JPS62284346A - Silver halide photographic sensitive material having excellent drying property - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of accelerating the rate of drying at the time of processing by hardening a non-photosensitive layer between a silver halide emulsion layer and a substrate body with a high polymer hardener. CONSTITUTION:At least one layer of the non-photosensitive layer between the silver halide emulsion layer and the substrate body is hardened by the high polymer hardener. The hardener is exemplified preferably by a compd. having >=2 the hardening group (such as an aldehyde group) capable of reacting with a hydrophilic colloid such as gelatin in a same molecular, and for example, a polymer having aldehyde group such as dialdehyde starch, polyacrolein and acrolein copolymer, a polymer having an epoxy group, a polymer having a dichlorotriazine group, and a polymer having an active ester group, etc. Thus, the titled material having an excellent drying property and capable of rapidly processing at a high temp. is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a silver halide photographic material.
This invention relates to a silver halide photographic material F+ with improved drying properties.

[Background of the Invention 1 Many silver halide photographic materials contain gelaboon as a hydrophilic colloid binder.

These gelatin-containing photosensitive materials are developed with various aqueous solutions having different pHs or temperatures, but the gelatin-containing layer that is not treated with a hardening agent has poor water resistance.
It swells excessively in aqueous solutions and becomes easily damaged, especially when
In extreme cases, the gelatin layer could dissolve or even flow out when the processing solution was heated to temperatures above ℃.

A number of compounds have been known to be effective for hardening gelatin and increasing the water resistance, heat resistance and scratch resistance of the gelatin layer.

These are known as hardening agents used in the production of silver halide photographic materials. For example, non-Nada compounds such as chromium alum, aldehyde compounds such as formalahide, glutaraldehyde, U.S. Pat. No. 3,288.
Compounds having active halogens as described in U.S. Pat. No. 775, etc., compounds having reactive ethylenically unsaturated groups as described in U.S. Pat. Organic compounds such as the aziridine compounds described in US Pat. No. 3,091,537, epoxy compounds described in US Pat. No. 3,091,537, and halogenocarboxaldehydes such as mucochloric acid are known.

On the other hand, from the perspective of photographic performance of silver halide photographic materials, the degree of hardening of gelatin by a hardening agent is reduced, and the degree of swelling of the silver halide emulsion layer during development is increased. From the viewpoint of saving silver, it is required to improve the optical density, that is, to obtain the required optical density with a minimum amount of coated silver.

The effect of increasing the developability of silver halide by reducing the degree of hardening is particularly noticeable in high-temperature processing, but as mentioned above, high-temperature treatment can cause the silver halide emulsion layer, which has a small degree of hardening, to become excessively hard. Photosensitive materials that contain a large amount of photographic additives in their gelatin, such as color photosensitive materials, are particularly prone to swelling and scratching, and therefore, the degree of hardness is generally determined by the degree of swelling and scratch resistance. Ta.

However, increasing the degree of swelling has a negative effect not only on scratch resistance but also on drying properties. In other words, the greater the amount of moisture absorbed during development, the longer the drying time is required.

Generally, in color photosensitive materials, multiple layers are coated simultaneously, so when using a diffusive low-molecular hardening agent, it is difficult both technically and cost-wise to harden only a certain layer particularly strongly. Ta. Therefore, it is non-photosensitive and does not require swelling during development processing.

Although it is desirable to harden the layers, especially the layers between the silver halide emulsion layer and the support such as the antihalation layer, from the viewpoint of drying properties, this is not done for the reasons mentioned above. Ta.

[Object of the Invention] Accordingly, an object of the present invention is to provide a silver halide photographic material that has excellent drying properties and can be rapidly processed at high temperatures.

[Structure of the Invention] The object of the present invention is to provide a silver halide emulsion layer having at least one silver halide emulsion layer on a support, and which is located closest to the support. In a silver halide photographic light-sensitive material having at least one non-photosensitive layer on the support side, the at least one non-light-sensitive layer is hardened using a polymer hardening agent. achieved.

[Specific structure of the invention] The polymer hardener of the present invention has at least two hardening groups in the same molecule for reacting with hydrophilic colloids such as gelatin.
It means a compound having a molecular weight (number average molecule 1) of 3,000 or more.

Examples of hardening groups for reacting with hydrophilic colloids such as gelatin include aldehyde groups, epoxy groups, active halide groups (dichlorotriazine, etc.), active vinyl groups,
Examples include active ester groups. The number of these groups in the same molecule of the polymeric hardener is at least two, but preferably 10 to 5,000. Further, the molecular weight may be 3,000 or more, but a molecular weight of about 3,000 to 500,000 is preferably used.

Generally, a hydrophilic polymer moiety having a hardening group for reacting with a hydrophilic colloid such as gelatin is preferably used, but a hydrophilic colloid (
For example, it can also be used by emulsifying and dispersing it in gelatin (dissolving and dispersing it in an organic solvent if necessary).

Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, and U.S. Pat. No. 3,396.
．． Polymers with aldehyde groups, such as the acrolein copolymers described in US Pat. No. 3,623,87
A polymer having a No. 8 epoxy group, a polymer having a dichlorotriazine group described in U.S. Pat.
Polymers having active ester groups as described in No. 841, JP-A-56-142524, U.S. Pat. No. 4,1
61,407, JP-A No. 54-65033, Research Disclosure Magazine 16725 (197g), etc. Polymers having an active vinyl group or a group that is a precursor thereof, etc. Polymers having a group or a group serving as a precursor thereof are preferred, and in particular, as described in JP-A-56-142524, a long spacer allows an active vinyl group or a group serving as a precursor thereof to be added to the polymer. Particularly preferred are such polymers that are attached to the main chain.

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

Margin below HP-21 Co　　　　　　　　　　　　　　C0HP-23 0HOO I c=o　　　　c=.

(CHz+C0OHNHC'H2C0NHCH2CHO
HP-24 HP-25 HP-26 HP-27 HP-28 (The numbers represent molar ratios) In addition, as the polymer hardener of the present invention, like the previously mentioned polymer, hydrophilic gelatin or the like is used from the beginning. Polymers that have at least two hardening groups in the same molecule for reacting with colloids can be used, but they can react with hydrophilic colloid hardeners such as gelatin and harden! !
The polymer ti! in the coated hydrophilic colloid 1 using a polymer that provides a polymer having at least two ``l'' in the same molecule! Agent II can be made and thereby couple the objects of the present invention.

Thus, as hardeners for gelatin used to make polymer hardeners in hydrophilic colloid layers, low molecular hardeners, such as T.H.
The Theory or
the Photoaraphic Processes
s) J, 4th edition, pages 77 to 84 are used, and among them, low molecular hardeners having a nitrogen sulfone group or a triazine ring are preferred;
In particular, JP-A Nos. 53-41221 and 60-22514
The low molecular weight hardeners described in No. 3 are preferred.

Specific examples of gelatin hardeners that provide polymeric hardeners according to the present invention are shown below.

(CH2=CH3O2CToCONHCH)2-(CH
2=CI-ISO2CH2CONHIJb)2CH2C
H2=CH3O2CH2CHCH2SO2CH=CH2
H Below margin H-4 CH2=CHSO2CH=CH2 CH2=CH-3O2CH20CH2SO2CH=CH
2CH2=CHSO2CH2CH2CH2SO2CH=
CH2Na 0HC+CH2+CH0 Formalin H3 CH2=CHSO2CH2CH2S 02 CH=CH
4F-15 (CH=CH2C(CH2=CHSO2CHz+C:]・H2N C
H2CH2SO3 with salt CHO CHO C1CHO Na Polymers used to make polymeric hardeners in hydrophilic colloid layers include gelatin li! It is necessary to have at least two nucleophilic groups in the same molecule that react with the l agent; for example, British Patent No. 2.011,9
Polymer having a primary amino group described in No. 12, JP-A No. 1973
Polymers with sulfinic acid groups as described in US Pat. No. 6-4141, polymers with phenolic hydroxyl groups as described in US Pat. Examples include polymers having methylene groups.

Specific examples of the polymer that provides the polymer hardening agent name of the present invention are shown below.

The following margin Q-1 SO2K 1,000 CH2-CH violet-l: cHz-CH÷H2 +CH2-CH-)- 硼 H2 H2 C H2 N H2 (FH3 The following margin shows the polymer hardening agent used in the present invention The synthesis method is shown.

Synthesis Example 1 Poly-N-(3-(vinylsulfonyl)propioyl)aminemethylacrylamide-co-acrylamide-
Synthesis of sodium 2-methylpropanesulfonate (HP-3) (a) Synthesis of N-(3-(chloroethylsulfonyl)propioyl)aminomethylacrylamide In the reaction vessel of 22, 140 g of distilled water (h+2, 224 g of sodium sulfite, Add 220 g of sodium bicarbonate, dissolve with stirring, cool to 5°C and leave for about 1 hour.
In 0 minutes, 260 g of chloroethanesulfonyl chloride was added dropwise. After the dropwise addition, 160 g of 49% sulfuric acid was added, and the precipitated crystals were filtered and washed roughly with 400 x Q distilled water. This filtrate and Washing solution was added to 32 reaction vessels, and 246 g of methylene bisacrylamide was added to 48
A solution dissolved in 0iff distilled water and 1480d ethanol was added dropwise at 5° C. over about 30 minutes. After the reaction sample was left in the refrigerator for 5 days to complete the reaction, the precipitated crystals were collected by filtration, washed with cooled distilled water, and then mixed with a 50% ethanol aqueous solution of 2000 g. A white powder of 210Q was obtained by recrystallization from . Yield is 49
%, the melting point of this compound was above 192°C (decomposition).

(b) Synthesis of HP-3 200% reaction solution was added with monomers s and esg of (a).
, 9.16 g of acrylamide-2-methypropanesulfonic acid, and 80% 50% aqueous ethanol solution were added.
Stir to dissolve, heat to 80°C while passing nitrogen gas, add 0.19 of 2,2'-azobis(2,4-dimethylvaleronitrile), and add the same after roughly 30 minutes. A colleague was added and heating and stirring continued for 1 hour. then 10
Cool to ℃ and add 25 g of ariethylamine to 80 sQ.
After stirring was continued for 1 hour, the reaction sample No. 12 was added with acetone, and the resulting precipitate was collected by filtration and dried under vacuum to obtain 12.4 g of a white polymer. The yield was 85%, the intrinsic viscosity [η] of this polymer was 0227, and the vinyl sulfone content was 0.95XIO-3.
equivalent/g polymer.

Synthesis Example 2 Poly-N-(2-(vinylsulfonyl)acetyl)aminomethylacrylamide-coacrylamide()-I
Synthesis of P-7) (a>N-(2-O-loethylsulfonyl>acetyl)
To the reaction solution of aminomethylacrylamide synthesis 12,
Methanol 720d, N-meglol acrylamide 8
Add 08g and mix with V-wet to make it 8! Hydrochloric acid 4011
After stirring was continued for 16 hours, 0.4 g of hydroquinone monomethyl ether was added, and methanol was distilled off using an evaporator. To the remaining 62.4 (l) of oil,
Add chloroethanesulfonylacetamide 100 (J, hydroquinone monomethyl ether 0.32 (1, p-toluenesulfonic acid 0.22 g) and heat to 150 ° C.
The generated CH30H was distilled off. The reaction was completed in about 15 minutes, and the remaining crystals were recrystallized from a 50% aqueous ethanol solution of 2501ffi to obtain a white powder of 61 (7. The yield was 42%.

(b) Synthesis of HP-7 Is the product (a) used in the 3000vf reaction vessel? -53,
7g, acrylamide 163.3q, methanol 19
Add 55 g of 2,2-azobis(2
4-dimethylvaleronitrile) was added, heated for 4 hours, cooled to room temperature, and added 20% of triethylamine.
After adding O(l), the mixture was stirred for 2 hours, and the precipitate was collected by filtration and dried under vacuum to obtain 194.3 g of a white polymer.

The yield was 92.7% and the vinyl sulfone content of the polymer was 0.50 X 10-3 equivalent Ji/g polymer.

A method for synthesizing a polymer that provides a polymeric hardener is shown below.

Synthesis Example 3 Synthesis of poly-vinylbenzenesulfine-acrylamide-2-methylpropanesulfonic acid sodium (Q-1>) In a 500-inch reaction vessel, 45.8 g of acrylamide-2-methylpropanesulfonic acid soda, 1 vinylbenzene were added. Potassium refinate 206g, ethanol 180i
R. Add distilled water, heat to 75°C while stirring, add (2,2'-azobis-(2-amine)propane) dihydrochloride 082Q, heat for 4 hours, and then bring to a boil. After cooling, ethanol 721Q and 2781 g of distilled water were added and filtered to obtain a colorless and transparent viscous liquid. The viscosity of this polymer solution at 25° C. was 3.25 centivoise (Cβ), the solid content concentration was 10.3% by weight, and the sulfinic acid content was 62×10 −6 equivalents/9.

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

The usage period of the polymer hardener of the present invention can be arbitrarily selected depending on the purpose. Usually, for 100 g of hydrophilic colloid such as gelatin in the layer to be added, the number of functional groups that react with hydrophilic colloid such as gelatin is 0.5X10-3 to 5
Polymeric hardeners corresponding to a range of up to x10-2 equivalents are used. Particularly preferred is a range from 0.5XiO-3 equivalents to 2X10=2 equivalents.

Furthermore, the polymer hardener of the present invention may be used alone as a hardener, or
No. 48221, No. 60-225143, U.S. Patent 3□
No. 325.287, No. 3.945.853, Japanese Unexamined Patent Publication No. 1973
No. 9-31944, No. 55-736, No. 55-987
No. 41, No. 55-46745, No. 54-13093
It may be used in combination with other low-molecular hardeners or polymer hardeners such as those described in No. 0. In the present invention, it is preferable to use them together. Hardeners that can be used in combination include compounds with reactive halogen atoms such as 2-hydroxy-4,6-dichloro-1,3,5-triazine, and compounds with reactive olefins such as divinylsulfone. , isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chromium chloride, and aldehydes, and specific examples include the compounds shown in H-1 to H-21 above.

It has also been found that when a cationic monomer is used as the monomer to be copolymerized with the hardening agent monomer, the diffusion of anionic dyes and the like is suppressed, resulting in increased sensitivity. The effect was particularly remarkable in X-ray photosensitive materials.

Examples of the non-photosensitive layer located closer to the support than the silver halide emulsion layer closest to the support of the present invention include an antihalation layer and a gelatin intermediate layer in negative color light-sensitive materials. There may be two or more of these non-photosensitive layers.

In that case, in order to make the effects 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. Most preferably, all of these non-photosensitive layers are hardened.

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

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method for producing seed particles and the method for growing them may be the same or may be two different methods.

In the silver halide emulsion, halide ions and limiting ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling l) HlpAg in the mixing tank. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of Agx to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, it is possible to contain these metal elements on the particle surface, and by placing the particle in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research [11s
Closure (hereinafter abbreviated as RD)) No. 17643, Section 2 can be carried out.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

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

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). 020 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projected image in the case of grains with shapes other than spherical. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

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

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

As the binder (or protective colloid) for the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and polymers, other proteins, m-derivatives, cellulose derivatives, etc. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers may also be used.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section XI.8.

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

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, ethylene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The emulsion layer of the light-sensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even though these dye-forming couplers are monovalent, in which four silver ions need to be reduced in order to form one molecule of dye, only two silver ions need to be reduced. Either 2-equivalent property may be used. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Included are compounds that release photographically useful fragments, such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized form of the aromatic 1m-amine developer but do not form dyes can also be used in combination with dye-forming couplers.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3, No. 265.506, No. 3.4
No. 08.194, No. 3,551,155, No. 3.
No. 582.322, No. 3.725.072, No. 3
, No. 891.445, West German Patent No. 1,547,868,
West German Application No. 2,219,917, No. 2,261,3
No. 61, No. 2.414.006, British Patent No. 1.42
No. 5.020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 50-63
No. 41, No. 50-87650, No. 50-12334
No. 2, No. 50-130442, No. 51-21827
No. 51-102636, No. 52-82424, No. 52-115219, No. 5g-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenmiidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
No. 9, No. 3,311.476, No. 3,419,3
No. 91, No. 3.519.429, No. 3.558.
No. 319, No. 3.582.322, No. 3,615
．． No. 506, No. 3.834.908, No. 3.89
1.445, West German Patent No. 1,810,464, West German Patent Application (OLS) 2, 408.665, OLS 2,41
No. 7,945, No. 2,418,959, No. 2.42
No. 4,467, Japanese Patent Publication No. 1973-6031, Japanese Patent Application Publication No. 1973-
No. 74027, No. 49-74028, No. 49-12
No. 9538, 5o-60233j%, 50-15
No. 9336, No. 51-20826, No. 51-2654
No. 1, No. 52-42121, No. 52-58922,
Examples include those described in Japanese Patent Application No. 53-55122 and Japanese Patent Application No. 55-110943.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan coloring couplers that can be used in addition to those related to the present invention include U.S. Pat. Nos. 2,423,730 and 2,474,2
No. 93, No. 2,801.171, No. 2,895,
No. 826, No. 3.476, No. 563, No. 3.737
．． 326, 3.758.308, 3.89
3.044 Mei 1B1 JP 47-37425, 5
No. 0-10135, No. 50-25228, No. 50-
No. 112038, No. 50-117422, No. 50-
Couplers described in Japanese Patent Application Laid-open No. 130441, etc., and couplers described in Japanese Patent Application Laid-Open No. 58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method, and usually a high-boiling point solvent with a boiling point of approximately 150°C or higher is mixed with a low-boiling point solvent and/or water-soluble solvent as necessary. A stirrer, a homogenizer, a colloid mill, a flow jet mixer, a hydrophilic binder such as an aqueous gelatin solution, and a surfactant are used in combination with a hydrophilic organic solvent to dissolve the gelatin.
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point wired solvent simultaneously with the dispersion or dispersion may be included.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents 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 dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants are used as dispersion aids when a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or HA sound waves.
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

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

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

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

When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant layer such as a cationic polymer.

A phenomenon retarder and a bleach accelerator can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material.

Compounds that can be preferably used as development retardants are the compounds described in Section XXI B to D of No. 17643, and the development retarders are compounds described in Section XXI E of No. 17643. black and white developing agent for phenomenon promotion and other purposes;
and/or its precursor may be used.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in RD 17643, item 7.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
It can be added as a matting agent for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is preferably 0.05μ to 10μ. The amount of water to be added is 1 to 300111 (] /f
is preferred.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 XI.

The photographic emulsion layer and/or other water-based colloid layer of a light-sensitive material has various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promotion of development, hardening, sensitization, etc.). ) Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. Alternatively, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath. You can also do this.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed with a 7 cutipator solution, or an activator treatment step may be performed in the monobath treatment. Processing can be applied.

Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - bleaching process Constant color fixing process - Colored coral image process - bleach fixing Processing process/Pre-hardening process - Color development process - Stop fixing process - Water washing process - Bleaching process Constant fixation process - Water washing process - Post hardening process/Color development process - Washing process - Supplementary color development process - Stop process - Bleach process Constant monitoring process/Activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath process Processing temperature is usually 10 It is selected in the range of ℃~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

The color developing liquid generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenyrezine amine derivatives. These color developing agents can be used as salts of organic and inorganic acids, such as hydrochloric acid, sulfate, p-toluenesulfonate, sulfite
Salts, oxalates, benzenesulfonates, etc. can be used.

These compounds generally have a concentration of about 0.01 for color developer 11.
A concentration of ˜30° is used, more preferably a concentration of about 1-159° for color development liquid 11. If the amount added is less than 0.19, sufficient color density cannot be obtained.

Examples of the above amine phenol developer include 0-amine phenol, p-amine phenol, 5-amino-phenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful primary aromatic amine color developer is N-N
=-dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N-dimethyl-〇-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N.

N-dimethyl-〇-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3 −
Examples include methylaniline-o-toluenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of the color-developing liquid, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, doloxamic acid, and pentose. or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, 1-
Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, 7-minobolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane1. Examples include phosphonocarboxylic acids such as 2.4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As a bleaching agent, a gold fluoride complex salt with RM is used, for example, a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt, or copper is used. It will be done. Among the above m-acids, the most preferred 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, and iminodiaminetetraacetic acid. acetic acid, dihydroxyethylglycine (citric acid or tartaric acid), ethyl ether diamine tetraacetic acid, greenyl ether diamine tetraacetic acid,
Examples include ethylenediaminetetrapropionic acid and phenylenediaminetetraacetic acid.

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

These bleaches are used at 5-450 g/ffi, more preferably 20-250 g/Il.

In addition to the above-mentioned bleaching agent, the bleaching solution may contain a sulfite salt as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used in addition to ammonium bromide. can.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． 0 to 9.5, preferably 4.5 to 8.0, and most preferably 50 to 1.0. A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5a
/(11;!, above, it is used in the range of 2 that can be dissolved,
Generally, 70 (1 to 250 g/4 is used. Note that a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank. .

In addition, the bleaching solution and/or fixing solution may contain various pH lI agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. may be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as droxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and illic acid salts, and water-soluble aluminum salts. A hardening agent, a specific solvent such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be added.

The pH of the fixer used is 30 or higher, but generally it is 4.
5 to 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 bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, a solution having a composition containing a strain value MMA as a preservative is applied. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron(m) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halogen such as ammonium bromide may be used. A bleach-fix solution with a composition containing a large amount of a chemical compound, or a special bleach-fix solution with a composition consisting of a combination of an ethylenediaminetetraacetic acid iron <m>ts salt bleach and a large amount of a halide such as ammonium bromide, etc. can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH 1lli agent and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

[Effect of the invention 1] According to the silver halide photographic light-sensitive material of the present invention, swelling is not required during development processing, and non-photosensitivity between the support and the silver halide emulsion layer located closest to the support is achieved. The layer can be hardened particularly strongly to reduce the degree of swelling.
The drying properties of the photosensitive material can be improved and the drying time can be shortened.

[Example 1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added to the silver halide photographic material is per 1 f unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

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

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

Polymer hardener of the present invention (Table 1) Gelatin 2.20/l' Second layer: Intermediate layer (1, L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone .

Polymer hardener of the present invention (Table 1) Gelatin 1.2 g/l' Third layer: Low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size (bottom) 0.30 μm, A ! ;l 1
Monodisperse emulsion consisting of AgBrI containing 6 mol% (emulsion technology)... Silver coating amount 1.8 g/f Sensitizing dye technology... 6X10-5 mole increase per 1 mole of silver Sensitive dye ■・・・・・・ Per mole of silver 1. Ox 1 Q-5 Morcian coupler (C-1) --- 0.0 per mole of silver
6 mole colored cyan coupler (CC-1)...Silver 1
0.003 mol DIR compound (D-1) per mol of silver DIR compound (D-2) 0.0015 mol per mol of silver 1. : versus TO, 002t Lugelatin 1.4
1) /f 4th layer: Highly sensitive floor! ::41! Silver halide emulsion layer (R
H-1) Average particle size (r) 0.54 am', A'J
Monodisperse emulsion consisting of AgBr I containing 7.0 mol% (emulsion ■)... Silver coating amount 1.3 g/f Sensitizing dye processing... 3 X for 11 mol 10-5 mole sensitizing dye...
...... 1.0 x 1.0-5 mole cyan coupler (C-1) for 1 mole of limit...0.02 for 1 mole of silver
Mol colored cyan coupler (CC-1)・・・Silver 1
0.0015 mol to mol DIR compound (D-2>...0.001 mol to 1 mol of silver gelatin +, Og/v2 5th layer: Intermediate layer (1, L,) Gelatin layer, same as layer 2.

Gelatin 1.0! II/f 6th layer: low-sensitized silver halide emulsion layer (G, L-1
) Emulsion-1... Coated silver 1i 1.50 /*' Sensitizing dye ■... 2.5x 1Q-5 mol Sensitizing dye IV per 1 mol of silver
...... 1.2x 1Q-5 mole magenta coupler (M-1) for 1 mole of silver... o, o for 1 mole of silver
somolar colored magenta coupler (CM-1>...0.009 mol DIR per 1 mol silver Compound (D-1)... 0.0010 mol DIR per 1 mol silver Compound (D-3>...0.0030 lugelatin 2.0 per 4111 mol)
(J /v' 7th layer: High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion - ■... Coated silver amount i, ag /f Sensitizing dye ■... 1.5x10-5 mol sensitizing dye for 1 mol silver
... 1 mole of silver. OX 10' mole magenta coupler (M-1)...0.02 per mole of silver
0 mol colored magenta coupler (CM-1)...0.002 mol DIR compound per 1 mol silver (D-3>... 0.0010 mol gelatin L8 per 1 mol Wi) (1/i2 8th layer: Yellow filter single layer (YC-1) Gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2.5-G C-octylhydroquinone.

Gelatin 1.5g/f 9th layer: Low sensitivity blue-sensitive silver halide emulsion layer (BL-1) Average grain size 0.48 μm, AQ 3 containing 6 mol% Agl
Monodispersed emulsion consisting of r I (emulsion ■)... Silver coating amount 0.9 g/f Sensitizing dye V... 1.3 x 10-S mol yellow coupler per 1 mol of silver (Y-1)...0.29 per mole of silver
Morgelatin 1.9 (] / f 10th layer: High sensitivity blue-sensitive emulsion layer (BH-1) Average grain size 0
．． 8 μm, monodispersed emulsion (emulsion ■) consisting of AaBrI containing 115 mol% of Ag... Silver type cloth 1 o, 5 g/f Sensitizing dye V... 1 per mole of silver ．． OX 10' mole Yellow coupler (Y-1)...O, O per mole of silver
a mol DIR compound (D-2) 0.0015 mol gelatin per 1 mol silver 1.61 J/II' 11th layer: 1st protective layer (Pro-1> Silver iodobromide ( Ag 11 mol% average 0.07 μm) Silver coating amount 0.5 (1/1') Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

Gelatin 1.2 (1/1" 1q12 .5 μm) and formalin scavenger
Gelatin layer containing (H8-1) Gelatin 1.2 g/f In addition to the above composition, a high boiling point sterile solvent and surfactant-jlJ were added to each layer.

The low molecular weight hardening agent was added to the second protective layer because it diffused and hardened the entire gelatin layer when added to the protective layer.

Hardener (H-7) 3.0x10-3 equivalents/10og gelatin.

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

Sensitizing dye: Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye ■: 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 ■: Anhydro 9 -ethyl-3,3'-di(3-sulfopropyl)-5,6
,5'.

6'-Dibenzooxalpocyanine hydroxy sensitizing dye V: Anhydro 3.3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine Below margin Q ○-L H3 CM-1cL tY-I CtC<H9
(L) V-2 Margin below Each sample thus prepared was exposed to a wedge using white light, and then subjected to the following development treatment.

In addition, the scratch strength was measured by the following method immediately after drying at 60° C. for 10 seconds and 2 minutes.

Sensitivity is the comparison sample sensitivity of fog + 0.5 concentration by 100
It is expressed as relative sensitivity.

The results are shown in Table-1.

[Measurement of scratch strength] A sapphire needle with a tip of 0.8 mm (radius) is pressed onto the sample surface, and a load is applied continuously in the range of 50 to 200 g while moving it in parallel on the membrane surface at a speed of 1 cm per second. The needle load that caused damage to the membrane surface of the sample was determined by varying the load.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds
Arrival: 6 minutes 30 seconds Washing: 3 minutes 15 seconds Stabilization: Drying: 1 minute 30 seconds The composition of the treatment liquid used in each treatment process is as follows.

[Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25 (1 hydroxylamine 1/2 sulfuric acid Salt 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide
1.30 Nitrilotriacetic acid trisodium salt (monohydrate) 25g Potassium hydroxide 1.0g Add water and make 11
shall be.

[Bleaching solution] Ethylenediaminetetraacetic acid iron ammonium salt 100 ethylenediaminetetraacetic acid 2 ammonium salt 10.0 Q Ammonium bromide 150.0 g Glacial acetic acid 10.0i12 Add water to make 11, and use ammonia water to make p)-1 =6.0.

[Fixer ammonium cothiosulfate 175. OQ anhydrous sodium sulfite 8.5Q sodium metasulfite 2.3 g - Add water to make 1 tl, and adjust to pH=6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5112 Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7. Add FhR water to 11
shall be.

From the results in Margin Table 1 below, comparative sample No. 9 was heated at 60°C;
Even after drying for 2 minutes, the scratch strength was 97 g, indicating that the drying was still insufficient, but samples No. 1 to 8 of the present invention were dried at 60°C and 2
After drying for a few minutes, the scratch strength reached ioog or higher, and the drying progressed to such an extent that there was no problem in practical use, and it is clear that the samples of the present invention have excellent drying properties.

Example 2 Samples were prepared in the same manner as in Example 1, except that the first and second layers of Example 1 contained Polymer Q, which provides the polymer hardener of the present invention, instead of the polymer hardener. Samples Nos. 10 to 15 were prepared and evaluated in the same manner as in Example 1.

The results are shown in Table-2.

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

Example 3 Each layer having the composition shown below was sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain an X-ray photosensitive material sample.

For additives other than silver halide, m per mole of tM halide is shown unless otherwise specified.

1st B Crossover cut layer Dye (I) 31110/l' Gelatin layer Gelatin 0.2 g/f 2nd layer Emulsion layer Average grain size 1.2 μ, A!+l containing 1.5 mol% of A(] I Sr I Emulsion coated silver amount consisting of...-49/v' 4-Hydroxy-6-methyl 1,3゜3a,7-chitrazaindene 129 Diethylene glycol 110g Varanitrophenyltriphenylphosphite chloride 02 Kugelatin 2.0Q/m ' 3rd layer Protective layer Sodium diethylhexyl succinate sulfonate (1,1+15g/
*'Grioki (f-ru 0.02g/n
"Mucochlor 9 0.015Q /*'
Polymethyl methacrylate particles 50111Q/i'
(Average particle size: 3 to 4 μm) Gelatin 1.0 (]/m′ The low-molecular hardening agent was added to the protective layer so that it would diffuse and harden the entire gelatin layer.

Dyeing F'l (I > After the sample thus obtained was subjected to the following development treatment,
Immediately after drying for 10 seconds and 20 seconds, the scratch strength was measured in the same manner as in Example 1.

The results are shown in Table-3.

[Processing process] Development 30℃ 45
Second fixation 25℃ 3
Wash with water for 5 seconds at 15℃
Dry for 35 seconds at 45℃
20 seconds [Developer] Phenidone 0.4g Metol 5g Hydroquinone
1Ω anhydrous sodium sulfite
60 C1 hydrated sodium carbonate
54 (15-nitroimidazole
100mg potassium bromide 2
．． Add 5 g water to make 1000tR pl-110,2
Set to 0.

Constant liquid deposition] (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g Boric acid
6.5g glacial acetic acid
12112 Sodium citrate (dihydrate) 2.51J Add water to finish to 275d.

(Bert B) Aluminum sulfate 15 (198
Add %ti acid 2.5g water to make 401g.

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

From the results shown in Margin Table 3 below, it can be seen that the effects of the present invention can be obtained even when the present invention is applied to X-ray photosensitive materials.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural written formal statement (spontaneous) November 26, 1985

Claims (1)

[Claims] It has at least one silver halide emulsion layer on a support, and at least one non-photosensitive layer is disposed closer to the support than the silver halide emulsion layer located closest to the support among the silver halide emulsion layers. 1. A silver halide photographic material having a photosensitive layer, wherein at least one of the non-photosensitive layers is hardened using a polymer hardening agent.