JPH03239252A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow the formation of thinner layers without degrading film quality by incorporating specified compds. into the above material. CONSTITUTION:The compd. expressed by formula I, the compd. expressed by formula II and the compd. expressed by formula III are incorporated into this photosensitive material and at least the compd. of the formula I is dispersed under an alkaline condition of >=10 pH and is introduced into the photosensitive material. In the formula I, one of R1, X1, R2 denotes a carboxyl group, sulfonic acid group, or the group contg. the salts thereof; R1 denotes an alkyl group, aryloxy group, etc.; R2 denotes an acyl group, sulfonyl group; (L) denotes a specific alkylene group, or phenylene group; X denotes an aryloxy group, arylthio group, etc. In the formula II, L denotes a bivalent combination group; n denotes 0 or 1 to 10 integer; M denotes hydrogen or cation. In the formula III, B denotes -o- or -NH-; A denotes an aliphat. bivalent group having 1 to 50C; M denotes a cation or cationic radical which can form a salt with sulfonic acid; n denotes <=3. The formation of the thinner layers is possible in this way and the degradation in the film quality is obviated.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material. On the other hand, as a method for improving color reproducibility, it is also important to use a coloring dye that has a bright hue with little sub-absorption and to use an intermediate layer that does not mix colors. U.S. Patent No. 3,725,067 and Japanese Patent Application Laid-open No. 1983-1982 as a magenta coupler that provides a magenta dye with little side absorption.
No. 71956, No. 61-53644, No. 61-652
No. 43, No. 62-186262, No. 61307453
Pyrazolotriazoles are known, but these couplers have an adverse effect on silver halide emulsions when used as photographic materials, and can cause problems such as decreased sensitivity and poor storage stability. The harm was great. In addition, as a method of thinning the layer while using these couplers, it is possible to drastically reduce or remove the high boiling point organic solvent, but this may result in a decrease in color development, resulting in a decrease in density or softening, There were drawbacks in terms of manufacturing suitability, such as poor stability of the dispersion and precipitation of crystals during the manufacturing process. (Problems to be Solved by the Invention) The third aspect relates in detail to the Miyako material with improved sharpness and color reproducibility. (Prior Art) In recent years, high image quality, particularly high sharpness and good color reproducibility, have been required for I-G silver monide photographic materials, especially photographic materials. As a way to increase sharpness, by thinning the photosensitive material,
%p by shortening the optical scattering bus during exposure and shortening the diffusion bus of the development main oxidant formed during development.
Methods of improving the parent 7f are known. In order to make the layers thinner, it is necessary to lower the ratio of binders such as gelatin, but photosensitive materials made thinner in this way have the disadvantage of poor film quality. In other words, the film may peel off and break the bond at the part bonded with adhesive tape or heat-sealable tape, or the layer of sensitive material may peel off when trying to remove something that has been bonded to another object. Since the film quality must be strong enough for any practical purpose, it is difficult to reduce the film quality without deteriorating the film quality. It is an object of the present invention to provide a color photosensitive material that is thin, has good color reproducibility, and has good manufacturing suitability using a dispersion having good dispersion stability. (Means for Solving the Problems) As a result of intensive studies, it has been found that the above objects of the present invention can be achieved by the following configuration. That is, in a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, a compound represented by the following -Funenin (+) and a general formula (n
) and a compound of the general formula [■], at least the compound of the general formula [I] is dispersed and introduced into the photosensitive material through alkaline conditions with a pH of 10 or more. Color photographic material. - Shipman [1] However, R,, X, R, (11) are groups containing a carboxyl group, a sulfonic acid group, or a salt thereof, and R4 is substituted or unsubstituted Al4! L group, substituted or unsubstituted alkino 7 (3L represents a substituted or unsubstituted aryloxo group, R7 represents an acyl group or a sulfonyl group. (L 3- is shell-CH, :l -Naru Ano Denki [nW or -?Uran 4 represents Enyren Rei, '43 ?a' of alkyl L・N group
The carbon atoms substituted by R3 and R4 are connected to the Kafler mother nucleus, and R, , R, are hydrogen atoms, alkyl groups, or aryl groups. However, R2U and R are never hydrogen atoms at the same time. X is a substituted or unsubstituted aryloxy group, alkoxy group, 1-azolyl group, alkylthio group, or arylthio group, respectively. R+, R2, or 6n represents 3 or more. -・Replacement in Shipman (1), 79R,,R,,(i,
+ ) −, − and X will be explained in detail. R1 is a substituted or unsubstituted alkyl group, alkoxy group, aryloxy group, carboxyl group, or sulfo group, and specifically, a straight chain or branched alkyl group having 1 to 30 carbon atoms, or a C 1 to 20 Alcoquine group or having 6 to 20 carbon atoms? They are lyloxy group, carboxyl group, and sulfo group. More specifically, methyl, ethylpropyl, isopropyl, t-butyl, 2-ethylhexyB,
[decyl, 1-ethylpentyl, tridecyl, 2methanesulfonethyl, 3-(3-pentadecylphenoxy)
Propyl, 3-(4-(2-[4(4-Hi-l-roxyphenylsulfonyl)phenoxy] dodecanamide)
phenyl)propyl, 2-ethoxytridecyl, triflumeromethyl, cyclohexyl, 3-(2,4-di-t-
Either alkyl such as amylphenoxy or 4-carboxylbutyl or χ represents a simple bond or a linking group, through which it is bonded to the vinyl group. )-Sailor rll
) R-(11-1ISO, -M゛ [wherein, R is an alkyl group, an aryl group, an aralkyl group,
It represents an alkenyl group, and the total number of carbon atoms contained in R is between 8 and 36. L represents a divalent linking group, and n is O or an integer from 1 to 10. M represents hydrogen or a cation. ] In the formula, R represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. m and m2 each represent 0 or 1. B represents 10- or -NH-. A is 1 to carbon atom
Represents an aliphatic divalent group having 50 aliphatic groups. M is a group capable of forming a salt with sulfonic acid and a substituted alkyl group, methgin, ethoxyisopropoxy, t-butoxy, 2-
Alkoxy groups such as methoxyphenoxy, 2-dodecylethoxy, 2-methanesulfonyletogyne, 2-phenoxyethquine, substituted alkoxy groups, phenoxy, 2-naphthyloxy, 2-methylphenoxy, 2
-Methoxyphenoxy, 4-methoxyphenoquino, 4-
L-butylphenoquine, 3-nitrophenoxy, 3-acetamidophenoquine, 2-benzamidophenoxy,
These include aryloxy groups such as 2-carboxyphenoxy and 4-sulfophenoxy, and substituted aryloxy groups, carboxyl groups, and sulfo groups. Among these groups, groups that can have further substituents include halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nido tetragroups, carboxyne groups, sulfo groups, amino groups, and alkoxy groups. , aryloki group, anruamino group, alkylamino group, anilino group, ureido group, sulfamoylamino 21! ,,alkylthio group, arylthio group, Al0 koxycarponylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclicoxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group , an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group, an azolyl group, and the like. R is preferably an alkyl group such as methyl, ethyl, isopromol, or t-butyl, an alkoxy group such as methoxy, ethoxy, isopropoxy, 2-methoxyethoxy, or 2-phenoxyethoxy, or phenoxy,
2-methoxyphenoxy, 4-methoxyphenoxy, 2-
It is an aryloxy group of methylphenoxy, and these may be substituted with a carboxyl group or a sulfo group. R2 represents an acyl group or a sulfonyl group; specifically, an acyl group having 8 to 40 carbon atoms, such as furcyl and aryloyl, and styloxy-5-1-octylbenzene, which is an alkylsulfonyl or arylsulfonyl group having 10 to 40 carbon atoms; Sulfonyl, 1-octyloxy-4-naphthylsulfonyl, 2-octyloxy-5-1-ofthicbenzenesulfonyl, 2-(2-hexyloxyethoxy)-5-L-octylbenzenesulfonyl, 2-(
2-ethoxyethoxy)-5-(2-octyloxy-
An arylsulfonyl group such as 5-t-octylbenzenesulfonamido)benzenesulfonyl, 2-octyloxy-5-(2-octyloxy-5-t-octylbenzenesulfonamido)benzenesulfonyl, or a part thereof. It is an arylsulfonyl group containing a carboxyl group or a sulfo group. These may further include a substituent as indicated by R1. R2 is preferably a substituted alkanoyl or substituted arylsulfonyl group represented by general formula (A). Mr. R1. Although it represents a phenylene group, specifically Rs and R- are 3 sulfonyl groups, and a portion thereof may contain a carboxyl group or a sulfo group. More specifically, straight chain or branched alkanoyl groups such as 2-ethylhexinoyl, decanoyl, tetradecanoyl, pentadecanoyl, stearoyl, isostearoyl, straight chain alkanoyl groups represented by the following general formula (A), - Ali such as stearyloxyhenzoyl, 3-(2edylhexanoylamino)benzoyl, 2,4dioctyloxybenzoyl, 4-(4-dodecyloxyhenzenesulfonamido)benzoyl, 1-octyloxy-2-naphthoyl, etc. - Alkylsulfonyl groups such as loyl group, dodecylsulfonyl, octadecylsulfonyl, 2
- hydrogen atoms, alkyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, and octyl, and aryl groups such as phenyl, tolyl, and 2-naphthyl, and R3 and R4 are not hydrogen atoms at the same time. R8 represents a phenylene group such as 1.2-phenylene, 1.3-phenylene, 1°4-phenylene, 4-methoxy-1,3-phenylene, 5-methyl-13-phenylene, etc. Preferably (L)- is an alkylene group where R2 and R4 are a hydrogen atom, methyl or phenyl group, or a phenylene group where R2 and R4 are 1,3-phenylene or 1,4-phenylene. X is an aryloxy group, an alkoxy group, a 1-azolyl group, an alkylthio group, or an arylthio group, and specifically phenoxy, 4-methylphenoxy, 4cyanophenoxy, 4-methanesulfonamidophenoxy, 4-acetamidophenoxy, 4ethoxy Carbonylphenoxy, 4-carboxy4-phenoxy, 3-carboxyphenoxy, 2-carboxyphenoxy, 4-[1,1-dimethyl1-(4-hydroxyphenyl))methyl]phenoxy, 4-(4-
Aryloxy groups such as hydroxybenzenesulfonyl) phenoxy, 4-methoxyphenoxy, 1-naphthoxy, 2-phenethyloxy, 5-phenyltetrazolyloxy, 2-hendithiazolyloxy, methoxy, ethoxy, isopropoxy, butoxy , ethoxycarbonylmethoxy, 2-ethoxycarbonylethoxy, 2-cyanoethoxy, 2-methanesulfonylethoxy, 2-benzenesulfonylethoxy, 2-phenoxyethoxy,
Alkoxy groups such as 1-pyrazolyl, 1-imidazolyl, 3,5-dimethyl-1,2,4-)lyazole-1
-yl, 5 or 6-promobenzotriazole-1-
yl, 5-methyl-1,2,3,4-tetrazole l-
yl, 1-benzimidazolyl, 4-chloro-pyrazol-1-yl, 4-nitro-pyrazol-1-yl, 4
-ethoxycarbonyl-1(lvl-1) (M-2) l-fil, 3 or 5-acetamidopyrazol-1yl,
1-Azolyl groups such as 2-acetamidoimidapril-1-yl, alkylthio groups such as dodecylthio, 1-carpoquine dodecylthio, phenylthio-2-naphthylthio, 2-butquine 5-octylphenylthio, 2
-pivaloylaminophenylthio, 4-1 decyl phenylthio, 4-octyloxyphenylthio, 2-octyloxy-5-calphokydiphenylthio, 2-(3carpoxypropyloquino)-5-1-octyl It is an arylthio group such as phenylthio. These may further have a substituent represented by R. Preferably, X is an aryloxy group, a l-azolyl group, or an arylthio group, and more preferably, may have been done. Next, specific examples of the coupler represented by the general formula (+) of the present invention will be shown, but the present invention is not limited thereto. (M-3) ゝCaLt(t) (M-4) 8 (M 5) (M 6) (M 7) 9 (M 11) (M 12) 1 (M 8) Shi! (M 9) (M 10) 0 (M 13) (M 14) 2 (M 15) (M-16> 3 (M 19) 4 (M 17) (M 18) 4 Set the reflux condenser and dropping funnel. 103g of anhydrous potassium carbonate (0°75mof
f) and 150 mf of acetonitrile were added and stirred at room temperature. Here, p-cresol 54゜0g (0,5m
of) was added, and the mixture was stirred while heating under reflux. Furthermore, 41.5 g of chloroacetonitrile (0.55 m
of) was added dropwise over about 5 minutes, being careful not to reflux too much. After the dropwise addition, the mixture was refluxed and stirred for 2 hours, and then cooled with water until the internal temperature reached about 30°C. This material was filtered with suction, and the filtrate after removing inorganic substances was mixed with 150 mf of ethyl acetate, 50 mj2 of saturated saline, and 1 ml of water.
00mj! was added to perform the extraction operation. The obtained ethyl acetate layer was mixed with 50 mj2 of saturated brine and 10 mj water.
0m, i! After washing with a mixed solution three times, it was dried with anhydrous sodium sulfate. The residue obtained by removing ethyl acetate using a rotary evaporator was distilled under reduced pressure to obtain 64.9 g (0
, 44woN). Obtained with a yield of 88%. Boiling point: 85-88°C10,2mmHg Melting point = 31-3
After the mixture was added dropwise while being careful to maintain the temperature at 3°C, the mixture was stirred under heating under reflux for 3 hours. The mixture was cooled with water until the internal temperature reached approximately 30°C, and after the desired crystals were precipitated, the mixture was stirred at room temperature for 3 hours. here water 1
After adding 00mf and stirring for 3 hours, suction filtration was carried out to obtain 33.7g (0.16mol, 33.7g from the top).
Obtained with a yield of 1%. Melting point 174.0-176.5°C 300 rne of dimethylacetamide was added to 33.7 g (0.16 mof) of grass and heated until it melted. Once melted, cool to about 35"C and add 60 g of methyl 2-methyl-3-phthalimidopropioimidate hydrochloride (0
, 21 mof) and stirred at room temperature for about 24 hours. An aqueous solution of 22 g (0.32 moj2) of hydroxyamine hydrochloride and 13 g (0.16 moj2) of sodium acetate was added to the reaction mixture and heated to 50°C. After about 1 hour, stop heating and stir for about 10 hours while gradually returning to room temperature. Pour into 1°5 ice cubes while stirring, filter out the precipitated crystals, wash thoroughly with water, and then dry. 69
g (yield 96%). 4.69g (0.15moj2) with a dimethylacetate dropping funnel, thermometer, and drying tube (CaC-poor 2) set 3
00rnI! , 1 methyl propionate in a Mitsuro flask
02g (1.0mof) was added thereto and stirred under a water bath. To this, 56.1 g of potassium L-butoxide (
0.50 moI2) was added, and while stirring was continued, 73.6 g (0.50 mof) of compound j was heated to an internal temperature of 10°C.
I dripped it, being careful not to exceed it. After the dropwise addition was completed, the internal temperature was kept between 5 and 10°C while stirring for 3 hours, and then 150 mff of water and 150 m of n-hexane were added.
j2 was added and extracted. Concentrated hydrochloric acid 42.9% was added to the resulting aqueous layer.
Neutralize by adding mf and add 200m of ethyl acetate! Extraction was performed. The obtained ethyl acetate layer was mixed with 50 mf of saturated brine and 100 mj of water! It was washed twice with a mixed solution of and dried with anhydrous sodium sulfate. Ethyl acetate was distilled off using a rotary evaporator to obtain 46.1 g of target compound 2 as a crude product. 246° 1 g of the compound and 100 ml of isopropyl alcohol were placed in a 300 mN Mitsuro flask equipped with a reflux condenser and a dropping funnel, and the mixture was stirred while heating under reflux. To this, 19.7 g of an 80% aqueous solution of hydrazine hydrate was added with 200 mol of amide to prevent the reflux from becoming too vigorous, and the mixture was stirred. Although 4 was not completely dissolved, 28.6 g of para-toluenesulfonyl chloride dissolved in 80 mL of acetonitrile was added dropwise over about 30 minutes while cooling in a water bath. After the dropwise addition, the mixture was stirred for about 1 hour, 12.1 mff1 of pyridine was added, the water bath was removed, and the mixture was further stirred for about 1 hour. Then add about 1
Pour into 5p of ice water, remove the aqueous solution by decantation, and add 1. ! M! was added, crushed and filtered to obtain the tosylate compound of 4 as a colorless powder. Immediately add methanol 1.31! 12.1rr+42 of pyridine was added thereto, and the temperature was raised to reflux. When the tosylate was melted, heating was stopped, and the mixture was stirred while gradually returning the temperature to room temperature. After stirring at room temperature for about 2 days, methanol was distilled off under reduced pressure and concentrated to about 300rr+j2, and then about 1. ! M! The reaction solution was poured into water. By filtering and drying the precipitated powder crystals, 5 was converted to 29.
8g (yield 52%) could be obtained. To 5.15 g (0,039 moff) of isopropyl afrecol, 2.5 g (0,062 moff) of 80% hydrazine Hiller was added overnight, and after heating under reflux for about 8 hours, the mixture was returned to room temperature and the chloroporm was added. and saturated saline were added, and suction filtration was carried out to remove the precipitated phthalate. The filtrate was extracted three times with chloroporum, and the combined extracts were washed with saturated saline, dried over magnesium sulfate, and then subjected to d#Iυ and evaporated F- to obtain the amine compound as crystals. . This amine compound is dimethylacetamide and acetonitrile:
1/H match? Dissolve in 100mff of medium, add 4.7mp of toluethylamine, and add 40mj of dimethylacetamide while stirring under water cooling. 10.4 g (0,039 moff) of 2-gawa-denl succinic anhydride dissolved in 2-gawa-denle was added dropwise. After Ura F, the mixture was stirred for about 3 hours, extracted, dried, and then subjected to boration.
15.5g (yield 72%)
) could be obtained as an exemplary coupler (M2S). The above-mentioned shipman [II] that can be used in the present invention will be explained in detail. Shipman ([[), when R represents an alkyl group,
Can be straight chain, cyclic, or branched, and has 8 carbon atoms
-36, more preferably 12 to 24. When 6R represents a substituted alkyl group, examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a halogen atom, an alkoxycarbonyl group, and a carbonamide group. can be mentioned. Moreover, the alkyl group here includes -0-1-8-1-CO-1-CO in the carbon chain. C0NR'--1-3O□, -8O□N R'NR'
Those having one or more CO--NR' SO2- are also included (R' represents a hydrogen atom, an alkyl W, or an aryl group). R'0COCH. Preferred examples include hydroxyl group, R'0COC1iR'
0COCH(')HR'0COCH2R' 0CO
CH-1R'0COCHOH1R'0COCH The magenta coupler represented by -M formula (1) of the present invention is added to the green-sensitive emulsion layer and/or its adjacent layer, and the total amount added is 0.01 to 1. .0 g/rri, preferably 0.05 to 0.8 g/rri, more preferably O,] to 0.5 g/rri. It includes C0NR'-. When R represents an aryl group, it preferably has a phenyl group or a naphthyl group;
When represents a substituted alkyl group, it may have any of the groups listed above as a substituent. More preferred aryl groups include an alkylphenyl group having a total number of carbon atoms of 12 to 24;
Examples include those having an alkylnaphthyl group. When R represents an alkenyl group, it may have a carbon-carbon double bond at any position, and when R represents a substituted alkyl group, it may be substituted with a group listed as a substituent. Preferably, it has 12 to 24 carbon atoms and 1 to 5 double bonds. L represents a divalent linking group, particularly preferably ○--
-NH--CON H-(OCH,CH2), (OCH□CH,3-60(
OCH□CH)-Il, (OCH7CH)-110CI
(, CH. (m is an integer of 1 to 10, particularly preferably 1 to 5). M represents a hydrogen atom or a cation, and preferable examples include H", K', Na"'lz Mg''/,C
a' Waz Ba, NHa", Ag' and N'R'(R' is an alkyl group which may be the same or different and has a total carbon number of 4 to 32, preferably 4 to 16). General Specific examples of the compound represented by formula [II] are shown below, but are not limited thereto. A-1 A-8 t CIIzCOOCHzCHCJ. Na5Oi-CHCOOC1ltCHCJqt n-CaH+z00CCL n-CaLzoocclI SO, Na C+J:++C0N -CHz-CHzSOsNaA C11i(CIlz) acH=cl'1cllzsOJa A AA A n-C+zllzs-0-5OJa The above-mentioned -Sailor (III) that can be used in the present invention will be explained in more detail.The above-mentioned -Sailor [■] R is an aliphatic hydrocarbon group having 4 to 22 carbon atoms, and may be linear or branched (
, and may have an unsaturated bond. The number of carbon atoms in R is preferably about 6 to 18. Examples of R include butyl, octyl, nonyl, dodecyl,
Examples include alkyl groups such as octadecyl, and alkenyl groups such as cis-9-octadecyl. Further, A represents an aliphatic divalent group having 1 to 50 carbon atoms, and preferably includes divalent groups such as an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or an alkyleneoxy-alkylene group. . For example, ethylene, trimethylene, octamethylene, ethyleneoxy,
Examples include polyethyleneoxy, polypropyleneoxy, ethyleneoxytrimethylene groups, and the like. Examples of the cation or cationic root represented by M include hydrogen, sodium J1, potassium, Ildium, calcium, barium, ammonium, and alkyl ammonium having 1 to 4 carbon atoms. The surface-active polymer used in the present invention contains at least 5 mol %, preferably at least 10 mol %, of units represented by Ill. The above surface-active polymer may be a copolymer or a homopolymer; if it is a copolymer,
It is particularly preferable that it contains about 5 to 95 mol % of the trophic units shown in [II], and about 10 to 95 mol % of the above-mentioned units. - The unit copolymerized with the unit represented by the binding margin (Ill) may be one type or two or more types may be used. The unit to be copolymerized is a divalent unit consisting of a benzene ring having a methylene group or a naphthalene ring having a methylene group, and the benzene ring or naphthalene ring has a substituent such as an alkyl group (the alkyl group has 4 to 22 carbon atoms). Preferred examples include butyl group, octyl group, nonyl group, dodecyl group, octadecyl group, halo 11, and the like. However, Ro represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. The molecular weight of the surface-active polymer used in the present invention is not particularly limited, but is preferably about 600 to about 10,000, particularly preferably 900 to 5,000. Next, specific examples of typical surface active polymers used in the present invention will be shown. (Each of the exemplified compounds is a surface active polymer containing the following structural units in the following proportions.) B-1 01 (0(Cllz) tsOJax; y=50:50 bromine atom, iodine atom, etc.), hydroxyl group, alkokene group (the alkyl moiety preferably has 4 to 22 carbon atoms, for example, ofthyloquine group,
-. can be replaced. Preferably, at least one substituent is substituted. Examples of copolymerized units include: I 11 OCIl, C, HzOI+ 0 B 11 0(CIlz)4sOJa x:y=55:45 X(-3'+7B H0(CH2) zsO3Na x:y=20: 80 x+y:6 B 11 0 (CI+2) +5OJ x:y=75:25 x+y16 B 5 H OCIIzCHzO(CIlz):+SO3Naχ:
y=5 : 5 χ+)+4-6 B 11 OCHzCLOCJCLSOJa x : y 228 10 in x+y B H OCHzCHzOCIIzCHzSO,NaX : y 2:8 xfy 125 4 ゛\Kino B 11 0 (CH2)3SO,Na χ: y I: 9 x + y : 10 B H 0 (CHz) 3sO3Na x : y=4-: 6 χ+y+8 B 2 11 0 (CI+2) asOJa 0■ 5OaNa x : y=6 : 4 X 10 y+6 5 B 14 11 B5SO,Na0(Ctlz)3sOJax:y:z=4:3:3x+y+z+69H190(CH2)3SO3KX÷6 These compounds used in the present invention can be synthesized by conventional methods. For example, the synthesis of formalin polycondensates of alkylphenols is described in Industrial Chemistry Journal, Vol. 66, p. 391 (19
It can be easily synthesized according to the method described in 1963), Yukagaku Vol. 12, p. 625 (1963). In addition, the introduction of sulfonic acid is described in, for example, Industrial Chemistry Miscellaneous Chapter 73.
Volume 563 (1970), Volume 59, page 221 (1970)
56) and J, Hem, Chem, Soc, No. 77@,
It can be synthesized according to the method described on page 2496 (1955). The surfactant represented by the general formula [■] or (I [I) of the present invention can also be used when dispersing other organic photographically useful reagents used in the light-sensitive material of the present invention in water or in a hydrophilic colloid composition. Can be used. The surfactants represented by the general formulas [11) and (Ill) of the present invention can also be used when dispersing other organic photographically useful reagents used in the light-sensitive material of the present invention in water or in a hydrophilic colloid composition. . Photographic preservation reagents that can be used in the present invention include dye image-forming couplers, ultraviolet absorbers, electron donors used for the purpose of preventing color mixture, oxidation, and fading, antifoggants, development inhibitors, and developing agents. , fogging agents, silver halide solvents, bleaching accelerators, filter dyes, etc. On the other hand, these surfactants have high water solubility and flow out to a certain extent into the processing solution during the processing of the photosensitive material. When these anionic compounds leak out, they form poorly soluble ionic complexes with cationic compounds in the processing solution (such as antistatic agents eluted from the sensitive material), causing problems in the processing process. Therefore, the general formula [■] or (I
The content of the surfactant represented by II) is 0.6 g.
/rd or less is preferable. Furthermore, it has been reported in Japanese Patent Application Laid-Open No. 6016814 that the compound represented by general II (III) has a large effect on emulsion stability.
1. However, in the case of the magenta coupler of the present invention, it is highly effective when used in combination with a compound represented by Hitsunenin CI+). Also, general 2 (Ill)
The compound represented by is a polymer, and the amount that flows out into the processing solution during development processing is quite small. Therefore, when the magenta coupler of the present invention is dispersed in water or in a hydrophilic colloid composition, it is preferable to contain at least one compound represented by the general formula (Ill), and - More preferably, the amount of the compound is 20% or more of the total amount of surfactant used when dispersing the magenta coupler of the present invention. In addition, the amount of surfactant expressed in general 2 (lit) is:
The amount of -F is preferably 1% or more of the total amount of surfactants in the photosensitive material of the present invention, and more preferably 10% or more. The surfactant used in the present invention can be used in combination with a nonionic surfactant. As the above-mentioned nonionic surfactant, JP-A No. 48-3
It is preferable to use the nonionic surfactant described in No. 0933 and the fatty acid ester surfactant of polyhydric alcohol. The polyhydric alcohol fatty acid ester surfactant preferably has at least two, preferably at least three, hydroxyl groups, and preferably has 6 to 25 fatty acid carbon atoms. In terms of length, sorbitan fatty acid ester nonionic surfactants described in US Pat. No. 3,676,141 are advantageously used in the present invention. In the present invention, it is preferable that the compound of -Funenin [I] is prepared as a dispersion through alkaline conditions with a pH of 10 or higher, and then the photographic light-sensitive material is produced by coating with this dispersion. . For example, after dissolving the coupler of Shipman [I] in an alkaline aqueous solution with a pH of 10 or more or an alkaline mixed solvent of an organic solvent and alkaline water, if necessary, a binder or surfactant such as gelatin, a fading prevention side, There is a method of preparing a dispersion by mixing with other additives and gradually adding an acid component (for example, hydrochloric acid, acetic acid, citric acid, etc.) to lower the pH. In the present invention, it is sufficient that there is a step in which the compound of general formula CI) is subjected to alkaline conditions with a pH of 10 or more to prepare a so-called dispersion or solution. In the present invention, the dispersion broadly includes not only so-called emulsions, but also those dispersed or solubilized in the form of micelles, and homogeneous solutions. - It is necessary that the compounds of Shipman [II] and [I] be contained in the same layer as the layer containing the compound of the general formula [I], but preferably the photosensitive material of the present invention of the general formula is included in the dispersion. teeth,
It is sufficient that at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is provided on the support; There are no particular restrictions on the number of layers or the order of the layers. As a typical example, at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity is provided on the support.
The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and the multilayer silver halide color photographic material has In general, the unit photosensitive layers are arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer. Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
1343([), CI+), and (III) are preferably included. Particularly preferably, the compounds of general formulas (1), [II], and (III) coexist in an alkaline aqueous solution having a pH of 10 or higher. In the present invention, when the compound of -Funenin [I] is dispersed under alkaline conditions with a pH of 10 or higher, and the compounds of -Funenin (I[) and (I[[)] are included, color reproducibility is good, I was surprised to find out that it has excellent performance, with extremely high color development, strong enough film quality even when the gelatin content is reduced to a large extent, making it possible to achieve a large thin layer, and the stability of the dispersion being good. Should have. In the prior art, there was no method that satisfied all of these requirements. 8, No. 59-113440, No. 61-20037, and No. 61-20038, such as couplers, DIR compounds, etc., may be included, and a color mixing inhibitor as commonly used may be included. May contain. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support. As a specific example, from the side farthest from the support, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitivity Ji (Bll) /
High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (Gshi) / High sensitivity red photosensitive layer (R1+) / Low sensitivity red sensitive layer (
RL) or BH/BL/GL/GH/R11/
RL order or Bll/IIL/GH/GL/RL/
They can be installed in the order of RH, etc. Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of RH/GL/R1. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive Jig/GL/RL/GH/RH may be arranged in the order from the farthest side from the support. . In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a silver halide emulsion layer with a lower sensitivity than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with low photosensitivity is arranged, and the photosensitivity decreases sequentially toward the support. Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. The grain size of the layered silver halide may be either fine grains of about 0.2 microns or less or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N. 17643 (December 1978), pp. 22-23, °
“■, Emulsion preparation
ion and types)”, and the same No.
18716 (November 1979), p. 648, same No. 307105 (November 1989), 863
~865 pages, and “Physics and Chemistry of Photography” by Grafkide
, published by Paul Montell (P, GIafkides, C
hemie et Ph1sique Photogr
aphique, Paul Montei, 196
7), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, I) uffinPhotograph
ic HIIulsion Chemistry (F
ocal Press 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (v
, L., Zelikmanetal, , Makin
g and coating photography
c HIIulsion, Focal Press+
(1964) and others. /high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order. In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc. Furthermore, even in the case of four or more layers, the arrangement may be changed as described above. As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 mole percent silver iodide. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof. U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred. Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434.226, 4,414.310, 4,
433.0.18, No. 4,439,520, and British Patent No. 2.112.157. The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used. The above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this core/shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm. The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure + -No.
, 17643, N. 307105 (L 18716 and N. 307105), and the relevant parts are summarized in the table below. Size distribution, halogen composition, particle shape,
Silver bromide, silver iodobromide, which differ in at least one property of sensitivity,
Any of silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.
75 μm, particularly 0°05 to 0.6 uTa is preferred. There are no particular limitations on the particle shape; regular particles may be used, or polydisperse emulsions may be used, but monodisperse (
At least 95 in weight or number of silver halide grains
% has a particle diameter within ±40% of the average particle diameter)
It is preferable that In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. Two or more types of emulsions can be mixed and used in the same layer. The photosensitive material of the present invention includes U.S. Patent No. 4,082,553.
Silver halide grains covered with grain surfaces described in US Pat. No. 4,626,498, JP-A-59-2148
The silver halide grains and colloidal silver in which the inside of the grain is covered, as described in No. 52, can be preferably used in the photosensitive silver halide emulsion layer and/or the substantially non-photosensitive hydrophilic colloid layer. Silver halide grains with their interiors or surfaces covered include both unexposed and exposed areas of a photosensitive material.
- Refers to silver halide grains that can be developed in a non-imagewise manner. A method for preparing silver halide grains in which the inside or surface of the grain is covered is described in U.S. Pat. No. 4,626,498 and JP-A-59
-214852. The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. As silver halide coated inside or on the surface of grains, silver chloride and fine salt grain silver halide have an average grain size (
Average value of circle equivalent diameter of projected area) is 0.01 to 0.5μ
m is preferable, and 0.02 to 0.2 μm is more preferable. Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound. This layer containing fine silver halide grains can preferably contain colloidal silver. The coating silver amount of the photosensitive material of the present invention is 6.0 g/rr? The following is preferable, and 4.5 g/nf or less is most preferable. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. Specific examples are the above-mentioned Nori Search Disclosure No. 17643, ■-C-C, and same-face 3.
No. 07105, ■-C-G. As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4,022,620, 4.3
No. 26.024, No. 4.401,752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476,760, U.S. Patent No. 3,973,968, British Patent No. 4,314.
No. 023, No. 4,511.649, European Patent No. 24
9.4738, etc. are preferred. As magenta couplers, those of the present invention include:
U.S. Patent No. 4.310.619, U.S. Patent No. 4.35L89
No. 7, European Patent No. 73,636, U.S. Patent No. 3.06
L432, No. 3.725,067, Research Disclosure No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-6
No. 0-43659, No. 61-72238, No. 60-3
No. 5730, No. 55-118034, No. 60-185
95], U.S. Pat. No. 4,500,630, U.S. Pat.
+540.654, and in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 411.987 and No. 4.435.503. The photosensitive material of the present invention includes U.S. Pat. No. 4,740.454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551. To the photosensitive material of the present invention, JP-A-H! , No. 106052, which releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof, regardless of the amount of developed silver produced by the development process. Dyeing agent 4 or EP 3 dispersed in the photosensitive material of the present invention by the method described in International Publication No. WO 38104794 and Japanese Patent Publication No. 11-502912] 7,308 A., U.S. Patent No. 1.420.555; The dye described in JP-A-1-259358 can preferably be included. The present invention uses various color couplers.
Particularly preferred are those described in No. 56.630, International Publication No. 088104795, and the like. Examples of cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052.212.
No. 4,146.396, No. 4.228.23
No. 3, No. 4.296.200, No. 2.369.9
No. 29, No. 2,801, No. 171, No. 2,772.
No. 162, No. 2.895,826, No. 3.772
, No. 002, No. 3.758, 308, No. 4,33
4.0], No. 1, No. 4.321.113, West German Patent Publication No. 3329,729, European Patent No. 121,365
No. A, No. 249453A, U.S. Patent No. 3,446,
No. 622, No. 4,333.999, No. 4,775
．． No. 616, same number! , No. 451.559, No. 4.4
No. 27.767, No. 4.690.889, No. 4.
No. 254212, No. 4,296.199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.367.282, No. 4.409,32
No. 0, No. 4.576910, British Patent No. 2.102.
1.37, European Patent No. 341188A, etc. Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred. Research Disclosure N is a colored coupler for correcting unnecessary absorption of coloring dyes. ■-G term of 17643, ■-G term of Doyo 307105,
U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-394
No. 13, U.S. Patent No. 4,004,929, U.S. Patent No. 4,1
No. 38,258 and British Patent No. 1,146,368 are preferred. Also, U.S. Patent No. 4,774,1
Couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in US Pat. No. 81, and dye precursors that can react with developing agents to form dyes as described in US Pat. It is also preferred to use couplers having groups as leaving groups. Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F term and interval, 307105, ■
-Patents described in Section F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248,
Preferably, those described in US Pat. No. 63-37346, US Pat. No. 6,337,350, and US Pat. Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred. Also, JP-A-60-107029, JP-A No. 60-2523
No. 40, JP-A-144940, and JP-A-1-45687, the oxidation-reduction reaction with the oxidized form of the developing agent produces a fogging agent, a development accelerator, and halogenation! [Compounds that release 8 agents and the like are also preferred. Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173°302
No. A, a coupler that releases a dye that recovers its color after separation as described in No. 313,308A, R, D, No. 11449, No. 2
4241, a bleaching accelerator-releasing coupler described in JP-A No. 61-201247, etc. Gantt-releasing coupler described in U.S. Pat. No. 4,555,477, etc., JP-A-63-757
Couplers that emit leuco dyes as described in US Pat. No. 4,774,181 and couplers that emit fluorescent dyes as described in U.S. Pat. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl Phthalate, bis(2,4-G)

[-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(l,1-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids Zyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexynol phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (to 2-ethyl Xylhenshade,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides 19 (N,N-diethyldodecanamide, N,N diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4
-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctylsidetrade, etc.), aniline derivatives (N, N -Nbuchi 712
-butoxy-5-tert-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodenlebenzene, isopropylnaphthalene, etc.). Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or more, preferably 50°C or more and about 160'C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and chlorohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like. The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Patent No. 4. +99.363, West German Patent Application (OLS) No. 2,541,274 and OLS No. 254], OLS No. 230, etc. The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-2722.1
No. 8, and 1,2- described in JP-A No. 1-80941.
Pen switch azolin-3-one, n-butyl p-hydroquineshade, phenol, 4-chloro-3,
5 dimethylphenol, 2-phenoxyethanol, 2
~(4) Can be measured according to known methods. For example, Green et al., Photogr, Sci, Eng, Vol. 19, 2.
No. 1, pp. 124-129.
T1/2 can be measured by using a swollen film), and T1/2 is the saturated film thickness, which is 90% of the maximum swelling film thickness that reaches ze1 when treated with a color developer at 30°C for 3 minutes and 15 seconds. 1
It is defined as the time until reaching 72. The membrane swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness. The photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry thickness of 2 μm to 20 μm) on the opposite side to the side where the emulsion layer is present.
It is preferable to provide a back layer (referred to as a back layer). It is preferable to add various preservatives or antifungal agents such as the above-mentioned light absorbing agent and benzimidazole to the back layer. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, same No. 187
16, page 647 right column to page 648 left column, and the same No.
307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
The film swelling rate 'rl/2 means the film thickness measured in
It is preferable to include an anti-static agent, a hardening agent, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent, and the like. The swelling ratio of this back layer is preferably 150 to 500%. The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, same No. 187
16, 651, left column to right column, and Nα307105, pages 880 to 881 of the same. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, l-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-ethyl-β-methoxyethylaniline and their sulfates and hydrochlorides Alternatively, examples include p-toluenesulfonate. Among these, 3-methyl-4-amino-N-ethyl-
1β-hydroxyethylaniline sulfate is preferred. These compounds may be used in combination of two or more depending on the purpose. Color developers include PL+buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, hendithiazoles or mercapto compounds. It typically contains an inhibitor or antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, and dye-forming turnips. The pH of the color developer and the black and white developer is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but -m + 3 per square meter of light-sensitive material! It can also be reduced to 500 d or less by reducing the bromide ion concentration in the replenisher. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, the aperture ratio of L is preferably 0.1 or less, more preferably 0.001 to 005. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, there are also methods for reducing the aperture ratio.
A method using a movable lid described in No. ', JP-A-632
Srinorer, competition coupler described in No. 16050,
Auxiliary developing agents such as 1-phenyl-3-pyrazolyne, viscosity imparting agents, various calcinates such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids; For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-Ll-
Typical examples include diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine di(0-hydroxyphenylacetic acid) and salts thereof. I can do it. Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-virapritone, or amine phenols such as N-methylyl-aminophenol, alone or in combination. It can be used as The following development processing methods can be mentioned. It is preferable to reduce the aperture ratio not only in both color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color development process is usually set between 2 and 5 minutes, but the process time can be further shortened by using a high temperature and high ρ and a high concentration of the color developing agent. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, 21-chloride compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (I[l), such as ethylenediaminetetraacetic acid, dielenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methylimidazole, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Aminopolycarboxylic acids such as , or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (In) complex salts, including ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropane tetraacetic acid iron (III) complex salt, are preferable from the viewpoint of rapid processing and environmental pollution prevention. . In addition, iron aminopolycarboxylate (I
II) Complex salts are particularly useful both in bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I
II) The pil of a bleach or bleach-fix solution using a complex salt is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the process. A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary. A compound having a group is preferable from the viewpoint of a large promoting effect,
In particular, U.S. Patent No. 3,893.858, West German Patent Box 1.
Compounds described in No. 290,812 and JP-A No. 53-95,630 are preferred. Additionally, U.S. Patent No. 4.552,8
Compounds described in No. 34 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography. In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred. Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of a thiosulfate and a thiocyanate, a thioether compound, a thiourea, etc. is also preferred. Specific examples of useful bleaching accelerators are described in U.S. Pat. No. 3,893,858 in the following specification. , West German Patent Box No. 1.290,812, West German Patent Box No. 2.059.988,
JP 53-32736, JP 53-57831, JP 53-374+8, JP 53-72623, JP 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
23, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc. Compounds having a mercapto group or disulfyl I"group; Thiazolidine derivatives described in JP-A-50-140129: Special Publication No. 45-8506, Japanese Patent Publication No. 52-20
No. 832, No. 53-32735, U.S. Patent No. 3,70
Thiourea derivatives described in No. 6,561; West German Patent No. L
No. 127.715, iodide salts described in JP-A-58-16,235;
Polyoxyethylene compounds described in No. 48.430;
Polyamine compounds described in Japanese Patent Publication No. 45-8836; other Japanese Patent Publications Nos. 49-40,943 and 49-59.644
Compounds described in No. 53-94,927, No. 54-35.727, No. 55-26.506, No. 58-163, and No. 940; bromide ions, etc. can be used. Among these, a mercapto group or a disulfide group is preferred. As preservatives for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfites ((J additive or European Patent No. 29476
The sulfinic acid compounds described in No. 98 are preferred. Furthermore,
It is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixer or bleach-fixer contains p)t
Compounds with pKa of 6.0 to 9.0, preferably imidazole, ■-methylimidazole, 1
0.1 to 10 mol/! of imidazoles such as ethylimidazole and 2-methylimidazole! It is preferable to add. The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50'C1 is preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is increased and the occurrence of staining after processing is effectively prevented. During the desilvering process, it is preferable that the stirring be as strong as possible.Specific methods for strengthening the stirring include:
A method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material described in JP-A-62-183460, and JP-A-62-18
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there is a method to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface, and a method to increase the circulation flow rate of the entire processing liquid. can be mentioned. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator. The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
The use of the photosensitive material conveying means described in Japanese Patent No. 191259 causes problems such as generated floating substances adhering to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems were solved by the method disclosed in Japanese Patent Application Laid-Open No. 62-288, 83.
The method for reducing calcium ions and magnesium ions described in No. 8 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8,542, and other benzotriazoles, as well as other antibacterial and fungicides by Hiroshi Horiguchi, Chemistry J (1986
Sankyo Publishing, Hygiene Technology Kintin [Microbial sterilization, sterilization, anti-mildew technology, (1982) Society of Industrial Technology, Japan Society of Antibacterial and Antifungal Research, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) Fungicides can also be used. The pl+ of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a temperature range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. is preferred. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment. The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Te1evis
ion Engineers Volume 64, P, 248~
253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but the increased residence time of water in the tank causes bacteria to multiply, and in such stabilization treatment, No. 57-8543, No. 58-148
All known methods described in No. 34 and No. 60-220345 can be used. Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glucuraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process. When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compound described in No. 7, No. 3.342,
No. 599, Research Disclosure + -Nα14,
850 and N115.159, aldol compounds described in U.S. Patent No. 13.924, metal salt complexes described in U.S. Pat. Compounds can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438. The various treatment liquids in the present invention are used at 10'C to 50C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, and conversely, lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. (Sample 101) First layer (Hazisin prevention layer) Black colloidal silver gelatin Second layer (intermediate layer) 25-G L Hydroquinone X-1 X-3 X-12 1-1 -2 -3 B5-1 B5-2 Gelatin third layer (first red emulsion layer) Emulsion A Emulsion B Sensitizing dye I Pentadecyl silver 0.18 1.40 0.18 0.07 0.02 0.002 0.06 0.08 0. 10 0.10 0.02 1.04 0.25 0.25 6.9X10-' The silver halide photosensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like. (Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below. (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrt units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer. Sensitizing dye ■ Sensitizing dye ■ X-2 X-10 -1 -2 -3 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ -2 X-3 X-10 J-1 -2 -3 1,8X10-S 3, I .0 5, l X 10-' 1.4 X 10-5 2.3 ) Emulsion sensitizing dye ■ Sensitizing dye ■ Enhanced dye ■ X-3 X-4 X-2 B5-1 B5-2 Gelatin 6th layer (intermediate layer) X-5 B5-1 Gelatin 1st NC 1st green sense Emulsion layer) Emulsion A Emulsion B Sensitizing dye V 1.30 Silver 1.60 5.4X10-' 1.4X10-5 2.4X10-' 0.010 0.080 0.097 0.22 0.10 1. 63 0.040 0.020 0.80 0.15 0.15 3.0X10-5 No. 971 (Third green emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ X-13 X- 11 X-1 B5-1 B5-2 Gelatin 1st ON (yellow filter layer) Yellow colloidal silver .5X10-'8.0X10-'3.0X10-' 0.015 0.100 0.025 0.25 0.10 1.54 Silver 0.05 0.08 0.03 0.95 Silver 0.08 0 .07 0.07 Enhancing dye■ Sensitizing dye■ X-6 X-1 x-7 X-8 B5-1 B5-3 Gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitization Dye■ Sensitizing dye■ X-6 X-8 0.63 8! 0.45 2, lX10-' 7, OX 10-5 2.6X10-' 0.094 0.018 0.026 0.160 0.00B 0.50 Aggravating pigment■ X-9 X-8 B5-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Enhanced dye ■ Eχ-9 X-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Enhanced dye ■ X-9 B5-1 Gelatin No. 14 layers (first protective layer) Emulsion ■ 3.5X10-' 0.721 0.042 0.28 1.10 Silver 0.45 2, lX10-' 0.154 0.007 0.05 0.78 Silver 0 .77 2.2
Layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 um) 0.5
4S -10,20 Geladin 1.20 In addition to the ingredients listed in ``-'', each layer contains gelatin hardening agent H-1, gelatin preservative/mold preservative 1.2-benzisothiazolin-3one, 2-phenoxyethanol, phenethyl alcohol. and surfactants were added. X I X X 01+ Cb) Ir+(n) X 7 I Dylphosphate di-n-butyl phthalate 01 Sensitizing dye I Sensitizing dye■ Sensitizing dye■ 02 Sensitizing dye■ CHz℃C1l Sow C1h C0NII CI+
2CHz=CHSOz CHt-CON+l CNz
04 Sensitizing Dye V Sensitizing Dye ■ Sensitizing Dye ■ 03 Processing was carried out at 38°C in the following steps. Color development 3 minutes 15 seconds bleaching 1 minute bleach fixing 3 minutes 15 seconds washing 40 seconds washing ■ 1 minute stabilization 40 seconds drying (50'C) 1 minute 15 seconds In the above processing steps, washing ■ and ■ are A countercurrent water washing method was used from to ■. Next, the composition of each treatment liquid will be described. The amount of replenishment of each processing solution was 1200 m for color development per color photosensitive material, and 800 m for all others including water washing. Also, the amount of pre-bath carried into the washing process was per color photosensitive material. (Color developer) Mother solution Replenisher diethylenetriaminepentaacetic acid 1.0g 1.1g1-
Hydroxyethylidene ~1. ] - Shibo 05 Sulfonate Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-Ethyl-N-β-bitroxyethylamino)-2 Add methylaniline sulfate water and make 2.0g 4. 0g 30.0g 1.4g 1.3■ 2.4g 4.5g 1.0! pH 10.0 (Bleach solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium chloroammonium bromide 06 2.2g 4.4g 32.0g 0.7g 2.6g 5.0g 1.02 10.05 (Unit: g) 120゜10゜100゜ Water was passed through a column filled with ion exchange resin and OH type strong basic anion exchange resin, and calcium ions were collected at 1.2 ■/l.
, magnesium ion 0. In water treated to 4■/l,
1 sodium isocyanurate dichloride! It was used by adding 20 μg/kg. (Stabilizing solution) Common to mother liquor and replenisher Formalin (37% w/v) 2.0 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Ethylenediaminetetraacetic acid di-sodium salt 0.05 g Water Add 1. ! pH 5.8 (Drying) Drying temperature was 50'C. Samples 102 to 10 were prepared in the same manner except that the type of material and the coating amount were changed for layers 7 to 9 of sample 101 as shown in Table 1.
9 was produced. In Table 1, power 08- Ammonium nitrate 10.0 Bleach accelerator 0.005 mol Aqueous ammonia (
27%) Add 15.0d water
1. ONp+ (6,3 (Bleach-fix solution) Common to mother liquor and replenisher (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5,0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0sj! Add ammonia water pH 7.3 Add water 11 (washing water) Calcium ion 32■/It, Magnesium ion 7
．． H-type strongly acidic tap water containing 3 μ/l was used.The change in puller was made the same on a molar basis. After these samples were exposed to white light through a continuous wedge and then subjected to the above-described processing, the green density was measured and the gradation was determined as a gradient in the density range of 1.0 to 2.5. If the color development is low, the tone will be soft. These samples were exposed through a pattern for MTF measurement,
After passing through the treatment described below, the concentration was measured using a microdensitometer to determine the MTF value at a frequency of 25 cycles/degree. Further, the untreated sample was scratched vertically and horizontally with a canter knife in a lattice pattern at 5-square intervals, and cellophane tape was applied and peeled off. At this time, the peeled area in the photosensitive material layer was determined and recorded in Table 2. Of course, the smaller the number, the better. On the other hand, in order to examine the stability of the dispersion, a dispersion was prepared using the following method, and after storing it in the refrigerator for 7 days, it was stored at 40°C for 24 hours.
After dissolving for a period of time, a filtration test was performed to examine the filtration performance using filtration pressure. Those that passed through the test without any problems were marked as ○, and those that caused a large pressure increase were marked as ×. × is a level that cannot be manufactured. 09 Emulsification formulation (for sample 101) After dissolving each method (1) and (2), the mixture was mixed and emulsified for 15000 rpmIO minutes using a homogenizer (Nippon Seiki). For samples Nos. 102 to 105, emulsions were prepared in the same manner except that the emulsion formulation was changed according to the changes made to layer 7 in Table 1. On the other hand, dispersions for samples 106 to 109 were prepared as follows. 10 was found to be necessary, and what was used in the coating and sample preparation in the Examples was a dispersion using IN NaOH. 12 isA-60.5g 5B-20.5g ■[14% Gelatin 20gllIr
Add citric acid (10zp) until it reaches 17.0 ■ [Water
After dissolving 1 liquid in the final amount of 100 g, add liquid ①, and while stirring strongly with a stirrer, adjust the pH
While measuring the pH, slowly drip the ■ solution until the pH is 7. ( ), and added water so that the total weight of 31 was 88 g with liquid (■). Samples 106, 108, and 109 include coupler and dispersant SA,
It was prepared in the same manner as [07] except that SB was changed. In addition, in the dispersion formulation for 107 mentioned above, IN NaOH
pH 8.5, pH 9.5, pH 11, p I instead of
(When using 12 alkaline buffer solutions, pH 8,
5 and pH 9.5, coupler M-1 did not dissolve and a dispersion could not be prepared, whereas in the buffer solution at pH] I and 12, a uniform dispersion was formed. From this, it is essential to practice the present invention that it is insoluble in alkaline water with a pH of at least 10 or more. Relationship with cases involving persons who commit crimes

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, comprising a compound represented by the following general formula [I] and a compound represented by the general formula [II]. and a compound of the general formula [III], wherein at least the compound of the general formula [I] is dispersed and introduced into the photosensitive material through alkaline conditions of pH 10 or more. material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, at least one of R_1, or represents an aryloxy group, and R_2 represents an acyl group or a sulfonyl group. ■L■ represents an alkylene group or a phenylene group, which has mathematical formulas, chemical formulas, tables, etc. In the case of an alkylene group, the carbon atoms substituted by R_3 and R_4 are connected to the coupler mother nucleus, and R_3 and R_4 is a hydrogen atom, an alkyl group or an aryl group. However, R_3 and R_4 are never hydrogen atoms at the same time. X is an aryloxy group, an alkoxy group, a 1-azolyl group, an alkylthio group, or an arylthio group. R_1, R_2 or Represents a bond or linking group through which it is bonded to the vinyl group. ) General formula [II] R■L■_nSO_3^-M^+ [In the formula, R is an alkyl group, an aryl group, an aralkyl group,
It represents an alkenyl group, and the total number of carbon atoms contained in R is between 8 and 36. L represents a divalent linking group, and n is 0 or an integer from 1 to 10. M represents hydrogen or a cation. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R represents an aliphatic hydrocarbon group having 4 to 22 carbon atoms. m_1 and m_2 each represent 0 or 1. B represents -o- or -NH-. A represents an aliphatic divalent group having 1 to 50 carbon atoms. M represents a cation or a cationic radical capable of forming a salt with a sulfonic acid. n represents 3 or more.