularly when the light source is emitting a large amount of ultraviolet rays.
Therefore, maximum prevention of light fading and dark fading of cyan dye images is necessary in order to maintain three color balance between yellow, magenta and cyan dye images for a long period of time. For the purpose of preventing light fading and dark fading of dye images, various kinds of investigations have been heretofore made, which mainly have followed to two approaches to the problem. One approach has been to develop novel couplers which can form dye images having less a tendency to fade. The other approach has been to develop novel additives capable of preventing fading.
A large number of phenol type cyan couplers which form cyan dyes are known. However, 2-(a-2,4-di-tert-amylphenoxybutanamido)-4,6-dichloro-5-methylphenol as described in U.S. Patent 2,801,171, for example, has the disadvantage that the dye formed therefrom has poor heat fastness while it has good light fastness.
Further, cyan couplers having an alkyl group containing 2 or more carbon atoms substituted on the 3-position or 5-position of phenol are described, for example, in JP-B-49-11572 (the term "JP-B" as used herein means an "examined Japanese patent publication"), JP-A-60-209735 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), and JP-A-60-205447. The heat fastness of cyan images formed from these couplers is improved to some extent but still insufficient.
Moreover, 2,5-diacylaminophenol type cyan couplers in which the 2-position and 5-position of the phenol are substituted with an acylamino group are described, for example, in U.S. Patents 2,369,929, 2,772,162 and 2,895,826, JP-A-50-112038, JP-A-53-109630 and JP-A-55-163537. Although the heat fastness of cyan images formed from these 2,5-diacylaminophenol type cyan couplers is improved, their color forming property is poor, cyan images formed therefrom are sensitive to light fading and yellow stain is apt to occur due to irradiation of the unreacted cyan couplers to light.
Also, further improvement in heat fastness is required.
l-Hydroxy-2-naphthamide type cyan couplers are generally not satisfactory with regard to both light fading and dark fading.
Further, cyan couplers in which a nitrogen-containing heterocyclic ring is condensed to a phenol nucleus are described, for example, in U.S. Patents 4,327,173, 4,564,586 and 4,430,423, JP-A-56-104333 and JP-A-61-390441. Although the light fastness and heat fastness of cyan images formed therefrom are improved to fair extent, the problem in that pink stain occurs upon the irradiation to light is encountered.
Furthermore, a method wherein a hydrophobic substance such as an oil-soluble coupler is dissolved in a water-miscible organic solvent and the solution is mixed with a loadable polymer latex whereby the hydrophobic substance is loaded in the polymer latex is described, for example, in U.S. Patent 4,203,716.
However, the method using such a loadable polymer latex has the disadvantage that cyan images are particularly inferior in light fastness in comparison with a case of ~ - 1338101 employing a water-immiscible coupler solvent having a high boiling point. In addition, it is necessary to employ the polymer in a large amount in order to load sufficient amount of coupler to obtain a sufficiently high maximum color density.
Still further, JP-B-48-30494 describes a photo-graphic material containing a coupler dispersion (dia-meter of dispersion particles being about 0.5 ~m to 5 ~m) which is prepared by using an organic solvent-soluble homopolymer of a hydrophobic monomer having a specific structure or copolymer of a hydrophobic monomer having a specific structure and a hydrophilic monomer having a specific structure in place of the coupler solvent having a high boiling point. Improved physical properties of the layer, improved re-coloring ability, light fastness and preservability before photographic processing, etc., are achieved. However, in the case wherein the homopolymer of a hydrophobic monomer as described in JP-B-48-30494 is employed in place of the coupler solvent, low color forming ability is encounter-ed. This tendency particularly manifests itself when a color developing solution which does not substantially contain a color forming accelerator such as benzyl alcohol is used, as described in the examples of the above-described patent publication. Another problem is that the stability of the emulsified dispersion is poor.
On the other hand, when using a copolymer containing a hydrophilic monomer such as acrylic acid, etc., the stability of the emulsified dispersion and color forming ability are improved to some extent, but are still insufficient. Further, when the ratio of hydrophilic monomer in the copolymer is increased in order to improve color forming ability, fading, particularly heat fading at high humidity, is accel-erated. In addition, both polymers have the problems of crystallization of couplers during storage of the emulsified dispersion, because t-he polymers are inferior in preventing the crystallization of couplers.
Further, when the method as described in JP-B-48-30494 is applied to cyan couplers, light fastness is severely degraded (1.5 to 3 times) compared with when the couplers are dispersed using a conventional solvent having a high boiling point (known as the oil dispersing method).
In addition, with the method as described in JP-B-48-30494, further problem is that the hue of cyan dyes changes over time. More specifically, the spectral absorption of cyan dyes formed upon color development is in a longer wavelength range just after development . .

`. 1338101 processing but readily shifts to a shorter wavelength during storage, particularly when exposed to high temperatures.
As described above, couplers that prevent dark fading by means of modification of their structure have significant disadvantages with regard to hue, color forming ability, stain, and/or light fastness. There-fore, a novel way to avoid these problems has been desired.
Also, a way to prevent dark fading using other additives or dispersing methods which are known has certain problems and an effective means free from such disadvantages has not been found heretofore.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a silver halide color photographic material which can form dye images in which light fading and dark fading are controlled in good balance and which exhibits excellent image preservability particularly when exposed to high temperature and high humidity.
Another object of the present invention is to provide a silver halide color photographic material which can form dye images having good color balance in the fading of yellow, magenta and cyan color images by controlling the degree of fading, whereby excellent .

-preservability is obtained when the photographic material is stored for a long period of time.
A further object of the present invention is to provide a silver halide color photographic material which can form dye images having improved image preserv-ability without adversely affecting the desired properties of the photographic material.
A still further object of the present invention is to provide a silver halide color photographic material having excellent image preservability which contains a coupler emulsified dispersion which exhibits sufficiently high color forming ability even when processed with a color developing 601ution which does not substantially contain benzyl alcohol and has good stability.
A still further object of the present invention is to provide a silver halide color photographic material having improved dark fastness without degrada-tion of light fastness of cyan dye images.
Other objects of the present invention will become apparent from the following detailed description and examples.
As a result of various investigations, it has been found that these objects of the present invention can be effectively accomplished with a silver halide ~ . . .. . .

color photographic material comprising a support having thereon at least one silver halide photographic emulsion layer containing a dispersion of oleophilic fine particles obtained by emulsifing and/or dispersing a mixture solution containing at least one oil-soluble coupler which is capable of forming a dye upon coupling with on oxidation product of an aromatic amine developing agent and represented by the general formula (I) described below and at least one non-color forming oil-soluble polymer.

OH
N ~ (I) Z

wherein Ql represents an atomic group necessary to form a 5-membered or more nitrogen-containing heterocyclic ring containing at least one nitrogen atom together with the carbon atoms; Zl represents a hydrogen atom or a group capable of being released upon a coupling reaction with an oxidation product of a color developing agent;
Rl represents an acyl group or a sulfonyl group; R2 represents a hydrogen atom or an aliphatic group having _ g _ from 1 to 8 carbon atoms, or Rl and R2 may combine with each other to form a ring; and the coupler may form a dimer or polymer coupler by a substituent for Rl, R2, Z
or Ql-DETAILED DESCRIPTION OF THE INVENTION
In the following, the cyan couplers represented by the general formula (I) according to the present invention are described in more detail.
In the general formula (I), the atomic group represented by Ql include groups which contain at least one nitrogen atom and a methylene bond, an ethylene bond, an imino bond, a sulfonyl group, a carbonyl group, an arylene group, a divalent heterocyclic group or a combination of two or more of these groups. These groups may further have one or more substituents.
In the general formula (I), Zl represents a hydrogen atom or a group capable of being released upon coupling. Examples of the groups capable of being released upon coupling include a halogen atom (for example, fluorine, chlorine, or bromine), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethyl-carbamoylmethoxy, carboxypropyloxy, or methylsulfonyl-ethoxy), an aryloxy group (for example, 4-chlorophenoxy, 4-methoxyphenoxy, or 4-carboxyphenoxy), an acyloxy group (for example, acetoxy, tetradecanoyloxy, or benzoyloxy), a sulfonyloxy group (for example, methanesulfonyloxy, or toluenesulfonyloxy), an amido group (for example, dichloroacetylamino, heptafluorobutyrylamino, methane-sulfonylamino, or toluenesulfonylamino), an alkoxy-carbonyloxy group (for example, ethoxycarbonyloxy, or benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), an aliphatic or aromatic thio group (for example, ethylthio, phenylthio, or tetrazolylthio), an imido group (for example, a succin-imido, or hydantoinyl), and an aromatic azo group (for example, phenylazo). These groups may contain a photo-graphically useful group.
In the general formula (I), Rl preferably represents a group represented by -CO-Xl-R4 or a group represented by -SO2-Xl-R4, wherein Xl represents -O-, -NR5- or a simple bond; and R4 represents a chain or cyclic aliphatic group, preferably an aliphatic group having from 1 to 32 carbon atoms (for example, methyl, butyl, tridecyl, or cyclohexyl), an aryl group (for example, phenyl, naphthyl), or a heterocyclic group (for example, 2-pyridyl, 2-imidazolyl, 2-furyl, or 6-quinolyl). These groups can be substituted with one or more substituents selected from an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, methoxy, or 2-methoxyethoxy), an aryloxy group 133~101 (for example, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, or 4-cyanophenoxy), an alkenyloxy group (for example, 2-propenyloxy), an acyl group (for example, acetyl, or benzoyl), an ester group (for example, butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, or toluenesulfonyloxy), an amido group (for example, acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methane-sulfonamido, or butylsulfamoyl), a sulfamido group (for example, dipropylsulfamoylamino), an imido group (for example, succinimido, or hydantoinyl), a ureido group (for example, phenylureido, or dimethylureido), an aliphatic or aromatic sulfonyl group (for example, methanesulfonyl, or phenylsulfonyl), an aliphatic or aromatic thio group (for example, ethylthio, or phenylthio), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, or a halogen atom.
The above aliphatic group may be linear, branched or cyclic and saturated or unsaturated.
R2 and R5 each represents a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms (for example, methyl, ethyl, iso-propyl, cyclohexyl, 2-ethylhexyl, or allyl), and R2 and R5 may further contain a substituent as described for R4.
R2 and Rl or R4 may form a cyclic structure, and it is preferably 5, 6, or 7 membered ring.

1~38101 The preferred Zl is a hydrogen atom, a halogen atom, an aryloxy group, an arylthio group or an alkoxy group, and a chlorine atom is particularly preferred.
A preferred cyclic structure which is formed by Ql is a 5 to 7 membered ring. Of these, 5 or 6 membered ring is particularly preferred, and the most preferred is a 5 membered ring.
In the general formula (I), Rl preferably repre-sents a group of -CO-Xl-R4. Of these groups, a group of -CO-R4 which is a group of -CO-Xl-R4 wherein Xl is a simple bond is particularly preferred.
In the general formula (I), R2 is preferably a hydrogen atom.
When the coupler represented by the general formula (I) forms a dimer coupler, it is preferred that it is formed via Ql or Rl.
Further, when the coupler forms a polymer coupler, it is preferred that it is formed via Zl or Rl, particularly via Rl.
The addition amount of the cyan couplers represented by the general formula (I) is lx10-3 mol to 1 mol per mol of silver halide. Preferably, it is lx10-3 mol to 7Xlo-l mol, and more preferably, it is lx10-2 mol to 5xlO-l mol per mol of silver halide.

1~38101 The cyan couplers represented by the general formula(I) are typically incorporated into a red-sensitive layer, but the present invention should not be construed as being limited thereto (e.g., it can be added into an infrared ray sensitive silver halide emulsion layer).
The synthesis method of the cyan couplers represented by the general formula (I) is disclosed, e.g., in U.S. Patents 4,327,173, 4,564,586, and 4,430,423.
Preferred examples of the cyan couplers repre-sented by the general formula (I) are specifically set forth below, but the present invention should not be construed as being limited thereto.

13~8101 ( C--1 ) Ç21~, HCOCHO~C,H" (t) ~ C~H" (t) H
(C--2) o~ hHl~ocho~csH I I (t) H CSH~l(t) (C--3) F F
C~NCO~

H CQ
(C-4) Ce HCONH ~ C~I

H O--~C8H 17 ( t) tC-5) ~ ,hlHCO#H ~

O N~ NHSO2CI hH33 H Ce (C-6) CH~
H C~ 15 'i 13~8101 ( C - 7 ) ,NHCO ~ \~
NHSO2ClbH33 H C~

( C - 8 ) C ~ HCO ~ C
o NHCOC,.H35 H C~

(C--~ ) ÇIZHz, . ~ YHCOCHO ~ OH

O h ~ C4H9(t) H OtCH2)3COOH

( C - 1 O ) O ~ HCOCHO ~ C,H,l(t) (C--1 1) C~H~
o ~ ~ ~HCOCHO ~ ,HII(t) o ~ C5H,I(t) C~

(C- 1 2 ) O H~IHCO~
~-N~ NHCOC, 7H3, (iso) H CQ

(C- 1 3 ) O~ hHCO~
N IYHCOC, 3H2, H C~

(C--1 4) N~ ~ ~NHCOCHO ~ OC4H9 .C~H9 tt) H C~

( C--1 5 ) CCH~
OH NHCO ~
CH3--N~( NHSO2~0CJ 2H25 H C~

(C-l 6) o~NllCO ~
o~N NRSOz (CH2) 20CI 2H2, H C~

.... ...... .

- 13~8101 (C--1 7) S f ~ ,~HCO ~ ~ ~ ~r'`~
o~N~ NHSOzCH2) JSO2NH c~

(C-l 8) o l N ~ NHCOCHO ~ CsHtl(t) C~ CsHIl(t) ( C - 1 9 ) jN'HCOCHC~H9 ,NHCO ~ C2H5 ~ ~ NHCOC~HC~H9 - H C~ CzHs ( C - 2 O ) ~C,2H2. NHSO2C4Hg H C~

( C - 2 l ) C~H, 7 ,NHCOCHO ~ C~H I 7 (t) H C~

(C-2 2) NllCOCHO~CsHI I (t) N C~ CsH~ I (t) (C--2 3) C~HCO~CHC H9 H C CsH,7(t) (C--2 4) N$~HC

H C~

(C--2 5) N~NIICO~ C 11 Csllll~t) H C~ CsHIl(t) tC--2 6) H ~ H~NHCO--~HO ~ NHSOZC4H9 C~
- 1 9 _ (C - 2 7) ~ HCOCHCI2H2s (C - 2 8) ~ N ~ NHCOCH0 ~ sHIl(t) (C - 2 9) C~H3 IOH HCo4~

~ N ~ NHSOz(CHz?~0 ~ CsHIl(t) (C - 3 0) ~ ~ ~ NHC0 ~
o 1~ ~ e NHSOzCI~H33 (C - 3 1) C2H~
~ N ~ NHCOCH0 ~ C~H " (t) o N ~ C,H" (t) .. ...

(C - 3 2) CH ~ ~ 'HCO ~ NHCOCH ~ CsHI~(t) CH3 NHSOz ~ C
H C

(C - 3 3) C,H "

C4H~ - ~ HCOCHO ~ C,H " (t) (C - 3 4) C2H~
NH ~ ~ HCOCHO ~ C~H~s(t) o~N~ C~HIs(t) H C~

( C - 3 5) (t)~H~ ~ OCNCON ~ NNCOCNzCNzCONU ~ /NHCOCNO ~ ~~CsN" (t) C~ NHcocH2cH2coNH T

(C - 3 6) HCOCH ~ CsHIl(t) H C~

1~38101 (C-3 7) C2H~
~_g~¢~HCoCHo$~C~H I ~ ( t) H C~

tC-3 8) OH NHCo4--3 NHSO2C~ oHs3 H C.e (C--3 9) ~NHCO~ ~H I J
g~N~ NHCOGNO~C~H~ I tt~
H C~¢ - . C~

(C-4 O) N~H~O~O ~H~ ~ (t) a~~ C,H, I ~t) C~
(C-4 1) CHs CIHs ~CH2-C )~, ( CH~-CH )30 (CHz-C~r IONH~COOC4Hq GOOH

CQ H

13381~1 (C--42) CH3 ~CH2-C ~o t CH2-CH )~o (CHz-C~
COOC<H~ COOH
C O.YH~/~
\CO~H ~ C~.CH3 \~Nr~ ' C~ H

(C-~ 3) ~CHt-CH )~o t CH2-CH )~o (CH2~ o COOC~H9 COOH

IIHC~'~
'.~ F

~C--4 4) CH~NHCO~
~N~ NHSOzC~H~
H O(CH2) 3SCHC, 2H25 cooa ~C--4 5~
C~ ,~iJco~C~

N rJ NHSO2~QCI ~Hz5 H C~

(C - 4 6) \N NHSO2C,~H33 H C

(C - 4 7) O=~N~g NHSOz~OC~ 2Hz~
H C

( C 4 8 ) CH~NHCO~ . ~ H

~N~ NHCOCHO ~S02~0H

( C--4 9 ) OC8H. 7 ~j NHSOz~
N'~r C8H,7(t) H C

(C-5 O) CHzCH20CH3 ~ NHCOCH -C,2H25 H C~

, 13~8101 ( C - 5 1) o~\~HCOCHO~NHSO2N(C3H7) 2 C~
~HCOC.H9(iso) (C - 5 2) HCO ~ C Q
NHSO2C,~H33 C~

(C - 5 3) C2H, O ~ ~ NHCOCHO ~ CN

C

(C - 5 4) O ~ NHCOCHO ~ 5H " (t) HN ~ C5HI,(t) C~
(C - 5 5) O~
N,l ~ SOzNHClbHss(n) H C~

.

_ 13~8101 (C - 5 6) CH ~ HCO ~ j C~2Hz~(n) O ~ N ~ NHCOCHO ~
H C NHSOzN(CH3)z ( C - 5 7) C ~ HCO ~ C ~ (t) N ~ NHSOz(CHz)40 ~ C,H " (t) H C~

( C - 5 8) HCO ~ C~
N ~ NH502(CHz)40C,zHz5(n) H C

tC - 5 9) <N 1 ~ NHSO ~ OC~zH 2 5 (n) H C~
t C - 6 O) - ~ ~ ~ NHSO C
H C~

(C - 6 1) CoH ~ H3 ~H HCO ~ C~
<hr ~ NHS02- ~ OCI2Hzs (n) H C~

( C - 6 2) C~
C~Hg~JlHCO~CQ
O = ~N ~ NHSO2C~zH2s (n) H C~

(C - 6 3) ClzHz ~ HCOC3F~

H CO

C - 6 4) H C~ CsH~7(t) (C - 6 5) CzH~
~ ~ OH~NHCO ~ C~H~(t) ~ ~ ~ NHSO2(CH~)~O ~ C,H " (t) C~
C2Hs (C - 6 6) CHsSO ~ ~ (t) ~ ~ ~ CO~H(CHz)30 ~ CsH~I(t) H C~

(C - 6 7) (t)C~H~ ~ O(CH2)~SO2NH ~ I H ,NHCO ~ F
CsH~l(t) O ~ ~ ~ F

H CQ
(C - 6 8) ~ NHC.OC~7H3s-n H C

(C - 6 9) ~ HC~
= ~ NHCOICHO ~
H C~ Cl2H2s NHSO2CH3 (C - 7 O) tn-)C IzH250 - CH ~ ~NHC ~ F

H C

1~38101 tC--7 1) N NHS02CI ~H3 ~ (-n) H o CBH,2(t) (C--7 2) NHCOCI~Hst (-n) C~HCO~

H O

(C--7 3) C~HCQ~
N~ NHCOOCI zH2~ (-n) H S\~

OC, 2Hzs-n (C--7 4) C~H~ NNCORH (CHz) JO~C,H " (t) H S\~ HI2(t) CsHI l (~) (n) C~H~O

NHC ~

N NHCOC,sH3s H C~

( C- 7 6 ) H C~ Cl zH25 (C-77) ~HCO~

H O

C4Hs tt) (C-78) ~

~ NHCONH ~H2)30 ~ C,H" tt) H O\ CsHI I ~t) ~, CsHI2(t) (C-79) IC,H, I (n) F F
~NHC~

H O
~, O-CI 2Hzs (n) -(C-80)CsH~s(n) NHCOC3~2 H O

C~

(C-81) C~

~N~ NHCOCI2H3s (n) H O -CN

(C-82) OCH3 CH~J~IHCO~ C~
O -- \ ~ NHCOCH-O ~ CsH" (t) H S ClbH33(n) \[~\
. OCI2H2s (n) ( C- 8 3 ) Iy~HCOC I zHs ~ (n) C~HCO~

H S Oc~Hs ~n) "\¢~ .

C8H~2(t) .. .. ..

(C-84) CH~ ~ NHC ~

--\ ~ NHSOzC,~Hl3(n) ~ 'HCOCH2COOC~2H2s (n) (C-85) ( )~ ~ HC ~ .

H O(CH2)2-SOzCH3 (C-86) C ~ HCO ~ NHSO2 ~ Cl 2H2s(n) H NHSOz ~ CH3 (C-87) ~ ~ HC ~

O = \N ~ NHCONH(CH2)3 ~ C~H,l(t) H OCOCzH~ CsH~I(t) ~HSOzC~2Hzs(n) ~C-88) C~ ~ HC ~

. ~N ~ Y ~HSO2CI2H2s(n) H OIP(OC2Hs)z .. ....

OH
(C-89) C ~ ~HCO ~

h' NHCOC,sH3,(n) H OCH ~

(C-9o) OCH, HC ~
N ~ NHSO2C,bH33(n) N O
C~2 I H-CH3 (C-91) ~ HNCOC~H3~(n) H O

CCHJ

(C-92) (n)C~zH~-O-CH2 ~ ~NHCOC3F2 H O

(C-93) CH ~ NNCO(CHz)30 ~ C,H,I(t?
H O ~ CQ

C Q CN

. .

13~81 01 (C-94) CH ~H3 IOH rHC ~

~ NHSO ~ OClzH2~ tn) H O ~

(C-95) C ~ H ~
\N ~ NHCO ~ C ~ t(t) H O ~ NHCOlCH ~ CsHIl(t) ~ C2Hs (t)HIlCs CsHIl(t) (C-96) ~ HCO ~ CONH

H C NH C~ H

~' OClzH2s(n) (C-97) 0 ~ ~ NHC ~
O = <N ~ NHCOCH2COOCC "H33(n) H F

(C-98) Q ~ NHC ~
~N ~ NHCOCIHCH2SO2C,2H~,~n) C~ CH3 - . _ . .

) ~NHCO~
N~J NHCOCIHCHzSOzC~ 2Hz~ (n) H O CHs (C-l O O ) lHCO~
N~NHCOCIHCHzSO2Cl zH2~ (n) H C~ CH3 (C-10 1 ) CHS~ NHCQ~ C O
NHCO ICH--O~C,H " (t) H C~CI~Hl~(n) O--~ ~
N~ NHCOC~ ,H3, (n) H O

0=~( C"H~NHSO CH
H C~

, .

In the following, the oil-soluble polymers which can be employed in the present invention are described in detail.
The non-color forming oil-soluble polymers which can be preferably employed in the present invention are those having a glass transition point of 60C or higher, more preferably 90C or higher.
According to the present invention, preferred embodiments with respect to the polymers are:
(1) Nater-insoluble and organic solvent-soluble homo-polymers or copolymers composed of a repeating unit Il having a linkage of -C- in the main-chain or side chain . thereof.
Preferred polymers are those having relative fluorescence quantum yield, K-value, of 0.2 or more preferably 0.25 or more, and more preferably 0.3 or more. The polymers having higher K-value are more preferred.
The K-value is a relative fluorescence quantum yield, in polymers, of compound A having the following structure, compound A being one of the dyes which are often used as fluorescent probes. The K-value is define by the following equation.

-13381~1 Compound A

3 ~ ~ C = C
CH3-''' CN

K=~a/~b wherein ~a and ~b are the fluorescence quantum yields of compound A in polymers a and b, respectively, and deterimined in accordance with the method described, for example, in Macromolecules, 14,587(1981). Specifically, the K-value was calculated using ~a and ~b r which were obtained by measuring at room temperature using thin films of polymers containing compound A at a concentration of 0.5 m mol/kg (note: The thin films were spin-coated on a slide glass in such a thickness that the absorbance of compound A at Amax was from 0.05-0.1.). In the present invention, the K-value specified above was that obtained when poly (methyl methacrylate) with a number average molecular weight of 20,000 was used as polymer b.
More preferred embodiments are:

13381 ~1 (2) Water-insoluble and organic solvent-soluble homo-polymers or copolymers composed of a repeating of o -C-O- in the main chain or side chain thereof, and (3) Water-insoluble and organic solvent-soluble homo-polymers or copolymers composed of a repeating unit o Gl Il /
having a group of -C-N (wherein Gl and G2, each re-presents a hydrogen atom, a substituted or unsubstitutedalkyl group or a substituted or unsubstituted aryl group, provided that both Gl and G2 are not hydrogen atoms at the same time) in the main chain or side chain thereof.
Further more preferred embodiments are water-insoluble and organic solvent-soluble homopolymers or copolymers as described in Item (3) above, wherein one of Gl and G2 is a hydrogen atom and the other is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group each having from 3 to 12 carbon atoms.
The polymers which can be used in the present invention are explained in more detail with reference to specific examples thereof, but the present invention should not be construed as being limited to these polymers.

(A) Vinyl polymers:
A monomer for forming a vinyl polymer used in the present invention include an acrylic acid ester, a methacrylic acid ester, a vinyl ester, an acrylamide, a methacrylamide, an olefin, a styrene, a vinyl ether and other vinyl monomers.
Specific examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyle acrylate, tert-octyl acrylate, 2-ethylhexyl acrylate, octyl acryl-ate, tert-octyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethyl-aminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acryl-ate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2, 2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acryl-ate, 3-methyoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ~-methoxypolyethylene glycol acrylate (addi-tion molar number: n=9), 1-bromo-2-methoxyethyl acryl-ate, 1, 1-dichloro-2-ethoxyethyl acrylate, etc.
Specific example of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl meth-acrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl meth-acrylate, stearyl methacrylate, sulfopropyl methacryl-ate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophen-oxyethyl methacrylate, furfuryl methacrylate, tetra-hydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monometh-acrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-aceto-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-isopropoxyethyl methacrylate, 2-butoxyethyl methacryl-ate, 2-(2-methoxyethoxy) ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ~-methoxypolyethylene glycol methacrylate - 13~8101 (addition molar number: n=6), allyl methacrylate, dimethylaminoethyl methacrylate methyl chloride salt, etc.
Specific examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl iso-butyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc.
Specific examples of acrylamides include acryl-amaide, methylacrylamide, ethylacrylamide, propylacryl-amide, butylacrylamide, tert-butylacrylamide, cyclo-hexylacrylamide, benzylacrylamide, hydroxymethylacryl-amide, methoxyethylacrylamide, dimethylaminoethylacryl-amide, phenylacrylamide, dimethylacrylamide, diethyl-acrylamide, B-cyanoethylacrylamide, N-(2-acetoacetoxy-ethyl)acrylamide, diacetonacrylamide, tert-octylacryl-amide, etc~
Specific examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylmethacryl-amide, propylmethacrylamide, butylmethacrylamide, tert-butyl-methacrylamide, cyclohexylmethacrylamide, benzyl-methacrylamide, hydroxymethylmethacrylamide, methoxy-ethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethyl-133~3101 methacrylamide, ~-cyanoethylmethacrylamide, N-(2-aceto-acetoxyethyl)-methacrylamide, etc.
Specific examples of olefins include dicyclo-pentadiene, ethylene, propylene, l-butene, l-pentene, vinyl chloride, vinylidene chloride, isoprene, chloro-prene, butadiene, 2, 3-dimenthylbutadiene, etc.
Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethyl styrene, isopropylstyrene, chloromethylstyrene, methoxy-styrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, etc.
Specific examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethy~ vinyl ether, dimethylaminoethyl vinyl ether, etc.
Specific examples of other vinyl monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acryl-ate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, methylene malononitrile, vinylidene, etc.

Two or more kinds of monomers (for example, those as described above) can be employed together to prepare the polymers according to the present invention depending on various purposes (for example, improvement in the solubility thereof). Further, for the purpose of adjusting color forming ability and solubility of the polymers, a monomer having an acid group as illustrated below can be employed as a comonomer within the scope in which the copolymer to be obtained does not render water-soluble.
Specific examples of such monomers having an acid group include acrylic acid; methacrylic acid;
itaconic acid; maleic acid; a monoalkyl itaconate (for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate); a monoalkyl maleate (for example, monomethyl maleate, monoethyl maleate, monobutyl maleate); citraconic acid; styrene sulfonic acid;
vinylbenzylsulfonic acid; vinylsulfonic acid; an acryloyloxyalkylsulfonic acid (for example, acryloy-loxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid); a methacryloyloxyalkyl-sulfonic acid (for example, methacryloyloxymethyl-sulfonic acid, methacryloyloxyethylsulfonic acid, meth-acryloyloxypropylsulfonic acid); an acrylamidoalkyl-sulfonic acid (for example, 2-acrylamido-2-methylethane-sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid); a meth-acrylamidoalkylsulfonic acid (for example, 2-methacryl-amido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl-butanesulfonic acid); etc.
The acid may be in the form of a salt of an alkali metal (for example, sodium, potassium), or an ammonium ion.
In the case where the vinyl monomer described above and a hydrophilic vinyl monomer which forms a hydrophilic homopolymer used in the present invention is employed as a comonomer, a ratio of the hydrophilic monomer contained in the. copolymer is not strictly limited so far as the copolymer does not render water-soluble. Usually, the ratio of the hydrophilic monomer is preferably not more than 40% by mole, more preferably not more than 20% by mole, and further more preferably not more than 10% by mole. Further, when a hydrophilic comonomer copolymerizable with the monomer of the present invention has an acid group, a ratio of the comonomer having an acid group contained in the copolymer is usually not more than 20% by mole, and preferably not more than 10% by mole from the standpoint . - 44 -1~8101 of image preservability. In the most preferred case the copolymer does not contain such a monomer.
Preferred monomers composed of the polymers according to the present invention are methacrylate type monomers, acrylamide type monomers and methacrylamide type monomers. Particularly preferred monomers are acrylamide type monomers and methacrylamide type monomers.
(B) Polymers obtained by condensation polymerization or polyaddition reaction:
As polymers obtained by condensation poly-merization, polyesters obtained from polyvalent alcohols and polybasic acids, and polyamides obtained from diamines and- dibasic acids, or w-amino-w'-caboxylic acids are generally known. As polymers obtained by polyaddition, polyurethanes obtained from diisocyanates and divalent alcohols are known.
Useful polyvalent alcohols include a glycol having a structure of HO-R1-OH (wherein R1 represents a hydrocarbon chain having from 2 to about 12 carbon atoms, particularly an aliphatic hydrocarbon chain) and a polyalkylene glycol, and useful polybasic acids include those represented by the formula HOOC-R2-COOH
(wherein R2 represents a single bond or a hydrocarbon chain having from 1 to about 12 carbon atoms).

Specific examples of the polyvalent alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, trimethylol propane, 1, 4-butanediol, isobutylenediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanidiol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1 ll-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, glycerol, diglycerol, triglycerol, 1-methylglycerol, erythritol, mannitol, and sorbitol, etc.
Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanecarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalate, terephthalate, tetra-chlorophthalate, mesaconic acid, isopimelic acid, cyclo-pentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct, etc.
Specific examples of diamines include hydrazine, methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecyl-methylenediamine, 1, 4-diaminocyclohexane, 1, 4-diamino-methylcyclohexane, o-aminoaniline, p-aminoaniline, 1, 4-diaminomethylbenzene, and di-(4-aminophenyl)ether, etc.

13~8101 Specific examples of w-amino-w-carboxylic acids include glycine, B-alanine, 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, ll-aminolauric acid, 4-aminobenzoic acid, 4-(2-aminoethyl)benzoic acid, and 4-(4-aminophenyl)butyric acid, etc.
Specific examples of diisocyanates include ethylenediisocyanate, hexamethylenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, p-xylenediisocyanate, and 1, 5-naphthyldiisocyanate, etc.
(C) Other polymers:
Polyesters or polyamides obtained by open ring codensation as shown below are examplified.
. Polyester or (CH2)m ~Open Ring polyamide having the \ Condensation jepeating unit of C-X- ( CH2 ) m -. C-X 11 Il O

\
wherein X represents -O- or -NH-; m represents an integer from 4 to 7; and the -CH2- chain may be a branched chain.
Suitable monomers for preparation of the polymers include B-propiolactone, ~-caprolactone, di-methylpropiolactone, a-pyrrolidone, a-piperidone, -caprolactam, and ~-methyl-~-caprolactam, etc.

Two or more kinds of the polymers according to the present invention described above may optionally be used in combination.
Molecular weight and degree of polymerization of the polymer according to the present invention are not substantially largely influenced on the effect of the present invention. However, as the molecular weight becomes higher, some problems are apt to occur that it takes much time to dissolve it in an auxiliary solvent and that emulsifiction or dispersion thereof becomes difficult due to high viscosity of its solution and coarse grains are formed, resulting in decrease in color forming property and coating property.
When a large amount of the auxiliary solvent is used to reduce its viscosity in order to traverse such difficulties, new problems on the process may occur.
From such a point of view, the viscosity of the polymer is preferably not more than 5,000 cps, more preferably not more than 2,000 cps when 30g of the polymer is dissolved in lOOml of an auxiliary solvent.
Also, the molecular weight of the polymer useful in the present invention is preferably not more than 150,000 more preferably not more than 100,000.
The term "water-insoluble" as used herein with respect to the polymer means that a weight of the polymer soluble in lOOg of distilled water is not more than 3g, preferably not more than lg.
A ratio of the polymer to an auxiliary solvent is different depending on a kind of the polymer used, and can be varied over a wide range depending on its solubility to the auxiliary solvent, its degree of polymerization, and solubility of coupler. Usually the auxiliary solvent is employed in an amount necessary to made viscosity sufficiently low for easily dispersing a solution containing at least a coupler, a coupler solvent having a high boiling point and the polymer dissolved in the auxiliary solvent in water or an aqueous solution of a hydrophilic colloid~ Since the viscosity of the solution increases as the degree of polymerization of the polymer is high, it is difficult that a ratio of the polymer to an auxiliary solvent is determined uniformly without depending on the kind of polymer. Usually, however, the ratio of about 1:1 to about 1:50 (by weight) is preferred. A ratio of the polymer according to the present invention to a coupler is preferably from 1:20 to 20:1 more preferably from 1:10 to 10:1 (by weight).
Specific examples of the polymers which can be used in the present invention are set forth below, but the present invention should not be construed as being limited to these polymers.
Examples Polymers P-l Polyvinylacetate P-2 Polyvinylpropionate P-3 Polymethylmethacrylate P-4 Polyethylmethacrylate P-5 Polyethylacrylate P-6 Copolymer of vinylacetate-vinylalcohol (95:5) P-7 Poly(n-butylacrylate) P-8 Poly(n-butylmethacrylate) P-9 Poly(iso-butylmethacrylate) P-10 Poly(iso-propylmethacrylate) P-ll Poly(decylmethacrylate) P-12 Copolymer of n-butylacrylate-acrylamide (95:5) P-13 Polymethylchloroacrylate P-14 1, 4-Butanediol-adipic acid polyester P-15 Ethyleneglycol-sebacic acid polyester P-16 Polycaprolactone P-17 Poly(2-tert-butylphenyl acrylate) P-18 Poly(4-tert-butylphenyl acrylate) .

P-l9 Copolymer of n-butylmethacrylate-N-vinyl-2-pyrrolidone (90:10) P-20 Copolymer of methylmethacrylate-vinyl chloride (70:30) P-21 Copolymer of methylmethacrylate-styrene (90:10) P-22 Copolymer of methylmethacrylate-ethylacrylate (50:50) p-23 Copolymer of n-butylmethacrylate-methylmethacrylate-styrene (50:30:20) P-24 Copolymer of vinylacetate-acrylamide (85:15) P-25 Copolymer of vinyl chloride-vinylacetate (65:35) P-26 Copolymer of methylmethacrylate-acrylonitrile (65:35) P-27 Copolymer of diacetoneacrylamide-methylmethacrylate (50:50) P-28 Copolymer of vinylmethylketone-iso-butylmethacrylate (55:45) P-29 Copolymer of ethylmethacrylate-n-butylacrylate (70:30) P-30 Copolymer of diacetoneacrylamide-n-butylacrylate (60:40) P-31 Copolymer of methylmethacrylate-cyclohexylmethacrylate (50:50) P-32 Copolymer of n-butylacrylate-phenylmethacrylate-diacetoneacrylamide (70:20:10) P-33 Copolymer of N-tert-butylmethacrylamide-methylmethacrylate-acrylic acid (60:30:10) P-34 Copolymer of methylmethacrylate-styrene-vinylsulfonamide (70:20:10) P-35 Copolymer of methylmethacrylate-phenylvinylketone (70:30) P-36 Copolymer of n-butylacrylate-methyl-methacrylate-n-butylmethacrylate (35:35:30) P-37 Copolymer of n-butylmethacrylate-pentylmethacrylate-N-vinyl-2-pyrrolidone (38:38:24) P-38 Copolymer of methylmethacrylate-n-butylmethacrylate-isobutylmethacrylate-acrylic acid (37:29:25:9) P-39 Copolymer of n-butylmethacrylate-acrylic acid (95:5) P-40 Copolymer of methylmethacrylate-acrylic acid (95:5) P-41 Copolymer of benzylmethacrylate-acrylic acid (90:10) P-42 Copolymer of n-butylmethacrylate-methylmethacrylate-benzylmethacrylate-acrylic acid (35:35:25:5) P-43 Copolymer of n-butylmethacrylate-methylmethacrylate-benzylmethacrylate (35:35:30) P-44 Poly(3-pentylacrylate) P-45 Copolymer of cyclohexylmethacrylate-methylmethacrylate-n-propylmethacrylate (37:29:34) P-46 Poly(pentylmethacrylate) P-47 Copolymer of methylmethacrylate-n-butylmethacrylate (65:35) P-48 Copolymer of vinylacetate-vinylpropionate (75:25) P-49 Copolymer of n-butylmethacrylate-sodium-3-acryloxybutane-l-sulfonate (97:3) 1~38101 .

P-50 Copolymer of n-butylmethacrylate-methylmethacrylate-acrylamide ( 35: 35: 30) P-51 Copolymer of n-butylmethacrylate-methylmethacrylate-vinyl chloride ( 37: 36: 27) P-52 Copolymer of n-butylmethacrylate-styrene (90:10) P-53 Copolymer of methylmethacrylate-N-vinyl-2-pyrrolidone (90:10) P-54 Copolymer of n-butylmethacrylate-vinylchloride (90:10) P-55 Copolymer of n-butylmethacrylate-styrene (70:30) P-56 Poly ( N-sec-butylacrylamide) P-57 Poly(N-tert-butylacrylamide) P-58 Copolymer of diacetoneacrylamide-methylmethacrylate ( 62: 38) P-59 Copolymer of cyclohexylmethacrylate-methylmethacrylate ( 60: 40) P-60 Copolymer of N-tert-butylacrylamide-. methylmethacrylate ( 40: 60) P-61 Poly(N-n-butylacrylamide) P-62 .Copolymer of tert-butylmethacrylate-N-tert-. butylacrylamide ( 50: 50) P-63 Copolymer of tert-butylmethacrylate-methylmethacrylate ( 70: 30) P-64 Poly(N-tert-butylmethacrylamide) P-65 Copolymer of N-tert-butylacrylamide-methylmethacrylate ( 60: 40) P-66 Copolymer of methylmethacrylate-acrylonitrile ( 70: 30) P-67 Copolymer of methylmethacrylate-vinylmethylketone ( 38: 62) P-68 Copolymer of methylmethacrylate-styrene (75:25) P-69 Copolymer of ethylmethacrylate-hexylmethacrylate (70:30) P-70 Poly(benzylacrylate) P-71 Poly(4-biphenylacrylate) P-72 Poly(4-butoxycarbonylphenylacrylate) P-73 Poly(sec-butylacrylate) P-74 Poly(tert-butylacrylate) P-75 Poly[3-chloro-2, 2-bis(chloromethyl)-propylacrylate]
P-76 Poly(2-chlorophenylacrylate) P-77 Poly(4-chlorophenylacrylate) P-78 Poly(pentachlorophenylacrylate) P-79 Poly(4-cyanobenzylacrylate) P-80 Poly(cyanoethylacrylate) P-81 Poly(4-cyanophenylacrylate) P-82 Poly(4-cyano-3-thiabutylacrylate) P-83 Poly(cyclohexylacrylate) P-84 Poly(2-ethoxycarbonylphenylacrylate) P-85 Poly(3-ethoxycarbonylphenylacrylate) P-86 Poly(4-ethoxycarbonylphenylacrylate) P-87 Poly(2-ethoxyethylacrylate) P-88 Poly(3-ethoxypropylacrylate) P-89 Poly(lH, lH, 5H-octafluoropentylacrylate) P-90 Poly(heptylacrylate) ` 1~38101 P-91 Poly(hexadecylacrylate) P-92 Poly(hexylacrylate) P-93 Poly(iso-butylacrylate) P-94 Poly(iso-propylacrylate) P-95 Poly(3-methoxybutylacrylate) P-96 Poly(2-methoxycarbonylphenylacrylate) P-97 Poly(3-methoxycarbonylphenylacrylate) P-98 Poly(4-methoxycarbonylphenylacrylate) P-99 Poly(2-methoxyethylacrylate) P-100 Poly(4-methoxyphenylacrylate) P-101 Poly(3-methoxypropylacrylate) P-102 Poly(3, 5-dimethyladamanthylacrylate) P-103 Poly(3-dimethylaminophenylacrylate) P-104 Poly(vinyl tert-butyrate) P-105 Poly(2-methylbutylacrylate) P-106 . Poly(3-methylbutylacrylate) P-107 Poly(l, 3-dimethylbutylacrylate) P-108 Poly(2-methylpentylacrylate) P-109 Poly(2-naphtylacrylate) P-llO Poly(phenylmethacrylate) P-lll Poly(propylacrylate) P-112 Poly(m-tolylacrylate) P-113 Poly(o-tolylacrylate) P-114 Poly(p-tolylacrylate) P-115 Poly(N, N-dibutylacrylamide) P-116 Poly(iso-hexylacrylamide) P-117 Poly(iso-octylacrylamide) P-118 Poly(N-methyl-N-phenylacrylamide) P-ll9 Poly(adamanthylmethacrylate) P-120 Poly(benzylmethacrylae) P-121 Poly(2-bromoethylmethacrylate) P-122 Poly(2-N-tert-butylaminoethylmethacrylate) P-123 Poly(sec-butylmethacrylate) P-124 Poly(tert-butylmethacrylate) P-125 Poly(2-chloroethylmethacrylate) P-126 Poly(2-cyanoethylmethacrylate) P-127 Poly(2-cyanomethlphenylmethacrylate) P-128 Poly(4-cyanophenylmethacrylate) P-129 Poly(cyclohexylmethacrylate) P-130 Poly(dodecylmethacrylate) P-131 Poly(diethylaminoethylmethacrylate) P-132 Poly(2-ethylsulfinylethylmethacrylate) P-133 Poly(hexadecylmethacrylate) P-134 Poly(hexylmethacrylate) P-135 Poly(2-hydroxypropylmethacrylate) P-136 Poly(4-methoxycarbonylphenylmethacrylate) P-137 Poly(3, 5-dimethyladamanthylmethacrylate) P-138 Poly(dimethylaminoethylmethacrylate) P-139 Poly(3, 3-dimethylbutylmethacrylate) P-140 Poly(3, 3-dimethyl-2-ethylbutylmethacrylate) P-141 Poly(3, 5, 5-trimethylhexylmethacrylate) P-142 Poly(octadecylmethacrylate) P-143 Poly(tetradecylmethacrylate) P-144 Poly(4-butoxycarbonylphenylmethacrylamide) P-145 Poly(4-carboxyphenylmethacrylamide) P-146 Poly(4-ethoxycarbonylphenylmethacrylamide) P-147 Poly(4-methoxycarbonylphenylmethacrylamide) P-148 . Poly(butylbutoxycarbonylmethacrylate) P-149 Poly(butylchloroacrylate) P-150 Poly(butylcyanoacrylate) P-151 Poly(cyclohexylchloroacrylate) P-152 Poly(ethylchloroacrylate) P-153 Poly(ethlethoxycarbonylmethacrylate) P-154 Poly(ethylethacrylate) P-155 Poly(ethylfluoromethacrylate) P-156 Poly(hexylhexyloxycarbonylmethacrylate) P-157 Poly(iso-butylchloroacrylate) P-158 Poly(iso-propylchloroacrylate) P-159 Trimethylenediamine-glutaric acid polyamide P-160 Hexamethylenediamine-adipic acid polyamide P-161 Poly(2-pyrrolidone) P-162 Poly(~-caprolactam) P-163 Hexamethylenediisocyanate-l, 4-butanediol polyurethane P-164 p-Phenylenediisocyanate-ethylene glycol polyurethane Synthesis methods of the polymers are speci-fically illustrated below, and other polymers can be synthesized in a known manner.

Synthesis of Polymethylmethacrylate (P-3) A mixture of 50.0 g of methyl methacrylate, 0.5 g of sodium polyacrylate and 200 ml of distillated water was heated at 80C with stirring under a nitrogen atmosphere in a 500 ml three-necked flask. 500 mg of dimethyl azobisisobutyrate was added thereto as a polymerization initiator thereby polymerization was initiated. After polymerization for 2 hours, the poly-merization solution was cooled and the bead-like polymer was collected by filtration and washed with water to obtain 48.7 g of P-3.

Synthesis of Poly (N-tert-butylacrylamide) (P-57) A mixture of 50.0 g of t-butylacrylamide and 250 ml of toluene was heated at 80C with stirring under a nitrogen atmosphere in a 500 ml three-necked flask. 10 ml of a toluene solution containing 500 mg of azobisisobutyronitrile was added thereto as a poly-.

13381~1 merization initiator thereby polymerization was initiated. After polymerization for 3 hours, the polymerization solution was cooled and poured into 1 liter of hexane. The solids thus-deposited were collected by filtration, washed with hexane and dried with heating under a reduced pressure to obtain 47.9 9 of P-57.
The dispersion of oleophilic fine particles containing the polymer according to the present invention can be preferably prepared in the following manner.
The polymer according to the present invention which may be synthesized by a solution polymerization method, an emulsion polymerization method, or a suspens-ion polymerization -method, and is not cross-linked (i.e., a so-called linear polymer), and the coupler are completely dissolved in an auxiliary organic solvent.
The solution is dispersed in water, preferably in an aqueous solution of a hydrophilic colloid, and more preferably in an aqueous solution of gelatin, with the assistance of a dispersant using ultrasonic agitation, or a colloid mill to form fine particles. Then, the dispersion is mixed with a silver halide emulsion.
Alternatively, water or an aqueous solution of a hydrophilic colloid such as an aqueous solution of 13~8101 gelatin is added to an auxiliary organic solvent containing a dispersant such as a surface active agent, the polymer according to the present invention and the coupler to prepare an oil droplet-in-water type dispersion accompanied by phase inversion.
Further, the dispersion prepared may be mixed with a photographic emulsion after removing the auxiliary organic solvent therefrom by an appropriate method such as distillation, noodle washing or ultrafiltration.
The term "auxiliary organic solvent" as used herein means an organic solvent which is useful in forming an emulsified dispersion, which is finally removed substantially from the photographic light-sensitive material during the drying step after coating or by the above-described method, and which is an organic solvent having a low boiling point or a solvent having a certain extent of solubility in water and removable by washing with water.
Specific examples of the auxiliary organic solvents include a lower alkyl acetate such as ethyl acetate, or butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ~-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone.

1~38101 Further, an organic solvent which is fully miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, or tetrahydrofuran may be partially employed together, if desired.
Two or more such organic solvents can be employed in combination.
The average particle size of the olophilic fine particles thus prepared is preferably from 0.04 ~m to 2 ~m, more preferably from 0.06 ~m to 0.4 ~m. The particle size of the oleophilic fine particles can be determined using an appropriate measuring apparatus, for example, Nanosizer (manufactured by Coulter Co., England).
In the step of emulsification and dispersion, a coupler solvent having a high boiling point may be employed together with the coupler, if desired.
Preferred examples of the coupler solvents having a high boiling point include those represented by the following general formulae (XXIII), (XXIV), (XXV), (XXVI), (XXVII) or (XXVIII):

1~8101 f W2-O-P=O (XXIII) f w3 Wl-COOW2 (XXIV) Wl-CON
\ W3 (XXV

Wl~ /W2 N (XXVI) ~3} (W4)n Wl-O-W2 ( XXVI I ) HO-W6 ( XXVI I I ) wherein Wl, W2 and W3 each represents a substituted or unsubstituted alkyl group, a substituted or unsub-stituted cycloalkyl group, a substituted or unsubsti-tuted alkenyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic 1~8101 .

group; W4 represents Wl, -O-Wl or -S-Wl; n represents an integer from 1 to 5, and when n is two or more, two or more W4~S may be the same or different; Wl and W2 in the general formula (XXVII) may combine with each other to form a condensed ring; W6 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group and the total number of carbon atoms included in W6 is not less than 12.
As the coupler solvent having a high boiling point which is employed in the present invention, any compound which has a melting point of 100C or lower and a boiling point of 140C or higher and which is immiscible with water and a good solvent for the coupler may be utilized, in addition to the above described solvents represented by the general formulae (XXIII) to (XXVIII). The melting point of the coupler solvent having a high boiling point is preferably not more than 80C. The boiling point of the coupler solvent having a high boiling point is preferably not less than 160C, more preferably not more than 170C.
When the melting point of the coupler solvent used exceeds about 100C, crystallization of couplers is apt to occur and the improving effect on color forming property tends to decrease.

Details of these high boiling point organic solvents are described in JP-A-62-215272, page 137, right lower colum to page 144, right upper column.
For the silver halide emulsion layers of the color photographic material according to the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride is used as the silver halide.
In particular, for the purpose of conducting a rapid processing, silver chlorobromide containing 90 mol% or more, more preferably 98 mol% or more, of silver chloride is preferred. Although such silver chloro-bromide may contain a slight amount of silver iodide, it is preferred that it does not contain silver iodide at all.
There is no particular restriction on the average grain size (the grain size being defined as the diameter of the grains when the grain has a spherical or a nearly spherical form and as the length of the edge when the grain has a cubic form, and being averaged based on projected area of the grains) of the silver halide grains in the photographic emulsions but it is preferred that the grain size be not more than 2 ~m, and particularly from 0.2 ~m to 1.5 ~m.

-The silver halide grains in the photographic emulsion layers may have a regular crystal form such as cubic, tetradecahedral, octahedral, etc., or an irregular crystal form such as spherical, tabular, etc., or may have a composite form of these crystal forms.
Also, a mixture of grains having various crystal forms may be used. Of these emulsions, the use of a photo-graphic emulsion of regular crystal form is preferred.
Further, a silver halide emulsion wherein tabular silver halide grains having a diameter/thickness ratio of at least 5 accounts for at least 50% of the total projected area of the silver halide grains may be used in the present invention.
A silver halide emulsion employed at least one layer of the light-sensitive layers is preferably a monodispersed silver halide emulsion having a coefficient of variation (a value which is obtained by dividing a statistical standard deviation with an average grain size and is indicated in terms of a percent) not more than 15%, more preferably not more than 10%.
Such a monodispersed emulsion may be a single emulsion having the coefficient of variation described above, or an emulsion composed of a mixture of two or more kinds of monodispersed emulsions prepared separate-r 1 3 3 8 1 0 1 .

ly and having different average grain sizes and each having the coefficient of variation not more than 15%, preferably not more than 10%. The difference in grain size and the mixing ratio of these monodispersed emulsions to be mixed can be appropriately selected.
However, emulsions having the difference in average grain size ranging from not less than 0.2 ~m to not more than 1.0 ~m are preferably employed.
The definition as to the coefficient of variation and the method of measurement therefor are described in T. H. James, The Theory of The Photographic Process, Third Edition, page 39, The Macmillan Company (1966).
The silver halide grains used in the present invent~on may have a composition or structure inside the grain which is different from that on the surface layer thereof. Also, the silver halide grains may be of the type that latent images are formed mainly on the surface thereof or of the ~ype that latent images are formed mainly in the interior thereof. The latter type grains are particularly useful for direct positive emulsions.
During the formation or physical ripening of the silver halide grains, a cadmium salt, a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, 1~38~Ql an iron salt or a complex salt thereof, etc., may coexist in the system.
Silver halide emulsion are usually chemically sensitized. To the chemical sensitization of the emulsion, conventional methods can be applied, details of which are described in JP-A-62-215272, page 12, from left lower column, line 18 to right lower column, line 16.
Further, silver halide emulsions are usually spectrally sensitized. For the spectral sensitization, methine dyes are ordinarily employed, details of which are described in JP-A-62-215272, from page 22, right upper column, line 3 from the bottom to page 38 and Attachment B to Amendment therefor filed March 16, 1987.
The silver halide emulsions used in the present invention can contain various kinds of compounds for preventing the occurrence of fog or for stabilizing photographic performance during the production, sotrage and/or photographic processing of color photographic materials. Examples of such compounds include many compounds known as antiforggants or stabilizers such as azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenz-imidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotri-1 3~8101 .

azoles, benzotriazoles, nitrobenzotriazoles, mercapto-tetrazoles (in particular, l-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.;
thioketo compounds such as oxazolinethione, etc.; aza-indenes (e.g., triazaindenes, tetraazaindenes, in parti-cular, 4-hydroxy-substituted 1,3,3a,7-tetraazaindene), pentaazaindenes, etc.; benzenethiosulfonic acid, benz-enesulfinic acid, benzenesulfonic acid amide, etc.
In the color photographic light-sensitive material according to the present invention, yellow couplers, magenta couplers and cyan couplers which form yellow, magenta and cyan colors upon coupling with oxidation products of aromatic amine type color develop-ing agents, respectively, are usually employed.
Of yellow couplers usable in the present invention, acylacetamido derivatives such as benzoyl-acetanilides and pivaloylacetanilides are preferred.
Among them, those represented by the general formula (Y-l) or (Y-2) shown below are more preferred as yellow couplers.

o O R22 ~ C-CH-C-N ~ R21 (Y-l) O o R22 (C~3)3C-C~-C-N ~ (Y-~) wherein X represents a hydrogen atom or a group capable of being released upon coupling; R2l represents a diffusion resistant group having from 8 to 32 carbon atoms in total; R22 represents a hydrogen atom, one or more of halogen atoms, lower alkyl groups, lower alkoxy groups or diffusion resistant groups having from 8 to 32 carbon atoms in total; and R23 represents a hydrogen atom or a substituent, when two or more R23's are present, they may be the same or different.
The pivaloylacetanilide type yellow couplers are described in detail in U.S. Patent 4,622,287, column 3, line 15 to column 8, line 39 and U.S. Patent 4,623,616, column 14, line 50 to column 19, line 41.
The benzoylacetanilide type yellow couplers are described in detail in U.S. Patents 3,408,194, 3,933,501,-4,046,575, 4,133,958 and 4,401,752.
More specifically, as pivaloylacetanilide type yellow couplers, Compounds (Y-l) to (Y-39) as described in the above mentioned U.S. Patent 4,622,287, column 37 to column 54 are suitable. Of the compounds, Compounds 1~3~101 (Y - 1), (Y - 4), (Y - 6), (Y - 7), (Y - 15), (Y - 21), (Y - 22), (Y -23), (Y-26), (Y-35), (Y-36), (Y-37), (Y-38) and (Y-39) are preferred.
Further, Compounds (Y-l) to ( Y-33) as described in the above mentioned U.S. Patent 4,623, 616, column 19 to column 24 are suitable. Of these compounds, Compounds (Y-2), (Y-7), (Y-8), (Y-12), (Y-20), (Y-21), (Y-23) and (Y-29) are preferred.
Moreover, Compound ( 34) as described in U.S.
Patent 3,408,194, column 6; Compounds (16) and (19) as described in U.S. Patent 3,933,501, column 8; Compound (9) as described in U.S. Patent 4,046,575, column 7 to column 8; Compound (1) as described in U.S. Patent 4,133,958, column 5 to column 6; Compound (1) as described in U.S. Patent 4,401,752, column 5; and Compounds a) to h) described below are also preferred.

( CH3) 3C-C-CH-C-NH~

X Cl Compound R22 X

-COOC~COOClzh25 ~ N N CH

(CH3)3C-C-CH-C-NH
X Cl Compound R22 X

b-COOCHcOOcl2~2s ~ N -N-C~2 c -NHCO(CH2)30 ~ CsHll-t ~ S02 ~ OCH
C5Hll-t d -NHCO(CH2)30 ~ CsHll-t ~
C5Hll-t CH3 CH ~ NHS02 ~ CH3 e -NHCOtCH2)3o ~ CsHll-t CsHll-t C6H130CO N

f-NHS02C12H2s -o ~ COOCH ~CH

g-NHS02C16H33 <N-N

N

h-NHCOCHCH2S02C12H25 ~ N

CH3 ~CH
~ 71 -Among the couplers described above, those having a nitrogen atom as a releasing atom are preferred.
As magenta couplers ugable in the present invention, oil protected indazolone type couplers and cyanoacetyl type couplers, preferably 5-pyrazolone type couplers and pyrazoloazole type couplers such as pyrazolotriazoles, are exemplified. Of 5-pyrazolone type couplers, those substituted with an arylamino group or an acylamino group at the 3-position thereof are preferred in view of hue and color density of the dyes formed. Typical examples thereof are described in U.S.
Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,563, 3,152,896, and 3,936,015. For two-equivalent 5-pyrazolone type couplers, nitrogen atom-releasing ~roups as described in U.S. Patent 4,310,619 and arylthio groups as described in U.S. Patent 4,351,897, as releasing groups are preferred. Further, 5-pyrazolone type couplers having a ballast group as described in European Patent 73,636 published Mar 9/83 are advantageous because they provide hi~h color density.
Examples of pyrazoloazole type couplers include pyrazolobenzimidazoles as described in U.S. Patent 3,369,879, and preferably pyrazolo~5,1-c]~1,2,41tri-azoles as described in U.S. Patent 3,725,067, pyrazolo-tetrazoles as described in Research Disclosure, No.

- 13381~1 24220 (June, 1984), and pyrazolopyrazoles as described in Research Disclosure, No. 24230 (June, 1984). The above described couplers may be in the form of polymer couplers.
These compounds are specifically represented by the following general formula (M-l), (M-2) or (M-3):

R31-NH~ ~ 2 (M-l) ` N

R31C-NH \ X
ll 1 2 (M-2) N~ N ~

R33~ ~ X2 (M-3) N .
.

wherein R31 represents a diffusion resistant group having from 8 to 32 carbon atoms in total; R32 represents a phenyl group or a substituted phenyl group; R33 represents a hydrogen atom or a substituent; Z re-presents a non-metallic atomic group necessary to form a 5-membered azole ring containing two to four nitrogen atoms, which azole ring may have one or more substituents (including a condensed ring); and X2 represents a hydrogen atom or a group capable of being released.
The substituents for R33 and the substituents on the azole ring are described in detail in U.S. Patent 4,540,654, column 2, line 41 to column 8, line 27.
Among the pyrazoloazole type couplers, imidazo-~1,2-b]pyrazoles as described in U.S. Patent 4,500,630 are preferred, and pyrazolo[l,5-b][1,2,4]triazoles as described in U.S. Patent 4,540,654 are particularly preferred in view of less yellow subsidiary absorption and light fastness of the dyes formed.
In addition, pyrazolotriazole couplers wherein a branched chain alkyl group is directly connected to the 2-, 3- or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245, pyrazoloazole couplers containing a sulfonamido group in their molecules as described in JP-A-61-65246, pyrazoloazole couplers having an alkoxyphenylsulfonamido ballast group as described in JP-A-61-147254, and pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in EP-A-226,849 published July 1/87 are preferably employed.
Specific examples of the magenta couplers u~ed in the present invention are set forth below, but the present invention should not be construed as being limited thereto.

13381~1 -u m-' X U ~ U
U~

,~ m r~~ ~3~ U
oN m ~Z ~UD t~ O ~ U~

NmP~ N oN oN O
' z rz Z m _Z ~ ~ N
=z' r ~ u r~ u rq )=\
~C . 5--U U--U U--U
Z

P~ O

r~ r. r.

o Q~ I I I
o ~
C~

13381()1 -.

X C~ ~ O

~ ~ J~
JJ ~ _ r~

~ O C ~ ~ D

~ m_m c~_ ~, _m r.~ I I
~;

o o U P~
, , m m m o u ~3 OU~ ~D ,1~ O
~ I .
C~

-CO
o,~3,U U
V~

I~ ~
U t~3, U

U~
~r m X 1 ~ N
~_z m m =Z
Z

o -o P: ~3 OU~

~, ~
O ~_ o~
~U~
~a o ~ O

" E3 :E ~
u .

N`N ~ NIH

R34 ~ N

CompoundR33 R34 X2 M-ll CH3- HO ~ SO2 ~ OCHCONH ~ CH2~ ce M-12as above (n)C6H13~ CHcH2so2(cH2)2 as above (n)C6H17 M-13 3 CH- OC4Hg as above CH3 ~ ~ SO2 tcH
CgH17(t) M-14 CH3 CH3-CH as above tlCH-CH2) 50(CH2-C)50 CH2NHSO2CH3 C;o o --X U ,.~ ~,u o~
U~

JJ JJ
m ~ $
3,V t~3,U

O O
Z Z
X $ ~ ~
~ v u =Z
~q O O
V

13381~1 M-17 ce Cl 3 ~2 7 C ON~ ~
ce~,ce M-18 ce O ~NH~

SJ

M-l9 ce O C 4 ~1 9 N
Cl3H27COI~N ~N O C8Hl 7(t ce M-20 ~ N~ce ~ N

(t)C5Hll~ C4Hg (~N ~NS~o C~

_ M-21 CQ NHCOC4Hg(t) (t)C5H~1 ~ o _ fHCNH ~ N ~ O
C2H5 CQ ~ CQ

CQ

M-22 CQ NHCOC4Hg(t) ~ NH ~ ~ S

( )H27C13cONH ~N ~ O
Cl~ ~ ,CQ

CQ

C Q NHCOC4Hg(t) M-23 O ~ I/

~ N~ N

C18H35 ~ O C Q~ C Q

CQ

13~8101 The condensed ring type cyan couplers represent-ed by the general formula (I) according to the present invention may be employed together with other cyan couplers. Most representative examples of cyan couplers which can be used together with the cyan couplers according to the present invention are phenol type cyan couplers and naphthol type cyan couplers.
Suitable examples of the phenol type cyan couplers include those having an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position thereof (including polymer couplers) as described, for example, in U.S. Patents 2,369,929, 4,518,687, 4,511,647 and 3,772,002. Representative specific examples thereof include the coupler as described in Example 2 of Canadian Patent 625,822, Compound (1) as described in U.S. Patent 3,772,002, Compounds (I-4) and (I-5) as described in U.S. Patent 4,564,590, Compounds (1), (2), (3) and (24) as described in JP-A-61-39045, and Compound (C-2) as described in JP-A-62-70846.
Suitable examples of the phenol type cyan couplers include 2,5-diacylamino-substituted phenol type couplers as described, for example, in U.S. Patents 2,772,162, 2,895,826, 4,334,011 and 4,500,635, and JP-A-59-164555. Representative specific examples thereof include Compound (V) as described in U.S. Patent 2,895,826, Compound (17) as described in U.S. Patent 4,557,999, Compound~ (2) and (12) as described in U.S.
Patent 4,565,777, Compound (4) a~ described in U.S.
Patent 4,124,396 and Compound (I-l9) as de~cribed in U.S. Patent 4,613,564.
Furthermore, other suitable examples of the phenol type cyan couplers include ureido type couplers as described, for example, in U.S. Patents 4,333,999, 4,451,559, 4,444,872, 4,427,767 and 4,579,813 and European Patent 067,689 Bl published Dec 22/82. R~~ ta~ve specific examples thereof include Coupler (7) as described in ~.S. Patent 4,333,999, Coupler (1) as described in ~.S.
Patent 4,451,559, Coupler (14) as described in ~.S.
Patent 4,444,872, Coupler (3) as described in U.S.
Patent 4,427,767, Couplers (6) and (24) as described in U.S. Patent 4,609,619, Couplers (1) and (11) as described in U.S. Patent 4,579,813, Couplers (45) and (50) as described in European Patent 067,689 Bl and Coupler (3) as described in JP-A-61-42658.
Suitable examples of the naphthol type cyan couplers include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus as described, for example, in U.S. Patent 2,313,586, those having an alkylcarbamoyl group at the 2-position of the 13~8101 .

naphthol nucleus as described, for example, in U.S.
Patents 2,474,293 and 4,282,312, those having an arylcarbamoyl group at the 2-position of the naphthol nucleus as described, for example, in JP-B-50-14523, those having a carbonamido group or a sulfonamido group at the 5-position of the naphthol nucleus as described, for example, in JP-A-60-237448, JP-A-61-145557 and JP-A-61-153640, those having an aryloxy releasing group as described, for example, in U.S. Patent 3,476,563, those having a substituted alkoxy releasing group as described, for example, in U.S. Patent 4,296,199, and those having glycolic acid releasing group as described, for example, in JP-B-60-39217.
The color photographic light-sensitive material according to the present invention may contain a hydroquinone derivative, an aminophenol derivative, an amine~ a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a non-color-forming coupler, or a sulfonamidophenol derivative, as a color fog preventing agent or a color mixing preventing agent.
In the color photographic light-sensitive material according to the present invention, various color fading preventing agents can be employed. More specifically, representative examples of organic color fading preventing agents for cyan, magenta and/or yellow 1~38101 images include hindered phenols (for example, hydro-quinones, 6-hydroxychromans, 5-hydroxycoumarans, spiro-chromans, p-alkoxyphenols, or bisphenols), gallic acid derivatives, methylenedioxybenzenes, aminophenols, hind-ered amines, or ether or ester derivatives thereof derived from each of these compounds by sililation or alkylation of the phenolic hydroxy group thereof.
Further, metal complexes represented by (bissalicyl-aldexymate) nickel complex and (bis-N,N-dialkyldithio-carbamate) nickel complexes may be employed.
Specific examples of the organic color fading preventing agents are described in the following patents or patent applications.
Hydroquinones: U.S. Patents 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425, British Patent 1,363,921, U.S. Patents 2,710,801 and 2,816,028, etc.;

6-hydroxychromanes, 5-hydroxycoumaraus and spirochrom-anes: U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, JP-A-52-152225, etc.; spiro-indanes: U.S. Patent 4,360,589, etc.; p-alkoxyphenols:
U.S. Patents 2,735,765, British Patent 2,066,975, JP-A-59-10539, JP-B-57-19764, etc.; hindered phenols: U.S.
Patent 3,700,455, JP-A-52-72225, U.S. Patent 4,228,235, JP-B-52-6623, etc.; gallic acid derivatives, methylene-dioxybenzenes and aminophenols: U.S. Patents 3,457,079 and 4,332,886, JP-~5~21144, etc.; hindered amines: U.S. Patents 3,336,135 and 4,268,593, British Patents 1,326,889 published Aug 15/73, 1,345,313 published May 30/74 and 1,410,846 published Oct 22/75, JP-B-51-1420, JP-A-5~
114036, JP-A-59-53846, JP-A-59-78344, etc.; ether or ester derivatives of phenolic hydroxy group: U.S. Patents 4,155,765, 4,174,220, 4,254,216 and 4,264,720, JP-A-54-145530, JP-A-55-6321, JP-A-58-105147, JP-A-59-10539, JP-B-57-37856, U.S. Patent 4,279,990, JP-B-53-3263, etc.
Further, specific examples of the metal cGm-plexes are described in U.S. Patents 4J 050,~38 and 4,241,155, British Patent 2,027,731 published Feb 27/80, etc.
The color fading preventing agent is co-emulsified with the corresponding color coupler in- an amount of from S to 100% by weight of the color coupler and incorporated into the light-sensitive layer to achieve the effects of the present invention.
In order to prevent from degradation of cyan dye image due to heat, particularly due to lisht, it is effective to introduce an ultraviolet light absorbing agent to both layers adjacent to the cyan color forming layer.

Among the above described color fading prevent-ing agents, spiroindanes and hindered amines are particularly preferred.
In accordance with the present invention, it is preferred to employ the compounds as described below together with the above described couplers, particularly pyrazoloazole couplers. More specifically, to employ individually or in combination a compound (A) which is capable of forming a chemical bond with the aromatic amine developing agent remaining after color development to give a chemically inactive and substantially color-less compound and/or a compound (B) which is capable of forming a chemical bond with the oxidation product of the aromatic amine developing agent remaining after coior development to give a chemically inactive and substantially colorless compound is preferred in view of preventing the occurrence of stain and after undesirable side-effects due to the formation of colored dye upon a reaction of the color developing agent or oxidation product thereof which remains in the photographic layer with the coupler during preservation of the photographic material after processing.
Among the compounds (A), those capable of reacting at a second order reaction rate constant K2 (in a trioctylphosphate at 80C) with p-anisidine of from .- 1338101 1.0 liter/mol-sec. to lx10-5 liter/mol-sec. are preferred. The second order reaction rate constant can be determined by the method as described in JP-A-63-158545.
When the constant k2 is larges than this range, the compounds per se are unstable and apt to react with gelatin or water to decompose. On the other hand, when the constant k2 is smaller than the above described range, the reaction rate in the reaction with the remaining aromatic amine developing agent is low, and as a result, the prevention of the side-effect of the remaining aromatic amine developing agent tends to be reduced.
Of the Compounds (A), those more preferred are represented by the following general formula (AI) or (AII):

Rl (A tn X (AI) R2 -C=Y
B (AII) wherein Rl and R2 each represents an aliphatic group, an aromatic group or a heterocyclic group; A represents a group that can react with the aromatic amine developing agent to form a chemical bond; X represents a group that can react with the aromatic amine developing agent to split off; B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a solfonyl group; Y represents a group that can facilitate the addition of the aromatic amine developing agent to the compound having formula (AII); and Rl and X
together or Y and R2 or B together may combine to form a ring structure.
Of ways wherein the remaining aromatic amine developing agent and the compound (A) chemically combine, typical ways are substitution reactions and addition reactions.
The preferred examples of the compounds represented by formula (AI) or (AII) include the compounds as described in JP-A-63-158545, JP-A-62-283338, Japanese patent application No. 158342/87, EP-A-277589publ~hed AuglO/88,etc.
More preferred examples of the compounds (8) that can chemically combine with the oxidation product of the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound are those represented by the following formula (BI):

R -Z (BI) `- 1338101 wherein R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z represents a nucleophilic group or a group that can decompose in the photographic material to relea~e a nucleophilic group.
In the compounds represented by the formula (BI), Z
preferably represents a group having a Pearson's nucleophilic nCH3I value (R.G. Pearson et al., J. Am.
Chem. Soc., 90, 319 (1968)) of 5 or more, or the group derived therefrom.
The preferred examples of the compounds represented by the formula (BI~ include the compounds as described in EP-A-255722 published Feb 10/88, EP-A-277589 published Aug 10/88, JP-A-62-143048, JP-A-62-229145, Japanese patent application Nos. 136724/88, 214681/87 and 158~42/87, etc.
The detailed explanation on combination of the aforementioned compound (A) and compound (B) is described in EP-A-277589.
The color photographic light-sensitive material according to the present invention may contain an ultraviolet light absorbing agent in the hydrophilic colloid layer. Suitable examples of the ultraviolet light absorbing agents used include aryl group-substituted benzotriazole compounds (for example, those as described in U.S. Patent 3,533,794), 4-thiazolidone compounds (for example, those as described in U.S.

` -1~38101 Patents 3,314,794 and 3,352,681), benzophenone compounds (for example, those as described in JP-A-46-2784), cinnamic acid ester compounds (for example,those as described in U.S. Patents 3,705,805 and 3,707,375), butadiene compounds (for example, those as described in U.S. Patent 4,045,229), and benzoxazole compounds (for example, those as described in U.S. Patent 3,700,455).
Furthermore, ultarviolet light absorptive couplers (for example, a-naphtholic cyan dye forming couplers) or ultraviolet light absorptive polymers may be used as ultraviolet light absorbing agents. These ultraviolet light absorbing agents may be mordanted in a specific layer.
The color photographic light-sensitive material according to the present invention may contain water-soluble dyes as filter dyes or for irradiation prevention or other various purposes in the hydrophilic colloid layers. Examples of such water-soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. In these dyes, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.
Useful oxonol dyes are described in detail in JP-A-62-215272, page 158, right upper column to page 163.

.

As the binder or protective colloids which can be used for the emulsion layers of the color photographic light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.
As gelatin, lime-treated gelatin or acid-treated gelatin can be used in the present invention. Details of the production of gelatin are described in Arther Weiss, The Macromolecular Chemistry of Gelatin, published by Academic Press, 1964.
As the support ~sed in the present invention, there are those conventionally employed in photographic light-sensitive materials, for example, cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, laminates of these films, thin glass films, papers, etc. Paper coated with baryta or an a-olefin polymer, in particular, a polymer of an a-olefin having 2 to 10 carbon atoms, such as polyethylene, polypropylene or ethylenebutene copolymer, vinyl chloride resin containing a reflective material such as titatium dioxide, and a support such as a plastic film having a roughened surface for improving 1~38101 the adhesion with other polymers as described in JP-B-47-19068 give good results. Also, a resin hardenable by the irradiation of ultraviolet rays can be used.
According to the purpose of the color photographic light-sensitive material, a transparent support or an opaque support may be used. Also, a colored transparent support containing dyes or pigments can also be used.
As opaque supports used in the present invention, there are paper which are opaque by themselves and transparent films which were opacified by the incorporation of dyes or pigments such as titanium oxide. Also, a plastic film surface-treated by the method as described in JP-B-47-i9068 can be used.
A subbing layer is usually provided on a support. Furthermore, for improving the adhesive property, a pretreatment such as corona discharging treatment, ultraviolet irradiation treatment, or flame treatment may be applied to the surface of the support.
The color photographic light-sensitive materials according to the present invention which are utilized to prepare color photographs are suitable for use as conventional color photographic materials, for example, color negative films, color paper, color reversal paper, and color reversal films, particularly color photographic light-sensitive materials for printing.
For development processing of the color photographic light-sensitive materials according to the present invention, a black-and-white developing solution and/or a color developing solution is employed.
A color developing solution which can be used is an alkaline aqueous solution containing preferably an aromatic primary amine type color developing agent as a main component. As the color developing agent, while an aminophenol type compound is useful, a p-phenylene-diamine type compound is preferably employed. Typical examples of the p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-B-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-B-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-~-methoxyethylaniline, or sulfate, hydrochloride, or p-toluenesulfonate thereof.
Two or more kinds of color developing agents may be employed in a combination thereof, depending on the purpose.
The color developing solution can ordinarily contain pH buffering agent such as carbonates, borates or phosphates of alkali metals; and development inhibitors or anti-fogging agents such as bromides, I3~lol iodides, benzimidazoles, benzothiazoles, or mercapto compounds. Further, if necessary, the color developing solution may contain various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydra-zines, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, or triethylenediamine(l,4-diazabicyclo-t2,2,2]-octane); organic solvents such as ethylene glycol, or diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quarternay ammonium salts, or amines; dye forming couplers;
competing couplers; fogging agents such as sodium borohydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting agents; and various chelating agents represented by aminopoly-carboxylic acids, aminopolyphosphonic acids, alkylphos-phonic acids, phosphonocarboxylic acids. Representative examples of the chelating agents include ethylene-diaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine-tetraacetic acid, hydroxyethyliminodi-acetic acid, 1-hydroxyethylidene-l,l-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenedi-amine-N,N,N',N'-tetramethylenephosphonic acid, ethylene-diamine-di(o-hydroxyphenylacetic acid), and salts thereof.

l3~al0l In case of conducting reversal processing, color development is usually conducted after black-and-white development. In a black-and-white developing solution, known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazoldione, or aminophenols such as N-methyl-p-aminophenol may be employed individually or in a combination.
The pH of the color developing solution or the black-and-white developing solution is usually in a range from 9 to 12. Further, an amount of replenishment for the developing solution can be varied depending to color photographic light-sensitive materials to be processed, but is generally not more than 3 liters per square meter of the photographic light-sensitive material. The amount of replenishment can be reduced to not more than 500 ml by decreasing a bromide ion concentration in the replenisher. In the case of reducing the amount of replenishment, it is preferred to prevent evaporation and aerial oxidation of the processing solution by-means of reducing an area of a processing tank which is contact with the air. Further, the amount of replenishment can be reduced using a means which restrain accumulation of bromide ion in the developing solution.

-After color development, the photographic emulsion layers are usually subjected to a bleach processing. The bleach processing can be performed simultaneously with a fix processing (bleach-fix processing), or it can be performed independently from the fix processing. Further, for the purpose of a rapid processing, a processing method wherein after a bleach processing a bleach-fix processing is conducted may be employed. Moreover, it may be appropriately practiced depending on the purpose to process using a continuous two tank bleach-fixing bath, to carry out fix processing before bleach-fix processing, or to conduct bleach processing after bleach-fix processing.
Examples of bleaching agents which can be employed in the bleach processing or bleach-fix processing include compounds of a multivalent metal such as iron(III), cobalt(III), chromium(VI), or copper(II);
peracids; quinones; or nitro compounds. Representative examples of the bleaching agents include ferricyanides;
dichloromates; organic complex salts of iron(III) or cobalt(III), for example, complex salts of amino-polycarboxylic acids (such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, cyclohexane-diaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, or glycol ether diamine-_ 99 _ tetraacetic acid), or complex salts of organic acids(such as citric acid, tartaric acid, or malic acid);
per~ulfates; bromates; permanganates; or nitrobenzene~.
Of these compounds, iron(TII) complex ~alts of aminopolycarboxylic acids represented by iron ~III) complex salt of ethylenediaminetetraacetic acid and persulfates are preferred in view of rapid processing and less environmental pollution. Furthermore, iron(III) complex salts of aminopolycarboxylic acids are particularly useful in both bleaching solutions and bleach-fixing solutions.
The p~ of the bleaching solution or bleach-fixing solution containing an iron (III) complex salt of aminopolycarboxylic acid is usually in a range from 5.5 to 8. For the purpose of rapid processing, it is possible to process at p~ lower than the above described range.
In the bleaching solution, the bleach-fixing solution or a prebath thereof, a bleach accelerating a~ent can be used, if desired. Specific examples of suitable bleach accelerating agents include compounds having a mercapto group or a disulfide bond as described, for example, in U.S. Patent 3,893,858, West German Pale~
1,290,812 published Mar 13/69, and 2,059,988 published June 15/72, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-62623, JP-A-5~

_ 1338101 95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and Research Disclosure, No. 17129 (July 1978); thiazolidine derivatives a~
de~cribed, for example, in JP-A-50-140129; thiourea derivatives as described, for example, in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and U.S. Patent 3,706,561;
iodides as described. for example, in We~t German Patent 1,127,715 published April 12/62 and JP-A-5~16235; polyoxyethylene compounds as described, for example, in West German Patents 966,~10 published Aug 1/57 and 2,748,430 published May 3/79; polyamine compounds as described, for example, in JP-W~8836; compounds as described for example, in JP-A~9-42434, lP-A~9-59644, JP-A-~94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940;
and bromide ions. Of these compounds, the compounds having a mercapto group or a disulfide bond are preferred in view of their large bleach accelerating effects. Particularly, the compounds as described in U.S. Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are preferred. Further, the compounds as described in U.S. Patent 4,552,834 are also preferred.
These bleach accelerating agents may be incorporated into the color photographic light-sensitive material.
These bleach accelerating agents are particularly effectively employed when color photographic light--133~101 sensitive materials for photographing are subjected to bleach-fix processing.
As fixing agents which can be employed in the fixing solution or bleach-fixing solution, thiosulfates, thiocyanates, thioether compounds, thioureas, or a large amount of iodide are exemplified. Of these compounds, thiosulfates are generally employed. Particularly, ammonium thiosulfate is most widely employed. It is preferred to use sulfites, bisulfites or carbonyl-bisulfite adducts as preservatives in the bleach-fixing solution.
After a desilvering step, the silver halide color photographic material according to the present invention is generally subjected to a water washing step and/or a stabilizing step.
An amount of water required for the water washing step may be set in a wide range depending on characteristics of photographic light-sensitive materials Idue to elements used therein, for example, couplers), uses thereof, temperature of washing water, a number of water washing tanks (stages), a replenishment system such as countercurrent or orderly current, or other various conditions. A relationship between a number of water washing tanks and an amount of water in a multi-stage countercurrent system can be determined 13~101 based on the method as described in Journal of the Society of Motion Picture and Television Enqineers, Vol.
64, pages 248 to 253 (May, 1955).
According to the multi-stage countercurrent system described in the above literature, the amount of water for washing can be significantly reduced.
However, increase in staying time of water in a tank causes propagation of bacteria and some problems, for example, adhesion of floatage formed on the photographic materials, occur. In the method of processing the silver halide color photographic material according to the present invention, a method for reducing amounts of calcium ions and magnesium ions as described in JP-A-62-288838 can be particularly effectively employed in order to solve such problems. Further, sterilizers, for example, isothiazolone compounds as described in JP-A-57-8542, thiabendazoles, chlorine type sterilizers such as sodium chloroisocyanurate, benzotriazoles, sterilizers as described in Hiroshi Horiguchi, Bokin-Bobaizai No Kaqaku, Biseibutsu No Mekkin-, Sakkin-, Bobai-Gijutsu, edited by Eiseigijutsu Kai, and Bokin-Bobaizai Jiten, edited by Nippon Bokin-Bobai Gakkai can be employed.
A pH of the washing water used in the processing of the photographic light-sensitive materials according to the present invention is usually from 4 to 9, preferably from 5 to 8. Temperature of washing water and time for a water washing step can be variously set depending on characteristics or uses of photographic light-sensitive materials. However, it is general to select a range of from 15C to 45C and a period from 20 sec. to 10 min. and preferably a range of from 25C to 40C and a period from 30 sec. to 5 min.
The photographic light-sensitive material of the present invention can also be directly processed with a stabilizing solution in place of the above-described water washing step. In such a stabilizing process, any of known methods as described, for example, in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be employed.
Further, it is possible to conduct the stabilizing process subsequent to the above-described water washing process. One example thereof is a stabilizing bath containing formulin and a surface active agent, which is employed as a final bath in the processing of color photographic light-sensitive materials for photographing. To such a stabilizing bath, various chelating agents and antimolds may also be added.
Overflow solutions resulted from replenishment for the above-described washing water and/or stabilizing .- - 1338101 solution may be reused in other steps such as a desilvering step.
For the purpose of simplification and acceleration of processing, a color developing agent may be incorporated into the silver halide color photo-graphic material according to the present invention. In order to incorporate the color developing agent, it is preferred to employ various precursors of color developing agents. Suitable examples of the precursors of developing agents include indoaniline type compounds as described in U.S. Patents 3,342,597, Schiff's base type compounds as described in U.S.Patent 3,342,599 and Research Disclosure, No. 14850 and ibid. No. 15159, aldol compounds as described in Research Disclosure, No.13924, metal salt complexes as described in U.S.
Patent 3,719,492, and urethane type compounds as described in JP-A-53-135628.
Further, the silver halide color photographic material according to the present invention may contain, if desired, various l-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of the compounds include those as described, for example, in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

In the present invention, various kinds of processing solutions can be employed in a temperature range from 10C to 50C. Although a standard temper-ature is from 33C to 38C, it is po~ible to carry out the processing at higher temperatures in order to accelerate the processing whereby the processinq time is shortened, or contrary at lower temperatures in order to achieve improvement in image guality and to maintain stability of the processing solutions.
Further, for the purpose of saving an amount of silver employed in the color photographic light-sensitive material, the photographic processing may be conducted utilizing color intensification using cobalt or hydrogen peroxide as described in West German Patent Application (OLS) No. 2,226,770 published Jan 4/73 or U.S. Patent 3,674,499.
In accordance with the present invention, color images having not only superior light fastness but also superior dark heat fastness and humidity and heat fastness as well as preventing from the occurrence of pink stain can be obtained.
The present invention will be explained in greater detail with reference to the following examples, but the present invention should not be construed as being limited thereto.

Sample 101:
On a paper support, both surfaces of which were laminated with polyethylene, were coated layers as shown below in order to prepare a multilayer silver halide photographic material which was designated Sample 101.
Construction of Layers The compositions of the layers are described below. The coated amounts are indicated in terms of g/m2 provided that the coated amounts of the silver halide emulsions are indicated in terms of g silver/m2.
Support:
Polyethylene laminated paper in which the polyethylene on the first layer side contained a white pigment (TiO2) and a blueish dye.
First Layer: Blue-sensitive Layer Monodispersed silver chlorobromide 0.16 emulsion (EMl) spectrally sensitized with Sensitizing dye (ExS-l) Monodispersed silver chlorobromide 0.10 emulsion ( EM2) spectrally sensitized with Sensitizing dye ( ExS-l) Gelatin 1.86 Color image stabilizer (Cpd-l) 0. 02 Yellow coupler (ExY-l) 0.83 Polymer (P-57) 0.08 Solvent (Solv-l/Solv-2=1:1 0.35 by volume ratio) Second Layer: Color-mixing Preventing Layer Gelatin o.gg Color mixing preventing agent (Cpd-3) 0.03 Solvent (Solv-3) 0.06 Third Layer: Green-sensitive Layer Monodispersed silver chlorobromide 0.05 emulsion (EM3) spectrally sensitized with Sensitizing dyes (ExS-2, 3) Monodispersed silver chlorobromide 0.11 emulsion (EM4) spectrally sensitized with Sensitizing dyes (ExS-2, 3) Gelatin 1.80 Magenta coupler (ExM-l) 0.39 Color imaqe stabilizer (Cpd-4) 0.20 Color image stabilizer (Cpd-5) 0.05 Color image stabilizer (Cpd-6) 0.04 Solvent (Solv-3) 0.12 Solvent (Solv-4) 0.25 Fourth Layer: Ultraviolet Light Absorbing Layer Gelatin 1.60 Ultraviolet light absorbing agent (Cpd-7/ 0.70 Cpd-8/Cpd-9=3/2/6 by weight ratio) Color mixing preventing agent (Cpd-3) 0.05 Solvent (Solv-5) 0.27 ~ 1338101 Fifth Layer: Red-sensitive Layer Monodispersed silver chlorobromide 0.07 emulsion (EM5) spectrally sensitized with Sensitizing dyes (ExS-4, 5) Monodispersed silver chlorobromide 0.16 emulsion (EM6) spectrally sensitized with Sensitizing dyes (ExS-4, 5) Gelatin 0.92 Cyan coupler (ExC-l) 0.30 Color image stabilizer (Cpd-l) 0.03 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-6) 0.01 Ultraviolet light absorbing agent (Cpd-7/ 0.17 Cpd-9/Cpd-10=3/4/2 by weight ratio) Solvent (Solv-2) 0.20 Sixth Layer: Ultraviolet Light Absorbing Layer Gelatin 0.54 Ultraviolet light absorbing agent (Cpd-7/ 0.21 Cpd-8/Cpd-9=1/5/3 by weight ratio) Color mixing preventing agent (Cpd-3) 0.02 Solvent (Solv-5) 0.06 Seventh Layer: Protective Layer Gelatin 1.33 Acryl-modified polyvinyl alcohol 0.17 copolymer (modification degree: 17%) Liquid paraffin 0.03 For preventing irradiation, irradiation prevent-ing dyes (Cpd-ll, 12), were used.

1~38101 To all the layers, Alkanol B (Du Pont), sodium alkylbenzenesulfonate, succinic acid ester, and Megafac F-12~ (Dai Nippon Ink and Chemical Co., Ltd.) were u~ed as an emulsifying dispersing agent and a coating aid.
For stabilizing silver halide, silver halide stabilizers (Cpd-13, 14) were used.
Further, to all the layers, 2-oxy-4,6-dichloro-s-triazine sodium salt was used as a gelatin hardener, and Cpd-2 was used as a viscosity imparting agent.
This silver halide emulsions used in this example are described in detail below.
Crystal Average Bromide Coefficient*
Emulsion Form Grain size content of variation (~m) (mol%) EMl cubic 0.96 80 0.06 EM2 " 0.64 80 0.07 EM3 " 0.52 70 0.08 EM4 " 0.40 70 0.09 EMS " O.44 70 0.09 EM6 " 0.36 70 0.08 * Coefficient of variation=standard derivation/
average grain size (s/r).
The compounds used in the above-described layers are illustrated below.

*Denotes trade mark -- ExY--1 1338101 CQ .
- (CH3)3COCHCONH ~

o~N~o c H~CsHIlt N I OC2Hs 2 5 CsHIlt I H

~H2 ExM- 1 CH3 // C~
~ ,9~ CHzCH20C2Hs N O
NHSO2 ~ O ~ 7 CH3 NHSO2 ~

C~HI7(t) ExC--1 C~3~NHCoCHo~3C5H" (t) HsC2 C~

E x S - 1 OH

(CHz)~So3~ tClH2)~
SO3NH(C2H3)3 6x10 mol/Ag mol E x S--2 CH=C - CH

(CH2) 3S03~ (,Hz)2 503NH(C2H3)3 4x10 4 mol/Ag mol - ExS- 3 ~o~ ~o ~ 1 3 3 81 0 1 (CHz) 4 so~3 tCH~ 4 So3NHtC2H5) 3 8x10 5 mol/Ag mol E x S--4 CH CHs ~CH~LCH~

CsHI I I~ CzHs 1 . 8x10 mol/A~ mol E x S - 5 ~/ );~ ~SO H

~3/ ,2 C p d--1 `H CH
J ~ I J
~,--CHr--C--CHs Hs CH3 Cp d--2 ~CH2 --CH ~ n SOsK
Cp d--3 C8HI7(t) tt)C~H
OH
Cp d--4 CaH70 CH~ CH, CJH70~(0G3H7 CH, CH ~ OC~H7 I3~81 01 .

C p d - 5 1l OCOCI~H33(n) C~ C~

CO2C;H5 C p d - 6 o C~sHIl(t) CNH(CH2)sO- ~ C~HIl(t) NaO2~
IClNH(CHz)a- ~ C,HIl(t) C,H~l(t) C p d - 7 C~ OH C4Hs(t) \ N ~

C4H9(t) C p d - 8 OH CsHIl(t) i ~ \ N ~
CsH " (t) C p d - 9 OH C4Hs(sec) C4Hs(t) - 13~8101 C p d - 1 0 OH
[~r~N~
C4Hs(t) C p d - 1 1 HO OH
HOCHzCHNC ~ 80 N

SO3Na I SO3Na C p d - 1 2 R 1l NaOC ~ CH -CH =CH ~ 11 CONa SOINa I SO3Na C p d - 1 3 ~N ~ \
~`N
OH

C p d - 1 4 NHCONHCHa ~tl Solv~ iso ) CgHlgOt3 P o Solv-2 C8Hl7C~C~(CH2 ~ 8 17 Solv-3 Tricresyl phosphate Solv-4 (C~HglHCH2Ot3--P=
c2~s Solv-5 COOCH2C~(C2H5)C~g (CH2)8 CoocH2cH(c2H5)c4H9 Sample 102 to 110:
Samples 102 to 110 were prepared in the same manner as described for Sample 101 except for using the equimolar amounts of the couplers and polymers as shown in Table 1 below in place of Cyan coupler (ExC-l) added to the fifth layer of Sample 101 respectively.
For emulsifing and dispersing of the coupler, etc., ethyl acetate was used as an auxiliary solvent in the preparation of Samples 101 to 110.
The color photographic light-sensitive materials thus-prepared were imagewise exposed to light and continuous~y processed (a running test) according to the processing steps shown below using a Fuji Color Paper Processor PP600, until the amount of the replenisher for the color developing solution reached twice the capacity of the developing tank.

~Denotestrade mark 1~38101 Amount of* Capacity Processinq Step Temperature Time Replenisher of Tank ( C ) Color Development38 1'40" 290 ml 17e Bleach-Fixing 33 60" 150 ml ge Rinse (1) 30 to 34 20" ~ 4e Rinse (2) 33 to 34 20" - 4e Rinse (3) 33 to 34 20" 364 ml 4e Drying 70 to 80 50"
* Amount of replenisher is indicated as an amount per m2 of the photographic light-sensitive material.
The rinse steps were conducted using a three-tank countercurrent system from Rinse (3) to Rinse (1).
The composition of each processing solution used was as follows:

Color Developinq Solution Tank Solution Replenisher Water 800 ml 800 ml Diethylenetriaminepentaacetic 1.0 g 1.0 g acid Nitrilotriacetic acid 2.0 g 2.0 g l-Hydroxyethylidene-l,l- 2.0 g 2.0 g diphosphonic acid Benzyl alcohol 16 ml 22 ml Diethylene glycol 10 ml 10 ml Sodium sulfite 2.0 g 2.5 g 1~38101 -Potassium bromide 0.5 g Potassium carbonate 30 g 30 g N-Ethyl-N-(B-methanesulfon- 5.5 g 7.5 g amidoethyl)-3-methyl-4-amino-aniline sulfate Hydroxylamine sulfate 2.0 g 2.5 g Fluorescent whitening agent 1.5 g 2.0 g (WHITEX 4B,~ manufactured by Sumitomo Chemical Co., Ltd.) Water to make 1,000 ml 1,000 ml pH at 25C 10.20 10.60 Bleach-Fixinq Solution Tank Solution Replenisher Water 400 ml 400 ml Ammonium thiosulfate 200 ml 300 ml (70~ soln.) Sodium sulfite 20 g 40 g Ammonium iron(III) ethylene- 60 g 120 g diaminetetraacetate Disodium ethylenediaminetetra-5 g 10 g acetate Water to make 1,000 ml 1,000 ml pH at 25C 6.70 6.30 Rinse Solution Ion exchange water (contents of calcium and magnesium each having not more than 3 ppm).
After the development processing, the samples were subjected to the following tests in order to ~Denotes trade mark evaluate their light fastness, heat fastness and humidity and heat fastness. More specifically, each of the samples were stored in a dark place at 100C for two weeks, stored in a dark place at 80C and 70%RH for 20 days, or irradiated to light in a fluorescent lamp fading tester (30,000 lux) for 5 months. Then, the rate of decrease in density in the area of the sample having an initial density of 1.5 with respect to the heat fastness or in the area of the sample having an initial density of 1.0 with respect to the light fastness was determined. The results thus obtained are shown in Table 1 below.

13~38101 a~
n 0 ''' ~ dP a: ~O
U ~ ~r ~ ~ ~ N N ~ N ~`~
C~' l~

C~ O
U~ o 0 C~
V U
0 U I _ ~ n t~
o N

L o L, 0 - ~ o CO~o ~ o ~:~ S I I I _~ o o o _i o o .,1 E- ~ a~
P~ .
L O a~ O

p~

a I N N N ~1 ~r O
~ N u~ N N ~r ~r U7 L ~ ~ ) U C,~
~J

O J ~:
O
~ ~ r,~ ~ ,~ ~ ~r In ~D 1` 00 a~ o ~ ~rt W .~ O O O _I
0 p~ I~ J
O --~:
H

As is apparent from the results shown in Table 1, the color photographic light-sensitive materials according to the present invention are excellent in the heat fast-ness and the humidity and heat fastness. Further, with the photographic light-sensitive materials of the present invention (Samples 104 to 110), the occurrence of pink stain due to irradiation to light is substantially not observed.

Sample 201 On a paper support, both surfaces of which were laminated with polyethylene, were coated layers as shown below in order to prepare a multilayer silver halide photographic material which was designated Sample 201.
Construction of Layers The compositions of the layers are described below. The coated amounts are indicated in terms of g/m2 provided that the coated amounts of the silver halide emulsions are indicated in terms of g silver/m2.
Support:
Polyethylene laminated paper in which the polyethylene on the first layer side contained a white pigment (TiO2) and a blueish dye.
First Layer; (Blue-sensitive Layer) Monodispersed silver chlorobromide 0.27 emulsion (EM7) spectrally sensitized with Sensitizing dye (ExS-7) Gelatin 1.86 Yellow coupler (ExY-l) 0.82 Polymer (P-57) 0.08 - Solvent (Solv-6) 0.35 Second Layer (Color mixing preventing Layer) Gelatin o.gg Color mixing preventing agent (Cpd-3) 0.06 Solvent (Solv-3) 0.12 Third Layer: (Green-sensitive Layer) Monodispersed silver chlorobromide 0.45 emulsion (EM8) spectrally sensitized with Sensitizing dyes (ExS-3, 6) Gelatin 1.24 Magenta couplr (ExM-2) 0.35 Color image stabilizer (Cpd-4) 0.12 Color image stabilizer (Cpd-15) 0.06 Color image stabilizer (Cpd-16) 0.10 Color image stabilizer (Cpd-17) 0.01 Solvent (Solv-3) 0.25 Solvent (Solv-4) 0.25 Fourth Layer (Ultraviolet light Absorbing Layer) Gelatin 1.60 Ultraviolet light absorbing agent 0.70 (Cpd-7/Cpd-9/Cpd-19=3/2/6 by weight ratio) Color mixing preventing agent (Cpd-3) 0.05 Solvent (Solv-7) 0.42 -Fifth Layer: (Red-sensitive Layer) Monodispersed silver chlorobromide 0.20 emulsion (EM9) spectrally sensitized with Sensitizing dyes (ExS-4, 5) Gelatin 0.92 Cyan coupler (ExC-2) 0.33 Color image stabilizer (Cpd-l) 0.02 Ultraviolet light absorbing agent 0.17 (Cpd-7/Cpd-9/Cpd-19=3/4/2 by weight ratio) Solvent (Solv-6) 0.20 Sixth Layer (Ultraviolet light Absorbing Layer) Gelatin 0.54 Ultraviolet light absorbing agent 0.21 (Cpd-7/Cpd-9/Cpd-17=1/5/3 by weight ratio) Solvent (Solv-7) 0.08 Seventh Layer (Protective Layer) Acid processed gelatin 1.33 Acryl-modified polyvinyl alcohol 0.17 copolymer (degree of modification: 17%) Liquid paraffin 0.03 For preventing irradiation, irradiation preventing dyes (Cpd-ll, 12) were used.
To all the layers, Alkanol B (Du Pont), sodium alkylbenzenesulfonate, succinic acid ester, and Megafac F-120 (Dai Nippon Ink and Chemical Co., Ltd.) were used as an emulsifying dispersing agent and a coating aid.
For stabilizing silver halide, silver halide stabilizers (Cpd-13, 14) were used.

Further, to all the layers, 2-oxy-4,6-dichloro-s-triazine sodium salt was used as a gelatin hardener, and Cpd-2 was used as a viscosity imparting agent.
This silver halide emulsions used in this example are described in detail below.

Crystal Average Bromide Coefficient*
Emulsion Form Grain size content of variation (~m) (mol%) EM7 cubic 0.85 0.6 0.10 EM8 " 0.45 1.0 0.09 EM9 " 0.34 1.8 0.10 * Coefficient of variation=standard derivation/
average grain size (s/r) The compounds used in the above-described layers are illustrated below.

ExM-2 Cl NH2 N
N~N~lo H27C13ClNH
Cl ~ Cl 1 3 ~ t ExC-2 C1~3, NHCOlHO~ ( t ) Cs CH3 ( t ) Cs ExS-7 ,~ ) OH <~

(CH2)3 (CH2)3 7x10-4 mol/mol A~

E x S - 6 CH-C- CH

~CH2) 3S05~ (,H2)z C p d - 1 5 ~03HN~
C~HI3(t) C~Hts(t) OH
C p d - 1 6 CHz CH3 CHs C p d - 1 7 \ OH
H3C ~ CH3 C p d - 7 CO OH C~Hs(t) , / ~
C~Hs~t) C p d - 9 OH C4Hs(sec) C~Hs(t) Solv-6 Dobutyl phthalate Solv-7 Dioctyl sebacate Sample 202 to 214:
Samples 202 to 214 were prepared in the same manner as described for Sample 201 except for using the equimolar amounts of the couplers, the same weight of the solvents and further polymers as shown in Table 2 below in place of cyan coupler (ExC-2) and the solvent added to the fifth layer of Sample 201 respectively.
For emulsifing and dispersing of the coupler, etc., ethyl acetate was used as an auxiliary solvent in the preparating of Samples 201 to 214.
The color photographic light-sensitive materials thus-prepared were exposed to light through an optical wedge and then processed according to the processing steps described below.

Processinq Step Temperature Time Color Development 35C 45 sec Bleach-Fixing30 to 36C 45 sec Stabilizing (1)30 to 37C 20 sec Stabilizing (2)30 to 37C 20 sec Stabilizing (3)30 to 37C 20 sec Stabilizing (4)30 to 37C 30 sec Drying70 to 85C 60 sec The stabilizing steps were conducted using a four-tank countercurrent system from Stabilizing (4) to Stabilizing (1).
The composition of each processing solution used was as follows:
Color Developinq Solution Water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 9 N-Ethyl-N-(B-methanesulfonamidoethyl)-3- 5.0 g methyl-4-aminoaniline sulfate N,N-Diethylhydroxylamine 4.2 g 5,6-Dihydroxybenzene-1,2,4-trisulfonic acid 0.3 g Fluorescent brightening agent 2.0 g (4,4-diaminostilbene type) Water to make 1000 ml pH (25C) 10.10 Bleach-Fixinq Solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 18 g Ammonium ethylenediaminetetraacetate55 g iron(III) Disodium ethylenediaminetetraacetate3 g ~lacial acetic acid 8 g Water to make 1000 ml -pH (25C) 5.5 Stabilizinq Solution Formaldehyde (37%) 0.1 g Formaldehyde-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 q 2-Methyl-4-isothiazolin-3-one 0.01 Cupric sulfate 0.005 g Water to make 1000 ml pH (25C) .4.0 After the development processing, the photographic properties of the samples were evaluated in the same manner as described in Example 1. The results are shown in Table 2 below.

~E~ 13381~1 rr r rn ~.c ~4 w C ~ I` ~O N ~ N C~ t) CO ~r ~1 N r o ~ e ~ u~ ~ r ~ N N N N N N N rr~ rr~ N
cr ~ In . ~

a ~ N O C~ ~ In r~ r q~ rr~ m r r~
Ir u _ u~
r~

O a~ d~ N ~ ) r~o r~ ~ t~ r~

N

O
~-N U ~
0 r r~ o o ~ ~ a~ r~o oo a ~, s o O O ~ o O O O O
e.,, o 3 P~

~ O N Cl~ O
aJ 1~ ~ ~1 1~ t~ N ~I N

t ID ~rr~ ~ ~ ~ ~ r~7rr) ~, I I I I I I I I I
,~ O O O O O O O O O
rn V~ rn u~ rn )' q, ~1 N N N N N N H ~r ~r L r~ ~ N N u~) m 11') N N N r.~ ~r ~ ~r ~ I ~ U C.) U C~ U ~) O ~ ~
a~ v~ C O
Q h --I N r~l ~ ut v ul ~ r~ co a~ o H N ~ ~r OOOO~,_OOOO0~1~1 ~ Q N N N NJ ~r,~ N N N N N N N N N
u~ E3 ~' ' O _~
H

- 1~381~1 As is apparent from the results shown in Table 2, the color photographic light-sensitive materials according to the present invention provide excellent image fastness.

Sample 301 On a cellulose triacetate film support were coated the first layer to the fourteenth layer shown below in order to prepare a multilayer color photographic light-sensitive material which was designated Sample 301.
Compositions of Liqht-Sensitive Layers:
The components used in each layer and the coated amounts thereof in terms of g/m2 are described below. The coated amount of silver halide and colloidal silver is indicated in terms of g silver/m2.
Eirst Layer: Antihalation Layer Black colloidal silver 0.30 Gelatin 2.50 W-l 0.05 W -2 0.10 UV-3 0.10 Solv-l 0.10 Second Layer: Intermediate Layer Gelatin 0.50 Third Layer: Low-Sensitive Red-Sensitive Layer Monodispersed silver iodobromide 0.50 emulsion (silver iodide: 4 mol%~
cubic, average particle size: 0.3 ~m, s/r: 0.15) 13381~1 ExS-l 1.40x10-3 ExS-2 6.00x10-5 Gelatin 0.80 ExC-l 0.3 Solv-2 0.15 Fourth Layer: Medium-Sensitive Red-Sensitive Layer Monodispersed silver iodobromide 0.50 emulsion (silver iodide: 2.5 mol~, tetradecahedral, average particle size: 0.45 ~m, s/r: 0.15) ExS-l 1.60x10-3 ExS-2 6.00x10-5 Gelatin 1.00 ExC-l 0 45 Solv-2 0.23 Fifth Layer: High-Sensitive Red-Sensitive Layer Monodispersed silver iodobromide 0.30 emulsion (silver iodide: 2.5 mol%, tetradecahedral, average particle size: 0.60 ~m, s/r: 0.15) ExS-l 1.60x10-3 ExS-2 6.00x10-5 Gelatin 0.70 ExC-l 0 3 Solv-2 0.15 Sixth Layer: Intermediate Layer Gelatin 1.0 Cpd-l 0.1 Solv-l 0.03 . . .

133~101 .

Solv-2 0.08 Solv-3 0.12 Cpd-2 0.25 Seventh Layer: Low-Sensitive Green-Sensitive Layer Silver iodobromide emulsion (silver 0.65 iodide: 3.0 mol%, mixture of regular crystals and twin crystals, average particle size: 0.3 ~m) ExS-3 3.30x10-3 ExS-4 1.50x10-3 Gelatin 1.50 ExM-l 0.10 ExM-2 0.25 Solv-2 0.30 Eiqhth Layer: High-Sensitive Green-Sensitive Layer Tabular silver iodobromide emulsion 0.70 (silver iodide: 2.5 mol%, particles having a diameter/thickness ratio of 5 or more occupying 50% of the projected area of the total particles, average.
thickness: 0.15 ~m) ExS-3 1.30x10-3 ExS-4 5.00x10-4 Gelatin 1.00 ExM-3 0.25 Cpd-3 0.10 Cpd-4 0 05 Solv-2 0.05 Ninth Layer: Intermediate Layer Gelatin 0.50 -Tenth Layer: Yellow Filter Layer Yellow colloidal silver 0.10 - Gelatin 1.00 Cpd-l 0.05 Solv-l 0.03 Solv-2 0.07 Cpd-2 0.10 Eleventh Layer: Low-Sensitive Blue-Sensitive Layer Silver iodobromide emulsion (silver 0.55 iodide: 2.5 mol%, mixture of regular crystals and twin crystals, average particle size: 0.7 ~m) ExS-5 l.OOx10-3 Gelatin o.go ExY-l 0.50 Solv-2 0.10 Twelfth Layer: High-Sensitive Blue-Sensitive Layer Tabular silver iodobromide emulsion 1.00 ~silver iodide: 2.5 mol%, particles having a diameter/thickness ratio of 5 or more occupying 50% of the projected area of the total particles, average thickness: 0.13 ~m) ExS-5 1.70x10-3 Gelatin 2.00 ExY-l l.oO
Solv-2 0.20 Thirteenth Layer: Ultraviolet Light Absorbing Layer Gelatin 1.50 UV-l 0.02 UV-2 0.04 UV-3 0.04 Cpd-5 0 30 Solv-l 0.30 Cpd-6 0.10 Fourteenth Layer: Protective Layer Fine grain silver iodobromide (silver 0.10 iodide: 1 mol%, average particle size:
0.05 ~m) Gelatin 2.00 H-l 0.30 The compounds used in the above-described layers are illustrated below.

ExS-l CH=C-CH ~ ~ Cl (CH2)4 C2H5 so3-ExS-2 (n)C4Hg~ ~ ,CH2CH20CH3 CII~C-Cli =~ ~3 13~8101 E x S - 3 ~¢~o~ ICzH

tC~ Hz) 3(ICHz) 3 SOs S03~1a E x S ~ 4 C~ ICzHs SO,-E x S--5 ~ CH~ ~) (Cl Hz), (CHz) 3-~N (CzH5) 3 ~, OH

( t) C~Hq (t)CJH9 , OH
CIH CHzCH3 C p d - 1 OH ,tt)C~H, 7 tt)CJH~7 OH

C p d - 2 Polyethyl acrylate C p d - 3 ~tt)C~H~s tt)CoHI J OCH3 C p d - 4 ,tt)C~H,~

(t)C~HI~ OH

C p d - 5 CzHs C0OC~2H2s - N-CH=CH-CH=C -13381~1 Cp d--6 NaO3S ~ N=N~ CCONa liO N
~`
¢~, SO3Na E x C--1 I H NHCOC3F7 (t) C,HI ,~ nl-C~H~
(t)CsH

E x M- 1 (t)C~H~ ~OCH2CONH-~
(t)CsH~ ICONH ll N~N~o CQ,¢~C~

C~
ExM--2 (t) C~H~ I~OCHCONH
(t)CsHI ICO~!H 11 N~N/~o C~CI

C~

13~8101 Solv-l: Dibutyl phthalate Solv-2: Tricresyl phosphate - Solv-3: Trinonyl phosphate - H-l: 1,2-Bis(vinylsulfonylacetamido)ethane Samples 302 to 310:
Samples 302 to 310 were prepared in the same manner as described for Sample 301 except for using the equimolar amounts of the couplers and further polymers as shown in Table 3 below in place of cyan coupler (ExC-l) added to the third layer, fourth layer and fifth layer of Sample 301 respectively.
For emulsifing and dispersing of the couplers, etc., ethyl acetate was employed as an auxiliary solvent in the preparation of Samples 301 to 310.
The silver halide color photographic materials thus-prepared were exposed to light and then processed according to the following processing steps.

Processinq Step Time Temperature First Development 6 minutes 38C
Washing with Water 2 minutes "
Reversal 2 minutes "
Color Development 6 minutes "
Controlling 2 minutes "
Bleaching 6 minutes "
Fixing 4 minutes "
Washing with Water 4 minutes "

'- - 1338lol -Stabilizing 1 minute 25C
The composition of each processing solution used was as follows:
First Developinq Solution:
Pentasodium nitrilo-N,N,N-trimethylene- 2.0 g phosphonate Sodium sulfite 30 g Potassium hydroquinonemonosulfonate 20 g Potassiumcarbonate 33 9 l-Phenyl-4-methyl-4-hydroxymethyl-3- 2.0 g pyrazolidone Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Water to make 1000 ml pH 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide.
Reversal Solution:
Pentasodium nitrilo-N,N,N-trimethylene- 3.0 g phosphonate Stannous chloride (dihydrate) 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water to make 1000 ml pH 6.00 . . .

The pH was adjusted with hydrochloric acid or sodium hydroxide.
Color Developinq Solution:

Pentasodium nitrilo-N,N,N-trimethylene- 2.0 g phosphonate Sodium sulfite 7.0 g Sodium tertiary phosphate (12 hydrate) 36 g Potassium bromide 1.0 g Potassium iodide 90 mq Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-Ethyl-N-(B-methanesulfonamidoethyl)-3- 11 g methyl-4-aminoaniline sulfate 3,6-Dithiaoctane-1,8-diol 1.0 g Water to make 1000 ml pH 11.80 The pH was adjusted with hydrochloric acid or potassium hydroxide.
Controllinq Solution Disodium ethylenediaminetetraacetate 8.0 9 (dihydrate) Sodium sulfite 12 g l-Thioglycerol 0.4 ml Water to make 1000 ml pH 6.20 The pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleachinq Solution Disodium ethylenediaminetetraacetate2.0 g (dihydrate) Ammonium ethylenediaminetetraacetate120 g iron(III) (dihydrate) Potassium bromide 100 g Ammonium nitrate 10 g Water to make 1000 ml pH 5.70 The pH was adjusted with hydrochloric acid or sodium hydroxide.
Fixinq Solution Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water to make 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia.
Stabilizinq Solution Formalin (37%) 5.0 ml Polyoxyethylene-p-monononylphenyl ether 0.5 ml (average degree of polymerization: 10) Water to make 1000 ml p~ not adjusted After the development processing, the samples were subjected to the following tests in order to evaluate their heat fastness. More specifically, each of the 13381~1 samples were stored in a dark place at 100C for 10 days, or stored in a dark place at 80C and 70%RH for 14 days.
Then, the rate of decrease in density in the area of the sample having an initial density of 1.5 was determined.
The results thus obtained are shown in Table 3 below.

133~101 dP
o U~
~1~ ~ ~
U
o ~
o, U
o ~_ o _ , ,, , o ,, a~ O
Q.-o ~a o u~
, .. ......
~, o o , o o , o al cr .

~, L
~ o oo o~
,. ......
o ~ P~

L U _I ul ,~ ,1 ", ,~ ~" ", ", X~I IIIIIII
o ~ ~ CJ U U

~ _ O ~ ~:
Ul ~ O
a~ ~
o _~
C~ H
-13~8101 From the results shown in Table 3, it can be seen that the color photographic light-sensitive materials according to the present invention are excellent in the dark heat fastness and the humidity and heat fastness.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (29)

1. A silver halide color photographic material comprising a support having thereon at least one silver halide photographic emulsion layer containing a dispersion of oleophilic fine particles obtained by emulsifing and/or dispersing a mixture solution containing at least one oil-soluble coupler which is capable of forming a dye upon coupling with on oxidation product of an aromatic amine developing agent and represented by the general formula (I) described below and at least one non-color forming oil-soluble polymer.

(I) wherein Q1 represents an atomic group necessary to form a 5-membered or more nitrogen-containing heterocyclic ring containing at least one nitrogen atom together with the carbon atoms; Z1 represents a hydrogen atom or a group capable of being released upon a coupling reaction with an oxidation product of a color developing agent;
R1 represents an acyl group or a sulfonyl group; R2 represents a hydrogen atom or an aliphatic group having from 1 to 8 carbon atoms, or R1 and R2 may combine with each other to form a ring; and the coupler may form a dimer or polymer coupler by a substituent for R1, R2, Z1 or Q1.

2. A silver halide color photographic material as claimed in Claim 1, wherein the group represented by Q1 contains at least one nitrogen atom and a methylene bond, an ethylene bond, an imino bond, a sulfonyl group, a carbonyl group, an arylene group, a divalent heterocyclic group or a combination of two or more of these groups.

3. A silver halide color photographic material as claimed in Claim 1, wherein the group capable of being released upon coupling represented by Z1 is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group a sulfonyloxy group, an amido group, and alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aliphatic or aromatic thio group, an amido group or an aromatic azo group.

4. A silver halide color photographic material as claimed in Claim 1, wherein R1 represents a group represented by -CO-X1-R4 or -SO2-X1-R4, wherein X1 represents -O-, -NR5- or a simple bond; R4 represents a chain or cyclic aliphatic group, an aryl group or a heterocyclic group each of which may be substituted, and R5 represents a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms and may further contain a substituent.

5. A silver halide color photographic material as claimed in Claim 4, wherein the aliphatic group represented by R4 is an aliphatic group having from 1 to 32 carbon atoms.

6. A silver halide color photographic material as claimed in Claim 4, wherein a substituent for the aliphatic group, the aryl group or the heterocyclic group represented by R4 is selected from an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an ester group, an amido group, a sulfamido group, an imido group, a ureido group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic thio group, a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo group, or a halogen atom.

7. A silver halide color photographic material as claimed in Claim 4, wherein R1 represents a group of -CO-X1-R4.

8. A silver halide color photographic material as claimed in Claim 7, wherein X1 is a simple bond.

9. A silver halide color photographic material as claimed in Claim 1, wherein R2 is a hydrogen atom.

10. A silver halide color photographic material as claimed in Claim 1, wherein the oil-soluble polymer is a water-insoluble and organic solvent-soluble homo-polymer or copolymer which is composed of a repeating unit having a linkage of in the main chain or side chain thereof.

11. A silver halide color photographic material as claimed in Claim 10, wherein the homopolymer or copolymer is composed of a repeating unit having a link-age of in the main chain or side chain thereof.

12. A silver halide color photographic material as claimed in Claim 10, wherein the homopolymer or copolymer is composed of a repeating unit having a group of (wherein G1 and G2, each represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, provided that both G1 and G2 are not hydrogen atoms at the same time) in the side chain thereof.

13. A silver halide color photographic material as claimed in Claim 12, wherein one of G1 and G2 is a hydrogen atom and the other is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group each having from 3 to 12 carbon atoms.

14. A silver halide color photographic material as claimed in Claim 1, wherein the polymer is a vinyl polymer composed of a monomer selected from an acrylic acid ester, a methacrylic acid ester, a vinyl ester, an acrylamide, a methacrylamide, an olefin, a styrene, a vinyl ether and other vinyl monomers.

15. A silver halide color photographic material as claimed in Claim 14, wherein the monomer is selected from a methacrylic acid ester, an acrylamide and a methacrylamide.

16. A silver halide color photographic material as claimed in Claim 1, wherein the mixture solution further contains an organic solvent having a high boiling point.

17. A silver halide color photographic material as claimed in Claim 16, wherein the organic solvent having a high boiling point is a compound represented by the following general formulae (XXIII), (XXIV), (XXV), (XXVI), (XXVII) or (XXVIII):

(XXIII) W1-COOW2 (XXIV) (XXV) (XXVI) W1-O-W2 (XXVII) HO-W6 (XXVIII)

18. A silver halide color photographic material as claimed in Claim 1, wherein silver halide in the silver halide photographic emulsion layer is silver chlorobromide.

19. A silver halide color photographic material as claimed in Claim 1, wherein a silver halide emulsion in the silver halide photographic emulsion layer is a monodispersed silver halide emulsion having a coeffici-ent of variation not more than 15%.

20. A silver halide color photographic material as claimed in Claim 1, wherein the silver halide photo-graphic emulsion layer is a red-sensitive silver halide emulsion layer.

21. A silver halide color photographic material as claimed in Claim 20, wherein the color photographic material further comprises at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer.

22. A silver halide color photographic material as claimed in Claim 21, the green-sensitive silver halide emulsion layer contains a magenta coupler and the blue-sensitive silver halide emulsion layer contains a yellow coupler.

23. A silver halide color photographic material as claimed in Claim 22, wherein the yellow coupler is a compound represented by the following general formulae (Y-1) or (Y-2);

[Y-1]

[Y-2]

wherein X represents a hydrogen atom or a group capable of being released upon coupling; R21 represents a diffusion resistant group having from 8 to 32 carbon atoms in total; R22 represents a hydrogen atom, one or more of halogen atom, lower alkyl groups, lower alkoxy groups or diffusion resistant groups having from 8 to 32 carbon atoms in total; and R23 represents a hydrogen atom or a substituent; when two or more R23's are present, they may be the same or different.

24. A silver halide color photographic material as claimed in Claim 21, wherein the magenta couple is a compound represented by the following general formula (M-1), (M-2) or (M-3):

[M-1]

[M-2]

[M-3]

wherein R31 represents a diffusion resistant group having from 8 to 32 carbon atoms in total; R32 represents a phenyl group or a substituted phenyl group; R33 represents a hydrogen atom or a substituent; Z
represents a non-metallic atomic group necessary to form a 5-membered azole ring containing two to four nitrogen atoms, which azole ring may have one or more substituents (including a condensed ring); and X2 re-presents a hydrogen atom or a group capable of being released.

25. A silver halide color photographic material as claimed in Claim 4, wherein R2 and R5 each represents a hydrogen atom or an aliphatic group having from 1 to 8 carbon atoms.

26. A silver halide color photographic material as claimed in Claim 4, where in R2 and R1 or R4 may form a cyclic structure.

27. A silver halide color photographic material as claimed in Claim 26, wherein said cyclic structure represents 5, 6, or 7 membered ring.

28. A silver halide color photographic material as claimed in Claim 1, wherein Z1 represents a hydrogen atom, a halogen atom, an aryloxy group, an arylthio group or an alkoxy group.

29. A silver halide color photographic material as claimed in claim 1, wherein said 5-membered or more nitrogen-containing heterocyclic ring which is formed by Q1 represents a 5 to 7 membered ring.