JPH09197634A - Photographic material for halogenated silver color photograph - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain the low fog and while to improve the sensitivity, and to improve the color reproducibility and the aging shelf life of the photographic material for a long time by including two or more kinds of specified compound. SOLUTION: One kind of the compound expressed with a formula I and one kind of the compound expressed with a formula II are included. In the formula I, R<11> means hydrogen atom or a group, which can be removed by the reaction with the oxide material of the aromatic first leveled amine color developing main material, and R<12> means aryl group, and R<13> means a substituent group. n1 mans a numeric among 1-5, and in the case where n1 is 2 or more, R" can be the same one or a different one. In the formula II, a means a magenta coupler residual group, and R<21> means a substituent group, and at least one of them means alkoxyl group having two or more carbon. n2 means a numeric among 1-5, and in the case where n2 is 2 or more, R21 can be the same one or a different one. Sensitivity can be thereby improved, maintaining the low fog.

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 (hereinafter, also simply referred to as a light-sensitive material), more specifically, it can achieve high sensitivity while maintaining low fog and color reproducibility. And a silver halide color photographic light-sensitive material excellent in long-term storage stability of the light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, conventional silver halide color photographic light-sensitive materials are exposed to light and then subjected to color development processing to react with an oxidation product of a para-phenylenediamine color developing agent and a coupler to form a dye, thereby forming a color image. Is formed.

Generally, in this photographic method, color reproduction by a subtractive color method is used to form yellow, magenta and cyan color images.

As the magenta dye-forming coupler (magenta coupler), pyrazolone type, pyrazolinobenzimidazole type, indanone type and the like are known, and various 5-pyrazolone derivatives have been widely used.

Examples of the substituent at the 3-position of the 5-pyrazolone ring of the 5-pyrazolone derivative include an alkyl group, an aryl group, an alkoxy group described in US Pat. No. 2,439,098, and 2,369,489. Same as 2,600,788
And the like, and the ureido group described in JP-A-3,558,319 and the like are used. However, the above-mentioned couplers have low coupling activity with the oxidized product of the developing agent and it is difficult to obtain a high density magenta color image, and the secondary absorption in the blue light region of the magenta color image obtained by color development is large. There were drawbacks such as poor cutting on the long wave side of absorption.

In addition, 3-described in US Pat. Nos. 2,311,081, 3,677,764, 3,684,514, British Patents 956,261, 1,173,513, etc. The anilino-5-pyrazolone type coupler has advantages such as high coupling activity, high color development, and small unnecessary absorption in the red light region. However, these conventionally known 3-anilino-5-pyrazolone type couplers have a main absorption in a relatively short wave, and therefore when used in a color negative silver halide photographic light sensitive material, the print color reproducibility is deteriorated.

Various investigations have been made for the purpose of improving the above-mentioned drawbacks. For example, JP-A-52-8002.
No. 7 has 1-pentahalogenophenyl-3-anilino-
5-Pyrazolone couplers have been proposed. The coupler has high coupling activity, high color development, and good spectral characteristics, but it has a drawback that the color development is deteriorated by storage in the presence of formalin gas. Further, it cannot be said that the demand for high sensitivity of the light-sensitive material is increasing year by year.

On the other hand, as described above, the conventional silver halide color photographic light-sensitive material undergoes color development processing, whereby the oxidation product of the para-phenylenediamine type color developing agent reacts with the coupler to produce yellow, magenta and cyan. Form a color image. However, these yellow, magenta, and cyan dyes do not always have ideal absorption characteristics. For example, a magenta dye image usually absorbs a small amount of blue light in addition to the required absorption of green light, which causes distortion in color reproducibility. In order to eliminate such distortion of color reproducibility, when the coupler does not undergo a coupling reaction with an oxidant of an aromatic primary amine color developing agent,
It has been practiced in color negative film systems to use couplers such as yellow or magenta, the former being the so-called colored magenta coupler and the latter being the so-called colored cyan coupler.

The automatic masking method using such a colored coupler is described in, for example, J. Photo. So
c. Am. , 13, 94 (1947), J. Opt. S
oc. Am. 40, 166 (1950), or J.
Am. Chem. Soc. , 72.1533 (195
0) and the like.

As a colored magenta coupler having a main absorption in the blue light region, US Pat. Nos. 2,428,054 and 2,449,966 disclose 1-phenyl-3-acylamino-4-phenylazo-5-pyrazolone. about,
No. 2,763,552 has a 4-methoxyallylazo group, and No. 2,983,608 has 1-phenyl-3-anilino-4-phenylazo-.
Regarding 5-pyrazolone, U.S. Pat. Nos. 3,519,429 and 3,615,506 have naphthylazo groups, and British Patent 1,044,778 has water-soluble groups. 3,476,56
4, JP-A-49-123625, JP-A-49-1314.
48 and 54-52532, those having a hydroxyphenylazo group, 52-42121
No. 53-63016, those having an acylaminophenylazo group, and Nos. 52-102723, those having a substituted alkoxyphenylazo group.
Nos. 1 and 2 respectively describe those having a thiophenylazo group.

These colored magenta couplers, for example, have a small molar extinction coefficient and thus require a large amount of addition, it is difficult to adjust the main absorption to a preferable region, and the developing activity is low, so that the masking effect is small. The development activity is high, but fogging is likely to occur, and the stability to light, heat, and humidity is low.Therefore, there is nothing satisfactory, and the performance is barely maintained by using several types in combination. It is the current situation.

In particular, with the adoption of magenta couplers having high coupling activity in recent years, high coupling activity has been required also for colored magenta couplers. In such a system, good color reproducibility is obtained. Using a sufficient amount of colored magenta couplers to increase emulsion fog,
There was a problem of impairing photographic performance. In addition, the fog rise width is also a serious problem in the long-term storage of the light-sensitive material.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photograph which can achieve high sensitivity while maintaining low fog and is excellent in color reproducibility and long-term storage stability of a light-sensitive material. To provide a light-sensitive material.

[0014]

The above object of the present invention is to contain at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. And a silver halide color photographic light-sensitive material.

[0015]

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[In the formula, R ¹¹ is a hydrogen atom or aromatic 1
Represents a group capable of splitting off upon reaction with an oxidation product of a primary amine color developing agent. R ¹² represents an aryl group. R ¹³ represents a substituent, and n ₁ represents an integer of ₁ to 5. R when n ₁ is 2 or more
¹³ may be the same or different. ]

[0017]

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[In the formula, A represents a magenta coupler residue. R ²¹ represents a substituent, and at least one is an alkoxyl group having 2 or more carbon atoms. n ₂ represents an integer of 1 to 5, and when n ₂ is 2 or more, R ²¹ may be the same or different. Hereinafter, the present invention will be described in detail.

First, the general formula [I] will be described. In the general formula [I], R ¹¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. R ¹¹ is preferably a group capable of splitting off by a reaction with an oxidation product of an aromatic primary amine color developing agent, and more preferably an arylthio group, from the viewpoints of saving silver and improving harmful gas resistance.

R ¹² represents an aryl group such as phenyl, pentachlorophenyl, 2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 2,4-
Dichlorophenyl group, 2,6-dichloro-4-methylphenyl group, 2,6-dichloro-4-methanesulfonylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2,6-dichloro-4-morpholinosulfonylphenyl group, 2,4-dichloro-6-methoxyphenyl group, 2,
4-dichloro-6-methylphenyl group and the like can be mentioned.

When the compound of the present invention is used in a color negative film, R ¹² is a pentachlorophenyl group and 2,6- is preferred in that the spectral absorption wavelength of a color dye obtained by reacting with an oxidized form of a color developing agent is preferable. Preferred are a dichloro-4-methanesulfonylphenyl group, a 2,6-dichloro-4-cyanophenyl group, and a 2,6-dichloro-4-morpholinosulfonylphenyl group.

R ¹³ represents a substituent, for example, chlorine, bromine,
Halogen atoms such as fluorine, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy group, 2,6
-Benzoylamino group such as dichlorobenzoylamino group, 2,6-dimethoxybenzoylamino group, alkylsulfonyl group such as hexadecylsulfonyl, acylamino group such as acetylamino group, cyano group, nitro group, carboxyl group, amino group, Examples thereof include an alkoxycarbonyl group such as an ethoxycarbonyl group, an alkyl group such as a methyl group, an ethyl group, and an isopropyl group, but needless to say, a monovalent substituent other than the above may be used.

It is preferable that at least one atom or group of R ¹³ is a halogen atom or an alkoxy group in terms of color development and spectral absorption wavelength.

Specific examples of the compound represented by the general formula [I] of the present invention are shown below, but the present invention is not limited to these.

[0025]

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[0026]

[Chemical 6]

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The compound represented by the general formula [I] according to the present invention (hereinafter, also referred to as magenta coupler represented by the general formula [I]) may be added to the photosensitive layer, and it is non-photosensitive. It may be added to the layer. In order to introduce the magenta coupler represented by the general formula [I] according to the present invention into a silver halide color photographic light-sensitive material, it may be added by being dispersed by various known dispersion methods described below. A mixture of a high boiling point solvent such as dibutyl phthalate and tricresyl phosphate and a low boiling point solvent such as butyl acetate and ethyl acetate, or only a low boiling point solvent, is used alone or in combination with the compound represented by the general formula [I]. , Then mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed using a high-speed rotary mixer, colloid mill or ultrasonic disperser, and then added directly to the silver halide emulsion. can do. Alternatively, the above emulsified dispersion may be set, shredded, washed with water, and then added to the silver halide emulsion.

Next, the general formula [II] will be described.

In the general formula [II], R ²¹ represents a substituent, at least one of which is an alkoxyl group having 2 or more carbon atoms, but when n ₂ is 2 or more, other substituents may be represented. good.

Specific examples of the alkoxyl group having 2 or more carbon atoms include an ethoxy group, an n-pyropyroxy group, an isopropyloxy group, a methoxyethoxy group and a chloroethoxy group.

Other substituents include, for example, methoxy group, phenoxy group, nitro group, sulfo group, halogen atom (fluorine atom, chlorine atom, iodine atom, etc.), amino group (amino group, methylamino group, dimethylamino group). , Diethylamino group, diisopropylamino group, etc., cyano group, oxycarbonyl group (ethoxycarbonyl group, phenoxycarbonyl group, etc.), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), alkyl group (methyl group, ethyl group, etc.) , An aryl group (phenyl group,
4-methoxyphenyl group etc.) and the like.

The alkoxyl group represented by R ²¹ is preferably an ethoxy group from the viewpoint that fog is small and the molecular weight of the colored magenta coupler is appropriately suppressed.

The substituent R ²¹ represents are points maximum wavelength of the blue portion mask absorption is proper, it is preferably an alkoxyl group, it is more preferably R ²¹ is a two alkoxy groups.

When R ²¹ is two alkoxyl groups,
These alkoxyl groups are preferably substituted at the 3 and 4 positions with respect to the azo group from the viewpoint that the maximum wavelength of mask absorption in the blue portion is suitable.

The magenta coupler residue represented by A is usually referred to as a photographic magenta coupler, and in the general formula [II], the azo group is the active site of the magenta coupler (aromatic primary amine color developing agent). Is bound to the site where the oxidant of is coupled.

As the magenta coupler residue represented by A, for example, 1-phenyl-3-acylamino-5-pyrazolone compound, 1-phenyl-3-anilino-5-pyrazolone compound, 1-phenyl-3-ureido-5 is used. -Pyrazolone compounds, pyrazolotriazole compounds, pyrazolobenzimidazole compounds, thioindoxyl compounds,
Examples thereof include a cyanoacetyl compound and a pyrimidazolone compound. However, a 1-phenyl-3-anilino-5-pyrazolone compound or a 1-phenyl-3-acylamino-5-pyrazolone is preferred in that the coupling rate with an oxidized developing agent is high. Preferably, it is a compound.

In addition, the 1-pentachlorophenyl-3-anilino-5-pyrazolone compound, or 1-pentachlorophenyl-3-anilino-5-pyrazolone compound, or 1-
More preferably, it is a (2,4,6-trichloro) phenyl-3-acylamino-5-pyrazolone compound.

Specific examples of the compound represented by the general formula [II] of the present invention (hereinafter, also referred to as the colored magenta coupler represented by the general formula [II]) of the coupler residue represented by "A" Examples are shown, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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Specific examples of the colored magenta coupler represented by the general formula [II] of the present invention are shown below.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The colored magenta coupler represented by the general formula [II] according to the present invention may be added to the photosensitive layer,
It may be added to the non-photosensitive layer. The general formula [I
In order to introduce the colored magenta coupler represented by the formula I) into the silver halide color photographic light-sensitive material, it can be added by being dispersed by various known dispersion methods described below, like the compound represented by the formula [I]. Good, for example, well-known dibutyl phthalate, a mixture of a high boiling point solvent such as tricresyl phosphate and butyl acetate, a low boiling point solvent such as ethyl acetate or only a low boiling point solvent, represented by the general formula [II] After dissolving the above compounds alone or in combination, they are mixed with a gelatin aqueous solution containing a surfactant and then emulsified and dispersed using a high speed rotary mixer, colloid mill or ultrasonic disperser, and then in a silver halide emulsion. It is possible to employ a method of directly adding to. Alternatively, the above emulsified dispersion may be set, shredded, washed with water, and then added to the silver halide emulsion.

The magenta coupler represented by the above general formula [I] and the colored magenta coupler represented by the above general formula [II] may be added to the same layer or different layers. The properties may be the same or different, but they are preferably added to the same color-sensitive layer. When they are added to the same layer, they may be separately dispersed and added, or may be simultaneously mixed and dispersed and added.

When the colored magenta coupler represented by the above general formula [II] is used, the amount thereof is arbitrary, but preferably the amount of the magenta coupler of the photosensitive material per unit area is ( The amount of the colored magenta coupler (excluding the colored magenta coupler) is 1 to 200 mol%, more preferably 5 to 100 mol%.

In the present invention, the following general formula [II
By containing at least one compound represented by I], the object of the present invention can be achieved more efficiently.

[0058]

[Chemical 21]

In the formula, R ³¹ and R ³² represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, and R ³³ , R ³⁴ and R ³⁵ represent a substituent.

R ³¹ and R ³² , R ³³ and R ³⁴ , and R ³⁴ and R ³⁵ may form a ring, respectively.

In the general formula [III], the substituents represented by R ³¹ and R ³² are, respectively, a hydrogen atom and an alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group). , N-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n
-Octyl group, n-dodecyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (For example, a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group,
Furyl group, prolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.). These substituents may themselves have a substituent.

In the general formula [III], R ³³ , R ³⁴ and R ³⁵
The substituent represented by is an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group,
tert-butyl group, n-pentyl group, cyclopentyl group,
n-hexyl group, cyclohexyl group, n-octyl group,
n-dodecyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, pyridyl) Group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, prolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., halogen atom (for example, chlorine atom) , A bromine atom, an iodine atom, a fluorine atom, etc.), an alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyl) Oxy group, n-dodecyloxy group, etc.) Si group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group Etc.), an aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), a sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino) Group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group) Group,
Dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2- Pyridylaminosulfonyl group), ureido group (for example,
Methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, n-octylureido group, n-dodecylureido group, phenylureido group,
A naphthylureido group, a 2-pyridylaminoureido group, etc., an acyl group (for example, an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, an n-pentylcarbonyl group, a cyclohexylcarbonyl group, an n-octylcarbonyl group, a 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group) , A cyclohexylaminocarbonyl group, an n-dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc., an amide group (for example, Acetamide group, an ethylcarbonyl group, a propyl carbonyl amino group, n- pentyl carbonylamino group, a cyclohexylcarbonyl group, a 2-ethylhexyl carbonylamino radical, n
-Octylcarbonylamino group, dodecylcarbonylamino group, benzoylamino group, naphthylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group) , Dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group,
Dimethylamino group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, carboxyl group, hydroxyl Group, sulfo group, hydrogen atom and the like.
These groups can be substituted by the alkyl groups represented by R ³¹ and R ³² , and the same groups as those shown as the substituents for the alkyl group.

Examples of the ring formed by R ³¹ and R ³² include a piperidine ring, a pyrrolidine ring, a morpholine ring, a pyrrole ring, a piperazine ring and a thiomorpholine ring. As the ring formed by R ³³ and R ³⁴ or R ³⁴ and R ³⁵ ,
For example, a benzene ring, a thiophene ring, a furan ring, a pyrrole ring and the like can be mentioned.

Specific examples of the compound represented by the general formula [III] preferably used in the present invention are shown below, but the invention is not limited thereto.

[0065]

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The general formula [II] preferably used in the present invention
The compound represented by I] is preferably added in the range of 1% by weight or more and 300% by weight or less with respect to the magenta coupler represented by the general formula [I]. More preferably, it is added in an amount of 5% by weight or more and 150% by weight or less. The layer to be added may be the same as or different from the layer to which the magenta coupler represented by the general formula [I] is added, but is preferably added to the same layer.

The compound represented by the general formula [III], like the magenta coupler represented by the general formula [I], can be introduced into the light-sensitive material by various known dispersion methods described later. The compound represented by the general formula [III] may be mixed and dispersed at the same time as the magenta coupler represented by the general formula [I] and added to the light-sensitive material, or may be separately dispersed from the magenta coupler and added. It is good, but it is desirable to mix and disperse them at the same time.

In the silver halide color photographic light-sensitive material of the present invention, the order of laminating the respective photosensitive layers is not particularly limited, and various laminating orders can be adopted according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer in order from the support side. Can be laminated.

The photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivity. For the purpose of improving color reproduction, a fourth or higher color-sensitive photosensitive layer may be provided in addition to the three layers of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer. The layer constitution using the fourth or higher color-sensitive photosensitive layer is described in JP-A-61-34541, JP-A-61-201245, JP-A-61-198236, JP-A-62-160448 and the like. These can be referred to.

In this case, the fourth or more photosensitive layers having color sensitivity may be arranged at any laminating position. Also, the fourth
Alternatively, the photosensitive layer having higher color sensitivity may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the above-mentioned photosensitive layers and as the uppermost layer and the lowermost layer.

These non-photosensitive layers are provided in JP-A-61-43.
748, 59-113438, 59-1134
Couplers, DIR compounds, and the like described in JP-A Nos. 40-61, 61-20037, and 61-20038 may be contained, and a color-mixing inhibitor may be contained as usually used. These non-photosensitive layers are RD3
08119, p. 1002, section VII-K, and may be an auxiliary layer such as a filter layer or an intermediate layer.

Examples of the layer structure that can be adopted in the light-sensitive material of the present invention include the forward layer, the reverse layer and the unit structure described in RD308119, page 1002, item VII-K.

When there are two light-sensitive layers having the same color sensitivity, these light-sensitive layers may be the same, or a high-sensitivity emulsion layer as described in West German Patent 923,045, It may have a two-layer structure of a low-sensitivity emulsion layer. In this case, it is usually preferable that the layers are arranged so that the sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the emulsion layers. Also, JP-A-57-112
No. 751, No. 62-200350, No. 62-2065
As described in JP-A Nos. 41 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, the low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green sensitive layer (GH) / Low sensitivity green sensitive layer (GL) /
Installed in the order of high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH Can be mentioned.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / from the side farthest from the support.
They can be arranged in the order of RH / GL / RL. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer / G
They may be arranged in the order of L / RL / GH / RH.

As described in JP-B-49-15495, three photosensitive layers having different sensitivities and having the same color sensitivity are used.
Layers can be used. These three layers are arranged as a high-speed emulsion layer in the upper layer, a medium-speed emulsion layer in the middle layer, and a low-speed emulsion layer in the lower layer. Further, as described in JP-A-59-202264, a medium-speed emulsion layer, a high-speed emulsion layer, and a low-speed emulsion layer may be arranged in this order from the side away from the support.

In the case of comprising three layers having different sensitivities, the order of laminating these three layers is arbitrary. For example, the laminating order includes a high sensitivity emulsion layer, a low sensitivity emulsion layer and an intermediate sensitivity emulsion layer. Order, or low-speed emulsion layer, medium-speed emulsion layer, high-speed emulsion layer and the like. Further, four or more photosensitive layers having the same color sensitivity can be provided, and in this case, the arrangement is arbitrary as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

The silver halide emulsion used in the present invention is, for example, RD17643, pages 22 to 23 (December 1978).
"I. Emulsion preparationan
dtypes), pp. 18716, 648, Grafkides, Physics and Chemistry of Photography, published by Paul Montell (P.
Glafkids; Chemic et Physi
que Photographie, Paul M
Ottel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo.
optic Emulsion Chemist
RY, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al; Makin).
g and Coating Photographi
c Emulsion, FocalPress, 196
It can be prepared using the method described in 4). U.S. Pat. Nos. 3,574,628 and 3,663;
Monodisperse emulsions described in, for example, 5,394 and British Patent 1,413,748 are also preferable.

In the silver halide emulsion, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include the aforementioned RD17643, pp. 23-27, 1871.
6,648-651 and 308119,996 II
Various compounds described in sections IA to 1011, section XX-B can be used.

In order to prevent the deterioration of the photographic performance due to formaldehyde gas, the light-sensitive material is described in US Pat.
It is preferable to add a compound which can react with formaldehyde described in 1,987 or 4,435,503 and can be immobilized.

The silver halide emulsion used in the present invention preferably contains silver iodobromide containing an average silver iodide content of 4 to 20 mol%, and an average silver iodide content of 5 to 15 mol%. It is particularly preferable to contain silver iodobromide containing Further, silver chloride may be contained as long as the object of the present invention is not hindered.

In the present invention, in the case of using a silver halide emulsion containing silver halide grains formed by deviating the development starting point to a specific position on the surface of the silver halide grain or in the vicinity thereof, the other silver halide emulsion is used. , Those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect or a composite form thereof.

The grain size of the silver halide grains other than those mentioned above may be fine grains of about 0.2 μm or less, large size grains with a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. .

The silver halide emulsion used in the present invention is
Research Disclosure (RD) 308
119 can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine structure 993I-A item Manufacturing method 993I-A item and 994E item Crystal habit Normal crystal 994E item Twin crystal 994E item Epitaxial 994E item Halogen composition uniform 993I- Item B Non-uniform 993I-B item Halogen conversion 994I-C item Halogen substitution 994I-C item Metal-containing 995I-D item Monodisperse 995I-F item Solvent addition 995I-F item Latent image forming position surface 995I-G item Inner surface 995I -G Item Applied Sensitive Material Negative 995I-H Item Positive (including internal fog particles) 995I-H Item used by mixing emulsions 995I-J Item Desalting 995II-A In the present invention, the silver halide emulsion is physically ripened. Use those that have been chemically aged and spectrally sensitized. The additives used in such a process are RD17643, 1871
6 and 308119.

The description is given below.

[0089]

[Table 1]

Known photographic additives that can be used in the present invention are also described in the above RD. Below are the relevant locations.

[0091]

[Table 2]

Various color couplers can be used in the silver halide color photographic light-sensitive material of the present invention.

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, 4,326,024, 4,401,752 and 4,248,961. Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 4,314,023.
No. 4,511,649, European Patent 249,473
Those described in No. A and the like are preferable.

As the magenta coupler, a magenta coupler other than the magenta coupler represented by formula (I) of the present invention can be used in combination. As the magenta coupler used in combination, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 3,061,432
Nos. 3,725,067, 4,310,619
No. 4,351,897, European Patent 73,636.
Issue, Research Disclosure (hereinafter referred to as RD)
24220, 24230 (June 1984), JP-A-5
5-118034, 60-33552, 60-
No. 35730, No. 60-43659, No. 60-185.
951, 61-72238, U.S. Pat.
0,630, 4,540,654, 4,55
6,630, International Publication WO88 / 04795, etc.

Examples of cyan couplers include known phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,228,233, 4,296,200, 2,369,929 and 2,810. 171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173. , West German Patent Publication 3,329,729, European Patent 121,36
Nos. 5A and 249,453A; U.S. Pat.
No. 622, No. 4,333,999, No. 4,775,6
No.16, No.4,451,559, No.4,427,76
No. 7, 4,690,889, 4,254,212
No. 4,296,199, JP-A-61-42658.
Those described in No. 5 and the like are preferable.

For the purpose of correcting unnecessary absorption of color forming dye, a coupler for correcting unnecessary absorption of color forming dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,744,181, and US Pat. No. 4,777. It is also preferable to use a coupler having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group described in JP-A No.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) 3,234. Those described in No. 533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,080,
No. 211, No. 4,367,282, No. 4,409,3
No. 20, 4,576,910, British Patent 2,10
2, 173, etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent 2,097,1
Nos. 40 and 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,472.
No. 4,338,393, and 4,310,618, multi-equivalent couplers described in JP-A-60-185950.
Compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound described in JP-A-62-24252.
IR redox compound-releasing redox compounds, couplers capable of releasing a dye that becomes bicolored after release described in EP 173,302A, RD11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, US Examples thereof include a ligand releasing coupler described in Japanese Patent No. 4,553,477 and a coupler releasing leuco dye described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are RD17643 mentioned above.
VII-CF and RD308119, 1001-2
Page VII-DF.

The additive used in the present invention is RD3081.
19, XIV, etc. can be added.

The light-sensitive material of the present invention includes, for example, the type and manufacturing number of the photographic light-sensitive material, the manufacturer's name, the emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

In the present invention, the magnetic recording layer is preferably coated on the side of the support opposite to the photographic constituent layer. The undercoat layer, the antistatic layer (conductive layer), It is preferable that the magnetic recording layer and the sliding layer are formed.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . The method for producing these magnetic powders is known and can be produced according to a known method.

The optical density of the magnetic recording layer is preferably small considering the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

The amount of magnetization of the magnetic recording layer per 1 m ² of the light-sensitive material is preferably 3 × 10 ^-2 emu or more. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation once with oe is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic photosensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm.
It is preferably from 0.05 to 15 μm, more preferably from 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form the binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Furthermore, it is necessary to adjust the physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add non-magnetic metal oxide particles, especially alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, polyolefin film and the like. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
No. 93641, No. 2-181749, No. 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

The supports preferably used in the present invention are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer and the undercoat layer, the same binder as used for the magnetic recording layer can be used.

Further, it is preferable to coat a higher fatty acid ester, a higher fatty acid amide, polyorganosiloxane, liquid paraffin, waxes, etc. on the magnetic recording layer as a sliding layer.

When the light-sensitive material of the present invention is used as a color light-sensitive material for roll-shaped photography, not only the downsizing of a camera or a cartridge can be achieved, but also resources can be saved, and a storage space for a developed negative film can be saved. Therefore, the film width is about 20 to 35 mm, preferably 20.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² , preferably 400 to 600 mm ² , it is possible to make a small format without deteriorating the image quality of the final photographic print, and a smaller patrone and a smaller camera than before can be achieved. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 sizes of 1: 1 and half sizes of 1: 1.4, 135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that it is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

To obtain a dye image using the color light-sensitive material of the present invention, a generally known color development process is carried out after exposure. That is, the aforementioned RD17643, pages 28 to 29, R
D18716, pp. 647 and RD308119, 101
It can be developed by the usual method described on page 0, section XIX.

[0120]

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

Example 1 A multilayer color photographic light-sensitive material sample 101 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support having an undercoat layer.

Unless otherwise specified, the addition amount is the number of grams per 1 m ² . Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First Layer: Antihalation Layer Black Colloidal Silver 0.16 Ultraviolet Absorber (UV-1) 0.20 High Boiling Organic Solvent (Oil-1) 0.12 Gelatin 1.53 Second Layer: Intermediate Layer Color Antifouling agent (SC-1) 0.06 High boiling point organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: low sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, iodide) Silver iodide content 8.0 mol%) 0.43 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.15 Sensitizing dye (SD-1) 2. 8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.025 High boiling point Solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.89 iodine Silver bromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1 .2 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-4 Cyan coupler (C-1) 0.45 Colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0 .017 High boiling point solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ^-4 Cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling point solvent (Oil-1) 0.57 Gelatin 1.10 Sixth Layer: Intermediate layer Color stain inhibitor (SC-1) 0.075 High boiling point organic solvent (Oil-2) 0.095 Gelatin 1.00 7th layer: Intermediate layer Gelatin 0.45 8th layer: Low sensitivity green sensitivity Layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 8.0 mol%) 0.64 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content rate 2.0 mol) %) 0.21 Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.19 Magenta coupler (M- 2) 0.49 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-2 0.81 Gelatin 1.89 9th layer: Mid-sensitive green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.76 Sensitizing dye (SD-6 ) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M-1) 0.043 magenta coupler (M-2) 0.10 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.37 Gelatin 0.76 10th layer: High-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.46 Sensitizing dye (SD-6) 0. 93 × 10 ^-4 sensitizing dye (SD-7) 0.97 × 10 -4 sensitizing dye (SD-8) 0.93 × 10 -4 magenta Puller (M-1) 0.08 Magenta coupler (M-2) 0.133 Colored magenta coupler (CM-2) 0.014 High boiling point solvent (Oil-1) 0.15 High boiling point solvent (Oil-2) 0 .42 Gelatin 1.08 Eleventh layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High boiling point solvent (Oil-2) 0 .21 Gelatin 0.73 12th layer: Intermediate layer Formalin scavenger (HS-1) 0.18 Gelatin 0.60 13th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, iodide) Silver content rate 8.0 mol%) 0.073 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content rate 3.0 mol%) 0.16 Silver iodobromide emulsion (average grain size 0. 27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-9) 2.1 × 10 ^-4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y-1) 0.89 DIR Compound (D-4) 0.008 High boiling point solvent (Oil-2) 0.37 Gelatin 1.51 14th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, containing silver iodide) Rate 8.0 mol%) 0.95 Sensitizing dye (SD-9) 7.3 × 10 ^-4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y-1) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin 0.80 Fifteenth layer: First protective layer Silver iodobromide emulsion (average grain size 0.05 μm, silver iodide content 3.0 mol%) 0.30 Ultraviolet absorber (UV-1) 0.094 Ultraviolet absorber (UV-2) 0.10 Formalin scavenger (HS-1) 0.3 High boiling point solvent (Oil-1) 0.10 Gelatin 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent PM-1 (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 04 Sliding agent (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizer ST-1, dyes AI-1, AI-2, antifoggant AF-1, two types of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, a hard agent Membrane agents H-1, H-2 and preservative DI
-1 was added. The amount of DI-1 added was 9.4 mg / m ^2.
Met.

The structures of the compounds used in the above samples are shown below.

[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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Sample 101's 8th, 9th and 10th layers M-1,
Samples 102 to 124 were prepared by replacing M-2, CM-1, and CM-2 as shown in Tables 3 and 4.

The amounts used at the time of replacement are shown in parentheses in Tables 3 and 4 in millimoles per square meter. If necessary, Compound III-5 was added in an amount corresponding to 30% by weight of the magenta coupler. The added samples and layers are shown in Tables 3 and 4 at the same time.

As a comparative compound, the colored magenta coupler CM-3 shown below was used.

[0137]

Embedded image

[0138]

[Table 3]

[0139]

[Table 4]

Samples 101 to 12 prepared as described above
4 was exposed to light in accordance with the performance evaluation shown below, and the color development processing shown below was carried out to evaluate the performance.

A) Photographic sensitivity The sample was subjected to gradation exposure with white light, the logarithmic value of the reciprocal of the exposure amount giving the density of minimum density + 0.3 was found from the characteristic curve of the magenta color image, and sample 101 was used as a reference. The difference (ΔS) was calculated. Here, the larger the value of ΔS is, the higher the sensitivity is.

B) Substantial fog, except that the developing agent was removed from the color developer,
Samples were processed as in a) photographic sensitivity determination. The difference between the green density of this sample and the green minimum density when the photographic sensitivity of a) was determined was determined as the actual fog of the magenta color image. The higher the value, the higher the actual fog.

C) Color turbidity: The sample is uniformly exposed to blue light for 1 lux · second, and then subjected to gradation exposure with green light for processing to give a green density of minimum density + 1.0. The value obtained by subtracting the blue density in the minimum density portion of the magenta color image from the blue density at the amount was evaluated as the color turbidity value (ΔD _B ). The smaller the numerical value, the smaller the color turbidity from the green-sensitive layer to the blue-sensitive layer and the better the color reproducibility.

D) Raw storability The sample was conditioned for 6 hours at a temperature of 23 ° C. and a relative humidity of 65%, then sealed in a sealable bag and stored at a temperature of 55 ° C. for one week. The raw preservation (substitute evaluation) sample thus obtained was exposed and processed in the same manner as the photographic sensitivity was determined in a) to determine the characteristic curve of a magenta color image. The difference (Δfog) between the minimum density value of this characteristic curve and the minimum density value when the photographic sensitivity was determined in a) was evaluated as the fog increase width during raw storage. The smaller the change, the better the raw preservability.

<< Color development processing >> (Processing step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml Fixed 1 minute 30 Second 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Dry 60 seconds 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

<Preparation of Processing Agent> (Color developer composition) Water 800 ml Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added 1 Make up to 0.01 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Color Development Replenisher Solution Composition) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make 1.0 l, and pH 1 was adjusted with potassium hydroxide or 20% sulfuric acid. Adjust to 0.18.

(Bleaching solution composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1.0 l and aqueous ammonia was added. Alternatively, adjust the pH to 4.4 using glacial acetic acid.

(Bleach replenisher composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Water was added to make 1.0 l, and ammonia was added. Adjust to pH 4.4 with water or glacial acetic acid.

(Fixing Solution Formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water is added to make 1.0 l, and the pH is adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Fixing Replenisher Solution Formulation) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Water was added to make 1.0 l, and the pH was adjusted to 6.5 with aqueous ammonia or glacial acetic acid.

(Stabilizer and stable replenisher formulation) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 ml Water was added to make 1.0 l, and pH was adjusted to 8 with ammonia water or 50% sulfuric acid. Adjust to 5.

Table 5 shows the evaluation results obtained as described above.

[0154]

[Table 5]

From the results shown in Table 5, only by substituting the compound of the present invention for the colored magenta coupler, the fog is somewhat reduced, but a large improving effect is not recognized. Further, it is understood that only by replacing the magenta coupler with the compound of the present invention, the sensitivity is greatly increased, and the fog is greatly increased, the color turbidity is increased, and the storage stability is deteriorated.

On the other hand, it can be seen that, by using the magenta coupler of the present invention and the colored magenta coupler in combination, high sensitivity can be achieved with a low fog, and color turbidity and raw preserved raw materials are not deteriorated but rather improved.

From the results shown in Table 5, the following facts can be seen.

1) In the general formula [I], R ¹¹ is an arylthio group, and R ¹² is a pentachlorophenyl group, a 2,6-dichloro-4-methanesulfonylphenyl group, a 2,6-dichloro- group. 4-cyanophenyl group, 2,
A 6-dichloro-4-morpholinosulfonylphenyl group is preferable for efficiently exhibiting the effects of the present invention.

2) In the general formula [II], R ²¹ is two alkoxyl groups, two alkoxyl groups are substituted at the 3 and 4 positions with respect to the azo group, and are represented by A. The magenta coupler residue is a 1-pentachlorophenyl-3-anilino-5-pyrazolone compound, or 1-pentachlorophenyl-3-anilino-5-pyrazolone compound.
A (2,4,6-trichloro) phenyl-3-acylamino-5-pyrazolone compound is preferred for efficiently exhibiting the effects of the present invention.

3) It is preferable to use the compound represented by the general formula [III] together in order to more effectively bring out the effects of the present invention.

Example 2 The support of Example 1 was changed to the following support, and evaluation was performed in the same manner as in Example 1.

<< Preparation of Support >> 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, ethylene glycol 6
0.1 part by weight of calcium acetate hydrate was added to 0 part by weight as a transesterification catalyst, and transesterification reaction was carried out according to a conventional method. The product obtained was treated with antimony trioxide 0.
05 parts by weight and 0.03 parts by weight of phosphoric acid trimethyl ester were added. Then gradually raise the temperature and reduce the pressure, 290 ° C,
Polymerization is performed under the condition of 0.05 mmHg and the intrinsic viscosity is 0.6.
0 of polyethylene-2,6-naphthalate was obtained.

After vacuum-drying this at 150 ° C. for 8 hours, it is melt-extruded in layers from a T-die at 300 ° C., adhered to a cooling drum at 50 ° C. while electrostatically applied, and cooled and solidified to give an unstretched sheet. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched by a tenter type transverse stretching machine at 50% of the total transverse stretching ratio at the first stretching zone of 145 ° C, and further at the second stretching zone of 155 ° C at the total transverse stretching ratio of 3. It was stretched so as to be three times. Then 1
Heat treatment at 00 ° C. for 2 seconds,
Heat set at 0 ° C. for 5 seconds, 1 second at 240 ° C.
Heat set for 5 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while performing a 5% relaxation treatment in the lateral direction to obtain a polyethylene naphthalate film having a thickness of 85 μm.

Wrap this around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to form a support.

12 W / m ² / min on both sides of this support
Of the undercoating coating solution B-1
To a dry film thickness of 0.4 μm and then apply 1
A 2 W / m ² / min corona discharge treatment was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment of 12 W / m ² / min, the undercoating coating solution B-3 was applied to give a dry film thickness of 0.
2 μm, and 12 W / m ² / m
An in-corona discharge treatment was performed, and a coating solution B-4 was applied so as to have a dry film thickness of 0.2 μm.

After coating each layer, each layer was dried at 90 ° C. for 10 seconds, and after four layers were coated, heat treatment was conducted at 110 ° C. for 2 minutes, followed by cooling treatment at 50 ° C. for 30 seconds.

<Undercoating Coating Liquid B-1> Copolymer latex liquid of butyl acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxyethyl acrylate 25% by weight (solid content 30% ) 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Undercoating coating solution B-2> Hydroxylation of styrene-maleic anhydride copolymer Aqueous sodium solution (solid content 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size 3 μ) 0.2 g Finish with water 1000 ml <Coating liquid B-3> Butyl Acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxy acrylate 25 % By weight of copolymer latex liquid (solid content 30%) 50 g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (ethylene urea) 1.1 g Finish with water 1000 ml

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Embedded image

<Coating Liquid B-4> 60 mol% of dimethyl terephthalate as dicarboxylic acid component, 30 mol% of dimethyl isophthalate, 10 mol% of sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol as glycol component, 50 mol% of diethylene glycol was copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

Aqueous dispersion of tin oxide-antimony oxide composite fine particles (average particle size 0.2 μ) (solid content 40% by weight)
109 g Aqueous dispersion A 67 g Finish with water 1000 ml << Coating of magnetic recording layer >> Undercoat layer U- of the above-mentioned undercoat support
On the layer coated with the coating liquid, the coating liquid for the magnetic recording layer having the following composition was dried at a dry film thickness of 0.1 using a precision extrusion coater.
The coating was applied so as to have a thickness of 8 μm, and at the same time as drying, the magnetic substance was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

[Composition and Preparation of Magnetic Recording Layer Coating Solution M-1] Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Specific surface area 40 m ² / g, Hc = 750 Oe) 10 parts by weight Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 3 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132, Japan) Polyurethane Co., Ltd. 15 parts by weight Stearic acid 2 parts by weight Cyclohexanone 920 parts by weight Acetone 920 parts by weight After thoroughly mixing and dispersing the above, a polyisocyanate of Coronate-3041 (manufactured by Nippon Polyurethane Co., Ltd., solid) 50% by weight), and then sufficiently stirred and mixed to obtain a magnetic paint M-1.

<< Coating of Lubricant Layer >> A lubricant coating solution (wax solution below) dispersed in a water / methanol mixed solution so as to contain 0.1% of carnauba wax on the magnetic recording layer was prepared, and the wax was prepared. The coating amount was 15 mg / m ² . The raw material after the wax application was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of Wax Liquid) Polyoxyethylene lauryl ether 4 was added to 100 parts by weight of water heated to 90 ° C.
After mixing with 40 parts by weight of carnauba wax separately melted at 90 ° C., the mixture was sufficiently stirred using a high-speed stirring homogenizer to prepare a carnauba wax dispersion (WAX1). .

Next, 995 parts by weight of water, 900 parts by weight of methanol and 10 parts of propylene glycol monomethyl ether.
0 parts by weight, and 5 parts by weight of WAX1 was added thereto.
The mixture was stirred to prepare a wax liquid.

A multilayer color photographic light-sensitive material 201 was prepared by sequentially forming the same layers as in Example 1 from the support side on the side opposite to the side having the magnetic recording layer of the support thus prepared. Further, Samples 202 to 205 were prepared by changing the magenta couplers, colored magenta couplers, and compounds of the general formula [III] of the eighth layer, the ninth layer, and the tenth layer of Sample 201 as shown in Table 6 below. Evaluation was carried out in the same manner as in Example 1. Table 7 shows the results.

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[Table 6]

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[Table 7]

As is clear from Table 7, good results were obtained in the constitution of the present invention even when the present support was used.

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According to the present invention, there is provided a silver halide color photographic light-sensitive material capable of achieving high sensitivity while maintaining low fog and excellent in color reproducibility and long-term storage stability of the light-sensitive material. I was able to.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. . Embedded image [In the formula, R ¹¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. R ¹² represents an aryl group. R ¹³ represents a substituent n ₁
Represents an integer of 1 to 5. When n ₁ is 2 or more, R ¹³ may be the same or different. [Chemical formula 2] [In the formula, A represents a magenta coupler residue. R ²¹ represents a substituent, and at least one is an alkoxyl group having 2 or more carbon atoms. n ₂ represents an integer of 1 to 5, and when n ₂ is 2 or more, R ²¹ may be the same or different. ]