JPH02293740A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and processing speed by forming a hydrophilic colloidal layer lowered in pH to the insoluble range of a dye contained in the layer at the time of coating or after coating and forming photosensitive silver halide emulsion layers on the side of a substrate reverse to the hydrophilic colloidal layer. CONSTITUTION:The silver halide photographic sensitive material is provided on the transparent substrate with at least one dye-colored hydrophilic colloidal layer containing the dye insoluble in water in a pH of <=7.0, in a state of coating fluid, and becoming substantially soluble in water in a pH of >=8.0 in a state of dissolved in molecules, and this layer is formed by lowering the pH to the insoluble range of the dye at the time of coating or after the coating, and the photosensitive silver halide emulsion layers are formed on the side of the substrate reverse to the hydrophilic colloidal layer, thus permitting the obtained photographic sensitive material to be used for the sensitive materials using X-rays and to be high in sharpness and processed at ultrahigh-speed.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a medical photographic material having at least one light-sensitive silver halide emulsion layer on both sides of a transparent support.
By having at least one colored filter layer between the light-sensitive silver halide emulsion layer and the support, sharpness can be greatly improved, and the presence of the colored filter layer can reduce sensitivity and reduce residual color (stain). The present invention relates to a technique for providing a double-sided X-ray photosensitive material that is suitable for ultra-rapid processing as a result of improving its disadvantages to an almost harmless level.

(Prior art) In direct medical X-ray photographic films, photosensitive silver halide emulsion layers are generally coated on both sides of the support in order to reduce the exposure dose of X-rays harmful to the human body. High sensitivity is achieved by placing a fluorescent intensifying screen in close contact with the image.

This inconvenience in the shooting system is called the "crossover" phenomenon. This phenomenon occurs because the light emitted by a fluorescent intensifying screen not only exposes the photosensitive emulsion layer adjacent to the intensifying screen, but also transmits through that emulsion layer and the support and becomes scattered light, which is exposed on the opposite side. This is a phenomenon that reaches the transparent emulsion layer and reduces the sharpness of the image, and is also called the "print-through" phenomenon.

Regarding the "Cross-O-Her" phenomenon, see Research Disclosure Vol. 184 August 1979,
Item 18431 Described in Section 5. U.S. Pat. No. 4,130,429 and Japanese Patent Application Laid-open No. 6,111,6349 disclose a technique for improving sharpness by adding magenta dye or yellow dye to an orthotype photosensitive material. However, simply adding a dye to the silver halide emulsion layer results in considerable photographic desensitization due to its optical absorption. Therefore, a method of adding these dyes to an intermediate layer between a silver halide emulsion layer and a support is often practiced in the art. However, simply providing an intermediate layer will cause dye diffusion when the emulsion layer is applied, resulting in photographic desensitization to varying degrees.

To address this drawback, JP-A-62-70830 and JP-A-5
No. 5-33172 discloses a means of using a basic polymeric mordant to fix water-soluble dyes that can be decolorized during photographic processing to the desired layer. This type of mordant technique requires a relatively low filter concentration (e.g., an absorbance of 0 at the absorption wavelength peak).
．． 2 or less), the objective was achieved to some extent, but in systems that required a sufficiently high filter concentration, problems occurred with the coatability and decolorization of the layer, and its versatility was not necessarily sufficient. .

On the other hand, JP-A No. 63-197943 uses a microcrystalline dispersion of dye, which has an excellent degree of immobilization of the dye in a specific layer, and is also excellent when the filter layer is adjusted to a high concentration. A technique having decolorizing properties has been disclosed. Furthermore, US Pat. No. 4,803.150 discloses that in a double-sided photosensitive X-ray printing material, a filter layer containing a microcrystalline dispersion of a dye is provided between the support and the photosensitive emulsion layer to achieve a cross-over of 10 A technique has been disclosed to reduce the amount to below %. This technique had very superior characteristics in terms of dye immobilization degree and decolorization ability compared to the mordant technique described above.

On the other hand, in the case of medical photographic materials, quick diagnosis and treatment of even one second is required in emergency situations, so reducing the processing time is a very important performance. In 1988, the dry-to-dry processing time for some X-ray materials was reduced from the conventional standard of 90 seconds to 45 seconds, achieving ultra-quick processing. In order to shorten processing time, it is necessary to shorten each process time of development, fixing, washing, and drying. A reduction in processing time means a reduction in the time required to decolorize the dye. Also, hydrophilic colloids (mainly gelatin) for providing the dye fill layer increase drying load and thus degrade ultra-rapid processing suitability.

For this purpose, the above-mentioned US patent US 4.803,1
No. 50 does not have sufficient adaptability.

The dye microcrystal dispersion that is the invention of this patent has an average size of 0.08 and 0.2 μm, and the larger one is 1 μm.
The length reaches μm. For this reason, even when trying to apply a thin layer of dye at high density, the microcrystal size becomes a constraint.
The coating amount of hydrophilic colloid in the filter layer was inevitably large, resulting in an unacceptably increased drying load in ultra-rapid processing. Furthermore, as the treatment time was shortened, the decolorization rate of the microcrystalline dispersion was not necessarily sufficient for ultra-rapid treatment.

(Objective of the Invention) The present invention solves the above-mentioned problems by suppressing the increase in drying load to the utmost by making the dye exist at a high density, and significantly increasing the decolorization speed of the filter layer. The object of the present invention is to provide a double-sided X-ray sensitive material with high sharpness and suitability for ultra-quick processing, which has improved the disadvantages such as decreased sensitivity and residual color (stain) to almost harmless levels.

(Means for Achieving the Invention) The above objects of the present invention were achieved by the following method. That is, 1) in a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer colored with a dye on a transparent support, the hydrophilic colloid layer is water-insoluble at pH≦7.0 in the state of a coating solution; Contains a dye that is substantially water-soluble with pI{≧8.0 in a molecularly dissolved state, and the PH of the hydrophilic colloid layer is adjusted during and/or after coating. A double-sided light-sensitive silver halide photographic material was prepared by forming a light-sensitive silver halide emulsion layer on the opposite side of the layer from the support.

Further, the effect was even more favorable when the hydrophilic colloid layer colored with a dye contained fine particles that provided a surface on which the dye could be adsorbed.

The effects of the present invention can be achieved if at least one hydrophilic colloid layer colored with a dye is present on one side of the transparent support, but it is preferable that the hydrophilic colloid layer is present on both sides of the transparent support.

The dye of the present invention is water-insoluble at pH≦7.0 and is water-insoluble at pH≧7.0.
8.0, the molecule must be substantially water soluble. The dyes usable in the present invention are preferably
It is selected from the group consisting of compounds represented by the following general formulas (1) to (V), and may be used alone or in combination.

(I) p+ R6 (II) p+ R6 (II) A=L (L!='L3→koHA' (TV) A +L 1 L2+T==B (In the formula, A and A' are the same or different. each represents an acidic nucleus, B represents a basic nucleus, 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;
2 represents an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R1 and R2 may be linked to form a 5- or 6-membered ring. R and R6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkoxy group, or a halogen atom, and R4 and R each represent a hydrogen atom or R1 and R
4 or R2 represents a group of nonmetallic atoms necessary for bonding with R to form a 5- or 6-membered ring. L+XLz and L
3 each represents a methine group.

m represents 0 or 1, n represents 0, ■ or 2, p
represents 0 or 1, and when P is O, R3 represents a hydroxy group or a carboxyl group, and R4 and R5 represent a hydrogen atom.

However, general formulas (1), (II), (III), (IV)
The compound represented by (V) has a pK, a of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:1.
It has at least one dissociable group in one molecule. ) General formulas (1), (II), (III), (IV) and (
V.) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-virazolin-5-one, rhodan, hydontoin, thiohydantoin, 2,4-oxazolidinesion, isoxazolidinone, barbylic acid, thiobarbituric acid, indanedione. , pyrazolopyridine or hydroxypyridine.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, thiosazole, penzoxazole, naph1-oxazole or pyrrole.

A group having a dissociable proton with a pAa (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 substantially disintegrates dye molecules at pH 7 or below. There are no particular restrictions on the type or substitution position on the dye molecule, as long as it makes the dye molecule insoluble in water and makes the dye molecule substantially water-soluble at pH 8 or above, but carboxy groups, sulfamoyl groups, and sulfonamide groups are preferable. , a hydroxy group, more preferably a carboxyl group. The dissociative group is not only directly substituted on the dye molecule, but also a divalent linking group (e.g. alkyl group, phenylene group).
It may be replaced via . Examples via divalent linking groups 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-cyamibenzenesulfonamido)phenyl, 3
-Hydroxyphenyl, 2-hydroxyphenyl, 4-
Hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2
-Methyl-4-phenylsulfamoylphenyl, 4-carpoxybenzyl, 2-carpoxybenzyl, 3-sulfamoylphenyl, 4-sulfamoyl, 2.5-disulfamoylphenyl, carpoxymethyl, 2- Examples include carboxyethyl, 3-carpoxyprobyl, 4-carboxybutyl, and 8-carpoxyoctyl.

R,R. Or the alkyl group represented by R6 has 1 carbon number
-20 alkyl groups are preferred, such as groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R- and R2 is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-
butyl, n-octyl, n-octadecyl, isobutyl, isopropyl), and substituents [e.g. chlorine,
Halogen atoms such as bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (e.g., methoxy, 1-oxy), alkoxy group (e.g., methoxy carbonyl, i-propoxy carbonyl), aryloxy group (e.g. phenoxy group), phenyl group,
It may have an amide group (e.g., acetylamino, methanesulfonamide), a carbamoyl group (e.g., methylrupamoyl, ethylrubamoyl), or a sphamoyl group (e.g., methylsulfamoyl, phenylfulfamoyl). .

The aryl group represented by R or R2 is preferably a phenyl group or a naphthyl group, and the substituent [the substituent is the above R
The substituents of the alkyl groups represented by 1 and R2 include the groups and alkyl groups (eg, methyl, ethyl). ].

The acyl group represented by R1 or R2 is preferably an acyl group having 1 to 10 carbon atoms, such as acetyl, propionyl,
n-octanoyl, n-decanoyl, isobutanoyl,
Mention may be made of groups such as henzoyl. R1 or R/
Examples of the alkylsulfonyl group or 7-arylsulfonyl group represented by include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, P-toluenesulfonyl, 0-
The amount of carboxybenzenesulfonyl and the like can be mentioned.

The alkoxy group represented by R3 or R has 1 to 1 carbon atoms.
0 alkoxy groups are preferred, and examples include groups such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isoptoxy, and isoproboxy.

The halogen atom represented by R3 or R6 is chlorine,
Examples include bromine and fluorine.

R. Examples of the ring formed by linking and R4 or R2 and R5 include a julolidine ring.

Examples of the 5- or 6-membered ring in which R and R2 are successively formed include a biperidine ring, a morpholine ring, and a pyrrolidine ring.

The methyl group represented by L+, L2 or L3 may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxyl atom).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted,
For example, acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl group, etc.), arylcarbonyl group (arylcarbonyl group that may be substituted, such as benzoyl, 4-ethoxycarbonylbenzoyl, (3-chlorobenzoyl group, etc.), alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, 1-oxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl), , 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl,
Octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)oxycarbonyl, 2- (2-
(chloroethoxy)ethoxy]ethoxycarbonyl group, etc.), ryoryloxycarbonyl group (an optionally substituted aryloxycarbonyl group, such as phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl) , 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2,4-di(t-amyl)phenoxycarbonyl group, etc.), carbamoyl group (which may be substituted) A carbamoyl group, for example, carbamoyl group, ethyl rubamoyl, dodecyl rubamoyl, phenyl rubamoyl, 4-methoxyphenyl rubamoyl,
2-fromophenylrubamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylrubamoyl, 4-probylsulfonylphenylruhamoyl,
4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di(1-amyl)phenylcarbamoyl,
2-chloro-3-(dodecyloxycarbonyl)phenylcarbamoyl, 3-(hexyloxycarbonyl)phenylrubamoyl group, etc.), sulfonyl group (e.g., tert, methylsulfonyl, phenylfulvonyl group, etc.), sulfamoyl group (This is a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl group, etc.).

Next, specific examples of dyes used in the present invention will be given, but the present invention is not limited thereto.

■-2 1-J ■Ichigu ■-2 I-A ■ ■Ichiza■ Ta■ I O ■ 1/ ■One 72 -438 Ichiri Umarusume Yoyo■ 3 j ■-t ■-2 ■- + IV-7 ■One♂ Iy-3 ■Kazuhiro■-,t ■Itta■-IO IV-// ■/! ■ / 3 ■ / Hiroshi ■ λ ■ ■ Hiroshi 2M5 ρp ■ / j ■ / t ■ l ■ j The dye used in the present invention is disclosed in International Application Publication (WO) 8 B
/0 4 7 9 4, European Patent (EP) 02
74723A1, 276,566, 299.4
No. 35, JP-A-52-92716, JP-A No. 55-1553
No. 50, No. 55-155351, No. 61-20593
No. 4, No. 48-68623, U.S. Patent No. 2,527,
No. 583, No. 3,486,897, No. 3,746.5
No. 39, No. 3,933,798, No. 4,130,42
No. 9, No. 4,040,841, etc., and can be easily synthesized according to the method.

The fine particles that provide a surface capable of adsorbing the dye of the present invention are those that form a discontinuous solid phase different from the continuous phase of a hydrophilic colloid (hereinafter referred to as binder), and mean those that are mixed and dispersed in the binder. do.

In order to mix and disperse, it is sufficient to make the surface of the fine particles (the so-called surface in contact with the binder) hydrophilic, and this requires a means for making the chemical structure of the powder on the surface have a hydrophilic part and a surfactant. It is preferable to use either one of the methods using powder surface-treated with a micelle layer, or to use both methods in combination.

As an example in which the chemical structural composition has a hydrophilic portion, the chemical structural composition includes at least a Lewis acid element such as an oxygen element, a sulfur element, or a halogen element.

For example, it may contain a species, and it is particularly preferred if it contains a carboxylic acid group, hydroxyl group, sulfonic acid group, phosphoric acid group, etc. as an atomic group.

Examples of the surfactant used as a dispersion aid for powder when surface-treating with a micelle layer using a surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, alkyl sulfate ester, and alkyl phosphate. Anionic surfactants such as esters, sulfosuccinates and sulfoalkylpolyoxyethylene alkyl phenyl ethers; nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives; amino acids, It is preferred to use amphoteric surfactants such as aminoalkyl sulfonic acids and alkyl betaquines; and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants can be found in "Surfactant Handbook" (Sangyo Tosho, 1966)
and [Collection of research and technical data on emulsifiers and emulsifiers] (Science Panronsha, 1978).

Furthermore, the surface may be activated by compounds themselves that can serve as binders, such as polyvinyl alcohol derivatives, gelatin, or celluloses.

Furthermore, the chemical composition of the microparticles used in the present invention may be a single substance or a mixture of two or more types of compounds, and the chemical composition of one particle may be uniform within, outside, or on the surface. It may be a mixture of two or more chemical compositions.

Specific examples of compounds constituting the microparticles used in the present invention are listed below, but the compounds of the present invention are not limited thereto.

First, minerals include the substances listed in Table 1.

: Ebu - JP-A-N Next, as specific examples, Au, Ag, Cu, Zn, Ti,
Sn, In, Mo, W, Fe, Al1Si, Co, Z
r, Ni. ．． PdXCdSRu, Rh, and Ir
metals or oxides of these metals.

Further, specific examples that can be easily obtained as commercially available microparticles include colloidal silica, colloidal alumina, and mixtures of both.More specifically, E.
I. Du Pont de Nemours Co. (
USA) to LudoxAM, LudoxAS. L
udoxLS, LudoxTM, LudoxHS
With product names such as, Snowtex 20 from Nissan Chemical ■,
Monsanto Co (U) with product names such as Snowtex C1 Snowtex N and Snowtex O
S A ) from 3ytonC-30, Syton20
0 etc. and also under the trade name Nalco Chem, Co.
(USA) Nalcoag 1030, Nal
coag 1060+Nalcoag 10en 21-6
Examples include those commercially available under the trade name 4 etc.

The microparticles used in the present invention contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, or an organic base such as tetramethyl-ammonium ion as a stabilizer. It's okay.

Sodium hydroxide, potassium hydroxide, and ammonium hydroxide are particularly preferred as stabilizers because the higher the pH, the more stable, and the lower the ionic strength, the more stable.

Colloidal silica, colloidal alumina, and colloidal silica alumina are particularly preferred as the microparticles used in the present invention.

Also included are crushed and classified products of organic polymer compounds such as polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, and starch.

Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound made into a spherical shape by a spray drying method or a dispersion method, or an inorganic compound can also be used.

Further, a polymer compound which is a polymer of one or more monomer compounds as described below may be made into particles by various means.

Specifically regarding monomer compounds of polymer compounds,
Acrylic acid esters, methacrylic acid esters, itaconic acid esters, crotonic acid esters, maleic acid diesters, and phthalic acid diesters are mentioned.Ester residues include methyl, ethyl, proyl, isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl,
Phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, ω-methoxypolyethylene glycol (
The number of added moles is 9).

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isozotylate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, Examples include vinyl salicylate.

Examples of olefins include cyclopentadiene, ethylene, propylene, l-butene, 1-payten,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2.3 dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, 1-limethylstyrene, ethylstyrene, isoprobylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, crossstyrene, dichlorostyrene, promustyrene, trifluoromethyl Examples include styrene and vinylbenzoic acid methyl ester.

Examples of acrylamides include acrylamide, methylacrylamide, ethyl acrylamide, probyl acrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, hendyl acrylamide, HA6 droxymethyl acrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, Phenyl acrylamide, dimethyl acrylamide, diethylacrylamide, β-cyanoethylacrylamide,
N-(2-acetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methyl methacrylamide, ethyl methacrylamide, proyl methacrylamide, butyl methacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, pendylmeccrylamito', hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β- Cyanoethyl methacrylamide, N-(2-acetoacetoxyethyl) methacrylamide, etc.; Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl Vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinyl Imidazole, N-hinyloxazolidone, N-vinyl 1-lyazole, N-vinylpyrrolidone, etc.; Unsaturated nitriles, such as acryloni-1-lyl, mecryloni-1-lyl, etc.; Polyfunctional monomers, such as divinyl Benzene, methylene bisacrylamide, ethylene glycol dimethacrylate-1, etc.

Furthermore, acrylic acid, methacrylic acid, iconic acid, maleic acid, itaconic acid, monoalkyl such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleate such as monomethyl maleate, monoethyl maleate, etc. Monobutyl maleate, etc.; citraconic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypyl sulfonic acid, etc.;
Meccryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypylsulfonic acid; acrylamide alkylsulfonic acids, such as 2-acrylamido-3-methylethanesulfonic acid acids, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acids, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylethanesulfonic acid. Acryloyloxyalkyl phosphates such as 2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, e.g.
3-acryloyloxyp-biru-2-bosphe-1, etc.; methacryloyloxyalkylbosphates, such as methacryloyloxyethylbosphe I, 3-
Examples include methacryloxypyl 2-phosphe-1. and the like; sodium 3aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups; These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Further, as other monomer compounds, U.S. Patent No. 3,459,79
No. 0, No. 3,438,708, No. 3, . 554,
No. 987, No. 4,215,195, No. 4,247
, No. 673, JP-A No. 57-205735, and the like can be used. Examples of such crosslinking monomers include N-(2acetoacetoxyethyl)acrylamide, N-
Examples include (2-(2-acetoacetoxyethoxy)ethyl)acrylamide and the like.

These monomer compounds may be used in the form of fine particles using a polymer obtained by polymerizing them alone, or may be used in the form of fine particles of a copolymer obtained by polymerizing a combination of a plurality of monomers.

Among these monomeric compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.

The present invention also includes JP-A-62-14647 and JP-A-62-14647.
Fine particles containing fluorine atoms or silicon atoms such as those described in No. 17744 and No. 62-17743 may also be used. Furthermore, silver halide crystals may be used as the fine particles.

The size of the fine particles of the present invention is 2 μm or less. ooi μm or more, preferably 1 μm or less, 0.005 μm or more, especially 0
．． The thickness is preferably 5 μm or less and 0.005 μm or more.

Next, a method of applying the filter dye layer of the present invention will be explained.

The dye of the present invention must be molecularly dissolved in the coating solution for the dye-containing layer, and therefore the pH of the coating solution for the filter dye layer must be sufficient to substantially dissolve the dye contained therein. It is alkaline. In order to form the filter dye layer of the present invention, it is necessary to lower the pH of the layer during and/or after application to a region in which the dyes contained therein are insoluble. There are no restrictions on how the pH can be lowered. For example, after applying a filter dye layer and drying it, you can apply an acidic coating solution (either an emulsion layer coating solution or an acidic coating solution other than the emulsion layer) to lower the pH of the filter dye layer by diffusion. Alternatively, an acidic coating liquid may be applied immediately after the filter dye layer is applied until it dries. Alternatively, a filter dye layer may be applied, dried once, and then immersed in an acidic solution.
The filter dye layer may be immersed in an acidic solution immediately after being coated until it is dried. pH of the filter dye layer during and/or after application of the layer
The coating solution for reducing the dye content to the insoluble region may be an adjacent layer, or there may be an intermediate layer between the filter dye layer and the layer of acidic coating solution. The coating method of the present invention can be used by appropriately combining these methods, but as shown in Japanese Patent Publication No. 5620534 and Japanese Patent Application Laid-open No. 63-54975, a very small amount of hydrophilic colloid layer or a very small amount of acidic water can be used. can preferably be applied to a layer adjacent to the filter dye layer.

The coating amount of the hydrophilic colloid constituting the filter dye layer can be adjusted as necessary, but for the purpose of reducing the drying load in rapid processing, it should be less than Ig/m per side, preferably less than 0.5 g/nf, especially It is desirable that it is 0.3 g/rrf or less. Known compounds such as gelatin, dextran, and polyacrylamide can be used as hydrophilic colloids.

The filter dye layer may be located on the side of the photographic element closer to the support than the light-sensitive silver halide emulsion layer, and there may be a further layer for another purpose below the filter dye layer. good. However, it is especially preferred to utilize the subbing layer in the photographic element as the filter dye layer.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention can contain ordinary silver halide grains (eg, spherical grains). These are P. Grafkides (P.G.
Chimie etPhysiq (Chimie etPhysiq)
ue Photographique) J (Paul Montel, 1967)
, G.F. Duffin
) Author [Photographic Emulsion
Chemistry ) J (The Focal Press, 1966),
V, L, Znlik et al.
Making and Coating Photographic Emulsions (Maki et al.)
ng and coatingphotography
It can be prepared by using the method described in C Emulsion) J (The Focal Press, 1964).

The silver halide may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, etc.

In the process of silver halide grain formation or physical ripening during silver halide production, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. They may coexist.

Furthermore, so-called silver halide solvents such as thiocyanates, thioether compounds, thiazolidine ethiones, and tetrasubstituted thioureas may be present during grain formation. Among them, thiocyanates, g-substituted thioureas and thioethers are preferred solvents for the present invention.

As a method for chemically sensitizing the silver halide emulsion used in the present invention, known methods such as sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization can be used. It is also used in Vi huose.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. A specific example is US patent x, a4tr, o
No. to, British Patent No. t/, and oti.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

The combined use of sulfur sensitization using thiosulfate and gold sensitization can effectively exhibit the effects of the present invention.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, sila/compounds, etc. can be used.

As the tabular grains used in the present invention, Japanese Patent Application No. 62-It
The vertex development initiation type particles described in TIITX are extremely useful.

The photographic emulsion used in the present invention contains chlorine, which is used in the chemical sensitization process of the invention, for the purpose of preventing scratches during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. Various compounds can be contained in addition to the silver oxide adsorbing substance. Namely, azoles {e.g. penzothiazolium salts, nitroimidazoles, trove/zimitazoles, chloropenzimidazoles, promobenzimidazoles, nitroindazoles, <benzotriazoles, aminotriazoles, etc.}
; mercazoto compounds {e.g. mercaptothiazoles, mercaptobenzothiazoles, mercaptove/zimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.}; thioketo compounds such as oxadorinthion; azaindene; {For example, triazaindenes, tetraazaindenes (especially ≠-hydroxy substituted (/, -?, 3a, 7) tetraazaindenes)
．． −? A number of compounds known as antifoggants or stabilizers can be added, such as benzene thiosulfonic acid, benzene sulfinic acid, benzene sulfonic acid amide, and the like.

Especially JP-A-Sho tO-7J7! No.j, same t O-4 73
Nitron and its derivatives described in Publication No. 22, JP-A No. 1
Mercapto compounds described in 0-gO♂39, heterocyclic compounds described in JP-A-7-641736, and complex salts of heterocyclic compounds and silver (e.g. l-phenylteramercabutotetrazole silver) etc. can be preferably used.

In addition to the photographic emulsion layer size and other hydrophilic colloid layers of the light-sensitive material produced using the present invention, coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.,
Various surfactants may be included for various purposes such as development acceleration, hardening, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene, coal condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicone), sugars. Nonionic surfactants such as alkyl esters of: alkyl sulfonates, alkylpanzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates anionic surfactants such as sulfoalkyl polyoxyethylene alkyl phenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; aliphatic or aromatic tertiary ammonium salts, pyridinium salts , imidazolium salts, and the like can be used.

Among these, saponin, dodecylbenzenesulfonic acid Na
fL Cy-2-ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxyethoxyethanesulfonic acid Na salt, dodecyl{i acid Na[, triisoprobylnaphthalene sulfo/acid Na salt, N-methyl-oleoyl Anions such as taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N', N'
, N'-trimethylammoniodiaminopro/ξambromite, cations such as todecylpyridium chloride, bemains such as N-dodecyl-N,N-dimethylcarboxybetaine, N-oley-N,N-dimethylsulfobutylbetaine, poly( Average degree of polymerization n=io) oxyethylene cetyl ether, poly(n=-jj) oxyethylene p-nonylphenol ether, bis(l-poly(n=/j) oxyethylene-oxy-2.4L-t 1 inch Particularly preferred are noniones such as (ruphenyl)ethane.

Perfluorooctane sulfonic acid K is used as an antistatic agent.
Salt, N-probyl-N-perfluorooctanesulfonylglycine Na[, N-probyl-N-monoξ-fluorooctanesulfonylaminoethyloxypoly(n=J)
Oxyethylene butanesulfonic acid Na salt, N-noξ-fluorooctanesulfonyl-N', N', N'
−}trimethylammoniodiaminopanchloride,
N-perfluorodecanoylaminoprobyl-N',
Fluorine-containing surfactant such as N'-dimethyl-N'-carboxybetaine, Japanese Patent Publication No. 2003-100000-Ror4tt, same t/
-//2/IIμ, patent application No. 4/-/339t, same j
/-nonionic surfactant described in ItOjt issue etc.,
Alkali metal nitrates, conductive tin oxide, zinc oxide, panadium pentoxide, or composite oxides obtained by doping these with anti-77 or the like can be preferably used.

In the present invention, as a matting agent, US Pat.
No. l, same. 270/. 2≠! No., same μl group λt9≠ No.,
It is possible to use organic compounds such as homobolymer of polymethyl methacrylate or copolymer starch of methyl methacrylate and methacrylic acid as described in No. 70A of Yotsuko 3 Yuotsu, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and barium strontium. can.

The particle size is /,0~/Opm, especially λ~! μ
It is preferable that it is m.

The surface layer of the photographic light-sensitive material of the present invention contains a lubricant as described in U.S. Pat.
The silicone compound described in
In addition to the colloidal silicone described in the above publication, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and chrycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

Gelatin and water-soluble polyester are used as the binder or protective colloid that can be used in emulsion 1, the intermediate layer, and the surface protective layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used.

Examples include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives. ; Polyvinyl alcohol, polyhinyl alcohol partial acetal, poly N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as polyvinyl Eimidazole, polyvinylpyrazole, etc., either singly or copolymers.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Among these, along with gelatin, average molecular weight ooo-
It is preferable to use 1,000,000 dextran or polyacrylamide together. Tokugan Sho J/-, 2/3 evening 03, same J/
-22gguO! The method described in is also effective in the present invention.

For example, chromium salts (chromium alum, etc.), aldehydes (
formaldehyde, glitaraldehyde, etc.), N-
Methylol compounds (dimethylonoleurea, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.),
Active vinyl compound (/,3,!-}lyacryloyl-hexahydro-S triazine, bis(hinyl sulfonyl)
Methyl ether, N,N'-methylenebis[β-(vinylsulfonyl)propionamide], etc.), active halogen compounds (-2 1 4'-dichloro-t-hydroxy-S-}riazine, etc.), mucono-rogenic acids ( Mucochloric acid, etc.) inoxazoles, dialdehyde starch, euchlor-6-hydroxytoazinylated gelatin, etc. can be used alone or in combination. Among them, Tokukai Showa 31≠/22/, same j3-yo7
Active vinyl compound and US patent as described in 2/7, 2011/tjJ4A, same to-♂O♂guz! ,3.2j,
The active halides described in No. 217 are preferred.

N-carpamoylpyridinium salts (e.g. (/-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (e.g. /-(/-chloro-1/-pyridinomethylene)hyrolidinium!-naphthalenesulfonate, etc.) ) are also useful.

Polymer hardeners can also be effectively used as hardeners in the present invention.

Examples of the high-density hardening agent used in the present invention include dialdehyde starch, polyaccholein, and U.S. Pat.
Polymers having aldehyde groups, such as the acrolein copolymers described in US Pat. No. 3, t23. Polymer having epoxy groups described in ♂7g, US Patent Nos. 3 and 3
t. 2, No. 1.27, Research Disclosure Magazine 77333 (/ta7), etc., a polymer having a dichlorotriazine group, JP-A-Sho tt-ttrμ
A polymer having an active ester group described in /,
Tokukai Akira! t1/Ko2 Yu. 24t, U.S. Patent No. 11, /t
/, lAOV issue, JP-A-Shoyu'l-tj033, Nosearch Disclosure magazine/t72j (/ta7.1'), etc. Polymers having an active vinyl group or a group that is a precursor thereof, etc. Polymers having an active vinyl group or a group serving as a precursor thereof are preferred, and among them, JP-A-Sho! i1-/4t. Particularly preferred are polymers in which an active vinyl group, or a group serving as a precursor thereof, is attached to the polymer main chain by a long swasher, as described in 2j2≠.

As the support, polyethylene terephthalate film or cellulose triacetate film is preferred.

In order to improve the adhesion with the support Vi hydrophilic colloid layer, it is preferable to subject the surface to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer.

Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

In the present invention, there are no particular limitations on the method of coating the emulsion layer, surface protective layer, etc. on the support, but for example, US Pat. ! Dr.91A
The multilayer simultaneous coating method described in No. 7, No. 2.7t/, No. 79/, etc. can be preferably used.

The developer used in the present invention can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-virazolidones (for example, l-phenyl-3-virazolido/), aminephenols (for example, N-methyl-p-aminephenol, etc.) can be used alone or in combination. .

The developing solution generally contains other known preservatives, alkaline agents, and
Contains H buffering agents, anti-fogging agents, etc., and further contains solubilizing agents, color toning agents, development accelerators (e.g., glucide salt, hydrazine, benzyl alcohol), surfactants, antifoaming agents, etc.
water softeners, hardeners (e.g. glutaraldehyde),
It may also contain a viscosity-imparting agent.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain an aqueous aluminum salt as a hardening agent.

The developing method using an automatic processor in the present invention includes U.S. Pat. No. 3,025,779, U.S. Pat.
No. 556, No. 3,573,914, No. 3,647
, 459, British Patent No. 1269.268, etc., it is preferable to use a roller conveyance type automatic developing machine.

The developing temperature is 18°C to 50°C, especially 30°C to
The temperature is preferably 45°C, and the developing time is preferably 6 seconds to 40 seconds, particularly 6 seconds to 25 seconds.

The entire development process from the start of development to the end of fixing, water washing, and drying is preferably 20 seconds to 200 seconds, particularly 30 seconds to 100 seconds.

(Example) Next, the present invention will be specifically explained.

Example 1 5g of potassium bromide, gelatin Log, 1,000 ether HO(CHz)zS(CHz)zs(CIlz)OB in Kawa-1 Otom water 1l
(7) 2.5 cc of a 5% aqueous solution was added to the solution kept at 75°C, and an aqueous solution of 8.33 g of silver sulfate was added while stirring;
An aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide was added in 45 seconds using a double jet method. Subsequently, after adding 2.5 g of potassium bromide, 8.33 g of silver nitrate was added.
An aqueous solution containing g was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition. Kototo 25%
20 cc of ammonia solution, 50% NH4 NO3 1
After adding 0 CC and physical ripening for 20 parts, 240 cc of IN sulfuric acid was added to neutralize it, and then 153 cm of silver nitrate was added.
．． 34g of an aqueous solution and an aqueous solution of potassium bromide, the potential is PAg.
4 using the controlled double jet method while keeping the temperature at 8.2.
Added in 0 minutes. The flow rate during stirring was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 45 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After that, the temperature was lowered to 35°C and soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C, 76 g of gelatin was added, and the pH was adjusted with sodium chloride and potassium bromide.
6.40 and PAg 8.10.

After raising the temperature to 56°C, 600 μg of a sensitizing dye having the following structure and 150 mg of a stabilizer were added.

After 10 minutes, 6.4 mg of sodium thiosulfate pentahydrate, 140+++ g of potassium thiocyanate, and 5.1 mg of chloroauric acid were added to each emulsion, and after 80 minutes, 1 g of phenoxyethanol was added.
g was added and quenched to fix the mixture to form an emulsion. In the resulting emulsion, 95% of the total projected area of all grains has an aspect ratio of 3.
The average projected area diameter of all the particles having an aspect ratio of 2 or more was 1.40 μm, the standard deviation was 19%, the average thickness was 0.190 μm, and the aspect ratio was 74.

(CH2)3 (CI+2)3 S03 SO3Na The following chemicals were added per mole of silver halide to the emulsion to prepare a coating solution.

rr-50 324mg ●Bolimer latex (poly(ethyl acrylate/methacrylic acid) = 97/3) 25.0g●Hardening agent 1.2-bis(sulfonylaceto●2,6-bis(hydroxyamino)-4- Diethylamino 1,3.5-}riazine 80 mg ● Sodium polyacrylate (average molecular weight 41,000) 4.0 g ● Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g The above coating solution was used as a surface protective layer coating solution. At the same time, it was coated on both sides of the support described below. At this time, the pH of the emulsion layer coating solution was 6.5.
Met.

The amount of silver coated was 2.0 g/rrf per side.

The surface protective layer was prepared so that each component was coated in the following amounts.

Table system 1! JL! Capacity 1 blood cloth ■ 1 ● Gelatin 1.15 g/po ● Polyacrylamide (average molecular weight 45,000) 0.25 ● Sodium polyacrylate (average molecular weight 400,000) 0.02 ● p-t-
Sodium salt of octyl phenoxy diglyceryl butyl sulfonate 0.02●Poly(degree of polymerization 10) Oxyethylene cetyl ether 0.035●Poly(degree of polymerization 10) Oxyethylene poly(degree of polymerization 3) Oxyglyceryl roup -Octyl phenoxy ether 0.01●C. F,7
SO3 K O. 003●Hydroquinone 0. 1CJ7 * CsF+7SOzN-{Cllz square "ICIIz
)-r-SOJa0.001 C3}17? CeF 1 73O■N-{CIIzCH20}r
r-{CII■C II C I+. 0) Go110.0
03? Polymethyl methacrylate (average particle size 3.5μm) 0.025●Bori (
Methyl methacrylate h/methacrylate) (mole ratio 723, average particle size 2.5 μm) 0.020 pH of surface protective layer coating solution was adjusted to 6.8.

[Force-Rel Kyokawa Negishi ■ Nidobe Tomi I Samples I-1 and ■-22 were each subjected to ball mill treatment by the method described in JP-A-63-197943.

6.7% aqueous solution of water 434 and Triton X-200 surfactant (TX-2000) 791
! into a ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 400
mj! (2 mm diameter) and the contents were ground for 4 days.

After this, 16 Qg of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. When the obtained dye dispersion was observed, the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm.

As a support, a blue-dyed transparent PET support with a thickness of 175 μm and stretched on two wheels was used. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was applied, and the upper layer was coated with 0.08 g of gelatin.
A second undercoat layer of /if was applied. A fine dispersion of the dye was coated as a gelatin dispersion solution on both sides of this support in the coating amount shown below. In this way, a crossover cut layer was prepared.

Piece L1 ffl amount ●Gelatin 1.88/nf ●Dye 1-1 ●Dye ■-8 ●Polystyrene sulfonic acid power (average molecular weight 600,000) 80■/Po160■/Volume 35■/Po10■/Bo ●Phenoxyethanol 18■/Bo●1.2
-Bis(sulfonylacetamido)ethane 100 µ/Po On the support coated with the cross-over cut layer for comparison, the above-mentioned emulsion layer and surface protective layer were further coated on both sides by co-extrusion method. The amount of silver coated was 2.0 g/portion per side.

-2 biaxially stretched polyethylene terephthalate film with a thickness of 175 μm was subjected to corona discharge treatment, and the first undercoating liquid having the following composition was applied at a coating amount of 5.1 cc/ffl.
Apply with a wire bar coater so that 17
It was dried at 5°C for 1 minute.

Next, a first undercoat layer was provided on the opposite side in the same manner.

●Dye 1-1 ●Dye I-22 9.412g 18. 824g On the first undercoat layer on both sides, a second undercoat liquid having the following composition was applied to each side at a coating amount of 8.5cc/rW using a wire/bar coater and dried. .

2nd undercoating liquid ● Gelatin 10 g ● Matting agent 0.3 g polymethyl methacrylate with an average particle size of 2.5 μm * Add NaOH (IN) and water to poto. The sample adjusted to 12 s was completely dissolved in molecular form in the coating solution. The coating amount of Samples 1-1 and ■-22 was prepared to be the same as that of Comparative Sensitive Material-1, and the coating amount was 80 μ/bore and 1 coat per side, respectively.
It was set at 60■.

After drying, the first and second undercoated supports were immersed in a 10% phosphoric acid aqueous solution at 15° C. for 30 seconds, and then dried to complete a primed film.

An emulsion layer and a surface protective layer were coated on both sides of this support in the same manner as in Photosensitive Material-1. The amount of silver coated was 2.0 g/bore per side.

of -3 of A first undercoat layer was provided in the same manner as in the photosensitive material-2 of the present invention.

Next, a liquid having the following composition was prepared as a second undercoating liquid.

Second undercoating liquid ● Gelatin 10 g ● Matting agent Polymethyl methacrylate with an average particle size of 2.5 μm 0.3 g ● Dye 1 as a finely dispersed form of Comparative Sensitive Material-1 19.412 g 1 -22 18.824 g ●Add water 1! (P11 was set to 58) This second undercoating liquid was coated with a wire coater in an amount of 8.5c.
When it was coated on the first undercoat layer so that c/r+{, the speed of the support after drying was extremely high. Further, when the surface came into contact with the support conveying roller of the coating machine or when the support was wound up, the dye peeled off from the support surface, causing contamination. The density of the support was also reduced and it was unsuitable as a photographic element for coating an emulsion layer.

The dye prepared by the method described in JP-A-63-197943 was unsuitable for the method of coating the dye in ultra-thin layers at high density.

Photosensitive material 4 was prepared in exactly the same manner as photosensitive material-2 of the present invention in Section-4. However, the composition of the second undercoating liquid was changed as follows.

Second undercoating liquid ● Geradine ● Matting agent 15 g of polymethyl methacrylate with an average particle size of 2.5 μm Rate 0. 3g. However, the composition of the second undercoating liquid was changed as follows.

2nd base coating liquid ● Gelatin 15g ● Mat 1
・Agent Polymethyl methacrylate 1-0.3g with an average particle size of 2.5μm●Average particle size 0
．． 02 μm colloidal silica ●Dye ■-1 ●Dye I-22 20g 9.412g 18. 824g ● Add NaOll (IN) and water II! ．． pl
(7) Preparation of photosensitive material 5 of the present invention Prepare photosensitive material 5 in the same manner as photosensitive material 4 of the present invention Colloidal silica with an average particle size of 0.02 μm is also dye 1-1 ● Dye 111-2 ● Add NaOH (IN) and water II2. pH11
．． Adjusted to 0 20g g, 412g 9,412g (8) Preparation of Photosensitive Material-6 of the Present Invention The first and second undercoat layers were coated in the same manner as the photosensitive material 5 of the present invention. However, after this, the step of immersing it in a 10% phosphoric acid aqueous solution was canceled.

Instead, when coating the emulsion layer and the surface protective layer, the emulsion layer and the second
1,0cc/r of 75% phosphoric acid aqueous solution between the undercoat layer and the undercoat layer.
RF, and simultaneously coated at a speed of 160 m/min and dried to obtain photosensitive material 6.

A support coated with an undercoat layer that was not immersed in an aqueous phosphoric acid solution was prepared in the same manner as in the photosensitive material 6 of the present invention in Section -7.

A surface protective layer and an emulsion layer were coated in the same manner as for photosensitive materials 1 to 5. At this time, the pH of the emulsion layer was lowered to 5.8 with phosphoric acid.

〇　　6　Sense　8　West. Li A first undercoat layer was applied in the same manner as for photosensitive material 2 of the present invention.

A photosensitive material 8 was prepared in the same manner as photosensitive material 2 after removing dyes 1-1 and -22 from the second undercoating solution.

11 Sensitivity 1 to 8 (2) To promote the crosslinking reaction between the hardener and gelatin, the coated photosensitive materials 1 to 8 were conditioned for 2 hours at 25° C. and 60% relative humidity, and then sealed in a moisture-proof bag. 1 at 40°C in a sealed state
After aging for 6 hours, the temperature was returned to 25° C. and 60% relative humidity, and the seal was opened.

2.i HR-4 manufactured by Fuji Photo Film ■ was used as a fluorescent intensifying screen. Photographic materials 1 to 8 were subjected to X-ray sensitometry using the distance method and subjected to the following treatment (1).

The sensitivity was expressed as the ratio of the reciprocal of the exposure amount that gave a density of Fog+1.0, and relative display was performed with the sensitive material 1 set as 100.

The results are summarized in Table-1.

Processing Plate Works Y <Developer Concentrate> Potassium hydroxide 56.6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate Hydroquinone diethylene glycol 4-Hydroxymethyl-4 Methyl-1-phenyl-3 Virazolidone 5-Methylbenzotriazo 16.7g 10g 83.3g 40g 11.0g Le 2
11 with g water! ．． (Adjust the pH to 10.60.)
Fixer concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium dihydrate 0.10g Sodium hydroxide
pH 5. with acetic acid. (adjust to 10).

Automatic developing machine developing tank 6, FM! '35°CX9.5 seconds fixing tank 6. ! M! 35゜CX 8 seconds washing tank 6.542' 20”CX 6 seconds drying
Drying 55°CDryt
o Dry processing time: 39 seconds When starting the developing process, each tank was filled with the following processing solution.

Developing tank: 333 d of the above developer concentrate, 667 d of water, 2 g of potassium bromide, and 1. Add 10ml of starter containing 8g and adjust the pH to 10.
It was set at 15.

Fixing tank: 250 d of the above fixer concentrate and 750 # of water
ll! The chart for MTF measurement was set at 38 KVp, 10 using MTF Fuji Photo Film HR-4 with fluorescent intensifying screens on both sides of the recording material.
Sensitive materials 1 to 8 were exposed under X-ray irradiation conditions of 0 mA. Thereafter, treatment (1) was performed.

Regarding MTF, please refer to T. H. James m collection” Th
eTheory of the Photography
c Process (1 9 7 7Macmi
MTF was measured using a 30 μm x 500 μm aperture, and evaluated using a value with a spatial frequency of 2.0 cycles/mm. 1.0
It was evaluated in this section.

The above results are summarized in Table 1.

The photosensitive materials 1 to 8 were subjected to the automatic development process described above in a size of 24.5x30.5c+n, and the dry state was checked by touching the film immediately after it came out of the drying zone. The results are summarized in Table-1. The evaluation criteria are as follows.

◎...The film that comes out is warm and dry enough.

○...The film that comes out is warm and dry.

▲...The film that comes out is damp and has not been sufficiently dried.

×: The film that comes out is wet, and the films adhere to each other.

The same treatment as in the above evaluation of photographic performance was performed without exposing the side-residue materials 1 to 8 to light. The residual color after the treatment was sensory evaluated and the results are summarized in Table-1. The following level classification was applied as evaluation criteria.

◎...No residual color bothers me at all.

○: There is a slight residual color, but there is no practical problem.

Δ...I'm concerned about residual color. There are practical problems.

From the results in Table 1, it is clear that the present invention has high sharpness, high clarity, little residual color, and suitability for ultra-rapid processing.

Example 2 (1) Preparation of photosensitive platelet-like grain emulsion Ammonia is first added to a container containing a water-soluble solution consisting of potassium bromide, potassium iodide, potassium thiocyanate, and gelatin, followed by an aqueous solution of silver nitrate. A silver iodobromide emulsion (AgI = 3 mol %) having a plate-like shape with an average equivalent sphere diameter of 0.95 μm was prepared by simultaneously adding a water-soluble solution consisting of potassium bromide and potassium iodide. death,
After desalting by the usual flocculation method and redispersing by adding water, gelatin, Proxel, potassium bromide, sodium hydroxide, and trimethylolpropane, gold Sulfur sensitization was performed and 4-hydroxy-6-methyl-1 was used as a stabilizer.
3.3a,7-tetrazaindene was added to obtain a photosensitive platelet emulsion. The Ag/Grl weight ratio was 1.3/1.

(2) Preparation of emulsion coating solution The following chemicals were added to the emulsion per mole of silver halide to prepare a coating solution.

n=5 0 ●Polymer latex (poly(ethyl acrylate/methacrylic acid) = 97/3) ●Hardening agent 1,2-bis (sulfonic ace 324 25.0 g ●2,6-bis(hydroxyamino)-4- Diethylamino 1,3.5-}riazine ● Sodium polyacrylate 80 family (average molecular weight 41,000) 4.0 g ● Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g The above coating solution was added to the surface protective layer coating solution. At the same time, it was coated on both sides of the support described below.At this time, the TIH of the emulsion layer coating solution was 6.5.

The amount of silver coated was 2.5 g/rrf per side.

The surface protective layer was prepared so that each component was coated in the following amounts.

Table 1 Exhaust J ■ 11 animals ● Gelatin 1.15 g/bo ● Polyacrylamide (average molecular weight 45,000) 0.25 ● Sodium polyacrylate (average molecular weight 400,000) 0.02 ● pt-
Sodium salt of octylphenoxy diglyceryl butyl sulfonate 0.02 ● Poly (degree of polymerization 10) oxyethylene cetyl ether 0.035 ● Poly (degree of polymerization 10) oxyethylene-poly (degree of polymerization 3) oxyglymolyl-p-octylph Enoxy ether ●C8Fl7SO3K ●Hydroquinone 0.003 0.1 U C . +1 7 @ CsF+, SOJ+CI{z+"÷CI{2-+
TsoJao. ooi C3H7? CaF I 7SO2N-cco2cn2o}-r
r{clI■CIC}+20}THO. 003 ● Polymethyl methacrylate (average particle size 3.5 μm) 0.025 ● Poly (
Methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) 0.020 The pH of the surface protective layer coating solution was adjusted to 6.8.

(3) Preparation of Comparative Sensitive Material-9 Sample I-1 was each subjected to ball mill treatment by the method described in JP-A-63-197943.

434 ml of water and Triton X-2000
6.7% aqueous solution of surfactant (TX-2000) 7 9
1 rrdl was placed in a 2L pole mill. dye 2
0 g was added to this solution. Zirconium oxide (Z r
400 mQ (2 mm diameter) of beads of O) were added and the contents were crushed for 4 days. After this, 12.5% gelatin 160
g was added. After defoaming, the ZrO beads were removed by filtration. When the obtained dye dispersion was observed, the particle size of the crushed dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm.
Met.

A biaxially stretched transparent PET support having a thickness of 175 μm and dyed blue was used as the support. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was provided, and the upper layer was coated with gelatin o. o8
A second undercoat layer of g/rrf was applied. A fine dispersion of the above dye was coated as a gelatin dispersion solution on both sides of the support in the coating amount shown below. In this way, a cross-over cant layer was prepared.

Piece 11Ω JJL ●Gelatin 1.8g/Bo ●Dye 1
-1125 mg/Po 1,2-bis(sulfonylacetamido)ethane 100 mg/PoPotassium polystyrene sulfonate (average molecular weight 600,000) 35 mg/Po (4) Preparation of photosensitive material 10 of the present invention Biaxially stretched thickness A corona discharge treatment was performed on the polyethylene terephthalate 1 film with a diameter of 175 μm, and a first undercoating liquid having the composition below was applied at a coating amount of 5.1 cc/n {
Coat with a wire har coater so that it becomes 175
It was dried for 1 minute at °C.

Next, a first undercoat layer was provided on the opposite side in the same manner.

10mg/retain ●Phenoxyethanol 18mg/n? On the support coated with the cross-over cut layer for comparison, the emulsion layer and surface protective layer described above were further coated on both sides by co-extrusion. The amount of silver coated was 2.5 g/portion per side.

? 8,day'77 soup. ■6o, yo,,,i,,i11
Yo. 7 A second undercoat liquid having the composition shown below was applied to each side of the first undercoat layer on both sides at a coating amount of 8.5 cc/rd using a wire/Harcok method and dried. .

2nd base coating liquid ● Gelatin Log ● Manl
・Agent: Polymethyl methacrylate with an average particle size of 2.5 μm. 3g ● Dye I 14.71g e Add NaOH (IN) and water and pllIO. 8
1 p. The Nigonshu-bushi sample was completely dissolved in molecular form in the coating solution. The coating amount of Sample 1-1 was prepared to be the same as that of Comparative Sensitive Material-9, and was 125 mg/Bot on each side.

After drying, the first and second undercoated supports were immersed in a 10% aqueous solution of phosphoric acid at 15° C. for 30 seconds, and then dried to complete a primed film.

An emulsion layer and a surface protective layer were coated on both sides of this support in the same manner as in Photosensitive Material-9. The amount of silver coated was 2.5 g/portion per side.

(5) Preparation of Comparative Photosensitive Material-11 Photosensitive material 11 was prepared in exactly the same manner as the photosensitive material-10 of the present invention. However, the composition of the second undercoating liquid was changed as follows.

Second undercoating liquid ● Gelatin 15 g ● Matting agent Polymethyl methacrylate 0.3 g with an average particle size of 2.5 μm ● Colloidal silica 10 g with an average particle size of 0.02 μm ● Dye I l 14.71 g ● NaOH (IN) and water Add 1 l pH 10
．． Adjustment to 8 (6) Preparation of Photosensitive Material-4 of the Present Invention A support coated with an undercoat layer that was not immersed in an aqueous phosphoric acid solution was prepared in the same manner as in the photosensitive materials-10 of the present invention.

A surface protective layer and an emulsion layer were coated in the same manner as for Photosensitive Materials 9 to 11. At this time, the pH of the emulsion layer was lowered to 5.8 with phosphoric acid.

(7) Preparation of Comparative Photosensitive Material-13 Photosensitive material 13 was prepared in the same manner as photosensitive material 10 of the present invention.
Dye I-1 was removed from the second undercoat layer coating solution.

(8) Evaluation of photographic performance Using 82 manufactured by Fuji Photo Film ■ as fluorescence enhancing paper, X-ray sensitometry was performed using the distance method on photographic materials 9 to 13, and an automatic processor FPM5000 manufactured by the same company was used. Processing was performed at 35°C for 45 seconds using developer RD7 and fixer Fuji F.

The sensitivity was expressed as the ratio of the reciprocal of the exposure amount that gave a density of Fog 11.0, with Sensitive Material 9 being set at 100.

(9) Evaluation of sharpness MTF was measured using fluorescence intensifying screen B-2.

The treatment was the 45 second treatment described in (7).

00) Evaluation of residual color and drying property According to Example 1. However, the treatment was 5 seconds as described in (Force).The results are summarized in Table 2.

Table 2

[Brief explanation of drawings]

Figure-1 shows sensitive material samples 9, 10, and 1 in Examples of the present invention.
1 and 12 show the spectral absorption of the colored dye layers of 1 and 12. The horizontal axis represents wavelength, and the vertical axis represents absorbance. As is clear from Table 2, the present invention has high sharpness, high sensitivity, and is excellent in terms of suitability for rapid processing. The absorption characteristics of the undercoated support before coating the surface protective layer and emulsion layer are shown in Figure 1. In order to distinguish between the blue color of the support itself and the absorption of the colored dye layer for crossover cutting, a support without an undercoat layer was used as a reference when measuring absorbance. From FIG. 1, it can be seen that the method of the present invention is a dye fixing method different from the method described in JP-A-63-197943. Patent Applicant: Fuji Photo Film Co., Ltd. 1011 Written Amendment

Claims (1)

[Scope of Claims] 1) A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer colored with a dye on a transparent support, in which the hydrophilic colloid layer has a pH value in the state of a coating solution.
The hydrophilic colloid layer contains a molecularly dissolved dye which is water-insoluble at pH 7.0 and substantially water-soluble at pH 8.0, when the hydrophilic colloid layer is applied and/or Double-sided photosensitive for medical use, which is formed by later lowering the pH of the layer to a region in which the dye contained therein is insoluble, and has a photosensitive silver halide emulsion layer on the opposite side of the layer from the support. Silver halide photographic material. 2) The double-sided photosensitive silver halide photographic material for medical use according to claim 1, characterized in that the hydrophilic colloid layer colored with a dye contains fine particles that provide a surface on which a dye can be adsorbed.