Silver halide light sensitive color photographic material

Abstract: A silver halide color photographic light-sensitive material containing a polyvalent alcohol is disclosed. The polyvalent alcohol has two or more hydroxy group and is water immissible. The polyvalent alcohol is used in combination with a dye forming coupler.

Description: Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color photographic light-sensitive material excellent in light-fastness for color images thereon and further excellent in coloring property. Background of the Invention In the field of a silver halide color photographic light-sensitive material, it is requested that dye images obtained from a coupler are stable against color changing and color fading even when they are exposed to light for a long time or stored under high temperature and high humidity conditions. However, it is known that the above-mentioned dye images do not have sufficient stability mainly against UV rays or visible rays so that they are subject to color change and color fading when they are exposed to the above-mentioned actinic rays. In order to solve the above-mentioned problems, there have been proposed methods including one choosing various couplers with a property of less color fading one using a UV absorber for protecting dye images from UV rays or one introducing to a coupler a group providing light flatness. However, in order to provide satisfactory light fastness to dye images by the use of a UV absorber, it is necessary to use UV absorbers in a relatively large amount. In such occasions, dye images were sometimes noticeably contaminated due to coloring of the UV absorber itself. In addition, a UV absorber does not work to prevent color fading of dye images caused by visible rays. In other words, there is a limitation in improving light fastness by a UV absorber. In addition, methods using a phenol hydroxyl group or an agent for preventing dye image fading having a group which generates, through hydrolysis, a phenol hydroxyl group are known. For example, Japanese Patent Publication Nos. 31256/1973, 31625/1973 and 30462/1976 and Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 134326/1974 and 134327/1974 propose methods using phenols and bisphenols. U.S.P. No. 3,069,262 proposes a method using pyrogallol and garlic acid and its esters, U.S.P. Nos. 2,360,290 and 4,015,990 propose methods using a-tocopherols and their acyl derivatives. Japanese Patent Publication No. 27534/1977, Japanese Patent O.P.I. Publication No. 14751/1977, and U.S.P. No. 2,735,765 propose methods using hydroquinone derivatives, U.S.P. Nos. 3,432,300 and 3,574,627 propose methods using 6-hydroxychromans. U.S.P. No. 3,573,050 proposes a method using 5-hydroxychroman derivatives and Japanese Patent Publication No. 20977/1974 proposes a method using 6,6'-dihydroxy-2,2'-spirobichromans. However, the above-mentioned compounds do not show sufficient effects for preventing color fading or color changing of dyes, though they show the effects to some extent. British Patent No. 1,451,000 discloses a method of improving stability of dye images against light by the use of azomethine extinction compounds whose absorption peak is more bathochromic compared with the peak of dye images. However, their influence on the hue of dye images is so noticeable and disadvantageous, because the azomethine extinction compounds themselves are colored. Methods of stabilizing dyes against light by the use of metal complexes are disclosed in Japanese Patent O.P.I. Publication No. 87649/1975 and Research Disclosure No. 15162 (1976). However, an amount capable of providing enough effects for preventing color fading cannot be added since these complexes have neither sufficient effects for preventing color fading nor high solubility in organic solvents. In addition, these complexes themselves are noticeably colored, so that they adversely affect the hue and purity of the dye images formed through color development processing, when a large amount of them are added. Summary of the invention The first object of the present invention is to provide a silver halide color photographic light-sensitive material wherein the spectral absorption characteristics of dye images formed therein is excellent and light fastness of the dye images has noticeably been improved. The second object of the present invention is to provide a silver halide color photographic light -sensitive material excellent in coloring property. The silver halide color photographic light-sensitive material of the invention comprises a polyvalent alcohol chosen from the following Formulae II to Formula VII: wherein R 21 , R 22 and R 23 each independently represent a hydrogen atom, or an acyl group and m is from 1 to 20. When m is two or more, two or more of R 23 may be the same or different. Preferably m is 2. When m is 1, two of R 21 , R 22 and R 23 are hydrogen atoms. When m is two or more, at least two of R 21 R 22 and R 23 are hydrogen atoms but all of R 21 R 22 and R 23 are not hydrogen atoms simultaneously. Preferably two or more of R 21 , R 22 and R 23 are hydrogen atoms and the other is an acyl group. wherein R 31 , R 32 , R 33 and R 34 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group and n is from 1 to 20. When n is two or more, two or more of R 33 or R 34 may be the same or different. When n is 1, at least two of R 31 , R 32 , R 33 and R 34 are hydrogen atoms. When n is two or more, at least two of R 31 , R 32 , R 33 and R 34 are hydrogen atoms but all of R 31 , R 32 , R 33 and R 34 are not hydrogen atoms simultaneously. wherein R 41 to R 46 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group, and at least two of R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are hydrogen atoms but all of R 41 to R 46 are not hydrogen atoms simultaneously. wherein R 51 is a substituted alkyl or substituted alkenyl group each of which has two or more hydroxy groups, R 52 is an alkyl, alkenyl, cycloalkyl or cycloalkenyl group, and R 51 and R 52 may form a lactone ring by condensation each other. In the silver halide color photographic light-sensitive material of the invention, the poly valent alcohol is preferably contained in a lipophilic fine grain comprising a dye forming coupler in a ratio by weight of not less than 50 % to the dye-forming coupler. Another embodiment of the silver halide color photographic light-sensitive material of the invention comprises a poly valent alcohol represented by the above-mentioned Formula VI or VII in the formulae, R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, acyl, sulfonly, phosphonyl, carbamoyl or sulfamoyl group, and at least two of R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 are hydrogen atoms but all of R 61 to R 64 and R 71 to R 74 are not hydrogen atoms simultaneously. Preferably two or more of R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 are hydrogen atom and the others are acyl groups. The poly valent alcohol represented by Formula VI is contained in a lipophilic fine grain comprising a dye image-forming coupler in a ratio by weight of not less than 50 % to the dye-forming coupler. Detailed Disclosure of the Invention The present invention will be explained in detail. Polyvalent alcohol compounds represented by Formulae II to VII of the present invention will be explained. In the following passages, R 3 to R 6 and R 9 to R 12 are defined as follows; R 3 to R 6 , R 9 and R 11 each represent an alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl group, R 10 and R 12 each represent a hydrogen atom, alkyl, alkenyl, cycloalkyl, cycloalkenyl or aryl group, provided that one of the carbon atoms of alkyl, alkenyl, cycloalkyl or cycloalkenyl in each of R 3 to R 6 and R 9 to R 12 is substituted with at least one hydroxy group and the number of alcoholic hydrocarbons in the molecule is two or more. In Formulae II to V, alkyl groups represented by R 31 , R 32 , R 33 , R 34 , R 41 , R 42 , R 43 , R 44 , R 44 , R 46 , R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 hereinafter (abbreviated as R 31 to R 74 ) may be either straight-chained or branched. Of them, those having from 1 to 32 carbons are preferable. For example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group, a heptadecyl group and a 2-ethylhexyl group are typically cited. Alkenyl groups represented by R 31 to R 74 may be either straight-chained or branched. Of them, those having from 2 to 32 carbons are preferable. For example, a vinyl group, a propenyl group, a 11-undecenyl group and a 1-methylpropenyl group are typically cited. As a cycloalkyl group represented by R 31 to R 74 , those having from 3 to 12 carbon atoms are preferable, and those having from 5 to 7 carbons are especially preferable. They may have a branch-structure. For example, a cyclohexyl group, a cyclopentyl group, a cyclopropyl group and a 2-methylcyclopropyl group are typically cited. As a cycloalkenyl group represented by R 31 to R 74 , those having from 3 to 12 carbons are preferable, and those having from 5 to 7 carbons are especially preferable. They may have a branch-structure. For example, a 1-cyclohexyenyl group and a 2-cyclopentenyl group are typically cited. As an aryl group represented by R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 , R 74 , those having from 6 to 14 carbons are preferable. A phenyl group, a 1-naphtyl group and a 2-naphtyl group are typically cited. In addition, the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group and aryl group may be substituted with a substituent. As the substituent therefor, an alkyl group, an alkenyl group, a cycloalkenyl group, an alkinyl group, an aryl group, a heterocycle group, an alkyl thio group, an aryl thio group, a heterocyclic thio group, a sulfonyl group, a sulfinyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkyl amino group, an anilino group, an acyl amino group, a sulfonamide group, an imide group, an ureido group, a sulfamoyl amino group, an alkoxycarbonyl amino group, an aryloxycarbonyl amino group, an alkoxycarbonyl group and an aryloxycarbonyl group, a spiro compound residual group, a bridged hydrocarbon residual group, a halogen atom and a hydroxyl group are cited. A substituted alkyl group or a substituted alkenyl group each containing 2 or more hydroxyl groups represented by R 51 represent an alkyl group and an alkenyl group (each including those substituted by a substituent) represented by the above-mentioned R 21 to R 52 wherein 2 or more arbitrary hydrogen atoms are substituted by a hydroxyl group. A 1,2-dihydroxypropyl group and a 1,1-dihydroxymethylethyl group are typically cited. As an acyl group represented by R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 34 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 (hereinafter abbreviated as R 21 to R 74 ) and Y, -C(=O)-R 3 (R 3 represents the above-mentioned compounds) is preferable; The sulfonyl group represented by R 31 to R 74 , is preferably -SO 2 -R 4 (R 4 represents the above-mentioned compounds); The preferable example of phosphonyl group represented by R 31 to R 74 , is -(O=)P<(OR 5 )(OR 6 ) (R 5 and R 6 represent the above-mentioned compounds); The preferable example of the carbamoyl group represented by R 31 to R 74 , and Y, is -C(=O)-N<(R 9 )(R 10 ) (R 9 and R 10 represent the above-mentioned compounds); and The preferable example of the sulfamoyl group represented by R 31 to R 74 and Y, is -SO 2 N<(R 11 )(R 12 ) (R 11 and R 12 represent the above-mentioned compounds). R 5 and R 6 , R 9 and R 10 , and R 11 and R 12 may be condensed with each other to form a ring. In Formula II, two arbitrary substituents chosen from R 21 , R 22 and R 23 (when m is 2 or more, each of them are regarded as an independent substituent), may be condensed with each other to form a ring. In Formula III, two arbitrary substituents chosen from R 31 , R 32 and R 33 (when n is 2 or more, plural R 33 and plural R 34 are respectively regarded as an independent substituent), may be condensed with each other for forming a ring. In Formula IV, two arbitrary substituents chosen from R 41 , R 42 , R 43 , R 44 , R 45 and R 46 may be condensed with each other to form a ring. In Formulae VI and VII, R 61 and R 62 and/or R 62 and R 63 and/or R 63 and/or R 64 are respectively condensed with each other to form a ring. An alkylene group represented by L may be of straight-chained and branched-chained. For example, an ethylene group, a 1-methylethyl group and a propylene group are cited. As an arylene group represented by L, a p-phenylene group, an o-phenylene group and a 1,4-naphtylene group are exemplified. An alkylene group and an arylene group represented by L may be substituted with other substituent which is the same as the substituent in the above-mentioned R 1 through R 3 . The total number of carbons in the polyvalent alcohol is preferably not less than 6 (provided that, it is not less than 10 for Formulae VI and VII). The compound is preferably immiscible in water. A polyvalent alcohol having a molecular weight of not more than 5,000 is preferable, and in the liquid state liquid at room temperature is particularly preferred. The number of hydroxy group in the polyvalent alcohol is preferably three or more. The more the number of the hydroxy group becomes, the more preferable a result is obtained. The molecular weight of the polyhydric alcohol is preferably not more than 5000 and one which is in the liquid state at normal temperatures is preferable. In the polyhydric alcohol, the hydroxyl group value is preferably 50 or more. Further, the logP value of the polyhydric alcohol is preferably not less than 3. Typical examples of the polyhydric alcohol preferably used in the present invention are given below: II-19 Decaglyceryltristearate II-20 Decaglycerylpentaoleate II-21 Decaglycerylheptaisostearate II-22 Hexaglyceryltristearate II-23 Hexaglycerylmonooleate II-24 Tetraglyceryltristearate II-25 Tetraglycerylmonooleate II-26 C 8 H 17 CH=CH(CH 2 ) 7 COO-CH 2 CH(OH)-CH 2 OH II-27 (i)C 17 H 35 COO-CH<(CH 2 OH) 2 The aliphatic polyhydric alcohol used in the present invention is suitably used as a solvent of a dye-forming coupler to form a fine oil particle containing a dye forming coupler. Preferable examples of yellow couplers used with the polyhydric alcohol include benzoyl acetoanilide and pyvaloyl acetoanilide couplers. Examples of magenta couplers include 5-pyrazolone, pyrazolotriazole and indazolone couplers, and examples of cyan coupler includes phenol, naphthol, pyrazoloquinazolone, pyrazolopilimidine, pyrazolotriazole and imidazole couplers. Preferable examples of cyan couplers used with the polyhydric alcohol include C-1 to C-24 cited in pp 59 to 61 JA OPI 4-313751. It is preferred to use a magenta coupler in combination with the polyhydric alcohol compound in the material of the invention. Preferable examples of the magenta coupler are represented by wherein Z is a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring which may have a substituent; X represents a hydrogen atom or a group which is capable of being released upon reaction with an oxidation product of a color developing agent; and R represents a hydrogen atom or a substituent. The coupler can usually be used in an amount of between 1×10 -3 mols and 1 mol per mol of silver halide and, more preferably within a range of between 1×10 -2 mol and 8×10 -1 mols/mol. Herein, a dye forming coupler and the aliphatic polyhydric alcohol, which is referred to as "polyhydric alcohol", are usually incorporated in at least one of the silver halide emulsion layers. In order to incorporate the dye-forming coupler and the polyhydric alcohol in the silver halide emulsion layer, the coupler and the polyhydric alcohol are, individually or in combination, dissolved in a mixure of high boiling solvent such as dibutylphthalate, tricresylphosphate and so on and a low boiling solvent such as butyl acetate, ethylacetate and so on, or in a low boiling solvent cited above, they are mixed with gelatin solution containing surfactant, then the mixure is emulsified by high speed mixer, colloid mill or hypersonic dispersing machine. The resulting emulsion is added directly to the silver halide emulsion. After the above-mentioned emulsification solution is set, finely divided and after washing, this may be added to the emulsion. The emulsion containing the magenta coupler or the polyhydric alcohol may be prepared and added to the silver halide emulsion separately, however, in accordance with the preferable embodiment of the present invention, both the magenta coupler and the polyhydric alcohol are dissolved, dispersed and incorporated in the silver halide emulsion simultaneously. The polyhydric alcohol is used in an amount of from 0.01 to 20 g, preferably from 0.5 to 8 g per 1 g of the coupler. The polyhydric alcohol may be used either alone or two or more kinds in combination. The weight ratio of the polyhydric alcohol to the coupler is preferably more than 50 %. As for the silver halide emulsion used for the light-sensitive color photographic material of the present invention, any conventionally known silver halide emulsion can be used. Said emulsion can be sensitized either chemically or optically in a desired wavelength region by the conventional method and using an appropriate sensitizing dye. To the silver halide emulsion, any conventionally known photographic additives such as an anti-foggant, a stabilizing agent, etc. can be added. As the binder used in the silver halide emulsion, gelatin is advantageous. Other emulsion layers and hydrophilic colloidal layers can be hardened and can comprise a plasticizer, or a dispersion of water-insoluble synthetic coupler is used in the emulsion layer of the color photographic light-sensitive material. The light-sensitive material can comprise a colored coupler and a competing coupler having color correction ability, a compound releasing such a photographically usable fragment, on reaction with an oxidation product of developing agent, as developing accelerating agent, toning agent, hardener, fogging agent, antifogging agent, chemical sensitizer, optical sensitizer or desensitizer. The light-sensitive material can comprise one or more auxiliary layers such as a filter layer, an anti-halation layer, an anti-irradiation layer. These auxiliary layers and/or the silver halide emulsion layer can comprise a dye which is capable of dissolving out from the light-sensitive material or is bleached during photographic processing. Further in the light-sensitive material, other photographic additives such as formalin scavenger, fluorescent brightening agent, matting agent, lubricant, image stabilizing agent, surfactant, anti color-foggant, development accelerator, development retarder, bleaching accelerator may also be incorporated. As for the support, a paper laminated with polyethylene, polyethylene terephthalate film, baryta paper, cellulose triacetate film can be used. To obtain a dye image by using the light-sensitive material of the present invention, conventional color photographic processes which are known and used in the art can be applied after imagewise exposure. Further in the green sensitive silver halide emulsion layer comprising the dye-forming coupler described above, it is preferable that at least one dye image stabilizing agent represented by formula AO-I or AO-II is incorporated. In the formula R 121 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a residue represented below: In the formula, R 121 a, R 121 b, and R 121 c individually represent a mono-valent organic group; R 122 , R 123 , R 124 , R 125 , and R 126 independently represent a hydrogen atom, a halogen atom or a group which is capable of substituting to the benzene ring; and R 121 to R 126 may individually be connected with each other to form a bond with each other and form a 5-membered or a 6-membered cyclic group. In the formula R 131 represents an aliphatic group or an aromatic group and Y represents a group of non-metal atoms necessary to complete a 5- to 7-membered ring together with a nitrogen atom. As for the alkyl group, the aryl group and the heterocyclic group represented by R 121 in formula AO-I, those listed for R 3 above may be mentioned and as for the heterocyclic group, for example, pyrazole grop, 2-imidazolyl group, 3-pyridyl group and 2-furyl group are listed. As for the mono-valent organic group which R 121 a, R 121 b, and R 121 c represent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom may be mentioned. As for R 121 , a hydrogen atom or an alkyl group is preferable. As for the group which is capable of being a substituent to the benzene ring, represented by R 122 to R 126 , those listed as R above may be mentioned. The hydrogen atom, the hydroxy group, the alkyl group, the aryl group, the alkoxy group, the aryloxy group, and the acyl amino group are preferable to R 122 , R 123 , R 125 , and R 126 and the alkyl group, the hydroxy group, the aryl group, the alkoxy group, and the aryloxy group are preferable to R 124 . R 121 and R 122 may connect with each other to form a 5-member or 6-member cyclic group. In the case, R 121 and R 122 may close ring to form a methylenedioxy ring. Still further, R 123 and R 124 can connect with each other to form a 5-member hydrocarbon ring and in that case, the alkyl group, the aryl group, or the heterocyclic group is preferable as R 121 . Specific examples of the compounds represented by formula AO-I are shown below: Further specific examples of compound represented by above-mentioned formula AO-I include Exemplified compounds A-1 to A-28, described at page 8-page 10 of JP OPI 60-262159, PH-1 to PH-29 described at page 8-page 10 of JP OPI 61-145552, Exemplified compounds B-1 to B-21 described at page 6 to page 7 of JP OPI 1-306846, Exemplified compounds I-1 to I-13, I'-1 to I'-8, II-1 to II-12, II'-1 to II'-21, III-8 to III-14, IV-1 to IV-24, and V-13 to V-17 described at pages 10 to 18 of JP OPI 2-958, Exemplified compounds II-1 to II-33 described at pages 10 to 11 of JP OPI 3-39956 can be given. Next, R 131 in the above-mentioned formula AO-II, represents an aliphatic group or an aromatic group, preferably an alkyl group or an aryl group or a heterocyclic group, and, most preferably, an aryl group. As for the heterocyclic group which Y forms together with the nitrogen atom, for example, a piperidine ring, a piperadine ring, a morpholine ring, a thiomorpholine ring, a thiomorpholine-1, 1-dione ring and a pyroridine ring may be mentioned. Specific examples of the compounds represented by formula AO-II are given below: Further specific examples of the compound of formula AO-II include exemplified compounds B-1 to B-65 at pages 8 to 11 of JP OPI 2-167543, and exemplified compounds (1) to (120) at pages 4 to 7 of JP OPI 63-95439. The added amount of the compounds of formulae AO-I or AO-II is usually from 5 to 500 mol% and, more preferably, from 20 to 200 mol% per 100 mol% of the dye-forming coupler. Moreover, in the silver halide emulsion layer which comprises the dye-forming coupler and the polyhydric alcohol, a metal chelate compound disclosed in eg. JP O.P.I. 61-158329 and 62-183459 may be incorporated. Examples Next, the present invention is further explained with reference to the following examples. Example 1 On a paper support, on one side of which polyethylene is laminated and the other side of which polyethylene containing titan ate oxide is laminated, photographic layers, of which compositions are given in Tables 1 and 2, were coated on the side where polyethylene containing titanate oxide is laminated, to prepare a multi-layered silver halide light-sensitive color photographic material, Sample 101. Coating solution was prepared as follows: To a mixture consisting of 26.7g of yellow dye-forming coupler(Y-9, a yellow coupler disclosed in page 51 of JA OPI 4-313751), 10.0g of dye image stabilizer(ST-1),6.6g of dye image stabilizer(ST-2),0.6g of anti-staining agent (HQ-1) and 6.67g of high boiling point organic solvent (DNP), were dissolved by adding 60 ml of ethyl acetate. Then, this mixture was emulsified in 220 ml of 10% gelatin solution using a ultra-sonic homogenizer and thus an emulsion comprising a yellow dye-forming coupler was prepared. This emulsion was then mixed with a blue-sensitive silver halide emulsion comprising 8.67 of silver by which this dispersant was shown below, anti-irradiation dye (AIY-1) was added, and the coating composition for the first layer was prepared. As to the second layer through the seventh layer, coating solutions were prepared in the same manner as in the first layer. Moreover, a gelatin hardener (HH-1) was added to the second layer and the fourth layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1) and (SU-3) were added to adjust the surface tension of the coating solution. Layer Composition Amount added (g/m 2 ) 7th layer (Protective layer) Gelatin 1.00 6th layer (UV absorbing layer) Gelatin 0.40 UV absorbent (UV-1) 0.10 UV absorbent (UV-2) 0.04 UV absorbent (UV-3) 0.16 Antistaining agent (HQ-1) 0.01 DNP 0.20 PVP 0.03 Anti-irradiation dye (AIC-1) 0.02 5th layer (Red-sensitive layer) Gelatin 1.30 Red-sensitive silver 0.21 chlorobromide emulsion (Em-R) Cyan coupler (C-3) 0.24 Cyan coupler (C-6) 0.08 Dye-image stabilizer (ST-1) 0.20 Antistaining agent (HQ-1) 0.01 HBS-1A 0.20 DOP 0.20 4th layer (UV absorbing layer) Gelatin 0.94 UV absorbent (UV-1) 0.28 UV absorbent (UV-2) 0.09 UV absorbent (UV-3) 0.38 Antistaining agent (HQ-1) 0.03 DNP 0.40 Layer Composition Amount added (g/m 2 ) 3rd layer (Green-sensitive layer) Gelatin 1.40 Green-sensitive silver chlorobromide emulsion (Em-G) 0.17 Magenta coupler (M-29) 0.75 DNP 0.20 Dye-image stabilizer (Is-8) 0.75 Anti-irradiation dye (AIM-1) 0.01 2nd layer (Interlayer) Gelatin 1.20 Antistaining agent (HQ-2) 0.03 Antistaining agent (HQ-3) 0.03 Antistaining agent (HQ-4) 0.05 Antistaining agent (HQ-5) 0.23 DIDP 0.06 Antimold (F-1) 0.002 1st layer (Blue-sensitive layer) Gelatin 1.20 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow coupler (EY-1) 0.80 Dye-image stabilizer (ST-1 0.30 Dye-image stabilizer (ST-2) 0.20 Antistaining agent (HQ-1) 0.02 Anti-irradiation dye (AIY-1) 0.01 DNP 0.20 Support Polyethylene-laminated paper sheet Amounts of the silver halide emulsions added were each shown in terms of the silver contents. The structural formulae of the compounds used in the respective layers are given below: Disclosed in JA OPI 4-313751 Disclosed in JA OPI 4-313751 Disclosed in JA OPI 4-313751 Disclosed in JA OPI 4-313751 DOP : Dioctyl phthalate DNP : Dinonyl phthalate DIDP : Diisodecyl phthalate PVP : Polyvinyl pyrrolidone Blue-sensitive silver halide emulsion (Em-B): Average grain size 0.85 microns, coefficient of variation =0.07, and silver chloride content 99.5 mol % Mono-dispersed cubic grain emulsion Sodium thiosulfate 0.8 mg/mol AgX Chloroauric acid 0.5 mg/mol AgX Stabilizing agent (STAB-1) 6×10 -4 /mol/AgX Sensitizing dye (BS-1) 4×10 -4 /mol AgX Sensitizing dye (BS-2) 1×10 -4 /mol AgX Green-sensitive silver halide emulsion (Em-G): Average grain size 0.43 microns; coefficient of variation =0.08 and silver chloride content 99.5 mol % Sodium thiosulfate 1.5 mg/mol AgX Chloroauric acid 1.0 mg/mol AgX Stabilizing agent (STAB-1) 6×10 -4 /mol AgX Sensitizing dye (GS-1) 4×10 -4 /mol AgX Red-sensitive silver halide emulsion (Em-R): Mono-dispersed cubic grain emulsion having average grain size 0.50 micron;, coefficient of variation =0.08 and silver chloride content 99.5 mol % Sodium thiosulfate 1.8 mg/mol AgX Chloroauric acid 2.0 mg/mol AgX Stabilizing agent (STAB-1) 6×10 -4 /mol AgX Sensitizing dye (RS-1) 1×10 -4 /mol AgX The structural formula of the compounds used in the respective mono-disperse emulsions containing cubic grains are given below: Next, Samples 102 to 120, 105' to 120', and 105'' to 105'' were prepared in the same manner as Sample 101 except that the high boiling point organic solvent DNP was replaced by the high boiling point organic solvent or the polyhydric alcohol given in Tables 3, 4 and 5 below: Thus prepared Samples and Comparative Samples were, after being exposed to green light through an optical wedge in the conventional manner, processed according to the conventional method, of which step, processing temperature and processing time are given below: Processing Step Temperature(°C) Time(sec.) Color development 35.0±0.3°C 45 Bleach-fixing 35.0±0.5°C 45 Stabilizing 30 to 34°C 90 Drying 60 to 80°C 60 The compositions of respective processing solutions are as follows: The replenishing amount of each processing solution is 80 ml per m 2 of silver halide light-sensitive color photographic material. Color developer Tank solution Replenisher Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N,N-Diethyl hydroxyl amines 5 g 9 g Potassium chloride 2.4 g 1-hydroxy ethylidene-1,1-di-phosphonic acid 1.0 g 1.8 g N-ethyl-N-beta-methane sulfonamide ethyl-4-(aminoaniline)-3-methyl sulfate 5.4 g 8.2 g Fluorescent brightening agent 4,4'-di-amino stilbene sulfonate derivative 1.0 g 1.8 g Potassium carbonate 27 g 27 g Add water to make the total volume 1000 ml and in the tank solution, the pH is adjusted to 10.10 and the pH of the replenisher to 10.60. Bleach-fixing solution (composition of the replenisher is same as that in the tank.) Ethylene-diamine-tetraacetic acid iron ammonium dihydrate 60 g Ethylene-diamine-tetraacetic acid 3 g Ammonium thiosulfate (70 % aqueous solution) 100 ml Ammonium sulfate (40 % aqueous solution) 27.5 ml Add water to make the total volume 1000 ml, and pH is adjusted with potassium carbonate or glacial acetic acid to 5.7. Stabilizing solution (composition of the replenisher is same as that in the tank.). 5-chloro-2-methyl-4-iso-thiazoline-3-on 1.0 g Ethylene glycol 1.0 g 1-hydroxyethylidene 1,1-di-phosphonic acid 2.0 g Ethylene-diamine-tetraacetic acid 1.0 g Ammonium hydroxide (20 % aqueous solution) 3.0 g Fluorescent whitening agent(4,4'-di-amino stilbene sulfonate derivative) 1.5 g Add water to make the total volume 1000 ml and pH of the solution was adjusted at 7.0 with sulfuric acid or potassium hydroxide. Samples processed continuously were tested in the following evaluation. 〈light stability〉 Rate of residual dye density to initial dye density at inintial density of 1.0, after irradiation by xenon fade-O-meter for 14 days. lmax; The maximum absorption wave length of the dye image having reflection density at 1.0 was measured. Half Peak-value width; Half peak-value width was measured from spectral absorption spectrogram of the dye image having reflection density at 1.0.Dmax; The maximum density of the developed dye image was measured. Results are shown in Tables 3, 4 and 5. Sample No. HBS in 3rd layer Amount of HBS (g/m 2 ) λmax Half Peak-value width Dmax Residual rate (%) 101 DNP 0.20 547 110 1.97 57 102 HBS-1 0.20 561 125 1.85 60 103 HBS-2 0.20 548 112 2.14 58 104 HBS-3 0.20 548 120 1.41 60 105 V-1 0.20 549 109 2.24 65 106 V-3 0.20 547 108 2.20 65 107 IV-1 0.20 549 110 2.20 67 108 II-1 0.20 547 108 2.22 73 109 II-5 0.20 548 107 2.24 71 110 II-13 0.20 547 110 2.28 73 111 DNP 0.60 548 108 1.94 62 112 HBS-1 0.60 561 122 2.27 65 113 HBS-2 0.60 549 110 2.15 63 114 HBS-3 0.60 549 117 1.50 64 115 V-1 0.60 548 104 2.25 72 116 V-3 0.60 549 105 2.20 72 117 IV-1 0.60 549 106 2.20 75 118 II-1 0.60 549 103 2.30 82 119 II-5 0.60 547 105 2.32 81 Sample No. HBS in 3rd layer Amount of HBS (g/m 2 ) λmax Half Peak-value width Dmax Residual rate (%) 101 DNP 0.20 547 110 1.97 57 102 HBS-1 0.20 561 125 1.85 60 103 HBS-2 0.20 548 112 2.14 58 104 HBS-3 0.20 548 120 1.41 60 105' VI-1 0.20 548 110 2.24 70 106' VI-2 0.20 549 107 2.20 66 107' VI-9 0.20 549 109 2.20 68 108' VII-1 0.20 549 109 2.22 70 109' VII-4 0.20 548 106 2.24 68 110' VII-14 0.20 549 110 2.28 67 111' DNP 0.60 548 108 1.94 62 112' HBS-1 0.60 561 122 2.27 65 113' HBS-2 0.60 549 110 2.15 63 114' HBS-3 0.60 549 117 1.50 64 115' VI-1 0.60 548 107 2.24 76 116' VI-2 0.60 548 104 2.34 73 117' VI-9 0.60 549 106 2.33 73 118' VII-1 0.60 547 108 2.25 77 119' VII-4 0.60 547 104 2.32 74 120' VII-14 0.60 549 107 2.29 74 Comparative HBS C 8 H 17 CH=CH(CH 2 ) 8 OH (High boiling point organic solvent disclosed in EP486,929.) (Disclosed in JP OPI 2-100048) It is apparent from Tables 3 and 4 that the light stability and the color forming property of the samples according to the present invention (Samples 105 to 110, and 105' to 110'), in which the compound of Formulae II to VII is used as a high boiling point organic solvent, have been greatly improved compared with Comparative Sample 101 and the color forming property has also been improved. Moreover, the effect of sharpening of the absorption without changing the maximum absorption wave length was observed. In sample 102 for which HBS-1, which is phenol derivative, is used, some improvement in the light stability was observed, however, the effect was insufficient. In addition, undesirable effects of bathochromic shift and broadening of the absorption were also observed. Sample 104 using a comparative HBS-3 results in inferior color developing ability and a broader absorption peak though it shows a certain improvement in stability against light. In Samples 111 to 119 and 115' to 120' HBS is used in an amount of three times that of Samples 101 to 110. The polyol compound defined herein works much more effectivly when a large amount thereof is used. The stability against light is improved and a sharp absorption peak is obtained. Example 2 In Example 1 a magenta coupler, HBS and dye stabilizer in the third layer of Sample 101 above were replaced with those shown in Table 5 to obtain Samples 200 to 214. The same test was conducted as in Example 1. The results are summarized in Table 5. Sample No. Magenta Coupler in 3rd layer HBS and amount in 3rd layer (g/m 2 ) Dye stabilizer and amount thereof (mmol/m 2 ) Light Stability (Residual rate of dye) 200 M-8 DNP (0.20) Is-9 (0.75) 41 IIs-2 (0.75) 201 ditto II-5 (0.20) ditto 65 202 ditto II-5 (0.60) ditto 74 203 ditto II-26 (0.20) ditto 63 204 ditto II-26 (0.60) ditto 70 205 ditto III-1 (0.20) ditto 57 206 ditto III-1 (0.60) ditto 69 207 ditto V-5 (0.20) ditto 55 208 ditto V-5 (0.60) ditto 68 209 ditto VI-3 (0.20) ditto 61 210 ditto VI-3 (0.60) ditto 70 211 ditto VI-7 (0.20) ditto 60 212 ditto VI-7 (0.60) ditto 68 213 ditto VII-4 (0.20) ditto 59 214 ditto VII-4 (0.60) ditto 64 Samples using the polyhydric alcohol of any of the Formula II to VII as a HBS in combination with a magenta coupler M-8 which has a secondary alkyl group at the 6 position show the improvement in stability against light. Samples containing increased amount of the polyhydric alcohol of any of Formulae II to VII (Samples 202, 204, 206, 208, 210, 212, and 214) show further improved stability to light. Example 3 In Example 1 HBS in the third layer of Sample 101 was replaced with those shown in table 6 to obtain Samples 201' to 212'. The same test was conducted as for Example 1. The results are summarized in Table 6. Sample No. HBS in 3rd layer, amount thereof (g/m 2) (HBS/Cp) Light stability (Dye residual ratio) Dmax 101 DNP (0.2) 0 57 1.97 201' DNP (0.18) 0.056 58 2.17 II-1 (0.02) 202' DNP (0.1) 0.28 58 2.19 II-1 (0.1) 203' DNP (0.02) 0.51 69 2.20 II-1 (0.18) 204' II-1 (0.2) 0.56 73 2.22 205' DNP (0.18) 0.056 57 2.16 VI-1 (0.02) 206 DNP (0.1) 0.28 58 2.17 VI-1 (0.1) 207' DNP (0.02) 0.51 67 2.18 VI-1 (0.18) 208' VI-1 (0.20) 0.56 70 2.21 209' DNP (0.18) 0.056 57 2.16 VII-1 (0.02) 210' DNP (0.1) 0.28 57 2.18 VII-1 (0.1) 211' DNP (0.02) 0.51 66 2.19 VII-1 (0.18) 212' VII-1 (0.20) 0.56 70 2.20 In the Example a part of amount of the polyhydric alcohol is replaced with a conventional high boiling solvent. Consequently the weight ratio of the polyhydric alcohol to a coupler is varied. The Table shows that the samples containing a polyhydric alcohol in an amount of more than 50 weight % to a coupler are more advantageous in the stability to light. Further samples containing no conventional HBS are much more effective. Example 4 In Example 1 HBS in the first layer of Sample 101 were replaced with those shown Table 7 to obtain Samples 302 to 311. The resulting samples were exposed wedgewise by blue light, and the same developing process and test was conducted as in Example 1. The results are summarized in Table 7. Sample No. HBS in 1st layer Amount of HBS (g/m 2 ) Dmax Light stability (Dye residual ratio) 301 DNP 0.20 2.58 81 302 HBS-2 0.20 2.27 75 303 II-2 0.20 2.49 88 304 III-9 0.20 2.47 86 305 IV-9 0.20 2.47 85 306 V-14 0.20 2.42 85 307 VI-4 0.20 2.45 84 308 VI-8 0.20 2.48 84 309 VII-3 0.20 2.41 86 310 VII-6 0.20 2.44 85 311 VII-7 0.20 2.39 86 Table 7 shows that the samples containing the polyhydric alcohol compound of any of Formulae II to VII (Samples 303 to 311) exhibit improved stability to light and color developabilty. HBS-2, that has one hydroxy group in the molecule, exhibits slight improvement in stability to light, but deterioration of color developability. Example 5 In Example 1 HBS in the fifth layer of Sample 101 were replaced with those shown Table 8 to obtain Samples 402 to 411. The resulting samples were exposed wedgewise by red light, and the same developing process and test was conducted as in Example 1. The results are summarized in Table 8. Sample No. HBS in 5th layer Amount of HBS (g/m 2 ) Dmax Light stability (Dye residual ratio) 401 DOP 0.20 2.07 70 402 HBS-2 0.20 2.05 72 403 II-2 0.20 2.24 82 404 III-9 0.20 2.20 82 405 IV-9 0.20 2.20 79 406 V-14 0.20 2.17 78 407 VI-4 0.20 2.19 80 408 VI-8 0.20 2.25 83 409 VII-3 0.20 2.25 81 410 VII-6 0.20 2.19 82 411 VII-7 0.20 2.30 77 Table 8 shows that the samples containing the polyhydric alcohol compound of any of Formulae II to VII (Samples 403 to 411) exhibit improved stability to light and color developabilty. HBS-2, that has one hydroxy group in the molecule, exhibits slight improvement of stability to light, but deterioration of color developability.

Claims: A silver halide color photographic light-sensitive material comprising a silver halide emulsion layer provided on a support, wherein the silver halide emulsion layer comprises a polyvalent alcohol chosen from Formulae II to VII; wherein R 21 , R 22 and R 23 each independently represent a hydrogen atom, or an acyl group and m is from 1 to 20; when m is two or more, two or more of R 23 may be the same or different, when m is 1, two of R 21 , R 22 and R 23 are hydrogen atoms, when m is two or more, at least two of R 21 , R 22 and R 23 are hydrogen atoms but all of R 21 , R 22 and R 23 are not hydrogen atoms simultaneously; wherein R 31 , R 32 , R 33 and R 34 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group and n is from 1 to 20; when n is two or more, two or more of R 33 or R 34 may be the same or different, when n is 1, at least two of R 31 , R 32 , R 33 and R 34 are hydrogen atoms, when n is two or more, at least two of R 31 , R 32 , R 33 and R 34 are hydrogen atoms but all of R 31 , R 32 , R 33 and R 34 are not hydrogen atoms simultaneously; wherein R 41 to R 46 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group, and a least two of R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are hydrogen atoms but all of R 41 to R 46 are not hydrogen atoms simultaneously; wherein R 51 is a substituted alkyl or substituted alkenyl group, each of which has two or more hydroxy groups, R 52 is an alkyl, alkenyl, cycloalkyl or cycloalkenyl group, and R 51 and R 52 may form a lactone ring by condensation with each other; wherein R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group, and at least two of R 61 , R 62 , R 63 , R 64 and at least two of R 71 , R 72 , R 73 and R 74 are hydrogen atoms but all of R 61 to R 64 and R 71 to R 74 are not hydrogen atoms simultaneously. A silver halide color photographic light-sensitive material of Claim 1, wherein the polyvalent alcohol is represented by the Formula II, VI or VII. A silver halide color photographic light-sensitive material of claim 2, wherein the total number of carbons in the polyvalent alcohol is not less than 6 for a compound of Formula II and not less than 10 for a compound of Formulae VI or VII. A silver halide color photographic light-sensitive material of claim 2, wherein the polyvalent alcohol is represented by the Formula II, VI or VII; wherein R 21 , R 22 and R 23 each represent a hydrogen atom or an acyl group and m is from 1 to 3; when m is two or more, two or more of R 23 may be the same or different, when m is 1, two of R 21 , R 22 and R 23 are hydrogen atoms, when m is two or more, at least two of R 21 , R 22 and R 23 are hydrogen atoms but all of R 21 , R 22 and R 23 are not hydrogen atoms simultaneously; wherein R 61 , R 62 , R 63 , R 64 , R 71 , R 72 , R 73 and R 74 each represent a hydrogen atom or an acyl group, and at least two of R 61 , R 62 , R 63 and R 64 are hydrogen atoms, but all of R 61 to R 64 are not hydrogen atoms simultaneously, and at least two of R 71 , R 72 , R 73 and R 74 are hydrogen atoms but all of R 71 to R 74 are not hydrogen atoms simultaneously. A silver halide color photographic light-sensitive material of claim 4, wherein the polyvalent alcohol is represented by the Formula II; wherein R 21 , R 22 and R 23 each represent a hydrogen atom or an acyl group and m is from 1 to 3; when m is two or more, two or more of R 23 may be hydrogen atoms, when m is two or more, at least two of R 21 , R 22 and R 23 are hydrogen atoms but all of R 21 , R 22 and R 23 are not hydrogen atoms simultaneously. A silver halide color photographic light-sensitive material of any preceding claim, wherein the silver halide emulsion layer comprises a dye-forming coupler and the polyvalent alcohol is present in a lipophilic fine grain comprising the dye-forming coupler. A silver halide color photographic light-sensitive material of claim 6, wherein the polyvalent alcohol is present in the lipophilic fine grain comprising the dye-forming a coupler in a ratio by weight of not less than 50% to the dye-forming coupler. A silver halide colour photographic light-sensitive material of claim 6 or 7, wherein the dye-forming coupler is a yellow coupler, a magenta coupler or a cyan coupler. A silver halide colour photographic light-sensitive material of claim 8, wherein the dye-forming coupler is a magenta coupler. A silver halide colour photographic light-sensitive material of any preceding claim, wherein the molecular weight of the polyvalent alcohol is not more than 5,000. A silver halide colour photographic light-sensitive material of any preceding claim, wherein the polyvalent alcohol is in the liquid state at room temperature. A silver halide colour photographic light-sensitive material comprising a support and a silver halide emulsion layer provided thereon comprising a lipophilic fine grain comprising a dye-forming coupler and a polyvalent alcohol represented by Formula II as defined in claim 4, wherein the ratio of the polyvalent alcohol to the dye-forming coupler is not less than 50% by weight. A silver halide colour photographic light-sensitive material of claim 1, wherein the polyvalent alcohol is represented by Formula II: wherein R 21 , R 22 and R 23 each represent a hydrogen atom or an acyl group, m is from 1 to 20, when m is two or more, two or more of R 23 may be the same or different, when m is 1, two of R 21 , R 22 and R 23 are hydrogen atoms, when m is two or more, at least two of R 21 , R 22 and R 23 are hydrogen atoms but all of R 21 , R 22 and R 23 are not hydrogen atoms simultaneously. A silver halide colour photographic light-sensitive material of claim 1, wherein the polyvalent alcohol is represented by the Formula VI: wherein R 61 , R 62 , R 63 and R 64 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group, and at least two of R 61 , R 62 , R 63 and R 64 are hydrogen atoms but all of R 61 to R 64 are not hydrogen atoms simultaneously. A silver halide colour photographic light-sensitive material of claim 1, wherein the polyvalent alcohol is represented by the Formula VII: wherein R 71 , R 72 , R 73 and R 74 each represent a hydrogen atom, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, acyl, sulfonyl, phosphonyl, carbamoyl or sulfamoyl group, and at least two of R 71 , R 72 , R 73 and R 74 are hydrogen atoms but all of R 71 to R 74 are not hydrogen atoms simultaneously. A silver halide colour photographic light-sensitive material of claim 4, wherein the polyvalent alcohol is represented by the Formula VI: wherein R 61 , R 62 , R 63 and R 64 each represent a hydrogen atom, or an acyl group, and at least two of R 61 , R 62 , R 63 and R 64 are hydrogen atoms but all of R 61 to R 64 are not hydrogen atoms simultaneously. A silver halide colour photographic light-sensitive material of claim 4, wherein the polyvalent alcohol is represented by the Formula VII: wherein R 71 , R 72 , R 73 and R 74 each represent a hydrogen atom or an acyl group, and at least two of R 71 , R 72 , R 73 and R 74 are hydrogen atoms but all of R 71 to R 74 are not hydrogen atoms simultaneously. A silver halide colour photographic light-sensitive material of claim 13, wherein the compound represented by formula II is exemplified compound II-1, 2, 5, 13 or 26. A silver halide photographic light-sensitive material of claim 14, wherein the polyvalent alcohol is exemplified compound VI-1, 2, 3, 4, 7, 8 or 9. A silver halide colour photographic light-sensitive material of claim 15, wherein the polyvalent alcohol is exemplified compound VII-1, 3, 4, 6, 7 or 14.

Inventors: KITA HIROSHI, SATO HIROKAZU, KITA, HIROSHI, SATO, HIROKAZU, KITA, HIROSHI, C/O KONICA CORPORATION, SATO, HIROKAZU, C/O KONICA CORPORATION
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1993
Main classification: G03C7
IPC codes: G03C7