JP2880604B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved dryness and sharpness after development processing.

[0002]

2. Description of the Related Art In a silver halide photographic material, a photographic emulsion layer or another layer is often colored in order to absorb light in a specific wavelength range. Light scattered when the incident light passes through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the emulsion layer and the light-sensitive material on the reflection side, and reenters the photographic emulsion layer. For the purpose of preventing the image from being blurred, that is, halation, a coloring layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. Further, in the X-ray photosensitive material, a colored layer for improving sharpness may be provided as a crossover cut filter for reducing crossover light.

The layers to be colored often consist of hydrophilic colloids and, for their coloring, usually contain dyes in the layers. This dye must satisfy the following conditions. (1) To have appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer must not be adversely affected in a chemical sense, for example, decrease in sensitivity, regression of a latent image, or fogging. (3) Decoloring during photographic processing but not dissolving and removing, leaving no harmful coloring on the processed photographic light-sensitive material.

[0004] When a colored layer such as an antihalation layer or a crossover cut layer is formed of a hydrophilic colloid, the bulk of the water-permeable layer is increased as a result, and the drying property after development is deteriorated. There were drawbacks.
In order to eliminate such disadvantages, dyes are fixed in a layer used for improving the adhesion between the hydrophilic colloid layer and the support. (The layer that plays a role of bonding the support and the hydrophilic colloid layer is called an undercoat layer here.) To fix the dye in the undercoat layer, a method of adsorbing the dye to a mordant (Japanese Patent Application No. Sho 62) −224444
No. 1), a method of emulsifying and dispersing a dye dissolved in oil in the form of oil droplets (Japanese Patent Application No. 1-142688), a method of adsorbing the dye on the surface of an inorganic substance (Japanese Patent Application No. 1-139691), and adsorbing the dye to a polymer. How to make it work (Japanese Patent Application No. 1-11985)
No. 1), a method of dispersing a dye as a solid (Japanese Patent Application No. 1-8)
No. 7367). Among these methods, the method of dispersing the dye in a solid state is excellent from the viewpoint that the dye is fixed in a specific layer or the residual color after the treatment is small.

The amount of hydrophilic colloid used in the undercoat layer is usually as small as 0.5 g / m ² or less. When a dye dispersed in the form of solid fine particles is introduced into such a hydrophilic colloid layer, the film itself becomes more brittle, and the surface of the undercoating coating material is easily damaged. The optical density of the scraped portion due to the dye is lower than that of the normal portion. The crossover light increases only in the area where the optical density has decreased, which has a negative effect on photographic performance.In addition, when the scraps that have been cut off adhere to the base, the crossover light in that area decreases. This also has a negative effect on photographic performance. As described above, deterioration of scratch resistance is an important problem.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an undercoat material having improved scratch resistance, and to provide a halation-preventing layer or a crossover cut layer with less residual color and to enable rapid processing with improved image quality. To provide a silver halide photographic light-sensitive material.

[0007]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
At least one hydrophobic polymer subbing layer and at least one non-photosensitive hydrophilic colloid are sequentially formed on the polyester.
Subbing layers, even without least have a silver halide emulsion layer
And contains a substantially solid particulate form in the dispersed dye is water-soluble at a substantially water-insoluble pH8 or more on the non-light-sensitive hydrophilic colloid layer in pH6 below, the non-light-sensitive hydrophilic colloid The coating amount of the hydrophilic colloid of the layer is 0.5 g / m ^2.
The following silver halide photographic light-sensitive material,
The photo-hydrophilic colloid layer further comprises one of the general formulas (A) to (D)
This has been achieved by using a silver halide photographic material characterized by containing at least one of them . The compound represented by formula (A) will be described. Where R ₁ ,
R ₂ and R ₂ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group which may have a substituent having 10 or less carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, a hydroxymethyl group , A hydroxyethyl group, etc.) or a phenyl group (a phenyl group which may have a substituent, for example, a methoxyphenyl group, a p-chlorophenyl group, etc.). Further, R ₂ and R ₃ may be linked to each other to form a ring. The addition amount is preferably 2 wt% to 40 wt%, more preferably 2 wt% to 15 wt%, and still more preferably 5 wt% based on the hydrophilic colloid.
% To 10 wt%. Specific examples of the compound (A) are shown below. However, the present invention is not limited to this. (A-1) 2, 5- dimethyl-3-hexyne-2,5-diol (A-2) 3, 6- dimethyl-4-octyne -3, 6- diol (A-3) 2, 4 , 7 , 9-tetramethyl-5-decyne -4, 7- diol (A-4) 2, 5- dimethyl-3-heptyn-2,5-diol (A-5) 3, 6- dimethyl-4-nonyne - 3, 6-diol these compounds Sho 50-40660 as a plasticizer
And so on. Next, the general formula (B) will be described. R ₄ and R ₅ in the general formula (B) each represent a hydroxyl group or an alkoxy group having at least one hydroxyl group. The alkoxy group has 1 to 1 carbon atoms.
0 is preferable, and 4 to 7 are more preferable.
The addition amount is preferably 2 wt% to 30 wt%, more preferably 5 wt% to 20 wt%, based on the hydrophilic colloid. Preferred compound examples are shown below. However, the present invention is not limited to this.

[0008]

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These compounds are disclosed in US Pat.
411913. General formula (C)
Will be described. R in the general formula (C)
_6, R ₇ represents an alkyl group, an aryl group, an aralkyl group. n ₁ and n ₂ represent an integer of 2 to 20. The addition amount is from 2 wt% to 40 w with respect to the hydrophilic colloid.
t% is preferable, and more preferably 2 wt% to 15 wt%.
%. Specific examples of the compound (C) are shown below. However, the present invention is not limited to this.

[0010]

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[0011]

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These compounds are known as plasticizers from Belgian Patent 636,304. The compound represented by formula (D) will be described. General formula (D)
R _{8 in the above} represents hydrogen or an alkyl group having 10 or less carbon atoms. The addition amount is 2 wt.
% To 40% by weight, more preferably 2% by weight.
To 15 wt%. Specific examples of the compound (D) are shown below. However, the present invention is not limited to this.

[0013]

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These compounds are described as plasticizers in Belgian Patent No. 691333. Other, Shoko 4
1-1905, Belgian patent 677961, and the plasticizer described in German patent 1447585 can also be preferably used.

As the polyester used in the present invention, polyethylene terephthalate is desirable. When used for photographic materials, polyethylene terephthalate processed into a film (hereinafter abbreviated as PET) is preferably used.

[0016] PET, to improving an adhesion to the hydrophilic colloid, a corona discharge treatment the surface, or glow discharge treatment or a method of UV irradiation treatment is not better good <br/>. A hydrophobic polymer layer on a polyester support,
Ie styrene-butadiene latex, Ru subbing layer comprising a vinylidene chloride latex (undercoat first layer). As the hydrophobic polymer of the undercoat first layer, styrene-butadiene copolymer, vinylidene chloride copolymer,
Water-soluble polyesters, polyacrylates and the like are used, preferably styrene-butadiene copolymer,
It is a vinylidene chloride copolymer, more preferably a styrene-butadiene copolymer. As a styrene-butadiene copolymer, 9/1 to 1
/ 9, and may have acrylic acid or the like as the third comonomer. The coating amount of the hydrophobic polymer in the undercoat layer is preferably from 100 to 500 mg / m ² .

The coating apparatus includes an extrusion slide hopper type (US Pat. Nos. 2,761,417, 2,761,418, and 276,179).
1), a curtain coating device (US Pat. No. 3,206,323) and the like, but in the present invention, the amount of the undercoat composition applied is small, and in such a case, it is preferable to apply the composition with a bar coater. If the drying temperature of the first undercoat layer is too low, the adhesion between PET and the first undercoat layer cannot be maintained. Therefore, the drying temperature of the first undercoat layer is preferably 80 to 200 ° C.

The hydrophobic polymer used for the undercoat layer is an aqueous dispersion (latex), and if necessary, a crosslinking agent, a surfactant, a swelling agent, a matting agent, an antistatic agent and the like are added to the aqueous dispersion. Is preferred. Examples of the crosslinking agent include, for example, U.S. Patent Nos. 3,325,287 and 3,288,7.
Nos. 75 and 3,549,377, Belgian Patent 6,6
Triazine compounds described in U.S. Pat. Nos. 02,226; U.S. Pat. Nos. 3,291,624 and 3,232,764; French Patent 1,543,694; British Patent 1,27
A dialdehyde compound described in U.S. Pat. No. 0,578; an epoxy compound described in U.S. Pat. No. 3,091,537 and JP-B-49-26580; U.S. Pat. No. 3,642,486
Compounds described in US Pat. No. 3,392,0
Aziridine compound described in No. 24; 3,549,37
No. 8 and the like; and an ethyleneimine compound; and a methylol compound. Of these compounds, dichlorotriazine derivatives are preferred.

The non-photosensitive hydrophilic colloid layer containing a solid-dispersed dye of the present invention is preferably applied as a second undercoat layer on the first undercoat layer. The drying temperature of the second undercoat layer is 8 for the purpose of strengthening the adhesion.
The temperature is preferably from 0 to 200 ° C. If the drying temperature is too high, the dye may be taken into the polymer layer of the first undercoat layer.
55 ° C. The surface of the undercoat first layer may be subjected to a corona discharge treatment, a glow discharge treatment or an ultraviolet irradiation treatment for the purpose of strengthening the adhesion between the undercoat first layer and the undercoat second layer.

The undercoat coating composition of the present invention comprises a dye and a hydrophilic colloid, which are substantially insoluble in water at a pH of 6 or less and are substantially water-soluble at a pH of 8 or more, and are dispersed in the form of solid fine particles. It is necessary to include at least one of the compounds of A) to (D). As the dye dispersed in the form of solid fine particles, there are used Tables I to X of International Publication WO88 / 04794, (I) to (VII) shown below, and others. General formula (I)

[0021]

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Formula (II)

[0023]

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Formula (III)

[0025]

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General formula (IV)

[0027]

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General formula (V)

[0029]

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General formula (VI)

[0031]

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Formula (VII)

[0033]

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Wherein A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, and X
And Y may be the same or different and each represents an electron-withdrawing group. R represents a hydrogen atom or an alkyl group; R ¹ and R ² each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group; even if R ¹ and R ² are linked to form a 5- or 6-membered ring, Good. R ³ and R ⁶ each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group or a halogen atom, and R ⁴ and R ⁵ are each a hydrogen atom or R ¹ and R ⁴ or R ² and R ⁵ are linked. Then 5 or 6
Represents a group of non-metallic atoms necessary for forming a member ring. L ¹ ,
L ² and L ³ each represent a methine group. m represents 0 or 1, n and q represent 0, 1 or 2, p represents 0 or 1, and when p is 0, R ³ represents a hydroxy group or a carboxyl group and R ⁴ and R ⁵ Represents a hydrogen atom. B 'represents a carboxyl group, a sulfamoyl group, or a heterocyclic group having a sulfonamide group. Q represents a heterocyclic group. However, the compounds represented by the general formulas (I) to (VII) have a dissociative property in which pKa is in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 in one molecule. It has at least one group.

First, the compounds represented by formulas (I) to (VII) will be described in detail. A is preferably an acid nucleus represented by A ', preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione , Pyrazolopyridine or hydroxypyridone. The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole. Examples of the heterocycle of B 'include pyrrole, indole, thiophene, furan,
Imidazole, pyrazole, indolizine, quinoline,
Examples include carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, and tetrazole. The heterocyclic ring represented by Q is preferably a benzo-fused ring.
And more preferably a 5-membered nitrogen-containing heterocyclic ring which may be benzo-fused. Examples of the heterocycle of Q include pyrrole, indole, pyrazole, pyrazolopyrimidone, benzoindole and the like.

A group having a dissociable proton having a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1: 1 is a dye molecule having a pH of 6 or less at pH 6 or less. Is made water-insoluble and pH 8 or pH
There are no particular restrictions on the type and substitution position of the dye molecule as long as the dye molecule is at least 8 so as to substantially render the dye molecule water-soluble, but preferably a carboxyl group, a sulfamoyl group,
A sulfonamide group and a hydroxy group are more preferable, and a carboxyl group is more preferable. The dissociable group may be directly substituted on the dye molecule, or may be substituted via a divalent linking group (for example, an alkylene group or a phenylene group). 2
Examples via a valent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl,
3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl,
2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl, 4- (p-cyanobenzenesulfonamido) phenyl, 3-hydroxyphenyl, 2-
Hydroxyphenyl, 4 hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4-
Carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl, 2,5-disulfamoylphenyl, carboxymethyl , 2-carboxyethyl, 3-
Carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl and the like can be mentioned.

The alkyl group represented by R, R ³ or R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include groups such as methyl, ethyl, n-propyl, isoamyl and n-octyl. . The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl), Substituents [eg, halogen atoms such as chlorine bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (eg, methoxy, ethoxy), alkoxycarbonyl group (eg, methoxycarbonyl,
i-propoxycarbonyl), an aryloxy group (for example, a phenoxy group), a phenyl group, an amide group (for example,
Acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), and a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R ¹ or R ² is preferably a phenyl group or a naphthyl group, and is a substituent (for the substituent, the groups mentioned above as the substituents of the alkyl group represented by R ¹ and R ² and Includes alkyl groups (eg, methyl, ethyl). ] May be provided. R ¹
Alternatively, the acyl group represented by R ² is preferably an acyl group having 2 to 10 carbon atoms, for example, acetyl, propionyl, n
Groups such as -octanoyl, n-decanoyl, isobutanoyl and benzoyl. Examples of the alkylsulfonyl group or arylsulfonyl group represented by R ¹ or R ² include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl,
Examples include groups such as benzenesulfonyl, p-toluenesulfonyl, and o-carboxybenzenesulfonyl. The alkoxy group represented by R ³ or R ⁴ has 1 carbon atom.
~ 10 alkoxy groups are preferred, for example, methoxy,
Examples include groups such as ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, and isopropoxy. Examples of the halogen atom represented by R ³ or R ⁶ include chlorine, bromine and fluorine. Examples of the ring formed by linking R ¹ and R ⁴ or R ² and R ⁵ include a julolidine ring. Examples of the 5- or 6-membered ring formed by linking R ¹ and R ² include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L ¹ , L ² or L ³ may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl). The electron-withdrawing group represented by X ¹ or Y ¹ may be the same or different and is a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group which may be substituted, for example, acetyl, propionyl, heptanoyl, Dodecanoyl, hexadecanoyl, 1-oxo-7
-Chloroheptyl), an arylcarbonyl group (optionally substituted arylcarbonyl group, for example, benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl), an alkoxycarbonyl group (optionally substituted alkoxycarbonyl group, , Methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t
-Amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2
-Cyanoethoxycarbonyl, 2- (2-chloroethoxy) ethoxycarbonyl, 2- [2- (2-chloroethoxy) ethoxycarbonyl), an aryloxycarbonyl group (optionally substituted aryloxycarbonyl group, for example, phenoxy Carbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4
-Fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl,
2,4-di- (t-amyl) phenoxycarbonyl),
Carbamoyl group (optionally substituted carbamoyl group, for example, carbamoyl group ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, -Propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di- (t-amyl) phenylcarbamoyl, 2-chloro-3- (dodecyloxycarbamoyl) Phenylcarbamoyl, 3-
(Hexyloxycarbonyl) phenylcarbamoyl), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), and a sulfamoyl group (optionally substituted sulfamoyl group, for example, sulfamoyl, methylsulfamoyl).

Next, specific examples of the dye used in the present invention will be described.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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The dye used in the present invention is described in International Publication WO8.
8/04794, European Patent Publication EP02747
No. 23A1, No. 276,566, No. 299,435
No., JP-A-52-92716, and JP-A-55-155350.
Nos. 55-155351 and 61-205934
No. 48-68623, U.S. Pat.
No. 3486897, No. 3746539, No. 39
No. 33798, No. 4130429, No. 4040841
No., Japanese Patent Application No. 1-50874, No. 1-103751,
It can be easily synthesized according to the method described in JP-A-1-307363 and the like and the method. The dye dispersed in the form of solid fine particles in the present invention cannot be present in a molecular state in the intended colored layer because the solubility of the dye itself is insufficient, and diffusion in the layer is substantially impossible. Means a solid state of any size.

The adjustment method is described in International Publication (WO) 88
/ 04794, European Patent Publication (EP) 02765
66A1, described in JP-A-63-197943, etc., but it is common to use a ball mill and stabilize with a surfactant and gelatin. The adjustment method in the present invention was in accordance with the method of JP-A-63-197943. 434m of water
l and Triton X-200R surfactant (TX
791 ml of a 6.7% aqueous solution of -200R) were placed in a 2 liter ball mill. 20 g of the dye were added to this solution. Zirconium oxide (ZrO ₂ ) beads 400
ml (2 mm diameter) was added and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. If you leave this as it is a fine particle with an average particle size of about 0.3 μm,
Thereafter, the particles are classified by centrifugation, and the particle size is 1 μm.
The following was made. The particle size of the dye dispersed in the form of solid fine particles used in the present invention is preferably 1.0 μm or less, more preferably 0.5 μm or less. The amount of the dye used is 5 mg / m ^{2 to} 300 mg / m ² , particularly 10 m / m ² .
is preferably ^{g / m 2 ~150mg / m 2} . In addition, the amount of gelatin used in the above adjustment can be appropriately used, which is an amount necessary to make the amount of gelatin used in the present invention, that is, 0.5 g / m ² or less. The gelatin coating amount of the dye layer (the non-photosensitive hydrophilic colloid layer in the undercoat layer) according to the present invention is 0.5 g / m ² or less, preferably 0.05 g / m ^{2 to} 0.3 g / g. a m ^2.

When the photographic emulsion layer is coated on the undercoat, if the total amount of the hydrophilic colloid is large, the amount of water contained in the film in the development step increases, which is not preferable because the load on the drying step is increased. Therefore, in the present invention, the coating amount of the total hydrophilic colloid is preferably 3 g / m ² or less per one side,
More preferably, it is 2.8 g / m ² or less. As the silver halide of the photosensitive silver halide emulsion used in the present invention, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide can be used, and silver iodobromide is preferably used. Can be Here, the content of silver iodide is preferably 30 mol% or less, particularly preferably 10 mol% or less. The distribution of iodine in silver iodobromide grains may be uniform, or may differ between the inside and the surface. The average particle size is preferably at least 0.4 μm. In particular, it is preferably from 0.5 to 2.0 μm. The particle size distribution may be narrow or wide. The silver halide grains in the emulsion are cubic, octahedral,
It may have a regular crystal form such as a tetradecahedron or a rhombic dodecahedron, or may have an irregular crystal form such as a sphere, plate, potato, or the like. It may have a compound form of a crystal form. It may consist of a mixture of particles of different crystal forms. Tabular grains having an average aspect ratio of greater than 5: 1 are preferred grains for providing a larger covering power than regular grains and for reducing the amount of coated silver. In the present invention, it is desirable that the tabular grains have an average aspect ratio of greater than 5: 1 in which 50% or more of the total projected area of all silver halide emulsion grains contained in the silver halide emulsion layer is more preferable, and more preferably 70% by weight. Desirably, the content is １００100 wt%. (For details, see RESEARCH DISCLOSURE, Volume 225, Item 22534.)
P. 20-P. 58, January, 1983, and JP-A-58-127921 and JP-A-58-113926).

In the present invention, the light-sensitive silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. The grain size, halogen composition, sensitivity, etc. of the emulsions to be mixed may be different. A substantially light-insensitive emulsion (the surface or inside of which may or may not be covered) may be mixed with the photosensitive emulsion and used, or may be separated into different layers (detailed description). U.S. Pat. No. 2,996,38
Nos. 2, 397, 987, etc.). For example, the same layer as a photosensitive silver halide emulsion consisting of a spherical or potato-like photosensitive emulsion and tabular grains having a grain size of 5 times or more the grain thickness or a layer described in JP-A-58-12.
It may be used in different layers as described in JP 7921. When used in different layers, the light-sensitive silver halide emulsion composed of tabular grains may be on the side closer to the support or, conversely, on the side farther away.

The photographic emulsion used in the present invention is P. Glafki
by des Chimie et Phisique Photograpique (Paul Mont
el, 1967), Photographi by GF Duffin
c Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating by VL Zelikman et al
Photographic Emulsion (The Focal Press, 1964
Years), JP-A-58-127921 and JP-A-58-113.
The adjustment can be performed using a method described in, for example, U.S. Pat. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used.

A method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion composed of silver halide grains having a regular crystal form and a nearly uniform grain size is obtained. Even if the crystal structure of silver halide grains is uniform up to the inside, it is also possible that the inside and outside have a different layered structure.
A so-called conversion type as described in U.S. Pat. No. 3,622,318 may be used.
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt coexist in the process of silver halide grain formation or physical ripening during silver halide production May be. During grain formation, a so-called silver halide solvent such as ammonia, a thioether compound, a thiazolidine-2-thione, a tetrasubstituted thiourea, a rodancali, a rhodamonmon, or an amine compound may be present to control the grain growth.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, and a gold sensitization method can be used, and they are used alone or in combination. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Examples are U.S. Pat. No. 2,448,060 and British Patent 6
18,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . The compounds used are described in JP-A-2-264936, page 10, lower right column, lines 7 to 11.
The 17th line in the upper left column of the page can be used. The surfactant is described in JP-A-2-264936, page 11, upper right column, line 4,
Those described on page 11, lower right column, second line can be used.
As the antistatic agent, those described in JP-A-2-264936, page 11, lower right column, lines 3 to 19 can be used.

In the present invention, a homopolymer of polymethyl methacrylate or a polymer of methyl methacrylate and methacrylic acid, fine particles of an organic compound such as starch, or fine particles of an inorganic compound such as silica or titanium dioxide can be used as a matting agent. . 1.0 to 1 as the particle size
It is preferably 0 μm, particularly preferably 2 to 5 μm.

In the surface layer of the photographic light-sensitive material of the present invention, US Pat. No. 3,489,576, US Pat.
No. 958, etc .;
In addition to the colloidal silica described in Japanese Patent No. 3139, paraffin wax, higher fatty acid ester, starch powder derivative and the like can be used.

The hydrophilic colloid layer containing the silver halide emulsion of the photographic light-sensitive material of the present invention and the surface protective layer of the emulsion layer contain polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin. It can be used as a plasticizer. further,
The hydrophilic colloid layer containing a silver halide emulsion of the photographic light-sensitive material of the present invention and the surface protective layer of the emulsion layer preferably contain a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, a styrene-butadiene copolymer, or a polymer or copolymer composed of a monomer having an active methylene group can be preferably used.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts, aldehydes (formaldehyde, krytalaldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), active vinyl compounds (1,3,5-
Triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compound (2,4-dichloro-6-hydroxy) -S-triazine, etc.), mucohalic acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholinocarbonyl-3-pyridinio) methanesulfonate), and haloamidinium salts (1- (1-chloro-1-) Pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate and the like can be used alone or in combination. Above all, Tokushou Sho 5
3-41220, 53-57257, 59-162
Preferred are the active vinyl compounds described in 546 and 60-80846 and the active halides described in U.S. Pat. No. 3,325,287.

The hydrophilic colloid layer of the light-sensitive material of the present invention is preferably hardened with these hardeners so that the swelling ratio in water is 300% or less, particularly 250% or less.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, dextran, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various kinds of synthetic hydrophilic high-molecular substances such as polyacrylamide and polyvinylimidazole single or copolymer can be used. As gelatin, lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and a hydrolyzate of gelatin can also be used. Among them, it is preferable to use dextran and polyacrylamide together with gelatin.

In the present invention, a silver halide photographic light-sensitive material for forming a black-and-white image and having a coated silver amount of 5 g / m ² or less is preferred. More preferably, it is 1 g / m ² -3.
g / m ² .

In the photographic processing of the light-sensitive material of the present invention, for example, a known method and a known processing solution for black-and-white photographic processing as described in Research Disclosure 176, pp. 28-30 (RD-17643). Any of the above can be applied. The processing temperature is usually selected between 18 ° C. and 50 ° C., but may be lower than 18 ° C. or higher than 50 ° C., but in the present invention, processing by an automatic developing machine at 20 ° C. to 40 ° C. is preferred. In this case, the processing time (time from input of the photosensitive material to drying out) is 1
It is preferably from 0 seconds to 3 minutes 30 seconds. Particularly preferred is 15 to 90 seconds. More preferably, from 15 seconds to 4
5 seconds. The developer used for black-and-white photographic processing is
Known developing agents can be included. As a developing agent, dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-
3-pyrazolidone), aminophenols (for example, N
-Methylol-p-aminophenol) can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants and the like, and further, if necessary, a solvent auxiliary agent, a color tone agent,
Development accelerators (eg, quaternary salts, hydrazine, benzyl alcohol), development inhibitors (eg, iodides, bromides, mercapto compounds, triazoles, etc.), surfactants, defoamers, hard water softeners, hardeners ( For example, glutaraldehyde), a viscosity imparting agent, and the like may be included.

As a special type of development processing, a method may be used in which a developing agent is contained in a light-sensitive material, for example, an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones are described in Research Disclosure 169 (RD-16928), U.S. Pat. No. 2,739,890, British Patent 813,253 or West German Patent 1,547,763. It can be included in the emulsion layer by various methods. Such a development process may be combined with a silver salt stabilization process using a thiocyanate. As the fixing agent, those having a commonly used composition can be used. Thiosulfate as fixing agent,
In addition to the thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing agent may include an aqueous aluminum salt as a hardening agent. When a compound which releases an inhibitor during development as described in JP-A-61-230135 and JP-A-63-25653 is used in combination, the effect of the present invention becomes more preferable.

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EXAMPLES Example 1 Preparation of Undercoat Compositions 1 to 5 Corona discharge treatment was performed on a biaxially stretched blue dyed polyethylene terephthalate film ^(*) having a thickness of 175 μm, and the hydrophobic polymer layer was coated to the following coating amount. Apply both sides with a wire bar coater so that
Dried for minutes. (Hydrophobic polymer layer) Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{/ 31/69 0.322g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8.4 mg / m ² * The latex solution contains 0.4 wt% of emulsifying dispersant (a) based on the solid content of latex.

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(*) The polyethylene terephthalate film contains 1,4-bis (2,6-diethylanilino) anthraquinone. Next, the hydrophilic colloid layer was coated on both sides with a wire bar coater so as to have the following coating amount, and dried at 150 ° C. for 1 minute. (Undercoat second layer (non-photosensitive hydrophilic colloid layer)) ・ Gelatin 80 mg / m ²・ Compound The compounds described in Table 1 and coating amount ・ Dye (AH-15) 10.5 mg / m ²

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Preparation Method of Dye 20 g of dye and 1% aqueous solution of carboxymethylcellulose 2
200 g, water 287g were mixed, at 5000rpm conditions in zirconium oxide having a diameter of 2mm Eiger mill using beads (ZrO ₂₎ (Eiger Japan Co., Ltd.) 8
Time processed.

Preparation of Undercoat Coating Material 6 The undercoat first layer hydrophobic polymer in preparation of the following coating material 2 was applied so as to have the following chemicals and coating amount. The others were prepared in the same manner as the undercoat coating 2. (Undercoat first layer) Vinylidene chloride latex 0.9 g / m ² Weight ratio of vinylidene chloride / methacrylic acid / methyl acrylate / methyl methacrylate / acrylonitrile = 90 / 0.3 / 4/4 / 1.7 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4.4 mg / m ²

Preparation of Undercoat Coated Product 7 The hydrophobic polymer layer in preparation of the undercoat coated product 2 was applied so as to have the following chemicals and coating amount. The others were prepared in the same manner as the undercoat coating 2. (Hydrophobic polymer layer) Aqueous polyester WD-SIZE (manufactured by Eastman Kodak Co.) 0.16 g / m ² · 2,4-dichloro-6-hydroxy-s-triazine sodium salt 3.8 mg / m ² · di Sodium isooctyl sulfosuccinate 0.04mg / m ²

Preparation of Undercoat Coating Material 8 The hydrophobic polymer layer in preparation of the undercoat coating material 2 was applied so as to have the following chemicals and coating amount. The others were prepared in the same manner as the undercoat coating 2. (First layer of undercoat) Polyacrylate: Julimer ET410 (manufactured by Nippon Pure Chemical Co., Ltd.) 0.16 g / m ² · 2,4-dichloro-6-hydroxy-s-triazine sodium salt 6.5 mg / m ²

1) Preparation of Emulsion The emulsion was prepared in the same manner as in the preparation of the emulsion layer in Example 1 of JP-A-2-264936. 2) Preparation of emulsion coating solution The preparation was carried out in the same manner as in the preparation of the emulsion coating solution in Example 1 of JP-A-2-264936.

Preparation of Photographic Materials 1 to 8 The above emulsion layer coating solutions were applied in the same manner to both surfaces of the above-mentioned undercoat coatings 1 to 8 to obtain photographic materials 1 to 8. At this time, the coating amount per one side of the emulsion layer and the surface protective layer was as follows. <Emulsion layer> ・ Amount of coated silver 1.9 g / m ²・ Amount of coated gelatin 1.2 g / m ² <Surface protective layer> ・ Gelatin 0.61 g / m ²・ Dextran (average molecular weight 39,000) 0.61 g / M ² · sodium polyacrylate (average molecular weight 41,000) A 70 mg / m ² hardening agent was coated with 1,2-bis (sulfonylacetamide) ethane at 56 mg / m ² per side. Matting agent (average particle size: 3.5 μm) Polymethyl methacrylate / methacrylic acid = 9/1 copolymer 0.06 g / m ²

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4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 15.5 mg / m ² Evaluation of scratch resistance An undercoating material heated to 120 ° C. was coated on a white paper having a size of 2 cm × 2 cm. Put a 3kg weight and rub it 5 times. Table 1 shows the results of counting the number of scratches per 1 cm. Evaluation of photographic performance For exposure, Fuji Photo Film HR-4 screen was used as a screen. HR according to the usual law
-4 A photographic material was sandwiched between two screens so as to be in close contact with each other, and X-ray exposure was performed through a 10 cm water phantom. Current image 35 ° C x 6.3 seconds Fixing 31 ° C x 6.7 seconds Squeeze 15 ° C x 4 seconds Drying 60 ° C x 8 seconds Dry-to-dry processing time 29 seconds The developing solution and fixing solution used have the following composition. did.

(Developer) Potassium hydroxide 29 g Potassium sulfite 44.2 g Sodium hydrogen carbonate 7.5 g Boric acid 1.0 g Diethylene glycol 12 g Ethylenediaminetetraacetic acid 1.7 g 5-Methylbenzotriazole 0.06 g Hydroquinone 25 g Glacial acetic acid 18 g Triethylene Glycol 12 g 5-Nitroindazole 0.25 g 1-phenyl-3-pyrazolidone 2.8 g Glutaraldehyde (50 wt / wt%) 9.86 g Sodium metabisulfite 12.6 g Potassium bromide 3.7 g Add water 1. 0 liter (fixer) ammonium thiosulfate (70 wt / vol%) 200 ml disodium ethylenediaminetetraacetate dihydrate 0.02 g sodium sulfite 15 g boric acid 10 g sodium hydroxide 6.7 g glacial acetic acid 15 g Aluminum sulfate 10 g Sulfuric acid (36N) 3.9 g Water is added to make a total volume of 1 liter. (PH adjusted to 4.25)

Evaluation of residual color The residual color was evaluated by visual observation of Dmin. ：: No problem in practical use Δ: Some problem in practical use ×: There is a problem in practical use The results are shown in Table 1.

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[Table 1]

As shown in Table 1, it can be seen that the undercoat composition having improved scratch resistance can be obtained with the compound of the present invention. Further, as the hydrophobic polymer, scan styrene - butadiene, a silver halide photographic material residual color problem is not excellent <br/> been in the use of vinylidene chloride that is obtained can be seen.

Continued on the front page (58) Fields surveyed (Int.Cl. ⁶ , DB name) G03C 1/91-1/92 G03C 1/825-1/835

Claims (2)

(57) [Claims] 1. A sequentially on a polyester, at least one layer of a hydrophobic polymer subbing layer, at least one layer of non-light-sensitive hydrophilic colloid subbing layer, have a silver halide emulsion layer even without low, the non-photosensitive hydrophilic PH in the aqueous colloid layer
Contains substantially solid particulate form in disperse dye which is substantially water-soluble at pH8 or more water-insoluble at 6 or less, the coating amount of the hydrophilic colloid of said non-light-sensitive hydrophilic colloid layer is 0.5g in the silver halide photographic light-sensitive material is / m ² or less
And the non-photosensitive hydrophilic colloid layer further has a general formula
A silver halide photographic material comprising at least one of (A) to (D) . General formula (A) R ₁ , R ₂ and R _{3 in the} general formula (A) each represent a hydrogen atom, an alkyl group or a phenyl group. Also R ₂ and R
₃ may be connected to each other to form a ring. General formula (B) R ₄ and R ₅ in the general formula (B) each represent a hydroxyl group or an alkoxyl group having at least one hydroxyl group. General formula (C) R ₆ and R ₇ in the general formula (C) represent an alkyl group, an aryl group, or an aralkyl group. n ₁ and n ₂ are each 2 to
Represents an integer of 20. General formula (D) R ₈ in the general formula (D) represents a hydrogen atom or an alkyl group having 10 or less carbon atoms. 2. The silver halide photographic material according to claim 1, wherein the hydrophobic polymer layer comprises a styrene-butadiene copolymer or a vinylidene chloride copolymer.