JP2000330239A - Photographic dispersion of lipophilic fine particles, photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic dispersion of fine lipophilic particles having good light resistance even after long-term preservation as a coating fluid in mass production and having high coloring density by incorporating a specified compound or a compound having its absorption maximum in a specified wavelength range and having a specified molar extinction coefficient and allowing the dispersion of lipophilic particles to have a specified average particle diameter. SOLUTION: The photographic dispersion of fine lipophilic particles contains a compound of formula I or II or a compound having its absorption maximum in the wavelength range of 330-390 nm and having a molar extinction coefficient of >=17,000 and has <=0.1 μm average particle diameter. In the formula I, R1 and R2 are each alkyl, aryl or the like and R3 is H, halogen or the like. In the formula II, R1 and R2 are each a substituent, at least one of R1 and R2 is alkoxy, aryloxy or the like, R is alkyl or aryl, X1 and X2 are each halogen, (m), (n), (p) and (q) are each an integer of 0-4, m+n<=4 and p+q<=4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic lipophilic fine particle dispersion, a photographic light-sensitive material and an image forming method, and more particularly to a photographic light-sensitive material capable of obtaining high image quality even after various processing and storage.

[0002]

2. Description of the Related Art Various types of color prints are known. A typical example is a color print produced by imagewise exposing and processing a silver halide photographic material. Various characteristics are demanded in a photographic material represented by a silver halide photographic material, but image storability is also one of the main items, and various improvement methods have been proposed. I have.

[0003] The application of an ultraviolet absorber to improve light resistance is well known as an effective means. Ultraviolet absorbers are essential materials for improving light resistance of various materials and images, and are used in many fields. In particular, products having an image formed on the surface are frequently used because the effect of light resistance is easily seen.

[0004] UV absorbers are generally required to have the following properties.

[0005] 1) It has substantially no absorption in the visible light region. 2) It does not affect other performances such as images. 3) It has a high ultraviolet absorption capacity. 4) The effect of long-time light irradiation. In order to use the compound for the purpose of suppressing, it is necessary that the compound itself has high light fastness.

[0006] When an ultraviolet absorber is applied to a photographic material, various problems arise because it must be added to a thin layer of the photographic material. A problem is particularly likely to occur when the amount of the ultraviolet absorber is increased in order to improve the light fastness. In order to improve the light fastness, as an ultraviolet absorber having a large absorbance, for example, improvements using an ultraviolet absorber described in JP-A-3-97925 and JP-A-7-134360 have been proposed. However, as a result of examining these ultraviolet absorbers, a new problem was found that light resistance was easily deteriorated and color density was easily reduced due to aging of the coating solution during production. As a result of various studies of these improvements, the present inventor has found that the claims 1, 2, 3, 7 of the present invention
It has been found that these problems are improved by the invention of the present invention, and the present invention has been accomplished.

[0007] On the other hand, the photosensitive material has the following characteristics:-The whiteness of the white image portion tends to fluctuate during high-speed processing.-When the formed image is stored at high temperature and high humidity, oily material seeps out on the surface (hereinafter, sweating).・ When the formed image is stored under high humidity and high temperature, the image density may decrease. ・ In addition, the light sensitivity tends to be insufficient, and high sensitivity is desired. However, the present inventors have found that these problems can be improved by using the ultraviolet absorbent according to the present invention in a specific method, and have reached the present invention.

[0008]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a photographic lipophilic fine particle dispersion having good light resistance and high color density even after storage of the coating solution over time during mass production. A photosensitive material using the same.

A second object of the present invention is to provide a light-sensitive material having a small variation in white background performance even during high-speed image formation.

A third object of the present invention is to provide a light-sensitive material which causes less image fading due to perspiration, heat and humidity.

A fourth object of the present invention is to provide a photosensitive material having high sensitivity even when scanning and exposing.

A fifth aspect of the present invention is to provide a photosensitive material having good light resistance of a formed image.

[0013]

The above object of the present invention has been attained by the following constitutions.

(1) General formula (1) or general formula (2)
Or a compound having an absorption maximum wavelength of 330 nm or more
A lipophilic fine particle dispersion containing at least one compound having a molar extinction coefficient of 17000 or more in a range of 390 nm and an average particle size of the lipophilic fine particle dispersion of 0.1 μm or less. Fine particle dispersion.

[0015]

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Wherein R ¹ and R ² are each an alkyl group,
Represents an aryl group, an alkoxy group, or an aryloxy group, and R ³ represents a hydrogen atom, a halogen atom, or a monovalent organic group. ]

[0017]

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[Wherein R ₁ and R ₂ each represent a substituent. Here, at least one of R ₁ and R ₂ represents an alkoxy group, an aryloxy group, an alkylthio group, an acylamino group, or —NHCOOR. R represents an alkyl group or an aryl group. X ₁ and X ₂ each represent a halogen atom. m, n, p and q each represent an integer of 0-4. However, the sum of m and n and the sum of p and q are each an integer of 0 to 4, and both m and n are not 0. Also, m, n,
When p or q is 2 or more, a plurality of R ₁ , R ₂ , X ₁ or X ₂ may be the same or different. (2) The compound represented by the general formula (1) or (2), or the compound having an absorption maximum wavelength of 330 nm to 390 n.
m, at least one compound having a molar extinction coefficient of 17000 or more, and having an oil phase refractive index of 1.48 to 1.58. liquid.

(3) In a photographic photosensitive material having at least one photosensitive layer and at least one non-photosensitive layer, at least one of the compounds represented by the general formula (1) or (2) Or the absorption maximum wavelength is 33
0 nm to 390 nm, and the molar extinction coefficient is 17
A photographic light-sensitive material comprising at least one compound selected from compounds having a molecular weight of 000 or more and a nonionic surfactant.

(4) At least one photosensitive layer (a) is provided on one surface of the support, and at least one photosensitive layer (a) is provided on the surface of the support opposite to the surface on which the photosensitive layer is provided. In the photographic photosensitive material having the non-photosensitive layer (b), at least one of the compounds represented by the general formula (1) or (2) is added to at least one of the non-photosensitive layers (b). A photographic material characterized by containing a compound.

(5) In a photographic light-sensitive material having at least one photosensitive layer and at least one non-photosensitive layer on a support, at least two layers have the general formula (1) or the general formula (2) And at least one compound represented by the formula (1) and a compound represented by the general formula (1) or (2) contained in a layer farther from the support than the photosensitive layer farthest from the support The total amount is larger than the total content of the compound represented by the general formula (1) or the general formula (2) contained in the photosensitive layer farthest from the support and the layer closer to the support than the photosensitive layer farthest from the support. A photographic material characterized by the following:

(6) In a photographic material having at least one photosensitive layer and at least one non-photosensitive layer, at least one photosensitive layer has the formula (1)
Alternatively, at least one compound represented by the general formula (2) and the following general formulas (3) to (7)
A photographic material comprising at least one compound selected from the group consisting of:

[0023]

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Wherein R ₃₁ represents an alkyl group having 2 to 6 carbon atoms. R ₃₂ represents a ballast group. X ₂₁ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. ]

[0025]

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[Wherein, R ₄₁ represents a hydrogen atom or a substituent, and R ₄₂ represents a substituent. m represents the number of substituents R _42.
When m is 0, R ₄₁ has a Hammett's substituent constant σp of 0.2
Represents an electron-withdrawing group of 0 or more, and when m is 1 or 2 or more,
At least one of R ₄₁ and R ₄₂ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Z ₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like.

R ₄₃ represents a hydrogen atom or a substituent, and Z ₂ is condensed with a pyrazole ring together with —NH— to form a nitrogen-containing heterocyclic 6
Represents a group of non-metallic atoms necessary for forming a membered ring, and the six-membered ring may have a substituent, and may form a condensed ring with a benzene ring or the like in addition to the pyrazole ring.

R ₄₄ and R ₄₅ are Hammett's substituent constant σp
Represents an electron-withdrawing group of 0.20 or more. Provided that the sum of σp values of R ₄₄ and R ₄₅ is 0.65 or more. Z ₃ represents a nonmetallic atom group necessary to form a nitrogen-containing 5-membered heterocyclic ring,
The 5-membered ring may have a substituent.

R ₄₆ and R ₄₇ each represent a hydrogen atom or a substituent; Z ₄ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; May be.

X ₃₁ , X ₃₂ , X ₃₃ and X ₃₄ each represent a group or an atom which is released by a coupling reaction with an oxidized form of a color developing agent. (7) At least one photosensitive layer and at least one photosensitive layer
A photographic material having at least one non-photosensitive layer, characterized in that at least one layer contains at least one compound selected from the compounds represented by formula (1) or (2) and an aliphatic alcohol. Photosensitive material.

(8) In a photographic material having at least one photosensitive layer and at least one non-photosensitive layer, at least one of the compounds represented by the general formula (1) or (2) A photographic material comprising at least one compound selected from the group consisting of a compound represented by the following general formula (8):

[0032]

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[Wherein R ¹² and R ¹³ represent a secondary or tertiary alkyl group. However, the total number of carbon atoms of the alkyl group represented by R ¹² and R ¹³ is 20 or more. (9) At least one photosensitive layer and at least one photosensitive layer
In a photographic material having at least one non-photosensitive layer, at least one layer contains at least one compound selected from the compounds represented by formula (1) or (2), A photographic light-sensitive material characterized in that the layer contains a tabular silver halide emulsion having an average silver chloride content of 95 mol% or more and 50% or more of the total projected area of the emulsion grains having an aspect ratio of 3.0 or more.

(10) In a photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, at least one of the above-mentioned formulas (1) and (2) A photographic light-sensitive material comprising at least one compound selected from the group consisting of the compounds represented by the formula (1) and a fluorescent whitening agent in the support.

(11) In a photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, at least one of the above-mentioned formulas (1) and (2) A photographic light-sensitive material containing at least one compound selected from the group consisting of the compounds represented by the formula (1) and a fluorine-containing surfactant in a layer farthest from the support.

(12) In a photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer, at least one of the compounds represented by the general formula (1) or (2) Containing at least one compound, and at least one photosensitive layer,
6 × 1 Ir compound with an average silver chloride content of 95 mol% or more
A photographic light-sensitive material comprising a silver halide emulsion containing ^0-8 mol / silver 1 mol or more.

(13) In an image forming method for forming an image after exposing the photosensitive material, the photosensitive material contains at least one compound selected from the compounds represented by the general formulas (1) and (2). And exposure is 400n
An image forming method, wherein scanning exposure is performed by a light beam having a light emission maximum at m to 450 nm.

Hereinafter, the present invention will be described in detail.

The compound represented by formula (1) according to the present invention will be described.

The alkyl group represented by R ¹ and R ² preferably has 1 to 18 carbon atoms, and may be linear, branched or cyclic. The alkoxy group represented by R ¹ and R ² preferably has 1 to 18 carbon atoms, and may be linear, branched, or cyclic. The aryl group represented by R ¹ and R ² is preferably a phenyl group. The aryloxy group represented by R ¹ and R ² is preferably a phenoxy group. These alkyl group, aryl group, alkoxy group and aryloxy group may have a substituent. Also,
At least one of R ¹ and R ² preferably contains 2-hydroxyphenyl group.

Examples of the monovalent organic group represented by R ³ include an alkyl group, an aryl group, an alkoxy group, and an aryloxy group, and an alkoxy group is particularly preferable. The alkyl group and the alkoxy group may be linear, branched, or cyclic. Also, the alkyl group,
The aryl group, the alkoxy group, and the aryloxy group may be substituted with another substituent.

Next, typical compounds represented by the above general formula (1) according to the present invention will be exemplified, but not limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The compound represented by the general formula (1) can be synthesized by the method described in JP-A-5-117282.

The compound represented by the general formula (1) may be added to either the photosensitive layer or the non-photosensitive layer, but is preferably added at least to the non-photosensitive layer, and more preferably, Is added to the non-photosensitive layer opposite to the support adjacent to the photosensitive layer farthest from the body. Although there is no limit to the amount, preferably 0.05~15g / m ^2, more preferably from 0.1-5 g / m ^2.

Next, the compound represented by formula (2) will be described.

In the general formula (2), among the substituents represented by R ₁ and R ₂ , alkyl groups include methyl, ethyl, hexyl and octyl, and aryl groups include phenyl group. And the like. Examples of the alkoxy group represented by at least one of R ₁ and R ₂ include methoxy, butoxy, hexyloxy and octoxy groups, and examples of the aryloxy group include a phenoxy group. Further, among the substituents represented by R ₁ and R ₂ ,
Examples of the alkylthio group include a 2-ethylhexylthio group, and examples of the acylamino group include a 2-ethylhexylacylamino group.
The group, like -NHCOOC ₈ H _17.
Further, a vinyl group may be contained in the group represented by R ₁ or R ₂ and vinyl polymerization may be performed to form a polymer or copolymer.

These groups may be linear, branched or cyclic, and may be further substituted with another substituent. or,
A plurality of substituents may combine with each other to form a ring.

As the halogen atom represented by X ₁ and X ₂ ,
Examples include atoms such as fluorine, chlorine, and bromine.

The representative compounds represented by the above general formula (2) according to the present invention are shown below, but are not limited thereto.

[0059]

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2-1: 2-OCH ₂ CH (C ₂ H ₅ ) C ₄ H
_{9 2-2: 2-OC 8 H} 17, 6-Cl 2-3: 1-CH 3, 2-OCH 2 CH (C 2 H 5) C
_{4 H 9, 6-Cl 2-4} : 1-CH 3, 2-OCH 2 CH (C 2 H 5) C
₄ H _9, 4,6-di _{-Cl 2-5: 1-CH 3,} 2-OCH 2 CH (C 2 H 5) C
_{4 H 9, 4-Br,} 6-Cl 2-6: 2-OCH 2 CH (C 2 H 5) C 4 H 9, 3-Cl 2-7: 2-OC 18 H 37, 3-Cl 2- _{8: 1-CH 3, 2} -OC 18 H 37 2-9: 1,3- di _{-C 4 H 9 (t),} 6-OCH 3 2-10: 1,3- di -C ₅ H ₁₁ ( _{t), 6-OCH 3 2-11} : 1,3- di _{-C 4 H 9 (t),} 6-OC 2 H 5 2-12: 1,3- di _{-C 5 H 11 (t),} 6 -OC ₂ H ₅

[0061]

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Further, besides the above compounds, JP-A-3-29
Exemplified compounds I-3 to I-2 described in No. 4846, pp. 3-4.
3 and the like.

Next, the absorption maximum wavelength is from 330 nm to 390.
A compound having a molar absorption coefficient of 17000 or more in the range of nm will be described.

The compound has an absorption maximum wavelength of 335 nm or more.
Any compound can be used as long as it is in the range of 390 nm and has a molar extinction coefficient of 17000 or more. However, it is preferable not to have an absorption maximum wavelength in the range of 400 nm to 700 nm.

The molar absorption coefficient at 335 nm to 390 nm is preferably 19000 or more.
It is more preferable that the number be 000 or more.

It is preferable that the molar extinction coefficient is 17000 or more and the absorption maximum wavelength is in the range of 344 nm to 370 nm.

As specific compounds, JP-A-7-239
Compounds represented by general formula (II) described in JP-A-539 can be exemplified.

Next, the compound represented by formula (3) will be described.

In the general formula (3), the alkyl group having 2 to 6 carbon atoms represented by R ₃₁ may be linear or branched, and includes those having a substituent. R ₃₁ is preferably an ethyl group.

The ballast group represented by R ₃₂ has an organic size and shape that gives the coupler molecules sufficient bulk to prevent the coupler from substantially diffusing from the layer to which the coupler is applied to other layers. Group. Preferable examples of the ballast group is represented by _{-CH (R 33) -O-Ar} .

R ₃₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent.

Examples of the atom or group capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₂₁ include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, and an acylamino group. , A sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), preferably a halogen atom, an aryloxy group, or an alkoxy group.

Next, specific examples of the coupler represented by the general formula (3) will be shown, but it should not be construed that the invention is limited thereto.

[0074]

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[0075]

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[0076]

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[0077]

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Specific examples of the cyan coupler which can be used in the present invention, including these, are described in JP-B-49-11-11.
572, JP-A-61-3142 and JP-A-61-9652.
No., No. 61-9653, No. 61-39045, No. 6
Nos. 1-50136, 61-99141, 61-1
No. 05545 and the like.

The cyan coupler of the present invention represented by the general formula (3) is usually used in an amount of 1 × 10 5 per mol of silver halide.
^-3 to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻² mol.

Next, the compounds represented by formulas (4) to (7) will be described.

The substituent having a substituent constant σp defined by Hammett of the present invention of +0.20 or more is specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, Carboxyl,
Examples include groups such as cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, and halogen-substituted arylsulfonyl; sulfinyl groups include alkylsulfinyl and arylsulfinyl; and sulfonyloxy groups include alkylsulfonyloxy and arylsulfonyloxy. Sulfamoyl groups include N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, and the like; phosphoryl groups include alkoxyphosphoryl, aryloxyphosphoryl, and alkyl Phosphoryl, arylphosphoryl and the like; carbamoyl groups include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-
N-arylcarbamoyl and the like; acyl groups as alkylcarbonyl, arylcarbonyl and the like; acyloxy groups as alkylcarbonyloxy and the like; oxycarbonyl groups as alkoxycarbonyl and aryloxycarbonyl and the like; halogen-substituted alkoxy groups as α -Halogen-substituted alkoxy and the like; halogen-substituted aryloxy groups include tetrafluoroaryloxy and pentafluoroaryloxy; pyrrolyl groups include 1-pyrrolyl and the like; tetrazolyl groups include 1-tetrazolyl and the like.

In addition to the above substituents, trifluoromethyl, heptafluoroisopropyl, nonylfluoro-
A t-butyl group, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used.

In the general formula (4), R ₄₁ or R ₄₂
Among the substituents represented by, the substituents other than the electron-withdrawing group include, but are not particularly limited to, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, and arylthio. ,
Alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide,
Ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto, spiro compound residue, bridged hydrocarbon compound residue, etc. Is mentioned.

The alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. As the aryl group, a phenyl group is preferable.

As the acylamino group, an alkylcarbonylamino group or an arylcarbonylamino group; as the sulfonamide group, an alkylsulfonylamino group or an arylsulfonylamino group; Groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5
To 7 are preferable, and the alkenyl group may be linear or branched. A cycloalkenyl group having 3 to 12 carbon atoms;
Particularly, those having 5 to 7 are preferable.

As the ureido group, an alkylureido group,
An arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a 5- to 7-membered heterocyclic group is preferable, specifically a 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- A phenyltetrazol-5-oxy group or the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3 , 5-
Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group;
3-heptadecyl succinimide group, phthalimide group, glutarimide group and the like; spiro compound residues such as spiro [3.3] heptane-1-yl; and bridged hydrocarbon compound residues as bicyclo [2.2. 1] heptan-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

These groups may further contain a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

In the general formula (4), the group or atom capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₃₁ includes, for example, a hydrogen atom, a halogen atom (hydrochloric acid, bromine, fluorine, etc.) and an alkoxy group. , Aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, N
Examples include nitrogen-containing heterocycles bonded with atoms, alkoxycarbonylamino, aryloxycarbonylamino, carboxyl, and the like, and among these, a hydrogen atom and alkoxy, aryloxy, alkylthio, arylthio groups, N A nitrogen-containing heterocyclic group bonded by an atom.

In the general formula (4), examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₁ include pyrazole, imidazole, benzimidazole, triazole and tetrazole. m is preferably from 0 to 5.

More specifically, the compound represented by the general formula (4) is represented by the following general formulas (4) -1 to (4) -7.

[0093]

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In the above general formula, at least one of R ₄₁ and R ₅₁ in the general formula (4) -1
At least one of R ₄₁ and R ₅₂ in 2, general formula (4) at least one of R _41, R ₅₃ and R ₅₄ in the -3, Formula (4) in -4 R ₄₁ , at least one, formula (4) at least one of R ₄₁ and R ₅₇ in -5, formula (4) in -6 R ₄₁ of the R ₅₅ and R _56, formula (4 ) -7, at least one of R ₄₁ and R ₅₈ is σ
p is an electron-withdrawing group of 0.20 or more.

X ₃₁ has the same meaning as X ₃₁ in formula (4), and p represents an integer of 0 to 4.

In the general formulas (4) -1 to (4) -7, among R ₄₁ and R _{51 to} R ₅₈ , those in which σp is not an electron-withdrawing group having 0.20 or more are a hydrogen atom or a substituted atom. Represents a group,
Among R ₅₈ , those which are not electron-withdrawing groups are not particularly limited as substituents. Specifically, in the general formula (4), R ₄₁
Or when R ₄₂ is other than an electron withdrawing group, R ₄₁ or R
_Examples of the substituent represented by ₄₂ include those mentioned above.

The cyan coupler having an electron-withdrawing group according to the present invention is disclosed in JP-A-64-554 and JP-A-64-555.
, And can be easily synthesized according to the methods described in JP-A Nos. 64-557 and JP-A-1-105251.

Next, the cyan coupler represented by formula (5) will be described.

The cyan coupler of the general formula (5) has a structure in which a 6-membered heterocyclic ring is condensed with a pyrazole ring, and the substituent represented by R ₄₃ is not particularly limited. Alkyl, aryl, anilino, acylamino,
Examples include sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups.In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, Sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfonic acid, etc., and spiro compound residues, bridged hydrocarbon compound residues, etc. That.

The alkyl group represented by R ₄₃ preferably has 1 to 32 carbon atoms, may be linear or branched, and the aryl group is preferably a phenyl group.

The acylamino group represented by R ₄₃ includes:
Alkylcarbonylamino group, an arylcarbonylamino group or the like; The sulfonamide group, an alkylsulfonylamino group, an aryl sulfonyl amino group; an alkylthio group, the alkyl moiety in the arylthio group, the aryl component is an alkyl group represented by R _43, Aryl groups.

The alkenyl group represented by R ₄₃ has 2 to 32 carbon atoms, and the cycloalkyl group has 3 carbon atoms.
~ 12, particularly preferably 5 ~ 7, and the alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

The sulfonyl group represented by R ₄₃ is an alkylsulfonyl group, an arylsulfonyl group, etc .; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; Oxyphosphonyl group, arylphosphonyl group, etc .; acyl group as alkylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group as alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group as alkylsulfamoyl group, arylsulfa Moyl group and the like; acyloxy group as alkylcarbonyloxy group and arylcarbonyloxy group and the like; carbamoyloxy group as alkylcarbamoyloxy group and arylcarbamoyloxy group and the like; As an id group, an alkylureido group, an arylureido group, etc .; as a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; as a heterocyclic group, a 5- to 7-membered group is preferable. Typically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
-Pyrrolyl group, 1-tetrazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyl As a heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3. , 5-triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutar Imido group and the like; spiro compound residue as spiro [3.3]
Heptane-1-yl and the like; as bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7
-Dimethyl-bicyclo [2.2.1] heptan-1-yl and the like. Each of these groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

[0104] Examples of the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _32, include the same groups as X ₃₁ in formula (I).

In the general formula [II], the nitrogen-containing 6-membered ring formed by Z ₂ is preferably a 6π-electron system or an 8π-electron system, and contains 1 to 4 nitrogen atoms including at least one —NH—. The at least one carbonyl group containing an atom and contained in the 6-membered ring represents a group such as> C = O or> C = S. Further, the at least one sulfonyl group the 6-membered ring contains -SO ₂ - represents a group.

Preferred specific examples of the cyan coupler of the present invention include compounds represented by the following formulas (5) -1 to (5) -6.

[0107]

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In the formula, R ₄₃ , R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R
₆₅ , R ₆₆ , R ₆₇ and R ₆₈ represent R ₄₁ in the general formula (4)
And X ₃₂ has the same meaning as X ₃₁ in formula (4), and in formula (5) -5, n represents an integer of 0 to 4, and when n is 2 or more, a plurality of R ₆₆ may be the same or different.

[0109] The generally formula (5) R ₆₄ in 4 and _{(5) -6, R 65,} R 67 and R ₆₈ have the same meanings as R ₄₁ in the general formula (4), R ₆₄ and R ₆₇ is It cannot be a hydroxyl group.

In the general formula (6), R ₄₄ and R ₄₅
Represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Examples of these electron-withdrawing groups include the same groups as the electron-withdrawing groups of R ₄₁ and R ₄₂ in the general formula (4). Can be mentioned. Provided that the sum of σp values of R ₄₄ and R ₄₅ is 0.65 or more.

Examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₃ include rings such as pyrazole, imidazole and tetrazole. These 5-membered nitrogen-containing heterocycles may have a substituent.

More specifically, the compound represented by the general formula (6) is represented by the following general formulas (6) -1 to (6) -8.

[0113]

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In the formula, R ₄₄ , R ₄₅ and X ₃₃ have the same meanings as in the general formula (6). R ₇₁ represents a hydrogen atom or a substituent, and R ₇₂ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more.

Examples of the substituent represented by R ₇₁ include the same groups as those of R _{43 in the} formula (5). Examples of the electron-withdrawing group represented by R ₇₂ include the same groups as those in the formula (4).
_{The same} groups as the electron-withdrawing groups ₄₁ and R ₄₂ can be mentioned.

The cyan coupler represented by the general formula (6) is preferably a cyan coupler represented by the general formula (6) -1, (6) -2 or (6) -3, and particularly preferably the cyan coupler represented by the general formula (6) )
The cyan coupler represented by -2 is preferred.

In the general formula (7), R ₄₆ and R ₄₇
Represents a hydrogen atom or a substituent, and examples of these substituents include the same groups as R _{43 in} formula (5).

Z ₄ in the general formula (7) represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocyclic ring. However, the heterocyclic ring has at least one dissociating group. Examples of four divalent linking groups for forming a nitrogen-containing 6-membered ring include -NH-, -N (R)-, -N =, -CH
(R)-, -CH =, -C (R) =, -CO-, -S
—, —SO—, and —SO ₂ — (R represents a substituent, examples of which include the substituents described for R ₇₁ ).

Examples of the dissociating group include -NH-, -CH
Examples thereof include those having an acidic proton such as (R)-, and preferably have a pKa in water of 3 to 12.

Among the couplers represented by formula (7), preferred specific examples are the following formulas (7) -1 to (7)-
6 is mentioned.

[0121]

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In the formula, R ₄₆ , R ₄₇ and X ₃₄ have the same meanings as in the general formula (7). R ₈₁ and R ₈₂ each represent a hydrogen atom or a substituent, and R ₈₃ represents an electro-attractive group having a Hammett's substituent constant σp value of 0.20 or more.

Specific examples of the substituent of R ₈₁ and R ₈₂ are the same as those of R _{43 in the} general formula (5), and specific examples of the electron-withdrawing group represented by R ₈₃ are the same as those of the general formula (4). ₄₁ and is similar to the electron-withdrawing groups R _42.

[0124] Examples of the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _34, include the same groups as X ₃₁ in formula (4).

Hereinafter, cyan couplers represented by formulas (4) to (7) (hereinafter referred to as cyan couplers of the present invention).
The following are specific examples, but the present invention is not limited to these.

[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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The cyan coupler of the present invention is generally used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-3 mol, per mol of silver halide.
It can be used in the range of × 10 ^-2 to 8 × 10 ^-1 mol. Further, the coupler of the present invention can be used in combination with another type of cyan coupler.

Next, the compound represented by formula (8) will be described.

In the general formula (8), R ¹² and R ¹³ are
Represents a secondary or tertiary alkyl group. Where R ¹² and R
The total number of carbon atoms of the alkyl group represented by ¹³ is 20 or more.

Examples of the alkyl group represented by R ¹² and R ¹³ include a s-dodecyl group and a t-dodecyl group.

Next, typical compounds represented by the above general formula (8) of the present invention will be shown, but the present invention is not limited thereto.

[0139]

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[0140]

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[0141]

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[0142]

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Next, the invention of claim 1 will be described.

The lipophilic fine particle dispersion has an average particle size of 0.10.
μm or less, more preferably 0.08 μm or less. Most preferably, it is 0.05 μm or less. The average particle size of the dispersion can be adjusted by the type and amount of the surfactant, the pressure of the disperser, and the like. Average particle size is 0.10μ
In a dispersion having a particle size of m or less, it is preferable that all layers far from the support have an average particle size of 0.10 μm or less than the photosensitive layer closest to the support.

Next, the oil phase refractive index according to the second aspect of the present invention will be described.

The refractive index was measured using an Abbe refractometer (ATAG).
O OPTICAL WORKSCo. (LTD). Regarding the refractive index of the solid, four types of solutions having different concentrations were prepared using a solvent such as ethyl acetate, and the respective refractive indices were measured. The refractive index of the oil phase was extrapolated from the volume ratio.

The refractive index of the oil phase is preferably from 1.48 to 1.58. More preferably, it is 1.50 to 1.56.

[0148] Those used for adjusting the refractive index include high boiling organic solvents and other photographic additives. Phosphate esters, phosphonate esters, benzoate esters, phthalate esters, fatty acid esters, carbonate esters, amides, and the like are preferably used for adjusting the refractive index.
High-boiling organic solvents such as ethers, halogenated hydrocarbons, alcohols, and paraffins are exemplified. Of these, phosphate esters, phosphonate esters, phthalate esters, benzoate esters, and fatty acid esters are particularly preferred. Also, benzotriazoles, triazines, benzophenones, styrene-based polymers and the like can be preferably used. Particularly, benzotriazoles are preferable.

The dispersion of the present invention may be added to any layer of the photographic material, but is preferably added to a layer farther from the support than the photosensitive layer closest to the support.

The oil phase as used herein means an oil component of a lipophilic fine particle dispersion added to a photographic light-sensitive material. The dispersion forms an oil-in-water emulsion, but as a dispersion production method, for example, an oil phase having the above-mentioned oil phase refractive index is prepared by using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. An emulsified dispersion can be obtained using a stirrer, a homogenizer, a colloid mill or the like.

Next, the nonionic surfactant according to the third aspect of the present invention will be described. The nonionic surfactant refers to a surfactant that does not contain an ionic group in the molecule, but a preferable one is represented by the following general formula (N).

Formula (N) R- (G) _m -X In the formula, R is an alkyl group (including those having a substituent), an alkoxy group (including those having a substituent), an alkenyl group. (Including those having a substituent), aryl groups (including those having a substituent),
Or an aryloxy group (including those having a substituent).

G represents a divalent linking group, X represents a nonionic hydrophilic group, and m represents 0 or 1.

G is preferably an alkylene group (including those having a substituent, for example, an ethylene group, a trimethylene group, etc.), an arylene group (including those having a substituent, for example, a propyl group, a phenylene group, etc.) ) Or arylalkylene group (including those having a substituent,
For example, a phenylethylene group), and these groups include an oxygen atom, an ester group, an amide group, a sulfonyl group,
Also included are divalent linking groups interrupted by heterogeneous atoms such as sulfur atoms or heterogeneous groups.

The nonionic group represented by X is, for example,-(BO) _n -Rs. Where B, -CH ₂ CH
_{2 -, - CH 2 CH 2} CH 2 -, - CH 2 CH (OH) -C
H ₂ — or —CH (CH ₃ ) —CH ₂ —, n represents an average degree of polymerization of a polyoxyalkylene group, and 1 to 50
Is an integer. Rs represents a hydrogen atom, an alkyl group including a substituent, or an aryl group including a substituent.

Specific examples of typical nonionic surfactants of the present invention are shown below, but those used in the present invention are not limited thereto.

[0157]

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[0158]

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[0159]

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The amount of the nonionic surfactant used in the present invention is preferably from 0.1 to 1000 mg, more preferably from 0.5 to 300 mg per 1 m ^{2 of the} silver halide photographic material.
mg is more preferable, and 1.0 to 150 mg is particularly preferable.

The nonionic surfactants may be used alone or in combination of two or more.

Next, the aliphatic alcohol according to the present invention will be described. Aliphatic alcohol refers to a compound in which one or more hydroxyl groups are substituted on an alkyl group, and the alkyl group has another substituent (such as a phenoxy group, an alkoxy group, or an alkoxycarbonyl group).
May be substituted.

The total carbon number of the compound is preferably from 20 to 50, more preferably from 25 to 40. Further, a compound containing two or more hydroxyl groups in the molecule is preferable.

Representative examples of the aliphatic alcohol according to the present invention are shown below.

[0165]

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These aliphatic alcohols may be added to either the non-photosensitive layer or the photosensitive layer, but are preferably the photosensitive layer and more preferably added to the coupler-containing oil. Is preferably added at 10 to 50% by weight based on the coupler.

Next, the tabular silver halide emulsion according to the ninth aspect will be described.

As tabular grains containing silver chloride at a high concentration, grains having a {111} major plane and grains having a {100} major plane are known.

Among these, many methods for forming tabular grains having {111} major planes have been proposed as described above, but methods for forming crystals such as aminoazaindene, pyrimidine, aminoazine, thiourea, and xanthinoids have been proposed. A method for forming particles in the presence of a habit controlling agent is known.

The silver halide emulsion of the present invention includes:
A tabular silver halide emulsion having a main plane of 00 ° is more preferred.

The process of preparing a silver halide emulsion having a {100} main plane can be divided into a process of forming nuclei of silver halide crystals, a process of physical ripening of nuclei, and a process of growing grains.

The step of forming silver halide crystal nuclei is performed by adding and mixing a silver salt aqueous solution and a halide salt aqueous solution with stirring in a dispersion medium such as an aqueous gelatin solution. At this time, a method of adding a {100} plane formation accelerator such as imidazole or 3,5-diaminotriazole, and a method of adding silver iodide and silver bromide to the nucleus due to the difference in crystal lattice size from silver chloride. A method is known in which strain is caused in the ligament and a spiral transition is introduced. When a spiral transition is introduced, the formation of a two-dimensional nucleus on that surface is no longer rate-determining,
Crystallization proceeds in this plane, and tabular grains are formed by introducing a spiral transition into two orthogonal {100} planes.

The pCl at the time of nucleation is preferably 1.5 to 2.5, and the temperature is preferably 90 ° C. or lower, more preferably 40 to 80 ° C. The amount of the protective colloid such as gelatin used for nucleation is preferably 0.1 to 5%, more preferably 0.2 to 3%.
Is more preferred. As the gelatin, a low methionine gelatin which is weakly adsorbed on silver halide grains is preferably used.

The content of silver iodide used at the time of nucleation is preferably 0.5 mol% or less as a whole average value.
0.1 mol% or less is more preferable. The local concentration of the portion containing silver iodide is preferably 2 mol% or less, more preferably 1 mol% or less. If the amount of silver iodide is too large, phenomena such as inhibition of bleach-fixing become remarkable, and in addition, there are problems such as broadening of the distribution in the ripening step following the nucleation step. Should be determined experimentally.

As a method for introducing a screw transition using silver bromide during nucleation, a method described in JP-A-6-337489 or the like can be used. After forming 5% of silver chloride, silver bromide of 1 to 5% of the whole is formed, and silver chloride is formed up to 20 to 30% of the whole to complete the nucleation process. Can be formed.

As with the crystal habit controlling agent used for preparing the tabular grains having the {111} major plane described above, {10}
Since the influence on the photographic performance of the 0 ° plane formation accelerator cannot be neglected, a method utilizing a halogen composition gap plane by silver iodide or silver bromide is preferably used.

Since it is impossible to prepare only silver halide grains having a screw transition during the nucleation process, the difference between the growth rates of the grains having the screw transition and the grains having no screw transition is utilized to carry out the screw transition. Physical ripening is performed following the nucleation process in order to eliminate particles having no particles. The ripening temperature is preferably set higher than the nucleation temperature,
About 50-90 ° C, more preferably 60-80 ° C. p
It is preferable to experimentally determine the aging speed because the aging speed varies depending on conditions such as Cl. Excessive aging is not preferred because the particle size distribution is widened.

In order to grow the nuclei of the tabular grains remaining in the ripening process, a commonly used method such as a double jet method can be preferably used. However, if the supply rate of the silver salt is too fast, the growth anisotropy is increased. When the silver salt supply rate is low, the tabular grains have a large specific surface area, causing phenomena such as obscured edges and reduced aspect ratio. There is a problem that the monodispersity of the particle size and shape is deteriorated. Appropriate addition conditions can be determined experimentally, but it is advantageous to use a method in which a silver salt is supplied using a fine grain silver halide emulsion since the appropriate addition conditions are easily maintained.

In order to keep the aspect ratio high, it is preferable to set the temperature at the time of crystal growth to be relatively high, and it is preferable to use a temperature of about 60 to 80 ° C., and more preferably a temperature of 65 to 75 ° C.

The grain size of the silver halide grains according to the present invention is not particularly limited, but rapid processing and photographic performance such as sensitivity, etc.
Is preferably 3 μm or less and 2.0 μm or less.
m is more preferable. The particle size of the silver halide grains can be measured by various methods generally used in the art. As a representative method, a "particle size analysis method" of Loveland (AST.
M. Symposium on light microscopy,
94-122, 1955) or "Theory of Photographic Process, 3rd Edition" (co-authored by Mies and James, Chapter 2,
Macmillan, 1966).

In the present invention, the particle size is represented by using the diameter of a circle having the same projected area as the projected area of the particle. The aspect ratio is defined as the particle size divided by the particle thickness.

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

The silver halide emulsion of the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time, or may be grown after the seed particles are made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble solution described in German Offenlegungsschrift 2,921,164. Apparatus for continuously changing the concentration of silver salt and water-soluble halide salt aqueous solution, Japanese Patent Publication No. Sho 56
For example, an apparatus described in JP-A-501776, which takes out a reaction mother liquor out of a reactor and concentrates the solution by ultrafiltration 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. Aminoazaindene,
Pyrimidine, aminoazine, thiourea, triazole,
3-amino-1H-1,2,4 triazole, 3,5-
A crystal habit controlling agent such as diamino 1H-1,2,4 triazole, imidazole, and xanthoid, a compound having a mercapto group, or a compound such as a sensitizing dye may be added during the formation of silver halide grains.

The silver halide light-sensitive material according to the ninth aspect of the present invention is particularly preferable when an image is formed by scanning exposure with a light beam having a light emission maximum at 400 nm to 450 nm, because the effect of improving sensitivity is greater.

Next, the fluorescent whitening agent according to the tenth aspect will be described. The fluorescent whitening agent is not limited as long as it is a compound that absorbs ultraviolet light and emits visible light fluorescence, but is preferably an oil-soluble fluorescent whitening agent, and is preferably an oxazole-based fluorescent whitening agent. The optical brightener is contained in the support and is preferably added to the polymer of the double-sided polymer laminated paper.

Next, the fluorine-containing surfactant according to the eleventh aspect will be described.

The fluorine-containing anionic surfactant preferably used in the present invention includes those represented by the following general formula [FA].

Formula (FA) (Cf)-(Y) _{n wherein} Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is —COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ wherein M represents a hydrogen atom or an alkali metal atom or an ammonium group, and n is 1 or 2.

More preferably used fluorine-containing anionic surfactants include those represented by the following general formula [FA '].

Formula [FA '] Rf- (D) _t- Y In the formula, Rf represents a fluorine-substituted alkyl group or an aryl group having 3 to 30 carbon atoms, and D represents -O-, -COO-, -C
ON (R ¹⁾ - or -SO ₂ N (R ¹⁾ - comprising coupling a represents a divalent group having 1 to 12 carbon atoms containing at least one,
Here, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and t 1
Is 1 or 2, and Y is -COOM, -SO
₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2,
Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group.

Next, specific examples of the compounds will be shown, but the present invention is not limited thereto.

[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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In addition, a fluorine-containing betaine surfactant,
Although a fluorinated cationic surfactant can be used, a fluorinated anionic surfactant is preferred.

When the fluorine-containing surfactant is contained in the layer farthest from the support, the effect of the present invention is great.

Next, the Ir compound according to the twelfth aspect will be described. The Ir compound refers to a compound containing iridium, and is preferably a compound containing chlorine or bromine.

Examples of the iridium compound used in the present invention are shown below, but the present invention is not limited thereto.

(Ir-1) K ₂ IrCl ₆ (Ir-2) K [IrCl ₅ (NO)] (Ir-3) K [IrBr ₅ (NO)] (Ir-4) K ₃ IrCl ₆ (Ir- 5) K ₂ IrBr ₆ (Ir-6) K ₃ [Ir (NO ₃ ) ₆ ] (Ir-7) IrCl ₄ (Ir-8) K ₂ [IrBr ₅ (OH ₂ )] (Ir-9) K _{2 [IrCl 5 (OH 2)]} (Ir-10) IrBr 3 (Ir-11) (NH 4) 2 [IrCl 6] (Ir-12) Na 3 [IrBr 6] (Ir-13) Na 2 [IrBr 6 _{] (Ir-14) Na 3} [IrCl 6] (Ir-15) [IrCl (NH 3) 5] Cl 2 (Ir-16) cis- [IrCl 2 (C 2 H 8 N 2) 2]
_{Cl (Ir-17) H 2} IrCl 6 (Ir-18) (NH 4) 2 [IrBr 6] (Ir-19) [Ir 4 (CO) 12] (Ir-20) H 2 [Ir 4 Cl 8 ( CO) ₈ ] The particle size of the silver halide grains is not particularly limited, but is preferably from 0.2 to 1.6 μm, more preferably from 0.25 to 1.6 μm, in consideration of rapid processing property and sensitivity, and various other photographic properties.
The range is 1.2 μm. The particle size of the silver halide grains can be measured by various methods generally used in the technical field. As a typical method, there is a “particle size analysis method” of Loveland (ASTM.
Symposium on Right Microscopy, 19
55, pp. 94-122) or "Theory of the photographic process"
(Mies and James, 3rd edition, published by Macmillan, Inc. (1966)). That is, the particle size can be determined using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle distribution can be described quite accurately using diameter or projected area. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. A monodispersed silver halide having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less, in the particle size distribution of silver halide grains. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined as follows.

The Ir compound is contained in an amount of at least 6 × 10 ⁻⁸ mol, preferably at least 1 × 10 ⁻⁷ mol, more preferably at least 1 × 10 ⁻⁷ mol, per mol of silver in grains having an average silver chloride content of 95 mol% or more. It is at least 1 × 10 ^-6 mol.

Next, 400 to 4 according to the thirteenth aspect of the present invention.
Scanning exposure using a light beam having a light emission maximum at 50 nm will be described.

According to the thirteenth aspect, 400 to 4
Scanning exposure using a light beam having an emission maximum wavelength at 50 nm is used. A light source of a light beam having a light emission maximum wavelength of 400 to 450 nm has been energetically researched and developed mainly for high-density recording on an optical disc such as a digital video disc (DVD). Are, for example, a semiconductor laser (e.g., GaAs-based) having an oscillation wavelength of 800 to 900 nm and a second high frequency generator (SH).
G) An element (for example, an inorganic crystal such as a LiNbO ₃ system or a LiTaO ₃ system, or an organic crystal such as 2-methyl-4-nitroaniline) can be used.

As another method, a blue semiconductor laser using an InGaN-based material and having an oscillation wavelength of 400 to 430 nm, a dye laser using a scintillator-based or coumarin-based dye, or the like can be used.

The emission wavelength is preferably from 400 to 430 nm.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. Quick processing,
From the standpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol%, of silver chloride is preferred.

For obtaining the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred. These metal ions are
It can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl ion. , Ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to make the silver halide emulsion according to the present invention contain heavy metal ions, the heavy metal compound must be physically added to the silver halide emulsion before silver halide grains are formed, during silver halide grains are formed, and after the silver halide grains are formed. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly 1 mol
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention can have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

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

The particle size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

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

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size mentioned here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

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

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

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 at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the magnitude of the expected effect, but 5 × 10 5 per mol of silver halide. ^In the range of ^{-10 to} 5 × 10 ^-5 mol,
Preferably, it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer according to the present invention, 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 the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide.
Preferably it is molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention has the object of preventing fog generated during the preparation process of a silver halide photographic material, reducing performance fluctuation during storage, and preventing fog generated during development. A known antifoggant,
Stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in JP-A No. 2-14 / 1990.
The compound represented by the general formula (II) described in the lower column of page 7 of JP-A-6036 can be mentioned, and a more preferred specific compound is (IIa-1) described on page 8 of the same publication. )-(IIa-8), (IIb-1)-(II
b-7) or 1- (3-methoxyphenyl)-
Compounds such as 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds may be used, depending on the purpose, in a step of preparing silver halide emulsion grains, a step of chemical sensitization,
At the end of the chemical sensitization step, it is added in a step such as a coating liquid preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 ×
It is preferably used in an amount of about 10 ^-4 mol. When added at the end of chemical sensitization, 1 × per mole of silver halide
An amount of about 10 ⁻⁶ mol to 1 × 10 ⁻² mol is preferable, and 1 ×
The amount is more preferably from 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. In the step of preparing a coating solution, when added to the silver halide emulsion layer, 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide is used.
An amount of about ^-1 mol is preferred, and 1 × 10 ^-5 mol to 1 × 10
^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

In the silver halide photographic light-sensitive material of the present invention,
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, dyes having absorption in the visible region include AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared-absorbing dye include general formulas (I) and (I) described in the lower left column of page 2 of JP-A-1-280750. The compounds represented by II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable without contamination by residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

In order to improve the sharpness, the amount of these dyes added was 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention since whiteness can be improved. Preferred examples of the compound include compounds represented by the general formula described in JP-A-2-232652.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, a halogen spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. As a method of adding the sensitizing dye, methanol, ethanol, fluorinated alcohol, acetone, may be added as a solution by dissolving in water-miscible organic solvents such as dimethylformamide or water or added as a solid dispersion. Is also good.

As the coupler used in the silver halide photographic light-sensitive material of the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm is formed by a coupling reaction with an oxidized form of a color developing agent. Although any compound obtained can be used, particularly typical ones are a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 6
Magenta dye-forming couplers having a spectral absorption maximum wavelength at 00 nm, and cyan couplers represented by the general formulas (3) to (7) can be used.

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include those represented by formulas (MI) and (M-I) described in the upper right column on page 4 of JP-A-4-114154. Couplers represented by II) can be mentioned. Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication, MC-1 to MC-.
11 can be mentioned.
More preferred among the above magenta couplers are couplers represented by the general formula (MI) described in the upper right column on page 4 of the specification of the same gazette.
The coupler of I) in which the RM is a tertiary alkyl group is particularly preferred because of its excellent light resistance. MC-8 to MC-11 described in the upper column on page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction power, and thus are preferable.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (Y-I) described in the upper right column of page 3 of JP-A-4-114154. Couplers can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Above all, a coupler in which RY1 of the general formula [Y-1] of the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone. preferable. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154 and JP-A-6-114.
No. 67388, page 13-14
o. Compounds represented by (1) to (47) can be mentioned. Further most preferred compounds are described in JP-A-4-818.
It is a compound represented by the general formula [Y-1] described in JP-A-47-47, page 1 and JP-A-47-175, page 11-17.

When an oil-in-water type emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material of the present invention, the boiling point is usually 15 or more.
It is dissolved in a water-insoluble high-boiling organic solvent at 0 ° C. or higher, if necessary, in combination with a low-boiling and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. . As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer,
An ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phthalate; Is preferably used. The high-boiling point organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

It is preferable to use an anti-fading agent in combination with the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541 and general formula IIIB described in JP-A-3-174150.
A phenolic compound represented by
Amine compounds represented by the general formula A described in JP-A-62-182741, JP-A-62-182741
Metal complexes represented by IV and XV are particularly preferred for magenta dyes. Also, a compound represented by the formula I 'described in JP-A-1-19649 and JP-A-5-11417
The compound represented by the general formula II described in JP-A No. 2-2,086 is particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, and the compound described in JP-A-4-114154, page 10, lower left column Compounds such as (A'-1) can be used. In addition, U.S. Pat.
No. 74,187 can also be used.

In the silver halide photographic light-sensitive material of the present invention,
It is advantageous to use gelatin as a binder, but if necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, a homopolymer or a copolymer A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener or a carboxy active hardener alone or in combination. JP-A-61-249054 and 61-245
It is preferable to use the compound described in JP-A-153-153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used for the silver halide photographic light-sensitive material of the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, A vinyl sheet, a polypropylene that may contain a white pigment, a polyethylene terephthalate support, baryta paper, or the like can be used. Among them, a support having a water-resistant 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 sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, 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 was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention 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 the coefficient of variation described in the above publication.

The center surface average roughness (SRa) value of the support is preferably 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is obtained, and it is more preferable. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, charging, etc.). Or one or more subbing layers for improving the anti-static property, dimensional stability, friction resistance, hardness, anti-halation property, frictional properties and / or other properties). .

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the silver halide photographic light-sensitive material of the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be converted into digital information, then formed into an image on a CRT (cathode ray tube), and the image may be formed on a silver halide photographic material to be printed. The printing may be performed, or the printing may be performed by changing the intensity of the laser beam based on the digital information 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 having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

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) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (methanesulfonamido) ethyl) aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 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 above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature of color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

In the color developer, in addition to the above-described color developing agent, a known developer component compound can be added. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed across rollers arranged in a processing tank.
An endless belt type in which the photosensitive material is fixed to the belt and transported may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported or a processing liquid is transported. A spray method of spraying, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. In the case of processing a large amount, it is normal to perform a running process using an automatic developing machine. At this time, the smaller the replenishment amount of the replenisher, the more preferable, and the most preferable processing form from environmental suitability, etc.
As a replenishment method, a processing agent is added in the form of a tablet, and the method described in JP-A-94-16935 is most preferable.

[0264]

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 High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a silver halide photographic material. The coating solution was prepared as described below.

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

Each of the coating liquids for the second to seventh layers was prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

(H-1), (H-2)
Was added. Surfactants (SU-
2) was added to adjust the surface tension. Each layer has F-1
Was added so that the total amount was 0.04 g / m ² .

[0269]

[Table 1]

[0270]

[Table 2]

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i -Decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octyl Hydroquinone HQ-2: 2,5-di-sec-dodecyl hydroquinone Image stabilizer A: Pt-octylphenol

[0272]

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[0273]

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[0274]

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[0275]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
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 further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (solution A) and (solution B) and (C solution) and (D
Liquid), the average particle size was 0.64 μm and the variation coefficient of the particle size distribution was 0.0
7. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-1B was obtained.

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

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 stability 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 diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a thickness of 0.08 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

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 stability 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 diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation of 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5% were obtained. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

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

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 stability 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 STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In a red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

[0284]

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[0285]

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[0286] The sample thus prepared was used as the sample 10
Let it be 1. Next, each sample was prepared in the same manner except that the ultraviolet absorber-containing fine particle dispersion to be added to the sixth layer and the fourth layer was changed in a combination shown in Table 3. However, in the preparation of each sample, the coating solution was applied after storage at 40 ° C. for 3 hours in order to cope with mass production.

Each sample thus prepared was exposed to a blue light wedge by a conventional method, and then developed by the following developing process to produce a color print having a yellow wedge image.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml 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 Pentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fixer tank solution and replenisher diammonium ferric diethylenetriaminepentaacetate dihydrate 65 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution 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 (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

The maximum blue light reflection density of the yellow image thus obtained was measured using PDA-65 manufactured by Konica Corporation.

Further, the light resistance of each sample having a yellow reflection density of 1.0 after storage for 2 weeks was evaluated by observing sunlight for 90 days using an underglass outdoor exposure table.
The red light reflection density before and after fading was measured. The fading rate due to light was determined as follows.

Fading ratio (%) = 100 × (D0−D) / D0 D0 = reflection density before photobleaching D = reflection density after photobleaching The results are shown in Table 3.

[0295]

[Table 3]

As is clear from Table 3, it was found that the sample using the dispersion of the present invention according to claim 1 had a high yellow maximum reflection density even when the dispersion was produced after storage. Also, the samples prepared after storing the dispersion had good light fastness.

Example 2 The dispersion used for the sample 102 of Example 1 was used, and the refractive index of the oil phase was further adjusted using a high boiling point organic solvent (DNP) and an ultraviolet absorber to be used. Produced. Table 4 shows the results of evaluation in the same manner as in Example 1 using the coated product after storage of the dispersion liquid as in Example 1.

[0298]

[Table 4]

As is apparent from Table 4, it was found that the sample using the dispersion of the present invention according to claim 2 had a high yellow image maximum reflection density even when the dispersion was produced after storage. Also, the samples prepared after storing the dispersion had good light fastness.

Example 3 A sample 301 was prepared in the same manner as in Example 1, except that the dispersion liquid used for the sample 101 of Example 1 was used. Next, each sample was prepared in the same manner except that the additives of the dispersion liquid were changed as shown in Table 5. Table 5 shows the results of evaluation in the same manner as in Example 1 using the coated product after storage of the dispersion liquid as in Example 1.

[0301]

[Table 5]

As is clear from Table 5, the samples of the present invention according to claims 3 and 7 have a high yellow maximum color density even when the dispersion is produced after storage. Also, the samples prepared after storing the dispersion had good light fastness.

Example 4 A sample 401 similar to the sample 101 of Example 1 was produced.
Except as shown in Table 6, the same samples were prepared and subjected to the same exposure treatment as in Example 1 except that red light wedge exposure was performed. After storage at 60% humidity for 2 weeks, the perspiration resistance of each image was visually observed by 10 observers on a scale of 10 based on the following criteria, and the average score was used as a measure of perspiration resistance.

Evaluation criteria for perspiration resistance: Large number of large oily components on the surface: 1 Oily component on the surface: 5 Slight generation of oily component on the surface: 8 No perspiration on the surface: 10 The results are shown in Table 6.

[0305]

[Table 6]

As is clear from Table 6, the samples of the present invention according to the fifth and eighth aspects exhibited good perspiration resistance. Light resistance was also good.

Example 5 A sample 501 similar to the sample 101 of Example 1 was produced.
Except as shown in Table 7, the same samples were prepared and subjected to the same exposure treatment as in Example 1 except that red light wedge exposure was performed. After storage at 60% humidity for 2 weeks, the cyan image fading rate of the image portion having a red light reflection density of 1.0 was measured to evaluate the heat and humidity preservability. Table 7 shows the results.

[0308]

[Table 7]

As is clear from Table 7, the sample of the present invention according to the sixth aspect had good cyan image preservability. Light resistance was also good.

Example 6 The same processing as in Examples 1 to 5 was performed as described below.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleaching and fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Drying 60 ８０80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml 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 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3. 5 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g of water to make the total volume 1 liter, Click solution pH =
At 10.10, the replenisher is adjusted to pH = 10.60.

Bleach-fix solution tank solution and replenisher tank solution Replenisher diethylenetriamine pentaacetate ammonium dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, use potassium carbonate or glacial acetic acid to make the tank solution pH = 7.0, and make up the replenisher solution pH = 6.
Adjust to 5.

Stabilizing solution tank solution and replenisher solution 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 PVP 1.0 g Aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was made in the same manner as in Example 1, and it was confirmed that the effects of the present invention can be effectively obtained with the sample of the present invention.

Example 7 A sample 701 similar to the sample 101 of Example 1 was prepared.
Next, each sample similar to the sample 701 was prepared except for the conditions shown in Table 8.

As an automatic developing machine, NPS- manufactured by Konica Corporation was used.
868J, using ECOJET-P as the processing chemical, running according to the process name CPK-2-J1. At this time, the apparatus was adjusted, and exposure and printing were performed at a processing speed of 2000 sheets / hour. The difference (ΔDm) between the maximum value and the minimum value of the blue light reflection density of the white portion of the obtained print
in) was measured, and it was set as variation resistance of whiteness. Table 8 shows the results.
Shown in

[0318]

[Table 8]

[0319]

Embedded image

The samples of the present invention according to Claims 4, 10, 11, and 12 provided images having good white background variation resistance. Further, an image having good light fastness was obtained.

Example 8 A sample 801 similar to the sample 101 of Example 1 was produced.
Except for those shown in Table 9, samples similar to the sample 801 were produced. These photosensitive materials were exposed to a portrait human image scene using the following laser scanning exposure apparatus.
The blue light sensitivity was measured, and the sensitivity ratio with the sample 801 was determined.

Laser exposure apparatus: The following were used as light sources.

B: 425 nm light obtained by converting the wavelength of a semiconductor laser GaAlAs (850 nm in wavelength) using an SHG crystal of MgO: LiNbO ₃ G: Semiconductor laser GaAlAs (oscillation wavelength: 809 n)
m) as an excitation light source and a YVO ₄ solid laser (oscillation wavelength, 1064 nm) as LiN having an inversion domain structure.
53 wavelength-converted and extracted by bO ₃ SHG crystal
2 nm light R: AlGaInP (oscillation wavelength: 688 nm) The laser beams of the above three colors were added in the scanning direction by the polygon mirror and moved in the vertical direction, so that the scanning exposure could be sequentially performed on the photosensitive material. Fluctuations in light quantity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. Exposure Exposure was provided by an external modulator. At this time, the scanning pitch is 4
The exposure time was 2.3 μm (600 dpi), and the average exposure time per pixel was 5 × 10 ⁻⁷ seconds. Table 9 shows the results.

[0324]

[Table 9]

As is clear from Table 9, the samples of the present invention according to the ninth and thirteenth aspects exhibited good sensitivity even when an image was formed by the short-wavelength blue light laser exposure.

[0326]

As described above, it is possible to provide a photographic lipophilic fine particle dispersion having good light resistance and high color density even after storage of the coating solution over time during mass production, and a photosensitive material using the same.

It is possible to provide a photosensitive material which has a small variation in white background performance even at the time of high-speed image formation, has little image fading due to perspiration, heat and humidity, has high sensitivity even after scanning exposure, and has good light fastness of formed images. Was completed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03C 5/08 G03C 5/08 7/38 7/38 7/392 7/392 A

Claims (13)

[Claims] 1. A compound represented by the general formula (1) or (2), or a compound having an absorption maximum wavelength of 330 nm to 390.
lipophilic photographic material comprising at least one compound having a molar extinction coefficient of 17000 or more in the range of nm and an average particle size of the lipophilic fine particle dispersion of 0.1 μm or less. Fine particle dispersion. Embedded image [Wherein R ¹ and R ² each represent an alkyl group, an aryl group,
Represents an alkoxy group or an aryloxy group, and R ³ represents a hydrogen atom, a halogen atom or a monovalent organic group. [Chemical formula 2] [Wherein, R ₁ and R ₂ each represent a substituent. Where R
_At least one of ₁ and R ₂ is an alkoxy group, an aryloxy group, an alkylthio group, an acylamino group, or -N
Shows the HCOOR group. R represents an alkyl group or an aryl group. X ₁ and X ₂ each represent a halogen atom. m,
n, p and q each represent an integer of 0-4. Here, the sum of m and n and the sum of p and q are each an integer of 0 to 4;
Are never 0. When m, n, p or q is 2 or more, a plurality of R ₁ , R ₂ , X ₁ or X ₂ may be the same or different. ] 2. The compound represented by the general formula (1) or (2), or the compound having an absorption maximum wavelength of 330 nm to 3
In the range of 90 nm, containing at least one compound among the compounds having a molar extinction coefficient of 17000 or more,
A lipophilic fine particle dispersion for photography, having an oil phase refractive index of 1.48 to 1.58. 3. A photographic material having at least one photosensitive layer and at least one non-photosensitive layer,
In at least one layer, the compound represented by the general formula (1) or (2) or the compound having an absorption maximum wavelength of 330
nm to 390 nm with a molar extinction coefficient of 170
At least one compound among the compounds that are 00 or more,
And a photographic material containing a nonionic surfactant. 4. At least one photosensitive layer (a) is provided on one surface of the support, and at least one photosensitive layer (a) is provided on the surface of the support opposite to the surface on which the photosensitive layer is provided. In a photographic material having a non-photosensitive layer (b), at least one of the compounds represented by the general formula (1) or (2) is added to at least one of the non-photosensitive layers (b). A photographic light-sensitive material comprising: 5. A photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, wherein at least two layers have the general formula (1) or the general formula (2). The total content of the compound represented by the general formula (1) or the general formula (2) contained in a layer farther from the support than the photosensitive layer farthest from the support, containing at least one compound among the compounds shown Is larger than the total content of the compound represented by the general formula (1) or (2) in the photosensitive layer farthest from the support and the layer closer to the support than the photosensitive layer farthest from the support. A photographic light-sensitive material comprising: 6. A photographic material having at least one photosensitive layer and at least one non-photosensitive layer,
In at least one photosensitive layer, at least one of the compounds represented by the general formula (1) or (2) and at least one of the compounds represented by the following general formulas (3) to (7) A photographic material characterized by containing a kind of compound. Embedded image [In the formula, R ₃₁ represents an alkyl group having 2 to 6 carbon atoms.
R ₃₂ represents a ballast group. X ₂₁ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. [Formula 4] [In the formula, R ₄₁ represents a hydrogen atom or a substituent, and R ₄₂ represents a substituent. m represents the number of substituents R _42. When m is 0, R
₄₁ Hammett's substituent constant σp represents 0.20 or more electron-withdrawing group, when m is 1 or 2 or more, at least one of R ₄₁ and R ₄₂ Hammett's substituent constant σp of 0.20
It represents the above electron-withdrawing group. Z ₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like. R ₄₃ represents a hydrogen atom or a substituent; Z ₂ represents a group of non-metallic atoms necessary for forming a nitrogen-containing hetero 6-membered ring by condensing together with —NH— with a pyrazole ring; It may have a substituent and may form a condensed ring with a benzene ring or the like other than the pyrazole ring. R ₄₄ and R ₄₅ represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Provided that the sum of σp values of R ₄₄ and R ₄₅ is 0.65 or more. Z ₃ represents a group of nonmetal atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent. R ₄₆ and R ₄₇ each represent a hydrogen atom or a substituent; Z ₄ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; Good. X ₃₁ , X ₃₂ , X ₃₃ and X ₃₄ each represent a group or an atom which is released by a coupling reaction with an oxidized color developing agent. ] 7. A photographic material having at least one photosensitive layer and at least one non-photosensitive layer,
A photographic material comprising at least one of the compounds represented by formula (1) or (2) and an aliphatic alcohol. 8. A photographic material having at least one photosensitive layer and at least one non-photosensitive layer,
At least one layer contains at least one compound of the compounds represented by the general formula (1) or (2), and at least one layer contains a compound represented by the following general formula (8). A photographic light-sensitive material comprising: Embedded image [In the formula, R ¹² and R ¹³ represent a secondary or tertiary alkyl group. However, the total number of carbon atoms of the alkyl group represented by R ¹² and R ¹³ is 20 or more. ] 9. A photographic material having at least one photosensitive layer and at least one non-photosensitive layer,
At least one layer contains at least one compound selected from the compounds represented by formula (1) or (2), and at least one photosensitive layer has an average silver chloride content of 95 mol% or more. And 5 of the total projected area of the emulsion grains
A photographic light-sensitive material wherein 0% or more contains a tabular silver halide emulsion having an aspect ratio of 3.0 or more. 10. A photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein at least one of the light-sensitive materials has the general formula (1)
Alternatively, a photographic light-sensitive material comprising at least one compound selected from the compounds represented by formula (2) and a support containing a fluorescent whitening agent. 11. A photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein at least one of the light-sensitive materials has the formula (1)
Or a layer containing at least one compound among the compounds represented by the general formula (2), and in a layer farthest from the support,
A photographic light-sensitive material comprising a fluorine-containing surfactant. 12. A photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer, wherein at least one layer comprises a compound represented by formula (1) or (2). And at least one photosensitive layer containing an Ir compound having an average silver chloride content of 95 mol% or more and 6 × 10 ^−8.
A photographic light-sensitive material comprising a silver halide emulsion containing at least 1 mol / silver. 13. An image forming method for forming an image after exposing a photosensitive material, wherein the photographic photosensitive material contains at least one compound of the compounds represented by the general formula (1) or (2). And exposure is 400n
An image forming method, wherein scanning exposure is performed by a light beam having a light emission maximum at m to 450 nm.