JP2532840B2 - Silver halide photographic light-sensitive material with excellent drying property - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having an improved drying property.

BACKGROUND OF THE INVENTION Many silver halide photographic light-sensitive materials contain gelatin as a hydrophilic colloid binder.

Photosensitive materials containing these gelatins are developed with various aqueous solutions having different pH or temperature, but the layer containing gelatin which is not treated with a curing agent has poor water resistance,
Excessive swelling in aqueous solution makes it vulnerable to damage, especially at 30 ° C
In the extreme cases, the gelatin layer was dissolved or even flowed out by the above high temperature treatment liquid.

It has been known that many compounds have been effective so far in order to harden gelatin to enhance the water resistance, heat resistance and scratch resistance of the gelatin layer.

These are known as hardeners used in the production of silver halide photographic light-sensitive materials. For example, inorganic compounds such as chromium alum, formaldehyde, aldehyde compounds such as glutaraldehyde, U.S. Pat. No. 3,288,775.
A compound having an active halogen described in, for example, a compound having a reactive ethylenically unsaturated group described in U.S. Pat.No. 3,635,718, an aziridine compound described in U.S. Pat. U.S. Patent No. 3,09
Organic compounds such as epoxy compounds described in 1,537 and halogenocarboxaldehydes such as mucochloric acid are known.

On the other hand, from the viewpoint of the photographic performance of the silver halide photographic light-sensitive material, the degree of hardening of gelatin by the hardener is reduced to increase the degree of swelling of the silver halide emulsion layer during development,
From the viewpoint of silver saving, it is required to enhance the developability of silver halide, that is, to obtain the required optical density with a minimum amount of coated silver.

The effect of enhancing the developability of silver halide by decreasing the degree of hardening is particularly remarkable at high temperature processing, but as described above, the silver halide emulsion layer that the degree of hardening is low swells excessively at high temperature processing. Photosensitive materials containing a large amount of photographic additives in gelatin, such as color photosensitive materials, have a strong tendency, and thus the degree of hardening is generally determined by the degree of swelling and scratch resistance.

By the way, when the degree of swelling is increased, not only the scratch resistance but also the dryness are adversely affected. That is, the amount of water absorbed during the development process becomes large, and the drying time is required accordingly.

In general, color light-sensitive materials are coated simultaneously in multiple layers, so when using a diffusible low-molecular hardener, it is technically and costly difficult to harden only a certain layer. It was Therefore, a non-photosensitive layer that does not require swelling during development, particularly a layer such as an antihalation layer between the silver halide emulsion layer and the support, is particularly strong from the viewpoint of dryness, and may be hardened. No, it was not done for the reasons mentioned above.

[Object of the Invention] Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material excellent in drying property and capable of rapid processing at high temperature.

[Constitution of the Invention] An object of the present invention is to provide a silver halide emulsion having at least one silver halide emulsion layer on a support and being positioned closest to the support among the silver halide emulsion layers. In a silver halide photographic light-sensitive material having at least one non-photosensitive layer on the support side of the layer, at least one non-photosensitive layer is a polymeric hardener, or a gelatin hardener which gives a polymeric hardener. It is achieved by a silver halide photographic light-sensitive material which is hardened with a polymer which gives a polymeric hardener.

[Specific Structure of the Invention] The polymeric hardener of the present invention has a molecular weight (number average molecular weight) of 3000, which has at least two hardener groups for reacting with a hydrophilic colloid such as gelatin in the same molecule. The above compounds are meant.

Examples of the hardener group for reacting with a hydrophilic colloid such as gelatin include an aldehyde group, an epoxy group, an active halide group (dichlorotriazine etc.), an active vinyl group and an active ester group. The number of these groups may be at least 2 in the same molecule of the polymeric hardener, but is preferably 10 to 5000. The molecular weight may be 3000 or more, but those having a molecular weight of about 3000 to 500,000 are preferably used.

Generally, the polymer part having a hardening group for reacting with a hydrophilic colloid such as gelatin is preferably hydrophilic, but even if it is not hydrophilic, it is emulsified and dispersed in a hydrophilic colloid (eg gelatin). It can also be used by dispersing (dispersing in an organic solvent if necessary).

Examples of the polymer hardener used in the present invention include dialdehyde starch, polyacrolein, and US Pat. No. 3,396,02.
Polymers having an aldehyde group such as acrolein copolymer described in No. 9, polymers having an epoxy group described in U.S. Pat. No. 3,623,878, U.S. Pat.No. 3,362,827, Research Disclosure 17333 (1978), etc. A polymer having a dichlorotriazine group,
Polymers having an active ester group described in JP-A-56-66841, JP-A-56-142524, U.S. Pat.
1,407, JP-A 54-65033, Research Disclosure Magazine 16725 (1978) and the like active vinyl group, or a polymer having a group as a precursor thereof, and the like, among them, active vinyl group, Alternatively, a polymer having a group serving as a precursor thereof is preferable, and an active vinyl group or a group serving as a precursor thereof is bound to a polymer main chain by a long spacer as described in JP-A-56-142524. Are especially preferred.

 Specific examples of the polymer hardener of the present invention are shown below.

Further, as the polymer hardener of the present invention, a polymer having at least two hardener groups in the same molecule for reacting with a hydrophilic colloid such as gelatin from the beginning, like the polymers described above. It can be used, but it is coated with a hydrophilic colloid hardener such as gelatin and a polymer which reacts with it to give a polymer having at least two hardener groups in the same molecule. A polymeric hardener can be made in the hydrophilic colloid layer, thereby achieving the objects of the invention.

Thus, as a gelatin hardener used to make a polymeric hardener in a hydrophilic colloid layer, a low molecular hardener, such as THJames (THJame).
s) 'The Theory of the Photographic Pro
cess) ", 4th edition, pp. 77-84, low molecular hardeners having a vinyl sulfone group or a triazine ring are preferred.
The low molecular weight hardeners described in JP-A Nos. 53-41221 and 60-225143 are preferable.

Specific examples of the gelatin hardener of the present invention which gives the polymer hardener are shown below.

_{H-1 (CH 2 = CHSO} 2 CH 2 CONHCH) 2 - H-2 (CH 2 = CHSO 2 CH 2 CONHCH 2) 2 -CH 2 _{H-4 CH 2 = CHSO 2} -CH = CH 2 H-5 CH 2 = CHSO 2 CH 2 OCH 2 -SO 2 -CH = CH 2 H-6 CH 2 = CHSO 2 CH 2 CH 2 CH ₂ SO ₂ CH = CH _{2 H-8 OHCCH 2 3 CHO H} -9 formalin H-14 CH ₂ = CHSO ₂ CH ₂ CH ₂ SO ₂ CH = CH ₂ H-15 (CH ₂ = CHSO ₂ CH _{2 4} C H-16 [(CH ₂ = CHSO ₂ CH ₄ C] ・ H ₂ NCH ₂ CH ₂ SO ₃ K salt In addition, the polymer used to make the polymeric hardener in the hydrophilic colloid layer must have at least two nucleophilic groups that react with the gelatin hardener in the same molecule. There are, for example, a polymer having a primary amino group described in British Patent No. 2,011,912, a polymer having a sulfinic acid group described in JP-A-56-4141, and a phenolic hydroxyl group described in U.S. Patent No. 4,207,109. And the polymers having an active methylene group described in US Pat. No. 42,151,956.

Specific examples of the polymer that provides the polymeric hardener of the present invention are shown below.

The method for synthesizing the polymeric hardener used in the present invention is shown below.

Synthesis Example 1 Poly-N- (3- (vinylsulfonyl) propioyl}
Aminomethyl acrylamide-co-acrylamide-2
-Synthesis of sodium methylpropane sulfonate (HP-3) (a) Synthesis of N- (3- (chloroethylsulfonyl) propioyl) aminomethyl acrylamide In the reaction vessel of 2, distilled water 1400 ml, sodium sulfite was added.
224 g and 220 g of sodium hydrogencarbonate were added, dissolved with stirring, cooled to 5 ° C., and 260 g of chloroethanesulfonyl chloride was added dropwise over about 1 hour and 30 minutes. After dripping 49
% Sulfuric acid (160 g) was added, and the precipitated crystals were filtered and washed with 400 ml of distilled water. Combine this filtrate and the washing solution with 3
Into the reaction vessel of No. 1 above, 246 g of methylenebisacrylamide dissolved in 480 ml of distilled water and 1480 ml of ethanol was added dropwise at 5 ° C. in about 30 minutes. After leaving the reaction sample in the refrigerator for 5 days to complete the reaction, the precipitated crystals were collected by filtration, washed with 800 ml of cooled distilled water, and washed with 200 ml of distilled water.
Recrystallization from 0 ml of 50% aqueous ethanol solution gave 210 g of white powder. The yield is 49% and the melting point of this compound is 19
It was 2 ℃ or more (decomposition).

(B) Synthesis of HP-3 In a 200 ml reaction solution, 5.65 g of the monomer of (a), sodium acrylamido-2-methylpropanesulfonate 9.16
g, 80 ml of 50% aqueous ethanol solution was added, and the mixture was stirred and dissolved. The temperature was raised to 80 ° C while passing nitrogen gas, and 0.1 g of 2,
2'-Azobis (2,4-dimethylvaleronitrile) was added and the same thing was added after another 30 minutes, and the stirring was continued for 1 hour. Then cool to 10 ° C and add 2.5 g of Aliethylamine mixed with 80 ml of ethanol,
Stirring was continued for 1 hour, the reaction sample was added to 1 of acetone, and the resulting precipitate was collected by filtration and vacuum dried to obtain 12.4 g of a white polymer. The yield was 85%, the intrinsic viscosity [η] of this polymer was 0.227, and the vinyl sulfone content was 0.95 × 10 ^-3.
It was equivalent / g polymer.

Synthesis Example 2 Poly-N- {2- (vinylsulfonyl) acetyl} aminomethylacrylamide-co-acrylamide (HP-
Synthesis of 7) (a) N- (2-chloroethylsulfonyl) acetyl)
Synthesis of aminomethyl acrylamide To the reaction solution of 1, 720 ml of methanol and 80.8 g of N-methylol acrylamide were added, 40 ml of concentrated hydrochloric acid was added at room temperature while stirring, and stirring was continued for 16 hours, and then hydroquinone monomethyl ether 0.4. g was added, and methanol was distilled off with an evaporator. To the remaining 62.4 g of oil, 100 g of chloroethanesulfonylacetamide, 0.32 g of hydroquinone monomethyl ether, 0.2 p-toluenesulfonic acid
2 g was added and heated to 150 ° C. to distill off the produced CH ₃ OH. The reaction was completed in about 15 minutes, and the remaining crystals were added to 250 ml of 50%.
Recrystallization from an aqueous ethanol solution gave 61 g of white powder. The yield was 42%.

(B) Synthesis of HP-7 Add 53.7 g of the monomer of (a), 163.3 g of acrylamide and 1955 g of methanol to a 3000 ml reaction vessel, dissolve by stirring and raise the temperature to 60 ° C while passing nitrogen gas. And 6.2g
2,2-azobis (2,4-dimethylvaleronitrile) was added and heated for 4 hours, cooled to room temperature, added with 20.0 g of triethylamine, stirred for 2 hours, and the precipitate was collected by filtration. Vacuum drying gave 194.3 g of white polymer. The yield is 92.7% and the vinyl sulfone content of this polymer is 0.50.
× 10 ⁻³ equivalent / g polymer.

The method for synthesizing a polymer that gives a polymeric hardener is shown below.

Synthesis Example 3 Potassium poly-vinylbenzenesulfinate-co-acrylamido-2-methylpropyne sodium sulfonate (Q
-1) Synthesis To a 500 ml reaction vessel, add 45.8 g of sodium acrylamido-2-methylpropanesulfonate, 20.6 g of potassium vinylbenzenesulfinate, 180 ml of ethanol and distilled water and heat to 75 ° C with stirring. , (2,2'-Azobis- (2-amine) propane) dihydrochloride 0.82g was added and heated for 4 hours, allowed to cool to room temperature, 72 ml of ethanol and 278 ml of distilled water were added and filtered. A colorless transparent viscous liquid was obtained. The viscosity of this polymer solution at 25 ° C. was 3.25 centipoise (cp), the solid content concentration was 10.3% by weight, and the sulfinic acid content was 6.2 × 10 ⁻⁶ equivalent / g.

Other polymeric hardeners can also be easily synthesized based on the above-mentioned synthesis examples or the methods described in the above-mentioned patent specifications. Also, some polymer hardeners are commercially available.

The amount of the polymeric hardener of the present invention used can be arbitrarily selected according to the purpose. Normally, 100 g of the hydrophilic colloid such as gelatin in the layer to be added has a functional group which reacts with the hydrophilic colloid such as gelatin in the range of 0.5 × 10 ⁻³ equivalent to 5 × 10 ⁻² equivalent. Molecular hardeners are used. Particularly preferred is the range from 0.5 × 10 ⁻³ equivalent to 2 × 10 ⁻² equivalent.

Further, the polymer hardener of the present invention may be used alone as a hardener, or JP-A-51-78788 and JP-A-53-48221,
No. 60-225143, U.S. Patent Nos. 3,325,287, and 3,945,853.
No. 59-31944, No. 55-736, No. 55-98741
No. 55-46745, No. 54-130930, and other low-molecular hardeners or high-molecular hardeners may be used in combination. In the present invention, it is preferable to use them together. As a hardening agent that can be used in combination, a compound having a reactive halogen atom such as 2-hydroxy-4,6-dichloro-1,3,5-triazine, a compound having a reactive olefin such as divinyl sulfone. , Isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chrome alum,
There are aldehydes, specifically, from the above H-1 to H-21.
The compounds shown in can be mentioned.

When a cationic monomer is used as the monomer to be copolymerized with the hardener monomer, the advantage that the diffusion of an anionic dye or the like is suppressed and the sensitivity is increased was also found. The effect was particularly remarkable in the light-sensitive material for X-ray.

Examples of the non-photosensitive layer on the support side of the silver halide emulsion layer located closest to the support of the present invention include an antihalation layer and a gelatin intermediate layer in a negative color light-sensitive material. These non-photosensitive layers may be two or more layers. In that case, in order to make the effect of the present invention noticeable, it is preferable to harden the non-photosensitive layer closest to the silver halide emulsion layer located closest to the support using a polymer hardener, and of course, Most preferably, all these non-photosensitive layers are hardened.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes, as silver halide, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any of those commonly used in ordinary silver halide emulsions such as silver halide can be used, but silver bromide, silver iodobromide and silver chloroiodobromide are particularly preferable.

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

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously at the same time while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. A conversion method may be used to change the halogen composition of the grains at any step in the formation of Agx.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

The silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming and / or growing the grain). By adding a metal ion using at least one selected from the group consisting of complex salts), these metal elements can be contained inside the particles and / or on the surface of the particles, and by placing in a suitable reducing atmosphere, Reduction sensitization nuclei can be provided inside the grain and / or on the surface of the grain.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (hereinafter R)
It can be carried out based on the method described in Item 17643, Item II.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.

The silver halide grains may have a size of 0.05 to 30 μm, preferably 0.1 to 20 μm.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown). Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, the sulfur sensitizing method, the selenium sensitizing method, the reduction sensitizing method, the noble metal sensitizing method using gold and other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a steryl dye and a hemioxanol dye are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The silver halide emulsion includes chemical ripening, chemical ripening at the end of chemical ripening, and / or chemical ripening for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage, or photographic processing, or maintaining stable photographic performance. After the completion of ripening, a compound known as an antifoggant or a stabilizer in the photographic art can be added by the time of coating the silver halide emulsion.

Silver halide emulsion binder (or protective colloid)
It is advantageous to use gelatin, but a gelatin derivative, a graft polymer of gelatin and another polymer,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic high molecular substances such as homopolymers and copolymers can also be used.

A plasticizer can be added to the silver halide emulsion layer and / or another hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII.

A photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or hardly-soluble synthetic polymer for the purpose of improving dimensional stability and the like.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, ethylene alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

In the color developing process, the emulsion layer of the photosensitive material undergoes a coupling reaction with an oxidized aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) to form a dye. Couplers are used. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers need only reduce four silver ions in order to form one molecule of dye, but even if they are four-equivalent, only two silver ions need to be reduced. Either equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardener, antifoggant, antifoggant,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and DIR compound used are those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via two values Those which are bound so as to release the inhibitor by an intramolecular nucleophilic reaction, an intramolecular electron transfer reaction, etc. (referred to as a timing DIR coupler and a timing DIR compound) are included. Further, as the inhibitor, those having a diffusibility after release and those having a low diffusivity can be used alone or in combination depending on the use. A colorless coupler that performs a coupling reaction with an oxidized form of an aromatic primary amine developer but does not form a dye (also referred to as a competitive coupler) can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color couplers that can be used include, for example, U.S. Pat.
No. 5,057, No. 3,265,506, No. 3,408,194, No. 3,5
No. 51,155, No. 3,582,322, No. 3,725,072, No. 3,
891,445, West German Patent 1,547,868, West German Application Publication 2,219,
No. 917, No. 2,261,361, No. 2,414,006, UK Patent No. 1,4
No. 25,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 50-6341, 50-87650, 50-12
No. 3342, No. 50-130442, No. 51-21827, No. 51-10263
No. 6, No. 52-82424, No. 52-115219, No. 58-95346 and the like.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzmimidazole couplers, pyrazolotriazole couplers, open chain acylacetonitrile couplers, indazolone couplers and the like can be used. Specific examples of magenta color couplers that can be used include, for example, U.S. Pat.Nos. 2,600,788 and 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,41
No. 8,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, Japanese Patent Laid-Open No. 49
-74027, 49-74028, 49-129538, 50-60
No. 233, No. 50-159336, No. 51-20826, No. 51-26541
No. 52-42121, No. 52-58922, No. 53-55122,
Examples include those described in Japanese Patent Application No. 55-110943.

As the cyan dye-forming coupler, a phenol or naphthol coupler is generally used. Specific examples of cyan color couplers that can be used in addition to the present invention include, for example, U.S. Pat.Nos. 2,423,730, 2,474,293, and 2,80.
1,171, 2,895,826, 3,476,563, 3,7
No. 37,326, No. 3,758,308, No. 3,893,044,
JP-A-47-37425, JP-A-50-10135, JP-A-50-25228,
The couplers described in JP-A Nos. 50-112038, 50-117422 and 50-130441, and the couplers described in JP-A-58-98731 are preferable.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color fogging inhibitors, ultraviolet absorbers, fluorescent brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solid Various methods such as a dispersion method, a latex dispersion method, and an oil-in-water type emulsification dispersion method can be used, and these can be appropriately selected according to the chemical structure of a hydrophobic compound such as a coupler. The oil-in-water emulsion dispersion method can be applied with various methods of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point in a high boiling point organic solvent having a boiling point of about 150 ° C. or higher, and / or water solubility. Dissolve in combination with an organic solvent and emulsify using a dispersing agent such as a stirrer, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc. in a hydrophilic binder such as gelatin aqueous solution. After dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

Organic solvents having a boiling point of 150 ° C or higher such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters and trimesic acid esters which do not react with the oxidized form of the developing agent as high boiling solvents A solvent is used.

A low boiling or water-soluble organic solvent can be used with or instead of a high boiling solvent. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

When the dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, color fogging inhibitor, ultraviolet absorber, fluorescent whitening agent, etc. have an acid group such as carboxylic acid and sulfonic acid, they are used as an alkaline aqueous solution. It can also be introduced into a hydrophilic colloid.

Dissolve the hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersing aid when dispersing in water using mechanical or ultrasonic, anionic surfactant,
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

Between the emulsion layers (same color-sensitive layers and / or different color-sensitive layers) of the light-sensitive material, the oxidant or electron transfer agent of the developing main chain moves to cause color turbidity or deterioration of sharpness, An antifoggant can be used to prevent the graininess from being noticeable.

The color antifoggant may be contained in the emulsion layer itself, or may be contained in the intermediate layer provided between adjacent emulsion layers.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds which can be preferably used are those described in RD17643, item VII J.

The hydrophilic colloid layer such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber to prevent fogging due to discharge caused by the photosensitive material being charged by friction or the like and to prevent deterioration of an image due to ultraviolet rays. Good.

In order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used for the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye or an ultraviolet absorber, it may be mordanted with a mordant such as a cationic polymer.

A development retarder or a bleaching accelerator can be added to the silver halide emulsion layer and / or the other hydrophilic colloid layer of the glaze material. The compound that can be preferably used as the development retarder is the compound described in Item XXI, Item B to D of 17643, and the development retarder is the compound described in Item XXI, Item E of 17643.
A black-and-white developing agent and / or a precursor thereof may be used for development promotion and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent brightening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. Compounds which can be preferably used as the optical brightening agent are described in RD17643, item V.

The photosensitive material includes a filter layer, an antihalation layer,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving writing properties, and preventing sticking of the light-sensitive materials to each other. As the matting agent, any can be used. For example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate,
Examples include polymers of calcium carbonate, acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates, and polymers of styrene and their copolymers. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant can be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support where the emulsion is not laminated, and a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side where the emulsion layer is laminated on the support. May be used. Antistatic agents preferably used are the compounds described in RD17643 XIII.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the photosensitive material, coating property improvement, antistatic property, slip property improvement, emulsification dispersion, adhesion prevention, photographic properties (development acceleration, hardening, sensitization, etc.)
Various surfactants can be used for the purpose of improvement and the like.

The support used in the light-sensitive material of the present invention includes paper laminated with α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer), a flexible reflective support such as synthetic paper, cellulose acetate, Films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and flexible supports provided with a reflective layer on these films, glass, metal, pottery, etc. included.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support as required, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness, It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

When coating the photosensitive material, a thickener may be used to improve the coating property. In addition, for example, for a hardener such as a hardener, which causes gelation before coating when added to a coating solution in advance due to its high reactivity, it is recommended to mix it immediately before coating using a static mixer or the like. preferable.

As an application method, extrusion coating and curtain coating, which can simultaneously apply two or more layers, are particularly useful, but bucket coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, for example, natural surfactants such as savonin, alkylene oxides, glycerin, nonionic surfactants such as glycidol,
Contains higher alkyl amines, quaternary ammonium salts, pyridine and other heterocycles, cation surfactants such as phosphonium or sulfonium, and acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, nitrate ester, phosphate ester, etc. Amphoteric surfactants such as anionic surfactants, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols may be added. For the same purpose, it is also possible to use a fluorine-based surfactant.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. Color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step if necessary, but instead of a processing step using a bleaching solution and a processing step using a fixing solution. In addition, a bleach-fixing treatment step can be carried out using a 1-bath bleach-fixing solution, or a mono-bath processing step using a 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath. You can also do

A pre-hardening step, a neutralizing step, a stop fixing step, a post-hardening step, etc. may be performed in combination with these processing steps. In these treatments, instead of the color development treatment step, a color developing agent or its precursor may be contained in the material and an activator treatment step in which the development treatment is carried out by an activator solution may be performed, or the monobath treatment may be performed by an activator. Treatments can be applied. Among these processes, representative processes are shown below. (In these processes, any of a water-washing process, a water-washing process, and a stabilization process is performed as a final process.)-Color developing process-Bleaching process-Fixing process-Color developing process-Bleaching-fixing process Process-Pre-hardening process-Color developing process-Stop fixing process-Rinsing process-Bleaching process-Fixing process-Rinsing process-Post-hardening process-Color developing process-Rinsing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ° C, but 65 ° C
The temperature may exceed ℃. The treatment is preferably performed at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylesinamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. it can.

These compounds are generally about 0.
It is used at a concentration of 1 to 30 g, more preferably at a concentration of about 1 to 15 g per color developing solution 1. If the amount is less than 0.1 g, a sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-
Aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N-
N′-dialkyl-p-phenylenediamine compound, wherein the alkyl group and the phenyl group are substituted,
Alternatively, it may not be substituted. Among them, examples of particularly useful compounds include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino- 5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylamino Examples thereof include aniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate and the like.

The color developing agents may be used alone or in combination of two or more kinds. Further, the color developing agent may be incorporated in a color photographic material.

In this case, the silver halide color photographic light-sensitive material can be processed with an alkali solution (activator solution) instead of the color developing solution, and bleach-fix processing is performed immediately after the alkali solution processing.

The color developing solution used in the present invention may contain an alkali agent usually used in the developing solution, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfite. May be. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher,
It is preferably about 9 to 13.

In the color developer used in the present invention, diethyloxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,
3-dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as a sequestering agent. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminopentaacetic acid, 1
Organic phosphonic acids such as -hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane 1, Examples thereof include polyhydroxy compounds and the like, such as phosphonocarboxylic acids such as 2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

The bleaching step may be performed simultaneously with the fixing step as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid, which is coordinated with a metal ion such as iron, cobalt, or copper is used. . The most preferred organic acids among the above organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N ′.
-Triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid and the like can be mentioned.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are 5-450 g /, more preferably 20-2 g
Use at 50g /.

As the bleaching solution, a solution having a composition containing a sulfite as a preservative, if necessary, in addition to the bleaching agent as described above, is required.
Further, a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex bleach and having a composition in which a large amount of a halide such as ammonium bromide is added may be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-A-46-280,
Japanese Patent Publication Nos. 45-8506 and 46-556, Belgian Patent No. 770,9
No. 10, JP-B-45-8836, JP-B-53-9854, JP-A-54-71
Various bleaching accelerators described in JP-A Nos. 634 and 49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0-
It is used at 9.5, preferably at 4.5-8.0, most preferably at 5.0-7.0. A fixing solution having a commonly used composition can be used. As a fixing agent, a compound capable of forming a water-soluble complex salt by reacting with silver halide used in a usual fixing process, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, and potassium thiocyanate And thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and the like. These fixing agents are used in an amount in which they can be dissolved in an amount of 5 g / or more, but generally 70 g to 250 g /.
A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethylsulfonamide and dimethylsulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or higher, but generally 4.5-
It is used at 10, preferably 5 to 9.5, most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above-mentioned bleaching step, and preferred compounds and the concentrations in the processing solution are the same as those in the above-mentioned bleaching step. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Also, a bleach-fixing solution having a composition in which a small amount of a halide such as ammonium bromide is added to the above-mentioned silver halide fixing agent and a bleach-fixing agent of ethylenediaminetetraacetate (III) complex salt, or conversely, a halogen such as ammonium bromide. Bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an iron (III) complex salt of ethylenediaminetetraacetate and a large amount of a halide such as ammonium bromide. Can do things.
As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the above fixing processing step. The concentration of the fixing agent and the pH buffer and other additives that can be contained in the bleach-fixing solution are the same as those in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but generally
Used in 5.0-9.5, preferably used in 6.0-8.5,
Most preferably, it is 6.5 to 8.5.

[Effect of the Invention] According to the silver halide photographic light-sensitive material of the present invention, the non-photosensitivity between the support and the silver halide emulsion layer located closest to the support does not require swelling during development processing. Since the layer can be hardened particularly strongly to reduce the degree of swelling, the drying property of the light-sensitive material can be improved and the drying time can be shortened.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

In the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified.
Also, silver halide and colloidal silver are shown in terms of silver.

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

First layer: antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Polymer hardener of the present invention (Table-1) Gelatin 2.2 g / m ² Second layer: Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Polymeric hardener of the present invention (Table-1) Gelatin 1.2 g / m ² Third layer: Low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size () 0.30 μm, containing AgI 6 mol% Monodisperse emulsion consisting of AgBrI (Emulsion I): Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ^-5 moles Cyan coupler (C-1) …… 0.06 moles per mole of silver Colored cyan coupler (CC-1) …… 0.003 moles per mole of silver DIR compound (D-1) …… 0.0015 mol of DIR compound (D-2) to 1 mol of silver ... 0.002 mol to 1 mol of silver Gelatin 1.4 g / m ² 4th layer: High-sensitivity red-sensitive silver halide emulsion layer (RH-1) average Monodisperse emulsion consisting of AgBrI with grain size () 0.54 μm and AgI 7.0 mol% (Emulsion II) …… Silver coating amount 1.3 g / m ² Sensitizing dye I …… 3 × 10 ⁻ per mol of silver ⁵ mol sensitizing dye II ...... silver 1 1.0 × 10 ^-5 mol cyan coupler (C-1) 0.02 mol colored cyan coupler relative ...... silver mole (CC-1) 0.0015 mol DIR compound against ...... silver mole relative Le (D- 2) ... 0.001 mol gelatin per mol of silver 1.0 g / m ² 5th layer: intermediate layer (IL) The same gelatin layer as the 2nd layer. Gelatin 1.0 g / m ² 6th layer: Low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I …… Coating silver amount 1.5 g / m ² Sensitizing dye III …… 2.5 per 1 mol of silver × 10 ^-5 mol Sensitizing dye IV: 1.2 mol per mol of silver 1.2 × 10 ^-5 mol Magenta coupler (M-1): 0.05 per mol of silver
0 mol Colored magenta coupler (CM-1) ... 0.009 mol to 1 mol of silver DIR compound (D-1) ... 0.0010 mol to 1 mol of silver DIR compound (D-3) ... to 1 mol of silver To 0.0030 mol
Gelatin 2.0 g / m ² 7th layer: High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II …… Coating silver amount 1.4 g / m ² Sensitizing dye III …… 1.5 per 1 mol of silver × 10 ^-5 mol Sensitizing dye IV: 1.0 mol of silver 1.0 × 10 ^-5 mol Magenta coupler (M-1): 0.02 mol of silver
0 mol Colored magenta coupler (CM-1) ... 0.002 mol per mol of silver DIR compound (D-3) ... 0.0010 mol per mol of silver
Gelatin 1.8 g / m ² Eighth layer: Yellow filter layer (YC-1) Gelatin containing yellow colloidal silver and an emulsion dispersion of 2,5-di-t-octylhydroquinone. Gelatin 1.5 g / m ² 9th layer: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI containing 0.48 μm average grain size and 6 mol% AgI. 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): 0.29 per mol of silver
Molar gelatin 1.9g / m ² 10th layer: High-sensitivity blue-sensitive emulsion layer (BH-1) Monodisperse emulsion (Emulsion IV) consisting of AgBrI with average grain size 0.8μm and AgI 15mol% …… Silver coating amount 0.5g / m ² Sensitizing dye V: 1.0 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): 0.08 per mol of silver
Molar DIR compound (D-2) ... 0.0015 mol per mol of silver
Gelatin 1.6 g / m ² 11th layer: 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average 0.07 μm) Silver coating amount 0.5 g / m ² UV absorber UV-1, UV-2 Including gelatin layer.

Gelatin 1.2g / m ² 12th layer: 2nd protective layer (Pro-2) Ethyl methacrylate: Methyl methacrylate: Methacrylic acid copolymer particles (average particle diameter 2.5μ) Polymethylmethacrylate particles (diameter 1.5μm) and formalin Gelatin layer containing scavenger (HS-1) 1.2 g / m ^{2 In} addition to the above composition, a high boiling point organic solvent and a surfactant were added to each layer.

The low-molecular hardener is added to the second protective layer because it diffuses when added to the protective layer and hardens the whole gelatin layer.

Hardener (H-7) 3.0 × 10 ^-3 equivalent / 100g gelatin.

 The compounds contained in each layer of the sample are as follows.

Sensitizing dye I: anhydro 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II: anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III: anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide Sensitizing dye IV: Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide Sensitizing dye V: anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanine Each of the samples thus prepared was subjected to wedge exposure using white light, and then the following development processing was performed. The scratch strength was measured by the following method immediately after drying at 60 ° C. for 10 seconds and 2 minutes.

The sensitivity was shown as relative sensitivity with the sensitivity of the comparative sample at a density of fog +0.5 as 100.

 The results are shown in Table 1.

[Measurement of scratching strength] A sapphire needle with a tip of 0.8 mm (radius) is pressure-bonded to the sample surface, and while moving parallel on the film surface at a speed of 1 cm for 1 second, 5
The load of the needle that damages the film surface of the sample was determined by continuously changing the load in the range of 0 to 200 g.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1

[Bleach] Ethylenediaminetetraacetic acid ammonium ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make pH 1 and use ammonia water to obtain pH = 6.0.
Adjust to.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metabisulfite 2.3 g Water is added to adjust the pH to 1 and the pH is adjusted to 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konishi Roku Kogyo Co., Ltd.) 7.5 ml Make up to 1 by adding water.

From the results shown in Table 1, the comparative sample No. 9 has a scratching strength of 97 g even after drying at 60 ° C. for 2 minutes, and the drying is still insufficient. It is clear that the sample of the present invention is excellent in drying property, since the scratching strength becomes 100 g or more after the partial drying, and the drying progresses to such an extent that there is no problem in practical use.

Example 2 A sample was prepared in the same manner as in Example 1 except that the first layer and the second layer of Example 1 contained polymer Q which gives the polymer hardener of the present invention instead of the polymer hardener. 10 to 15 were manufactured and evaluated in the same manner as in Example 1.

 The results are shown in Table-2.

From the results shown in Table 2, it can be seen that the effects of the present invention can be obtained as in Example 1 even if a type of hardener that forms a polymer hardener in the emulsion layer is used.

Example 3 An X-ray photosensitive material sample was obtained by sequentially forming layers having the compositions shown below on both sides of a polyethylene terephthalate support which had been subjected to subbing, from the support side.

Additives other than silver halide are shown in amounts per mol of silver halide unless otherwise specified.

First layer Crossover cut layer Dye (I) 3 mg / m ² Gelatin layer Gelatin 0.2 g / m ² Second layer Emulsion layer Emulsion consisting of AgBrI containing average grain size 1.2 μm, AgI 1.5 mol% Silver coating amount …… 4g / m ² 4-Hydroxy-6-methyl 1,3,3a, 7-tetrazaindene 1.2g Diethylene glycol 11.0g Paranitrophenyl triphenylphosphide chloride 0.2g Gelatin 2.0g / m ² Third layer Protective layer Ciethylhexyl Sodium succinate sulfonate 0.015g
/ m ² Glyoxal 0.02g / m ² Mucochloric acid 0.015g / m ² Polymethylmethacrylate particles (average particle size 3-4μ)
Since 50 mg / m ² gelatin 1.0 g / m ² low molecular hardener was added to the protective layer to diffuse and harden the whole gelatin layer, it was added to the protective layer.

The sample thus obtained was developed at
The scratch strength immediately after drying for 10 seconds and 20 seconds was measured in the same manner as in Example 1.

 The results are shown in Table-3.

[Processing step] Development 30 ℃ 45 seconds Fixing 25 ℃ 35 seconds Washing 15 ℃ 35 seconds Drying 45 ℃ 20 seconds [Developer] Phenidone 0.4g Metol 5g Hydroquinone 1g Anhydrous sodium sulfite 60g Hydrous sodium carbonate 54g 5-nitro Imidazole 100mg Potassium bromide 2.5g Add water to make 1000ml and adjust the pH to 10.20.

[Fixing solution] (Part A) Ammonium thiosulfate 170 g Sodium sulfite 15 g Boric acid 6.5 g Glacial acetic acid 12 ml Sodium citrate (dihydrate) 2.5 g Add water to make 275 ml.

(Part B) Aluminum sulfate 15 g 98% sulfuric acid 2.5 g Add water to make 40 ml.

When using, add water to Part A: 275 ml, Part B: 40 ml to make 1.

The results shown in Table 3 show that the effects of the present invention can be obtained even when the present invention is applied to an X-ray photosensitive material.

Comparative Example In Comparative Example 1, the polymeric hardener HP-3 of the present invention was added to the second protective layer of the twelfth layer instead of the first layer and the second layer in an amount shown in Table-4 and a comparative sample. Created 22 and 23. The comparative sample thus prepared was developed in the same manner as in Example 1,
Then, the scratch strength and the photographic performance were examined. The results are shown in Table-4.
Shown in

From the results shown in Table 4, the sensitivity decreases when the amount of swelling is added, and the amount of swelling cannot be reduced when the amount of swelling is added.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideo Ota, No. 1 Sakuramachi, Hino City, Konishi Roku Photo Industry Co., Ltd. (72) Inventor, Ichiro Oi, No. 1, Sakura Town, Hino City, Konishiroku Photo Industry Co., Ltd. (56) References JP-A-56-142524 (JP, A) JP-A-60-61742 (JP, A) JP-A-61-97649 (JP, A) JP-A-57-212427 (JP, A) JP-A-59 -31944 (JP, A) JP 59-113074 (JP, A) JP 60-83936 (JP, A) JP 60-112034 (JP, A) JP 59-121327 (JP, A) )

Claims (1)

(57) [Claims] 1. A support having at least one silver halide emulsion layer, which is closer to the support than the silver halide emulsion layer located closest to the support among the silver halide emulsion layers. In a silver halide photographic light-sensitive material having at least one non-photosensitive layer, at least one layer of the non-photosensitive layer is a polymer hardener, or a gelatin hardener and a polymer hardener which provide a polymer hardener. A silver halide photographic light-sensitive material characterized by being hardened with a polymer to give.