JP3517812B2 - Silver halide color photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, a halogen which is excellent in color forming property and light fastness and has improved generation of bleeding in dye images under storage conditions of high temperature and high humidity. The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material (hereinafter, also referred to as "color light-sensitive material" or simply "light-sensitive material"), the reaction between the coupler and the oxidized color developing agent proceeds efficiently, It is necessary to obtain a dye image with the highest density (high color development). Further, it is desired that the obtained dye image does not discolor even when exposed to light for a long period of time or stored under high temperature and high humidity.

However, recent demands for rapid processing have brought about a disadvantageous situation with respect to color development of couplers.

As a means for improving the color-forming property of the coupler, it is known to use a high-boiling point organic solvent having higher hydrophilicity, but the coupler-containing silver halide emulsion closest to the support which is most unfavorable for the color-developing reaction. When hydrophilic high boiling point organic solvent is used for the layer, color mixing occurs after storing the raw sample,
It was found that the color reproducibility was significantly reduced.

As a means for improving the color developability of couplers, a technique of using a glycerin derivative as a high boiling organic solvent is disclosed in JP-A-7-84350 and JP-A-63-119.
No. 35, etc., when the compound described in the patent is used as a high-boiling organic solvent, although the color developability is certainly improved, the fastness of the dye image to light is insufficient, or the high temperature -It was found that there is an inconvenience that the dye image bleeds when stored under high humidity conditions.

Further, when a pyrazoloazole-based magenta coupler is used as the magenta coupler, the dye image formed has less secondary absorption in the blue region than in the case where the conventional 5-pyrazolone magenta coupler is used, and the color reproduction is improved. It is preferred that US Pat. No. 3,725,067
No. 3,758,309, No. 3,810,761 and the like. However, the fastness to light of an azomethine dye formed from a pyrazoloazole-based magenta coupler is extremely low, and the performance of a color photographic light-sensitive material, particularly a print-based color photographic light-sensitive material is significantly impaired.

Techniques for improving the fastness to light include, for example, JP-A-59-125732 and JP-A-61-28.
No. 2845, No. 61-292639, No. 61-279.
Phenolic compounds, phenyl ether compounds described in JP-A No. 855 and the like, or JP-A-61-72246,
There are known techniques in which the amine compounds described in JP-A Nos. 62-208048, 62-157031, 63-163351 and the like are used in combination with a pyrazoloazole-based magenta coupler, but also in these technologies, The light fastness of the magenta dye image is insufficient, and its improvement has been strongly desired.

[0008]

Accordingly, the object of the present invention is to provide excellent color development of the coupler, excellent light fastness of the formed dye image, and further to prevent bleeding of the dye image under storage conditions of high temperature and high humidity. An object is to provide an improved silver halide color photographic light-sensitive material.

[0009]

The above object of the present invention has been achieved by the following constitution.

(1) A silver halide color photographic light-sensitive material containing at least one alcohol-based compound represented by the following general formula (A).

[0011]

[Chemical 5]

[Wherein R ^a1 is an alkyl group, an aryl group,
Alkenyl group, alkoxyl group, aryloxy group,
Syl group, acylamino group, carbamoyl group, alkoxy
Carbonyl group, aryloxycarbonyl group, cyano
Represents a group, a sulfonyl group, a hydroxyl group or a halogen atom , R
^a2 is a hydrogen atom , alkyl group, aryl group, alkenyl
Group, alkoxyl group, aryloxy group, acyl group,
Silamino group, carbamoyl group, alkoxycarbonyl
Group, aryloxycarbonyl group, cyano group, sulfoni
Group, a hydroxyl group or a halogen atom , and m represents an integer of 0-4. When m is 2 or more, a plurality of R ^a2 may be the same or different, and the total carbon number of R ^a1 and R ^a2 is 12 or more and 36 or less. (2) An alcohol compound represented by the above general formula (A) and at least one magenta image forming coupler represented by the following general formula (MI) are contained in the same silver halide emulsion layer. (1) The silver halide color photographic light-sensitive material as described in (1) above.

[0013]

[Chemical 6]

[In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. (3) The magenta image forming coupler has the following general formula (M-
A silver halide color photographic light-sensitive material described in (1) or (2), which is represented by A).

[0015]

[Chemical 7]

[Wherein R represents a hydrogen atom or a substituent,
L represents a divalent linking group, R ^m1 represents a substituent capable of substituting on the benzene ring, and Y represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom. , 1 represents an integer of 0 to 4. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. (4) An image stabilizer represented by the following general formula (SI) is contained in the emulsion layer in which the magenta image forming coupler is present, (1) , (2) or (3). ) The silver halide color photographic light-sensitive material as described above.

[0017]

[Chemical 8]

[Wherein R ^s1 and R ^s2 are each independently
It represents a hydrogen atom, an aliphatic group or an aromatic group, R ^s3 represents a substituent capable of substituting on the benzene ring, and k represents an integer of 0 to 4. When k is 2 or more, a plurality of R ^s3 may be the same or different, and when a plurality of R ^s3 are adjacent to each other, they may be condensed with each other to form a ring. However,
R ^s1 and R ^s2 are not hydrogen atoms at the same time. (5) The magenta image forming coupler has the above general formula (M-
The silver halide color photographic light-sensitive material according to (4), which is represented by A).

The present invention will be described in more detail below.

The alcohol compound represented by the general formula (A) will be described.

In the above general formula (A), it is represented by R ^a1.
That A The group alkyl group, an aryl group, an alkenyl group,
Alkoxyl group, aryloxy group, acyl group, acylamino group, carbamoyl group, alkoxycarbonyl group,
An aryloxycarbonyl group, a cyano group, a sulfonyl group, a hydroxyl group, include halogen atom, good Mashiku alkyl group, an aryl group, an alkoxyl group, and a halogen atom., And most preferably an alkyl group.

[0022] In the general formula (A), but as represented Ru group <br/> in R ^a2 has the same meaning as the groups you express in the foregoing R ^a1, R ^a1
When R represents a halogen atom, R ^a2 is preferably an alkyl group, an aryl group or an alkoxyl group. Further, R ^a1 and R ^a2 may be condensed with each other to form a ring, and when m is 2 or more, R ^a2 may be condensed with each other to form a ring.

The total number of carbon atoms of R ^a1 and R ^a2 is 12 or more and 36.
It is below, but is preferably 12 or more and 28 or less.

Typical examples of the alcohol compound represented by the general formula (A) (hereinafter, also referred to as the alcohol of the present invention) are shown below, but the invention is not limited thereto.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[Synthesis Method] The alcohol of the present invention can be easily synthesized by a general synthesis method shown in the following scheme.

[Synthesis Scheme]

[0033]

[Chemical 15]

The alcohol of the present invention can be prepared according to JP-B-54-24.
Although it can be synthesized by the method described in No. 289, sodium hydroxide is generally used as a catalyst for the reaction.
Inorganic bases such as potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, triethylamine, pyridine, guanidine, amidine and 1,4-diazabicyclo [2. 1.2.
2] Octane, 1,8-diazabicyclo [5.4.0]
Examples thereof include organic bases such as -7-undecene, and the amount used is 0.1 to 1000 mol%, preferably 1 to 50 mol% of the starting phenol.

The reaction solvent is solvent-free, hydrocarbons such as toluene, xylene and dodecane, esters such as ethyl acetate and butyl propionate, amides such as N, N-dimethylacetamide, ethers such as diisopropyl ether and tetrahydrofuran. Examples thereof include, but it is preferable to carry out without solvent.

The reaction temperature is preferably 40 to 250 ° C., more preferably 70 to 200 ° C.
Most preferably, it is carried out at 110 to 200 ° C.

[Synthesis Example-1] Synthesis of A-1 (1) To 34.6 g of 2,4-dinonylphenol was added 0.30 g of sodium hydroxide crushed with a bee and heated to 120 ° C. To this, 7.4 g of glycidol was added dropwise over about 30 minutes, and after the addition, the mixture was heated and stirred at 130 ° C. for 1 hour. The reaction product was cooled to about 60 ° C., 200 ml of ethyl acetate, 100 ml of brine and 10 ml of 1N hydrochloric acid were added for liquid separation, and the mixture was washed 3 times with 100 ml of brine. The obtained organic phase was dried over anhydrous magnesium sulfate, and ethyl acetate as a solvent was distilled off under reduced pressure to obtain 42.0 g of brown oily product 1.

Further, 30.0 g of the product 1 was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as a developing solvent to obtain 16.7 g of yellow oil A-1 (gas chromatography It was identified by graphy, ¹ HNMR and FD mass spectrum).

Gas chromatography was measured using the purified A-1 and biphenyl as an internal standard. When a calibration curve was prepared by changing the ratio of biphenyl and A-1, and the purity of the product 1 was determined from this calibration curve, it was found that the purity was 62.8%. The impurities contained are dinonylphenol (17.4%) as a raw material and a compound in which glycidol is added to phenol at a ratio of 1: 2 and 1: 3.
It was confirmed by HPLC and ¹ HNMR.

Synthesis Example-2 Synthesis of A-1 (2) 103.9 g of 2,4-dinonylphenol was heated to 120 ° C., and 3.0 g of triethylamine was added thereto. At an internal temperature of 125 ° C, 33.3 g of glycidol was added dropwise over about 30 minutes, and after the addition, the mixture was stirred at 140 ° C for 10 minutes. The reaction product was cooled to about 60 ° C., 300 ml of ethyl acetate, 100 ml of brine and 300 ml of 1N hydrochloric acid were added to separate the layers, and the mixture was washed with 200 ml of brine three times. The obtained organic phase was dried over anhydrous magnesium sulfate, and the solvent ethyl acetate was distilled off under reduced pressure to obtain 125.4 g of yellow oily product 2.

Further, in the same manner as in Synthesis example-1, 30.0
When g was purified, 18.0 g of A-1 was obtained (the structure was identical to that of Synthesis Example-1).

When the purity of the product 2 was measured by gas chromatography using this purified A-1, it was found to be 63.7% (the impurities contained were 15% of the raw material dinonylphenol). 0.6%, other phenol: glycidol 1: 2 and 1: 3 adduct 2
0.7%).

Next, in order to evaluate the coloring of Product 1 and Product 2, each 5% ethyl acetate solution was prepared and 10
The transmittance was measured with a mm cell (T%, 450 nm).

Product 1: 70.8% Product 2: 95.0% From the above results, the yield and purity are almost the same when sodium hydroxide is used as the catalyst and when triethylamine is used. However, it was found that the latter can suppress the coloring to be lower.

In the present invention, a compound purified by column chromatography or the like as in the synthesis example may be used, or unpurified (raw material by-product) such as product 1 and product 2 in the synthesis example may be used. It was also confirmed that a compound containing a small amount of the substance) may be used, and the performances of the two do not significantly differ (purification methods include column chromatography, distillation, recrystallization, etc.). .

Yellow image-forming couplers that can be used in combination with the alcohol of the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta image-forming couplers include 5-pyrazolone type and pyrazolotriazole type couplers. , And indazolone-based couplers, and cyan image forming couplers include phenol-based, naphthol-based, pyrazolotriazole-based,
Although there are pyrazolopyrimidine-based, pyrazoloquinazolone-based, imidazole-based couplers and the like, particularly preferred couplers for exhibiting the effects of the present invention are the above-mentioned general formulas (MI).
And a magenta image forming coupler represented by the formula (simply referred to as magenta coupler).

In the magenta coupler represented by the general formula (M-I), Z represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z has a substituent. May be. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Of alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclethio Each group, a spiro compound residue, a bridged hydrocarbon compound residue, etc. are also mentioned.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

As the sulfonamide group represented by R,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 carbon atoms.
The alkenyl group may be linear or branched.

The cycloalkenyl group represented by R is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxy group. Phosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, aryl group, aryl Sulfamoyl group etc .; Acyloxy group as alkylcarbonyloxy group, arylcarbonyloxy group etc .; Carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group Group or the like; ureido group alkylureido group, an arylureido group or the like; sulfamethoxazole The sulfamoylamino group alkylsulfamoyl group, an aryl sulfamoylamino group or the like; 5 is a heterocyclic group
A 7-membered one is preferable, specifically, a 2-furyl group, 2-
Thienyl group, 2-pyrimidinyl group, 2-benzothiazole group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy. Group, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4- Diphenoxy-1,3,5-triazine-6-thio group, etc .; Siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; Imido group, succinimide group, 3-heptadecyl succinimide group , Phthalimido group, glutarimido group, etc .; spiro [3.3] heptan-1-yl etc. as spiro compound residue; bridged hydrocarbon compound residue Is then bicyclo [2.2.1] heptane-1-yl, tricyclo [3.1.1.1 ^3.7]
Decan-1-yl, 7,7-dimethyl-bicyclo [2.
2.1] Heptan-1-yl and the like can be mentioned.

Examples of the group represented by X which can be eliminated by the reaction with the oxidation product of the color developing agent include halogen atom (chlorine, bromine, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy,
Alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxycarbonyl Amino, aryloxycarbonylamino, carboxyl,

[0058]

[Chemical 16]

(R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group), etc. Each group is mentioned, but a halogen atom, particularly a chlorine atom is preferable.

Examples of the nitrogen-containing heterocycle formed by Z or Z'include a ring such as pyrazole, imidazole, triazole or tetrazole, and as the substituent which the ring may have, those described above for R may be mentioned. Is mentioned.

What is represented by the general formula (MI) is more specifically, for example, the following general formulas (M-II) to (M-VII).
Represented by

[0062]

[Chemical 17]

In formulas (M-II) to (M-VII), R _{1 to} R ₈ and X have the same meanings as R and X described above.

Among the general formula (M-I), those represented by the following general formula (M-VIII) are preferable.

[0065]

[Chemical 18]

In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in formula (M-I).

Of the magenta couplers represented by formulas (M-II) to (M-VII), the magenta couplers represented by formula (M-II) are particularly preferred.

Most preferred as the substituents R and R ₁ on the heterocycle are those represented by the following general formula (M-IX).

[0069]

[Chemical 19]

In the formula, R ₉ , R ₁₀ and R ₁₁ are each R
Is synonymous with.

Two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ are combined to form a saturated or unsaturated ring (eg cycloalkane, cycloalkene, heterocycle). Alternatively, R ₁₁ may bond to the ring to form a bridged hydrocarbon compound residue.

Of the general formula (M-IX), preferred is
(I) When at least two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ such as R ₁₁ is a hydrogen atom and the other two R ₉ and R 11 _This is the case where ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) are R ₉ to
This is the case where two of R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Further, the ring formed by Z in the general formula (M-I) and the substituent which the ring formed by Z ₁ in the general formula (M-VIII) may have, and the general formula (M
-II) to (M-VI) R _{2 to} R ₈ are represented by the following general formulas (MX), (M-XI), (M-XII) and (M-XII).
Those represented by I) are preferred.

[0075] formula _{(M-X) -R 12 -SO} 2 -R 13 Formula _{(M-XI) -R 12 -NHCO} -R 13 Formula _{(M-XII) -R 12 -NHSO} 2 -R 13 in the general formula _{(M-XIII) -R 12 -O} -C (= O) -R 13 formula, R ₁₂ is an alkylene group, R ₁₃ represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ₁₂ preferably has 1 or more carbon atoms in the straight chain portion, more preferably 2 to 6, and may be straight chain or branched.

The alkyl group represented by R ₁₃ may be linear or branched.

The aryl group represented by R ₁₃ is preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group.

The cycloalkyl group represented by R ₁₃ is preferably a 5- or 6-membered one.

Each of the groups represented by R ₁₂ and R ₁₃ may be further substituted with a substituent, and examples of the substituent include those described for R in the above general formula (MI). .

In the general formula (MA), the substituent represented by R has the same meaning as R in the general formula (MI).

In the general formula ( ^MA ), the substituent represented by R ^m1 is not particularly limited, and preferred examples thereof include the same groups as the substituents represented by R in the general formula (MI). And more preferably an alkyl, alkoxyl group,
It is a halogen atom.

In the general formula (MA), 1 represents an integer of 0 to 4, preferably 0.

2 represented by L in the general formula (MA)
The valent linking group is preferably the following general formula [LI]
It is represented by.

[0085]

[Chemical 20]

R ⁰¹ , R ⁰² and R ^{03 in the} general formula [LI]
Each independently represents an alkylene group having 1 to 12 carbon atoms, an arylene group, an alkylenearylene group or an aralkylene group. The alkylene group, which may be linear or branched, is, for example, a methylene group, a methylmethylene group, a dimethylene group, a decamethylene group, a 1,1-dimethylethylene group or the like, and an arylene group is, for example, a phenylene group, A naphthylene group and the like, and as an aralkylene group and an alkylenearylene group,

[0087]

[Chemical 21]

And the like.

The alkylene group, arylene group, alkylenearylene group or aralkylene group represented by R ⁰¹ , R ⁰² and R ⁰³ may have a substituent, and the substituent may be each substituent represented by R. Groups.

Further, L ₁ , L ₂ and L in the general formula [LI]
₃ is

[0091]

[Chemical formula 22]

Represents However, R ⁰⁴ represents a hydrogen atom, an alkyl group or an aryl group, and when two R ⁰⁴ are present,
Each R ⁰⁴ may be the same or different. p, q, r, s, t
And u represents an integer of 0 or 1.

In the general formula (MA), the non-metal atom group represented by Y is

[0094]

[Chemical formula 23]

It is preferable to contain

R ⁰⁵ and R ⁰⁶ are each independently a hydrogen atom,
It represents an alkyl group or an aryl group, and n ¹ represents an integer of 0 to 2.

[0097]

[Chemical formula 24]

Typical examples of the magenta coupler of the present invention are shown below.

[0099]

[Chemical 25]

[0100]

[Chemical formula 26]

[0101]

[Chemical 27]

[0102]

[Chemical 28]

[0103]

[Chemical 29]

[0104]

[Chemical 30]

[0105]

[Chemical 31]

In addition to the specific examples described above, the magenta couplers of the present invention include compounds represented by 1 to 7 described in JP-A 61-292143, page 6, JP-A-62-215172.
No. 106 to 114, exemplary compounds M-16 to 3
4, M-37 to 39, M-41 to 47, JP-A-63-2
Exemplified Compounds 1 to 64 described in JP-A-53946, pages 5 to 9, M-1 to 1 described in JP-A-2-96133, pages 12 to 14.
Compound represented by No. 5, JP-A No. 2-100048, 5-6
Exemplified compounds M-1 to 29 described on page, JP-A-3-125
No. 143, Exemplified compounds 1 to 11, 1 described on pages 19 to 32
5,16,18-28,30-41, JP-A-4-128
Exemplified Compounds 1 to 24 described on pages 3 to 5 of No. 744, Exemplified Compounds 1 to 2 described on pages 5 to 7 of JP-A-4-242249.
2 etc. can be mentioned.

The couplers of the present invention are usually silver halide 1
1 × 10 ⁻³ to 1 mol per mol, preferably 1 × 10 ⁻² to
It can be used in the range of 7 × 10 ⁻¹ mol.

In the present invention, the coupler and the alcohol of the present invention comprise at least 1 part of the light-sensitive silver halide emulsion layer.
Contained in a layer.

In order to incorporate a coupler and an alcohol into the silver halide emulsion layer, a conventionally known method, for example, a known high-boiling solvent such as dibutyl phthalate, tricresyl phosphate, etc. and butyl acetate, ethyl acetate, etc., can be used. The coupler and alcohol are dissolved in a mixed solution of low boiling point solvents or a solvent of low boiling point solvents alone or in combination, and then mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer or colloid. A method of emulsifying and dispersing using a mill or an ultrasonic disperser and then directly adding it to the emulsion can be adopted. or,
After setting the emulsified dispersion, shredded, washed with water,
This may be added to the emulsion.

In the present invention, the magenta coupler and the alcohol may be separately dispersed by the above dispersion method and added to the silver halide emulsion, but both are dissolved at the same time and dispersed and added to the emulsion. Is preferred.

The addition amount of the alcohol of the present invention is preferably 0.01 to 20 g, more preferably 0.1 to 8.0 g per 1 g of the coupler.

The alcohol of the present invention may be used in combination with a known high boiling point organic solvent, and specific examples thereof are described in JP-A No. 62-215272, pages 140 to 144 (P-1). ~ (P-96) can be mentioned.

The composition of the silver halide photographic emulsion used in the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. Although it may be contained, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

To obtain such a silver halide emulsion,
A silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used. In this case, the portion containing silver bromide in a high concentration may be either epitaxy bonded to the silver halide emulsion grains or a so-called core / shell emulsion, or may not form a complete layer and may be only partially formed. There may be only regions having different compositions. The composition may change continuously or discontinuously. The portion in which silver bromide is present at a high concentration is particularly preferably the apex of crystal grains on the surface of silver halide grains.

It is advantageous to incorporate heavy metal ions into the silver halide emulsion. Heavy metal ions that can be used for such purposes include iron, iridium, platinum,
Group 8 to 10 metals such as palladium, nickel, rhodium, osmium, ruthenium, and cobalt, and cadmium,
Group 12 transition metals such as zinc and mercury, lead, rhenium,
Examples include molybdenum, tungsten, gallium, and chromium ions. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the heavy metal ions form a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl,
Ammonia etc. can be mentioned. Among them, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion and the like are preferable.

To add a heavy metal ion to the silver halide emulsion, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound can be dissolved together with a halide salt and continuously added over the whole or part of the grain forming process.

The amount of heavy metal ions added to the silver halide emulsion is 1 × 10 ^-9 to 1 per mol of silver halide.
X10 ^-2 mol is preferable, and particularly 1 x 10 ^{-8 to} 5 x 10 ^-5.
Molar is preferred.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. US Patent 4
No. 183756, No. 4225666, JP-A-55-2
No. 6589, Japanese Examined Patent Publication No. 55-42737, and The Journal of Photographic Science (JP
photogr. Sci. ) 21, 39 (1973) and the like, particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared and used. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are preferably grains having a single shape, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains is not particularly limited, but in view of rapid processability and sensitivity, other photographic performance, etc., it is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1 μm. It is in the range of 0.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately represented as a diameter or projected area.

The grain size distribution of the silver halide grains is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0.15 or less. That is, two or more emulsions are added to the same layer. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the grain size distribution, R is the average grain size) The grain size as used herein means the diameter of a spherical silver halide grain, or its cubic shape. In the case of particles having a shape other than or spherical, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Further, as one form of the simultaneous mixing method, p described in JP-A-54-48521, etc.
It is also possible to use the Ag-controlled double jet method.

Further, JP-A Nos. 57-92523 and 57-
No. 92524, etc., an apparatus for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition apparatus arranged in a reaction mother liquor, a water-soluble silver salt and a water-soluble halogen described in German Published Patent No. 292164, etc. Device for continuously adding concentration of aqueous solution of chloride compound, Japanese Patent Publication No. 56-501
For example, an apparatus described in No. 776, etc., in which the reaction mother liquor is taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant, may be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer to be applied, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur. The addition amount of the sulfur sensitizer is preferably changed depending on the type of silver halide emulsion used and the magnitude of the expected effect, but is 5 × 10 ⁻¹⁰ per mol of silver halide.
To 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3 × 10 ^-5
A molar range is preferred.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

A reduction sensitization method may be used as a chemical sensitization method for the silver halide emulsion.

The silver halide emulsion contains a known antifoggant for the purpose of preventing fog occurring during the process of preparing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Agents can be used. Examples of preferred compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A-2-146036, page 7, lower column, and more preferred specific compounds. Are (IIa-1) to (IIa-8) and (IIb-1) to (II) described on page 8 of the publication.
b-7) compound or 1- (3-methoxyphenyl)-
Examples thereof include compounds such as 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole.

These compounds are added in the steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 per mol of silver halide
The amount is preferably about 1 × 10 ⁻² mol, and 1 × 10 ^{−5 to} 5
× 10 ^-3 mol is more preferable. When it is added to the silver halide emulsion layer in the coating liquid preparation step, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 × 10 1. ^-2 mol is more preferred.
When it is added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per 1 m ^2.
Amounts on the order of molar are preferred.

Dyes having absorption in various wavelength ranges can be used in the light-sensitive material of the present invention for the purpose of preventing irradiation and halation. Any known compound can be used. Particularly, as the dye having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, page 308 and JP-A-6-3770 can be used. The dyes described are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II), and (III) described in JP-A 1-280750, page 2, lower left column are preferred. It is preferable because it has no influence on the photographic characteristics of the photographic emulsion and there is no contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

For the purpose of improving the sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the light-sensitive material is 0.7 or more, more preferably 0.8 or more. Is more preferable.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. The compound preferably used is a compound represented by the general formula described in JP-A-2-232652.
The compound shown by II is mentioned.

The color light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes. Any known compound can be used as the spectral sensitizing dye to be used, but as the blue-sensitive sensitizing dye, BS-1 described in JP-A-3-251840, page 28
~ 8 can be preferably used alone or in combination. As the green sensitizing dye, GS-1 to -5 described on page 28 of the same publication are preferably used, and as the red sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used.
Further, when image exposure is performed by infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye.
IRS-1 to 11 described in No. 285950, pages 6 to 8 are preferably used. In addition to these infrared, red, green and blue photosensitive sensitizing dyes, the supersensitizers SS-1 to SS-9 and JP-A-5-66515 described on pages 8 to 9 of JP-A-4-285950.
It is preferable to use the compounds S-1 to 17 described in No. 15 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluoroalcohol, acetone, dimethylformamide or water and adding it as a solution, or by adding it as a solid dispersion. Good.

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating are a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specific examples thereof include A-1 to A-11 described in JP-A 64-26854. Further, a surfactant having a fluorine atom substituted in the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time after dispersion is added to the coating solution and the time after addition to the coating solution is shorter. Each is preferably within 10 hours, more preferably within 3 hours, and further preferably within 20 minutes.

An anti-fading agent is preferably used in combination with each coupler in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include the compounds of formula I described on page 3 of JP-A-2-66541.
Phenyl ether compound represented by II, JP-A-3-1-1
No. 74150, a phenolic compound represented by the general formula IIIB, JP-A-64-90445, an amine compound represented by the general formula A, JP-A-62-182741, general formulas XII, XIII, XIV and The metal complex represented by XV is particularly preferable for the magenta dye. In addition, JP-A-1
The compound represented by the general formula I ′ described in JP-A-196049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

As the anti-fading agent for magenta dye image, it is most preferable to add the image stabilizer represented by the general formula (SI) to the same emulsion layer as the magenta image forming coupler.

In the general formula (SI), R ^S1 and R ^S2
The aliphatic group represented by is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, etc., which may be branched or linear, and further substituted It may be substituted by a group.
As the substituent which may be substituted, the above-mentioned general formula (M-
Each group represented by R in I) may be mentioned.

Examples of the aromatic group represented by R ^S1 and R ^S2 in the general formula (SI) include a phenyl group and a 1-naphthyl group, which may be further substituted with a substituent. Often, the substituents have the same meanings as those mentioned above for R ^S1 .

Of the substituents represented by R ^S1 and R ^S2 in the general formula (SI), preferred are aliphatic groups, and particularly preferred are alkyl groups.

In the general formula (S-I), the substituent capable of substituting on the benzene ring represented by R ^S3 is not particularly limited, and the substituent represented by R in the general formula (M-I) is preferable. The same groups as those mentioned above can be mentioned, more preferably an alkyl group, an aryl group, an alkoxyl group or a halogen atom, and most preferably an alkyl group.

Typical examples of the image stabilizer represented by formula (S-I) are shown below.

[0149]

[Chemical 32]

[0150]

[Chemical 33]

[0151]

[Chemical 34]

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound (A'-1), described in page 10, lower left column thereof. And other compounds can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or to a silver halide emulsion layer to fog. Is preferably improved. The compound for this purpose is preferably a hydroquinone derivative, more preferably 2,
It is a dialkyl hydroquinone such as 5-di-t-octyl hydroquinone. Particularly preferred compounds are the compounds represented by the general formula II described in JP-A-4-133056, and the compounds II-1 to 14 described on pages 13 to 14 of the same.
And compound 1 described on page 17.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Preferred UV absorbers include benzotriazoles, and particularly preferred compounds include the general formulas described in JP-A 1-250944.
Compounds represented by formula III-3, compounds represented by formula III described in JP-A-64-66646, JP-A-63-1
UV-1L to 27L described in 87240, JP-A-4-27
The compounds represented by the general formula I described in 1633, the compounds represented by the general formulas (I) and (II) described in JP-A-5-165144, and the like can be mentioned.

It is advantageous to use gelatin as a binder in the light-sensitive material, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose. Hydrophilic colloids such as derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

As a hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. JP 61-24
It is preferable to use the compounds described in No. 9054 and No. 61-245153. Further, in order to prevent the growth of molds and bacteria, which adversely affect the photographic performance and image storability, it is preferable to add an antiseptic agent and an antifungal agent as described in JP-A-3-157646 to the colloid layer. Further, in order to improve the physical properties of the surface of the raw sample of the light-sensitive material or the sample after processing, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer. .

Any material may be used as the support for the color light-sensitive material of the present invention. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet,
Polypropylene, which may contain a white pigment, polyethylene terephthalate support, baryta paper and the like can be used. Above all, a support having a waterproof resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, fine silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, oxidation Examples thereof include zinc, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the support is preferably 13% by weight or more, more preferably 15% by weight or more in order to improve the sharpness.

The degree of dispersion of the white pigment in the water resistant resin layer of the paper support which is preferably used can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as a coefficient of variation described in the publication. Further, the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm.
It is preferable that the thickness is less than or equal to μm because the effect that the glossiness is good can be obtained. Further, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after the treatment,
It is preferable to add a slight amount of a bluing agent or a reddishing agent such as ultramarine or an oil-soluble dye.

The light-sensitive material of the present invention is, if necessary, subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the surface of the support and then directly or undercoat layer (adhesiveness of surface of support, antistatic property, It may be applied via one or more subbing layers) to improve dimensional stability, abrasion resistance, hardness, antihalation, friction properties and / or other properties.

At the time of coating the silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

To form a photographic image using the color light-sensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the light-sensitive material to be printed, After the image is once converted into digital information, the image may be imaged on a CRT (cathode ray tube), and the image may be imaged and printed on a photosensitive material to be printed. Printing may be performed by changing the intensity of laser light and scanning.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material for forming an image for direct viewing. Examples thereof include color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for display, and a photosensitive material for color proof. In particular,
It is preferably applied to a light-sensitive material having a reflective support.

Known compounds can be used as the aromatic primary amine color developing agent used. The following compounds can be mentioned as typical examples.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-6: 4- Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline CD-7: 4-amino-3- (β-methanesulfonamido) ethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD- 9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-Ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-(Γ-Hydroxypropyl) aniline In the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0, and more preferably 9.8. Used in the range of 12.0.

The processing temperature for color development is preferably 35 ° C to 70 ° C. It is preferable that the temperature is higher because the treatment can be performed for a shorter time, but it is preferably not so high in view of the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C to 60 ° C.

Conventionally, the color development time is generally 3 minutes 30.
It is carried out in about 2 seconds, but from the viewpoint of rapid processing, it is preferably within 40 seconds, more preferably within 25 seconds.

To the color developing solution, known developer component compounds can be added in addition to the above color developing agent. Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative,
A chelating agent or the like is used.

The photographic material is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed.
Further, a stabilizing treatment may be performed as an alternative to the water washing treatment.
As a developing processing device used for developing the photosensitive material, even a roller transport type in which the photosensitive material is sandwiched between rollers arranged in a processing tank and conveyed, an endless belt system in which the photosensitive material is fixed to a belt and conveyed May be, but the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the processing solution is sprayed, and the processing solution is impregnated. A web method using contact with a carrier, a method using a viscous treatment liquid, and the like can also be used. When processing a large amount, it is usually a running process using an automatic processor, at this time, the smaller the replenishing amount of the replenisher is, the better.
The most preferable treatment form from the viewpoint of environmental suitability is to add the treatment agent in the form of tablets as a replenishing method, and the method described in Kokai Giho 94-16935 is the most preferable.

[0171]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp weighing 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed was laminated to prepare a reflective support.

After subjecting this reflective support to corona discharge treatment,
On top of the gelatin undercoat layer, each layer having the constitution shown in Table 1 and Table 2 was coated to prepare a multilayer color light-sensitive material sample 101. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34.
g, (ST-5) 3.34 g, stain inhibitor (HQ-
1) 0.34 g, image stabilizer (A) 5.0 g, high boiling point organic solvent (DBP) 3.33 g and (DNP) 1.67 g
Ethyl acetate (60 cc) was added to and dissolved, and this solution was added to 20
% WC (SU-1) 7 cc in 220% 10% gelatin aqueous solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared so as to have the coating amounts shown in Tables 1 and 2 similarly to the coating solution for the first layer.

Further, as a hardener (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension. Furthermore, the total amount of the antifungal agent (F-1) is 0.04 g / m ² in each layer.
Was added.

[0177]

[Table 1]

[0178]

[Table 2]

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: sulfosuccinate di (2-ethylhexyl) sodium salt SU-3: sulfosuccinate di (2,2,3,3,4) , 4,
5,5-octafluoropentyl) .sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-Di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A: p-octylphenol

[0180]

[Chemical 35]

[0181]

[Chemical 36]

[0182]

[Chemical 37]

[0183]

[Chemical 38]

(Preparation of blue-sensitive silver halide emulsion) 40 ° C.
In 1 liter of a 2% gelatin aqueous solution kept at
(Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were added to pAg = 8.0, pH. = 5.5 at the same time over the course of 180 minutes. At this time, pAg is controlled by the method described in JP-A-59-45437.
The control of H was performed using sulfuric acid or sodium hydroxide aqueous solution.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 cc (Solution B) Silver nitrate 10 g Water was added to 200 cc (Solution C) K ₂ IrCl ₆ 4 × 10 ⁻⁸ mol Sodium chloride 102.7 g K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Water was added to 600 cc (D liquid) Silver nitrate 300 g Water was added to 600 cc After the addition was completed, Kao Atlas Co., Ltd. Demol N 5 % Aqueous solution and magnesium sulfate 20% aqueous solution for desalting, and then mixed with gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, variation coefficient of particle size distribution 0.07, silver chloride content 99.
5 mol% of monodisperse cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (A liquid) and (B liquid) and the addition time of (C liquid) and (D liquid) were changed.
A monodisperse cubic emulsion EMP-1B having an average grain size of 0.64 μm, a variation coefficient of the grain size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained in the same manner as in Example 1.

The above-mentioned EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after optimal chemical sensitization, the sensitized EMP-1 and EMP-1B were mixed in a silver ratio of 1: 1 to prepare a blue-sensitive silver halide emulsion (Em-B). Got

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (green-sensitive silver halide emulsion) Preparation) (Solution A) and (Solution B)
The average particle size is 0.40μ in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained. A monodisperse cubic emulsion EMP-2 having an average grain size of 0.38 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% in the same manner as EMP-2.
B was obtained.

The above EMP-2 was optimally chemically sensitized at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after optimal chemical sensitization, the sensitized EMP-2 and EMP-2B were mixed in a silver ratio of 1: 1 to prepare a green-sensitive silver halide emulsion (Em-G). Got

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (Solution A) and (Solution B)
The average particle size is 0.40μ in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained. A monodisperse cubic emulsion EMP-3 having an average grain size of 0.38 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% in the same manner as EMP-3.
B was obtained.

The EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after optimal chemical sensitization, the sensitized EMP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to prepare a red-sensitive silver halide emulsion (Em-R). Got

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX Supersensitizer SS- 12 × 10 ⁻³ mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0193]

[Chemical Formula 39]

[0194]

[Chemical 40]

The magenta coupler of the third layer in Sample 101 was changed as shown in Table 3, and the high boiling point organic solvent DNP was used.
Also, Samples 102 to 112 having the same constitution except that the alcohol of the present invention shown in Table 3 and the comparative HBS were used were prepared.

The high boiling point organic solvent of the present invention shown in Table 3 was prepared by using triethylamine as a catalyst as in the synthesis (2) of A-1 in the above [Synthesis example-2].

Each sample was subjected to optical wedge exposure in the usual way and then processed according to the following development processing steps.

[0198]       Treatment process Treatment temperature Time Replenishment amount       Color development 38.0 ± 0.3 ° C 45 seconds 80cc       Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds 120cc       Stabilization 30-34 ° C 60 seconds 150cc       Dry 60-80 ℃ 30 seconds The composition of the developing solution is shown below.

Color developing solution tank solution and replenishing solution tank solution replenishing solution pure water 800 cc 800 cc triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0g 2.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter. = 1
Adjust the pH of the replenisher to 0.10 and adjust the pH of the replenisher to 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Water is added to bring the total volume to 1 liter, and pH is adjusted to 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

With respect to the treated color-developing sample, the color-developing property, the light resistance, and the color mixture after storage of the raw sample were evaluated as follows. The results are shown in Table 3.

<Coloring property> The blue light and green light reflection densities (D _B max, D _G max) of the maximum density portion of each sample were measured by PDA-
It was measured using a 65 densitometer (manufactured by Konica Corporation) and used as a standard for color development.

<Light resistance> Each of the samples was measured with a PDA-65 densitometer for the green light reflection density before and after exposure to sunlight for 3 months using an underglass outdoor exposure table. The degree of fading due to light (fading rate) was determined as follows.

Fading rate (%) = (D ₀ −D / D ₀ ) × 100 where D ₀ = concentration before light exposure (at 1.0) D = concentration after light exposure <color mixture> Each raw sample 16 at 55 ° C and 40% RH
After standing for a period of time, blue light wedge exposure was applied, and the green light reflection density ( _{DG / B} ') at the point where the blue light reflection density of 1.0 was measured in each of the samples processed in the development processing step was measured. on the other hand,
The green light reflection density ( _{DG / B} ) of each raw sample at the point where the blue light reflection density was 1.0 was measured when each raw sample was similarly exposed and developed without storage, and the difference (ΔD _{G / B} = (D _{G / B} 'after storage)-(D _{G / B} before storage)) was used as a standard for color mixing.

[0206]

[Table 3]

HBS-1: 2-hexyldecyl alcohol HBS-2: C ₈ H ₁₇ CH = CH (CH ₂ ) ₈ OH (EP
High-boiling point organic solvent described in 486,929) HBS-3: dodecyl alcohol (JP-A-53-134)
High boiling point organic solvent described in No. 14) Samples 105, 106, 109 and 112 of the present invention were all excellent in color development and light resistance, and it was found that color mixing after storage of raw samples was small.

Example 2 The magenta coupler in the third layer of Sample 101 prepared in Example 1 was replaced with the compound shown in Table 4 in an equimolar amount, and the dye image stabilizer and the high-boiling organic solvent were added in the compound shown in Table 4 and addition. The samples 201-220 which changed into the quantity were created.

As the high-boiling point organic solvent of the present invention in Table 3, those which were synthesized by using triethylamine as a catalyst as in the synthesis (2) of A-1 in [Synthesis example-2] were used.

The obtained sample was exposed to light in the same manner as in Example 1.
After processing, color development and light resistance were measured.

The light resistance was evaluated from the fading rate (%) when each sample was irradiated with a xenon fade meter of 70,000 lux for 400 hours.

Further, in order to evaluate the degree of bleeding of the dye image at high temperature and high humidity, each sample was contact-exposed to a sharpness evaluation pattern with white light and then developed under the same conditions as in Example 1. Create a sample, and use this sample at 85 ℃ and 60% RH
It was left for 14 days under the conditions.

The degree of bleeding of each sample in this state was visually judged.

[0214] A: No bleeding B: Some bleeding occurred C: Bleeding occurred D: Extreme bleeding occurred The above results are shown in Table 4.

[0215]

[Table 4]

[0216]

[Chemical 41]

As is clear from Table 4, when the alcohol compound of the present invention is used as a high boiling organic solvent for a magenta coupler, the total number of carbon atoms of the substituents of R ^a1 and R ^a2 in the general formula (A) is It was found that when it is 12 or more and 36 or less, the bleeding of the dye image under high temperature and high humidity can be effectively suppressed.

When the carbon number was less than 12, bleeding of the cyan dye was observed, and when the carbon number was 37 or more, the bleeding of the magenta dye was observed. This tendency was more remarkable in the samples 211 to 220 in which the amount of the high boiling point organic solvent added was increased, but the total carbon number of R ^a1 and R ^a2 was 12 or more and 3 or more.
Samples 215 to 2 using an alcohol compound of 6 or less
In 18 no dye bleeding was observed even in this case.

A sample using an alcohol compound having a substituent at the 2-position of the benzene ring represented by the general formula (A) (205
~ 208,215-218) are samples (209,210,21) using an alcohol compound having no substituent at the 2-position.
It has been found that the light resistance is improved more than that of (9,220).

Further, in the sample using the coupler corresponding to the general formula (MA), remarkable improvement in light resistance was observed.

Example 3 The magenta coupler of the third layer in Sample 101 prepared in Example 1 was replaced with the compound shown in Table 5 in an equimolar amount, and the dye image stabilizer and the high-boiling organic solvent were added in the compound shown in Table 5 and addition. Samples 301 to 320 which were changed in amount were prepared.

The high-boiling point organic solvent of the present invention shown in Table 3 was prepared by using triethylamine as a catalyst as in the synthesis (2) of A-1 in [Synthesis example-2].

The obtained sample was exposed and processed in the same manner as in Example 2, and the light resistance was measured under the same conditions as in Example 2.

[0224]

[Table 5]

As is clear from Table 5, the light resistance is further improved by combining the alcohol of the present invention with the image stabilizer represented by the general formula (SI).

Further, a magenta coupler is represented by the general formula (M-
By using the coupler corresponding to A), the light resistance is significantly improved, and the coupler, the image stabilizer represented by the general formula (SI) and the benzene ring represented by the general formula (A) are combined. It was found that the light resistance was remarkably improved when three of the alcohol compounds having a substituent at the 2-position were used in combination.

It was also clarified that the effect of the alcohol of the present invention is almost the same even when a known high-boiling point organic solvent (DBP, BBP, DNP) is used in combination.

[0228]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide color which is excellent in the color developability of the coupler, the light fastness of the formed dye image, and the bleeding of the dye image under the conditions of high temperature and high humidity is improved. It was possible to provide a photographic light-sensitive material.

─────────────────────────────────────────────────── --Continued front page (56) Reference JP-A-7-84350 (JP, A) JP-A-52-46816 (JP, A) JP-A-7-152129 (JP, A) JP-A-6- 266076 (JP, A) JP 7-175186 (JP, A) JP 6-230534 (JP, A) JP 8-248596 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/388 G03C 7/00 520 G03C 7/38 G03C 7/392

Claims (4)

(57) [Claims] 1. A silver halide color photographic light-sensitive material comprising at least one alcohol compound represented by the following general formula (A). [Chemical 1] [Wherein R ^a1 is an alkyl group, an aryl group, an alkenyl
Group, alkoxyl group, aryloxy group, acyl group,
Silamino group, carbamoyl group, alkoxycarbonyl
Group, aryloxycarbonyl group, cyano group, sulfoni
Represents a group, a hydroxyl group or a halogen atom, R ^a2 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy
Syl group, aryloxy group, acyl group, acylamino
Group, carbamoyl group, alkoxycarbonyl group, aryl
Ruoxycarbonyl group, cyano group, sulfonyl group, hydroxy
Represents a group or a halogen atom , and m represents an integer of 0 to 4.
When m is 2 or more, a plurality of R ^a2 may be the same or different, and the total carbon number of R ^a1 and R ^a2 is 12 or more and 36 or less. ] 2. An alcohol compound represented by the general formula (A) and at least one magenta image forming coupler represented by the general formula (MI) are contained in the same silver halide emulsion layer. The silver halide color photographic light-sensitive material according to claim 1, wherein [Chemical 2] [In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ] 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the magenta image forming coupler is represented by the following general formula (MA). [Chemical 3] [In the formula, R represents a hydrogen atom or a substituent, L represents a divalent linking group, R ^m1 represents a substituent capable of substituting on the benzene ring, and Y represents a 5-membered or 6-membered hetero group together with a nitrogen atom. It represents a group of non-metal atoms necessary for forming a ring, and l represents an integer of 0 to 4. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. ] 4. The image stabilizer according to claim 1 , 2 or 3, wherein an image stabilizer represented by the following general formula (SI) is contained in the emulsion layer in which the magenta image forming coupler is present. Silver halide color photographic light-sensitive material. [Chemical 4] [In the formula, R ^s1 and R ^s2 each independently represent a hydrogen atom, an aliphatic group, or an aromatic group, R ^s3 represents a substituent capable of substituting on the benzene ring, and k represents an integer of 0 to 4] . When k is 2 or more, a plurality of R ^s3 may be the same or different, and when a plurality of R ^s3 are adjacent to each other, they may be condensed with each other to form a ring. However, R ^s1 and R ^s2 are not hydrogen atoms at the same time. ]