JPH0862769A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material improved in physical film properties, such as trailing coating trouble, transparency, and scratching resistance, without impairing photographic characteristics, such as sensitivity, and causing no coating trouble. CONSTITUTION: This silver halide photographic sensitive material contains in at least one silver halide emulsion layer on a support at least one kind of compound represented by the formula in which R1 is a 6-30 C straight or cyclic alkyl or alkenyl or aralkyl group, and L is a 1-5 C alkylene or substituted alkylene group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter, simply referred to as a photographic light-sensitive material or a light-sensitive material), and particularly to a loss of photographic light-sensitive characteristics (hereinafter also referred to as photographic performance or photographic characteristics). And a silver halide photographic light-sensitive material having improved film physical properties and coating properties.

[0002]

2. Description of the Related Art In general, a hydrophilic colloid layer used for producing a photographic light-sensitive material is required not only to have no adverse effect on the photographic light-sensitive property but also to have a predetermined strength in terms of physical properties of a film. Therefore, conventionally, when a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, or a protective layer is coated on a support, a polymer latex is contained in the hydrophilic colloid layer to form a binder such as gelatin. In addition to reducing the content of hydrophilic colloids,
For example, various attempts have been made to improve the dimensional stability before and after development, the dimensional stability against heat and humidity, the flexibility, the pressure resistance, and the drying property. However, the use of polymer latex seriously affects photographic performance and the like. For example, desensitization of silver halide emulsions, devitrification during development, color contamination of dyes after development, deterioration of halftone dot quality of a photosensitive material for printing are known. Various attempts have been made to cover this drawback, but none of them have been satisfactory.

For example, US Pat. No. 3,525,620, Belgian Patent 738,558, US Pat. No. 3,142,568, and US Pat. No. 3,323,2.
86, Belgian patent 708,347, German patent 2,04
No. 7,150, British Patent No. 1,498,697, JP-A-57-50967 and the like describe that a latex is polymerized with a specific activator for this purpose. However, these techniques are insufficient in the effect of improving physical properties, and the types of emulsions used are limited, and none of them have an influence on fog, sensitivity and developing characteristics.

Further, JP-A-55-50240 and JP-B-55-47371.
No. 54-19772, JP-A No. 48-52882, and No. 48.
In order to solve the above-mentioned problems, Japanese Patent No. 52883, etc. disclose techniques of using a polymer latex using a polymer protective colloid. In these techniques, compatibility of the polymer latex with a hydrophilic colloid is disclosed. However, there is a problem that the quality of the photographic light-sensitive material is remarkably deteriorated, such as the occurrence of coating failure due to agglomeration in the coating solution and devitrification during development.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. A first object of the present invention is to improve the film physical properties without adversely affecting the photographic characteristics, and to provide an excellent silver halide photographic light-sensitive material. To provide. The second object is to provide a silver halide photographic light-sensitive material in which coating failure does not occur.

[0006]

The present invention has been achieved by the following constitutions.

A silver halide photographic light-sensitive material characterized in that at least one photographic constituent layer on a support contains at least one compound represented by the following formula (I).

[0008]

Embedded image

In the formula, R ₁ is a linear or cyclic alkyl group having 6 to 30 carbon atoms, an alkenyl group or an aralkyl group, and L is an alkylene group having 1 to 5 carbon atoms or a substituted alkylene group.

Further, at least one photographic constituent layer on the support contains at least one kind of polymer particles produced in the presence of the compound represented by the general formula (I). Photosensitive material.

The preferred embodiments of the present invention are described below.

(1) The above silver halide photographic light-sensitive material characterized in that at least one photographic constituent layer on the support contains at least one selected from an anionic surfactant and a nonionic surfactant. .

(2) The silver halide photographic light-sensitive material as described above, wherein at least one photographic constituent layer on the support contains at least one water-soluble polymer.

(3) The silver halide photographic light-sensitive material as described above, wherein at least one photographic constituent layer on the support contains at least one kind of polymer particles.

The silver halide photographic light-sensitive material of the present invention will be described in detail below.

In the compound represented by the general formula (I) used in the present invention, the substituent R ₁ is a linear or cyclic alkyl group, alkenyl group or aralkyl having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms. It is a base.

Examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and octadecyl group.

Examples of the alkenyl group include hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, octadecenyl group and the like.

Further, examples of the aralkyl group include a styryl group, a benzyl group and a cumyl group. The above alkyl group, alkenyl group and aralkyl group may be mixed in the compound represented by the general formula (I).

L represents an alkylene group having 1 to 5 carbon atoms or a substituted alkylene group, and is, for example, an ethylene group, a propylene group, a butylene group, an isobutylene group or the like, a homopolymer, a block polymer or a random polymer, or a mixture thereof. May be.

The compound represented by the general formula (I) of the present invention may be added at the time of synthesizing the polymer particles, or may be directly contained in the coating solution for forming the photographic constituent layer. Absent.

By containing the compound represented by the general formula (I) of the present invention, the polymer particles and the binder such as gelatin are smoothly compatible with each other while improving the surface activity without impairing various photographic characteristics. It is possible to achieve the improvement of the physical properties of the film.

Further, it is possible to reduce the occurrence of coating failure.

The compound represented by the general formula (I) used in the present invention can be easily industrially produced, and the compound represented by the general formula (I) is, for example, ISPE Japan Co., Ltd. or BASF Japan. There are some products that are marketed by stock companies.

Specific examples of the compound represented by formula (I) of the present invention are shown below.

[0026]

[Chemical 3]

The surfactant of the present invention includes anionic surfactants, nonionic surfactants, cationic surfactants,
Any of the amphoteric surfactants can be used, but anionic surfactants and nonionic surfactants are preferable. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used.

By using an anionic surfactant and a nonionic surfactant together with the light-sensitive material containing the compound represented by the general formula (I) of the present invention, coating properties such as repellency are improved, It is preferable because the same effect can be obtained by using a small amount of the surfactant.

Examples of the water-soluble polymer of the present invention include synthetic water-soluble polymers and natural water-soluble polymers.
Any of these can be preferably used in the present invention. Among these, the synthetic water-soluble polymer, for example, those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, Examples thereof include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof,
Examples thereof include a phosphoric acid group or a salt thereof and a sulfonic acid group or a salt thereof. Examples of the above-mentioned cationic group include 4
Examples thereof include a primary ammonium base and a tertiary amino group.

Further, as the above natural water-soluble polymer,
Those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, those having a nonionic group and a cationic group, anionic Examples thereof include those having a group and a cationic group.

In the present invention, the water-soluble polymer is dissolved in 100 g of water at 20 ° C. in an amount of 0.05 g or more, preferably 0.1 g or more.

Next, specific examples of the synthetic water-soluble polymer will be given.

[0033]

[Chemical 4]

[0034]

[Chemical 5]

[0035]

[Chemical 6]

The numerical values on the sides of the specific examples indicate mol%.

Examples of natural water-soluble polymers include lignin, starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, collagen, guar gum, gum arabic, carrageenan and the like, and derivatives thereof. As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated and salts thereof are preferably used. Particularly preferably,
Glucose, dextran, dextrin, cellulose and its derivatives.

By incorporating the water-soluble polymer in the light-sensitive material containing the compound represented by the general formula (I) of the present invention, the compatibility between gelatin and polymer particles is remarkably improved, White turbidity generated during the polymerization of gelatin and polymer particles is reduced, and a uniform and clean coating film can be formed.

The polymer particles of the present invention can be easily produced by various methods. For example, there are an emulsion polymerization method, a dispersion polymerization method, and a method of redispersing a polymer obtained by solution polymerization or bulk polymerization.

In the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of the monomer relative to water and the monomer are used.
Polymer particles are obtained by polymerizing under stirring at about 30 to 100 ° C, preferably 60 to 90 ° C for 3 to 8 hours using 0.05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant. The concentration of the monomer, the amount of the polymerization initiator, the reaction temperature, the time, etc. can be changed widely and easily. Examples of the polymerization initiator include water-soluble peroxides (eg potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (eg 2,2′-
Azobis- (2-amidinopropane) -hydrochloride etc.) and the like. Examples of the dispersant include anionic surfactants, cationic surfactants, nonionic surfactants, water-soluble polymers and the like.

In the dispersion polymerization method, water or an organic solvent is used as a dispersion medium, and a monomer soluble in the dispersion medium in an amount of 10 to 50% by weight and a divinyl monomer having two or more vinyl groups and a monomer are used. On the other hand, 0.1 to 5% by weight of a polymerization initiator (azobisisobutyronitrile, etc.), 0.1 to 20% by weight of a water-soluble polymer, a nonionic surfactant and other dispersants are used at about 30 to 100 ° C. Polymer particles are obtained by polymerizing with stirring for 3 to 8 hours.

In the solution polymerization, a mixture of monomers having a suitable concentration in a suitable solvent (eg, ethanol, methanol, water, etc.) (usually 40% by weight or less, preferably 10 to 25% by weight based on the solvent). Of a polymerization initiator (for example,
In the presence of benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at a suitable temperature (eg 40-
The copolymerization reaction is carried out by heating to 120 ° C, preferably 50 to 100 ° C.

Thereafter, the reaction mixture is poured into a medium in which the produced copolymer is not dissolved, the product is allowed to settle, and then the reaction mixture is dried to separate and remove the unreacted mixture.
Then dissolve the copolymer in a solvent that dissolves but not in water (eg ethyl acetate, butanol, etc.),
Polymer particles can be obtained by vigorous dispersion in the presence of a dispersant (eg, surfactant, water-soluble polymer, etc.) and then distilling off the solvent.

Examples of the ethylenic monomer compound forming the polymer particles of the present invention include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, and maleic acid. Acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds,
Examples thereof include glycidyl esters, unsaturated nitriles, polyfunctional monomers and monomer compounds selected from a combination of two or more kinds selected from various unsaturated acids.

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

The Tg of many polymers of ethylenic monomers used in the present invention are described in "Polymer Handbook" by Brand Wrap et al., Pages III-139 to III-179 (1966) (Wiley and Sun). The Tg (° K) of the copolymer is represented by the following formula.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂ + ... + v _W Tg _W However, in the above formula, v ₁ , v ₂ ... v _W represent the weight fraction of the monomer in the copolymer, and Tg ₁ , Tg ₂ ... Tg _W represents the Tg (° K) of the homopolymer of each monomer in the copolymer. The Tg of the polymer particles of the present invention is preferably -40 to 60 ° C, more preferably 0 to 30 ° C. The error of Tg calculated according to the above equation is ± 5 ° C.

Regarding the method for synthesizing the polymer particles of the present invention, US Pat. Nos. 2,852,386, 2,853,457 and 3,411,91
1, 3,411,912, 4,197,127, Belgian Patent 68
No. 8,882, No. 691,360, No. 712,823, Japanese Patent Publication No. 45-5331
No. 60-18540, No. 51-130217, No. 58-137831
No. 55-50240 and the like.

The average particle size of the polymer particles of the present invention is 0.01
Is preferably 8 to 8 μm, more preferably 0.005 to 2.0 μm, and the molecular weight is not particularly specified, but the weight average molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000.
It is 0 to 500,000.

The polymer particles of the present invention can be contained in the photographic constituent layers as they are or after being dispersed in water.
The content of the polymer particles is preferably 5 to 60% by weight based on the binder of the photographic constituent layer. The addition place may be a photosensitive layer or a non-photosensitive layer.

The polymer particles of the present invention include a case where a functional polymer such as a polymer coupler or a polymer ultraviolet absorber is added in the form of latex.

By incorporating the above-mentioned polymer particles in the photosensitive material, the physical properties of the coating film (such as scratch resistance and film strength)
Can be improved.

Further, by using the compound represented by the general formula (I) of the present invention in combination with the above-mentioned polymer particles, it is possible to suppress aggregation which occurs when the polymer particles are added to gelatin. It will be possible.

Next, an example of a method for producing polymer particles will be described.

(Production Method of Polymer Particles) Production Example 1 (Synthesis of Lx-1) A 1,000 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube and a reflux condenser, and nitrogen gas was supplied. While introducing and deoxidizing, 350 ml of distilled water was added and heated until the internal temperature reached 80 ° C. Dispersants following structure of SF-1 pC ₉ H ₁₉ as _{- (C 6 H 4) -O-} (CH 2 CH 2 O) 6 (CH 2) 3 SO 3 Na the 0.4g and activator of the present invention SL- 1 0.5 g was added, and further 0.45 g of ammonium persulfate was added as a polymerization initiator, and then 90 g of methyl methacrylate was added dropwise with a dropping funnel over about 1 hour. After the completion of the dropping, the reaction is continued for 5 hours as it is, and then unreacted monomers are removed by steam distillation.
Then, it is cooled and adjusted to pH 6 with aqueous ammonia to obtain polymer particles.

Production Example 2 (Synthesis of Lx-2) A 1,000 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, while introducing nitrogen gas to perform deoxidation. 350 ml of distilled water was added and the mixture was heated until the internal temperature reached 80 ° C. 3.0 g of the P-3 of the present invention as a dispersant and 1.5 g of the above SL-1 are added, and 0.45 g of ammonium persulfate is further added as a polymerization initiator, and then 90 g of methyl methacrylate is added dropwise by a dropping funnel over about 1 hour. . After the completion of dropping, the reaction is continued for 4 hours as it is, and then unreacted monomers are removed by steam distillation. Then, it is cooled and adjusted to pH 6 with aqueous ammonia to obtain polymer particles.

Production Example 3 (Synthesis of Lx-3) 200 ml of dioxane was placed in a 500 ml three-necked flask and deoxidized with nitrogen gas.

After that, 40 g of ethyl acrylate and 80 g of methyl methacrylate are added, 1.2 g of dimethyl azobisisobutyrate is further added as an initiator, and the reaction is continued at 60 ° C. for 6 hours. After completion of the reaction, the reaction solution is added to 3 l of distilled water with vigorous stirring to obtain white crystals. The white crystals were collected by filtration, dried, dissolved in 100 ml of ethyl acetate, added to 500 ml of distilled water containing 1.0 g of SF-1 and 1.0 g of SL-1 as a dispersant with vigorous stirring, and then ethyl acetate was added. Removal to obtain polymer particles.

Production Example 4 (Synthesis of Lx-4) A 1,000 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, while introducing nitrogen gas to perform deoxidation. Distilled water (175 g) and methanol (175 g) were added and the mixture was heated until the internal temperature reached 80 ° C. SL-1 2.5 g as a dispersant, P-5 (polyvinylpyrrolidone) 3.
5 g was added, and further 0.45 g of ammonium persulfate was added as a polymerization initiator, and then 75 g of acrylic acid and 15 g of ethylene glycol dimethacrylate were added dropwise with a dropping funnel over about 1 hour. After the completion of dropping, the reaction was continued for 5 hours as it was, then cooled and adjusted to pH 6 with aqueous ammonia to obtain polymer particles.

Specific examples of the polymer particles according to the present invention are shown below.

[0061]

[Chemical 7]

[0062]

Embedded image

[0063] The structure of the SF-2 _{is, C 12 H 25 - (C} 6 H 4) -SO
₃ Na, and the numerical value beside the specific example indicates% by weight.

Examples of the binder for the silver halide emulsion layer used in the present invention include gelatin and gelatin derivatives.

Examples of the gelatin include lime-processed gelatin, Bulletin of the Society of Scientific Photography of Japan (Bull.Soc.Sci.Phot.Japan) No. 16, 30. Page (196
The acid-treated gelatin as described in 6) may be used, and a hydrolyzate or an oxygen hydrolyzate of gelatin may also be used. Examples of the gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, and epoxy compounds in gelatin. What is obtained by reacting is used. A specific example is U.S. Pat.
No. 8, No. 3,132,945, No. 3,186,846, No. 3,312,553,
British Patents 861,414, 1,033,189, 1,005,784,
It is described in Japanese Patent Publication No. 42-26845.

The silver halide emulsion used in the present invention is used as a normal silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of the above can be used.

Further, even if the silver halide grains have a uniform silver halide composition distribution within the grains,
It may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer, or may be a grain in which a latent image is mainly formed on the surface, or is mainly formed inside the grain. Such particles may be used.

The silver halide grains 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. It is good, but it is particularly preferable that it has tabular crystals. Here, the tabular grains mean the diameter R of a circle having an area equal to the projected area of the tabular grains and the average thickness t of the tabular grains.
The aspect ratio (Aspect ratio As) is 3.0 or more.

As = R / t In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. The average grain size of silver halide grains (grain size represents the diameter of a circle having an area equal to the projected area) is 5
The thickness is preferably 3 μm or less, particularly preferably 3 μm or less.

The silver halide emulsion used in the present invention 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 used in the present invention may be a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion used in the present invention 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 a gold or other noble metal compound can be used alone or in combination.

A color light-sensitive material may be prepared by containing a dye-forming coupler in the silver halide emulsion layer. The color light-sensitive material comprises a cyan dye image-forming constituent unit comprising at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, and at least one green-sensitive compound having at least one magenta dye-forming coupler. A magenta dye image-forming constitutional unit comprising a silver halide emulsion layer and a yellow dye image-forming constitutional unit comprising at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler are supported together with a non-photosensitive layer. It is made up of paint.

In the multicolor color light-sensitive material, as the yellow coupler, for example, an open chain ketomethylene compound such as pivaloylacetanilide type or benzoylacetanilide type yellow coupler may be used.

As the magenta coupler, a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler, a pyrazoloazole type coupler such as a pyrazolotriazole type coupler and an open chain acylacetonitrile type coupler can be preferably used.

As the cyan dye forming coupler, a naphthol type coupler and a phenol coupler can be preferably used.

Further, in order to improve photographic characteristics, a coupler which forms a colorless dye, which is called a so-called computing coupler, can be contained.

In the silver halide emulsion layer, a so-called DI that releases a development inhibitor or its precursor in addition to the coupler is used.
An R substance, for example, a diffusible DIR substance, a timing DIR substance, or a hydroquinone derivative may be contained in order to prevent unnecessary fog and contamination due to air oxidation of the developing agent.

Specific examples of the compound used in the above-mentioned color light-sensitive material are, for example, Research Disclosure (Rese
arch Disclosure) 17643 (1978) p25 ”Color material
s ”and the like.

The silver halide light-sensitive material of the present invention is specifically applied to, for example, X-ray light-sensitive material, lith light-sensitive material, black-and-white photographic light-sensitive material, color negative light-sensitive material, color reversal light-sensitive material, color photographic paper and the like. When it is applied to a color photographic light-sensitive material, it can be used as a single-color color light-sensitive material or can be used as a multi-color color light-sensitive material.

The layers of the light-sensitive material, including the layers of the image-forming units, can be applied in various orders as known in the art.

For example, as a subbing layer, an antihalation layer, a cyan-sensitive red-sensitive emulsion layer, an intermediate layer, a magenta-colored green-sensitive emulsion layer, an intermediate layer, a yellow-colored blue-sensitive emulsion layer and a protective layer in this order from the support. The matting agent of the present invention may be contained in the protective layer which is the surface layer, and the latex of the present invention may be contained in each layer. Each color-developing layer can have a two-layer structure with high sensitivity and low sensitivity.

[0084]

EXAMPLES Examples of the present invention will be given below, but the present invention is not limited thereto.

Example 1 (Preparation of Photosensitive Material Sample 1, hereinafter also referred to simply as Sample 1) Undercoated polyethylene terephthalate support (thickness 100 μm
m) on the backing layer (coated gelatin amount 2.0 g / m ² ),
And backing protective layer (coated gelatin amount 1.0 g / m ² ).
4 layers of emulsion layer (coating gelatin amount: 2.0 g / m ² ) and emulsion protection layer (coating gelatin amount: 1.0 g / m ² ) on the opposite subbing layer with the support in between. Then, it was dried to prepare a photosensitive material sample 1. The preparation of the coating liquid used for each is shown below.

[Preparation of Coating Solution for Backing Layer] Gelatin
After swelling 36 g in water, heating and dissolving, 1.6 g of compound (C-1), 310 mg of compound (C-2) and compound (C
-3) An aqueous solution of 1.9 g and compound (N) 2.9 g was added, then 11 ml of a 20% saponin aqueous solution, 5 g of compound (C-4) as a physical property modifier were added, and 63 mg of compound (C-5) was added. A methanol solution was added.

To this solution, as a thickener, 800 mg of a water-soluble styrene-maleic acid copolymer water-soluble polymer was added to adjust the viscosity, and then the pH was adjusted to 5.4 with an aqueous citric acid solution to react polyglycerol with epichlorohydrin. 1.5g product
Add 144 mg of glyoxal, add water and add 960
The coating liquid for the backing layer was prepared after finishing to ml.

[Preparation of Coating Solution for Protective Layer of Backing Layer] 50 g of gelatin was swollen in water and dissolved by heating, and then 340 mg of 2-sulfonate-bis (2-ethylhexyl) succinate ester sodium salt was added, and sodium chloride was added. Was added, and glyoxal (1.1 g) was further added. As a matting agent, spherical polymethylmethacrylate with an average particle size of 4 μm
It was added to 0 mg / m ² and water was added to make 1 liter to prepare a coating liquid for protective film layer.

[Preparation of Silver Halide Emulsion Coating Solution] After adding 9 mg of the compound (A) to the following emulsion, the pH was adjusted to 6.5 with 0.5N sodium hydroxide solution, and then the compound (T) was 360 mg. In addition, 5 ml of a 20% saponin aqueous solution, 180 mg of sodium dodecylbenzene sulfonate, and 8 parts of 5-methylbenztriazole were added per mol of silver halide.
0 mg, compound (M) 60 mg, and styrene-maleic acid copolymer water-soluble polymer 280 mg as a thickening agent are sequentially added,
It was made up to 475 ml with water to prepare a silver halide emulsion coating solution.

[Preparation of Emulsion] A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows.

23.9 mg of pentabromorhodium potassium salt per 60 g of silver nitrate, an aqueous solution containing sodium chloride and potassium bromide, and an aqueous solution of silver nitrate were stirred in an aqueous gelatin solution at 40 ° C. for 25 minutes, and mixed at the same time. Particle size 0.
A 20 μm silver chlorobromide emulsion was prepared.

After adding 200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer to this emulsion,
It was washed with water and desalted. To this, 20 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added, followed by sulfur sensitization. After sulfur sensitization, gelatin was added, and the above-mentioned 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then water was added to 260 ml to prepare an emulsion.

[Preparation of Coating Solution for Emulsion Protective Film] Water was added to gelatin to swell it and dissolve it at 40 ° C., then as a coating aid,
A 1% aqueous solution of compound (Z), a 1% aqueous solution of 2-sulfonate-bis (2-ethylhexyl) succinate bis (2-ethylhexyl) ester, compound (N) as a filter dye, and compound (D) were sequentially added, and further with citric acid. It was set to pH 6.0. A matting agent (amorphous silica having a particle size of 4.0 μm) was added to prepare a coating solution for emulsion protective film.

[0094]

[Chemical 9]

[0095]

[Chemical 10]

[0096]

[Chemical 11]

(Preparation of Photosensitive Material Sample 2) Photosensitive Material Sample 2 was prepared in the same manner as in Sample 1 except that 400 mg of Comparative Compound 1 shown below was added to the emulsion protective film coating solution.

(Preparation of Photosensitive Material Sample 3) Photosensitive Material Sample 3 was prepared in the same manner as in Sample 1 except that 400 mg of Comparative Compound 2 (dextran) shown below was added to the emulsion protective film coating solution.
Was produced.

Preparation of Photosensitive Material Sample 4 Sample 1 above except that 500 mg of Comparative Compound 1 below was added to the emulsion coating solution.
Photosensitive material sample 4 was prepared in the same manner as in.

(Preparation of Photosensitive Material Sample 5) As shown in Table 1, except that 500 mg of Lx-10 containing the compound represented by the general formula (I) of the present invention as a dispersant was added to the emulsion coating solution. A light-sensitive material sample 5 was prepared in the same manner as Sample 1 above.

(Preparation of Light-Sensitive Material Sample 6) Light-sensitive Material Sample 6 was prepared in the same manner as in Sample 5 except that 800 mg of Lx-10 described above was added to the emulsion coating solution.

(Preparation of Photosensitive Material Sample 7) In the same manner as in Sample 3 described above except that the compound represented by the general formula (I) of the present invention was added to the coating solution for emulsion protective film as shown in Table 1. A photosensitive material sample 7 was prepared.

(Preparation of Photosensitive Material Sample 8) In the same manner as in Sample 2 described above except that the compound represented by the general formula (I) of the present invention was added to the coating solution for emulsion protective film as shown in Table 1. A photosensitive material sample 8 was prepared.

(Preparation of Light-Sensitive Material Sample 9) A light-sensitive material sample 9 was prepared in the same manner as in Sample 1 except that 800 mg of Lx-10 was added to the emulsion protective film coating solution as shown in Table 1.

(Preparation of Light-Sensitive Material Sample 10) As shown in Table 1, the emulsion coating solution and the emulsion protective film coating solution were mixed with the above-mentioned Lx-10
A light-sensitive material sample 10 was prepared in the same manner as in Sample 1 except that 00 mg was added.

[0106]

[Chemical 12]

Each of the obtained samples 1 to 10 was exposed to white light through a step wedge for measuring sensitometry,
Next, a sample subjected to the following treatment and a sample subjected to the following treatment without exposure were prepared.

The processing of the first embodiment will be described below.

[Processing conditions] Process temperature (° C) Time (sec) Development 34 15 Fixing 34 15 Washing at room temperature 10 Drying 40 9 [Developer formulation] (Composition A) Water 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to bring the pH of the solution to 10.9 Potassium bromide 4.5 g (Composition B) Water 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% w / w aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg When using the developer, the above composition A and composition in 500 ml of water are used. Object B
Were dissolved in this order, and water was added to make 1 liter.

[Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% w / v aqueous solution) 8.1 ml (Composition B) Water 17 ml Sulfuric acid (50% w / w aqueous solution) 5.8 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5 g Water when using fixer The above composition A and composition B were dissolved in this order in 500 ml and water was added to make 1 liter. The pH of this fixer was about 4.3.

The above% w / w is (% weight) / (weight)
And% w / v represents (% weight) / (volume). The obtained samples 1 to 10 were evaluated by the evaluation methods shown below.

[Evaluation Method] (Haze) The unexposed sample treated in the above treatment step was measured using a turbidimeter Model T-2600DA manufactured by Tokyo Denshoku Co., Ltd., and haze was shown in%.

(Finishing of Coating) Regarding the number of failures existing in 100 cm ^{2 of the} unexposed sample treated in the above treatment step,
The number was visually counted.

(Photographic Performance) The exposed sample processed in the above-mentioned processing step was measured with a photometer KS-1 manufactured by Konica Corporation.
Sensitivity is the reciprocal of the exposure amount that gives a density of fog +0.7,
The relative sensitivity is shown with the same day sensitivity of the control sample as 100.

(Scratch) After developing, fixing and washing with water in the above-mentioned processing step, the minimum metal that is scratched by scratching the film surface with a weighted metal needle while still immersed in the developing solution at the specified developing temperature. The needle weight g (scratch strength) was determined.

The results are shown in Table 1.

[0117]

[Table 1]

As is clear from the results shown in Table 1, Samples 5 to 10 of the silver halide photographic light-sensitive material of the present invention are all photographic performance (sensitivity), film physical properties [haze (turbidity, transparency), coating property]. It can be seen that the finish (troubleshooting coating failure due to lumping) and scratch (scratch) strength] are excellent. In particular, Sample 1 in which the compound represented by the general formula (I) of the present invention was added to each of the emulsion coating solution and the emulsion protective coating solution
It can be seen that when 0, the above effect is remarkable.

Example 2 (Preparation of Photosensitive Material Sample 21) An undercoating blue-colored polyethylene terephthalate support (thickness 180 μm) was provided on both sides with an emulsion layer (coating gelatin amount 1.7 g / m ² ), and an emulsion protective layer ( A light-sensitive material sample 21 was prepared by simultaneously coating four undercoat layers on both sides of the support with a coating gelatin amount of 1.0 g / m ² ) and drying.

The preparation of the coating liquid used for each is shown below.

[Preparation of Silver Halide Emulsion Coating Solution] The emulsion prepared below was kept at 55 ° C., ammonium thiocyanate, chloroauric acid and hypo were added to carry out gold / sulfur sensitization. After completion of sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. A sensitizing dye was added at the end of each of the above steps. To this emulsion, as an additive, per 1 mol of AgX t-butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol 5 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 1,1-Dimethylol-1-bromo-1-nitromethane 10 mg

[0122]

[Chemical 13]

Was added to prepare an emulsion coating solution.

[Preparation of emulsion] 60 ° C., pAg = 8, pH = 2.0
The average particle size is 0 by the double jet method while controlling
A monodisperse cubic emulsion of silver iodobromide containing 3 μm of 2 mol% silver iodide was obtained. From the electron micrograph of this emulsion, the incidence of twins was 1% or less in number.

Subsequently, 8.5 l of a solution containing protected gelatin kept at 40 ° C. and, if necessary, ammonia was added, and pH was adjusted with acetic acid. Using this solution as a mother liquor, an aqueous 3.2 N ammoniacal silver ion solution was added by the double jet method. At this time, the pAg was controlled to 7.3 and the pH was controlled to 9.7 to control the silver iodide content.
A 35 mol% layer was formed, and the pH was changed from 9 to 8 and the pAg was kept at 9.0 until the grain size reached 95%. After that, potassium bromide solution was added with a nozzle over 8 minutes, and pAg was adjusted to 11.
It was dropped to 0, and 3 minutes after the completion of the addition of potassium bromide, the mixing was completed. This emulsion had an average grain size of 0.55 μm and the silver iodide content of the entire bigrain was about 2.2 mol%. Next, in order to remove an excessive soluble salt of this reaction solution, the reaction solution was kept at 40 ° C., 5 g / AgX1 mol of Demol Na manufactured by Kao Atlas and 8 g / AgX1 mol of MgSO ₄ were added and stirred for 5 minutes. Then it was left still. After that, the supernatant liquid is discharged, and AgX1
The liquid volume was 200 ml per mole. Then, add pure water at 40 ℃
1.8 l / Ag X 1 mol was added and stirred for 5 minutes. Then MgS
O ₄ (20 g / Ag × 1 mol) was added, and the mixture was allowed to stand with stirring in the same manner as above, the supernatant was removed and desalting was performed. The solution was then stirred and gelatin was added to redisperse the AgX to prepare the emulsion.

[Preparation of Coating Solution for Emulsion Protective Film] The following compounds were added. The added amount is shown as an amount per 1 l of the coating liquid.

Gelatin 70 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (average particle size 3.5 μm) 1.1 g Colloidal silica 0.5 g C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0128]

Embedded image

Further, 0.4 g of glyoxal and 0.2 g of formalin were added to prepare a coating solution for emulsion protective film.

(Preparation of Light-Sensitive Material Sample 22) A light-sensitive material sample 22 was prepared in the same manner as the above-mentioned sample 21 except that 500 mg of the comparative compound 1 used in Example 1 was added to the emulsion coating solution.

(Preparation of Photosensitive Material Sample 23) A photosensitive material sample 23 was prepared in the same manner as in Sample 21 except that 500 mg of the comparative compound 2 (dextran) used in Example 1 was added to the emulsion protective coating solution. did.

(Preparation of Photosensitive Material Sample 24) A photosensitive material sample 24 was prepared in the same manner as in Sample 21 except that 500 mg of the water-soluble polymer P-1 was added to the emulsion protective film coating solution.

(Preparation of Photosensitive Material Sample 25) As shown in Table 2, except that 500 mg of Lx-10 containing the compound represented by the general formula (I) of the present invention as a dispersant was added to the emulsion coating solution. A light-sensitive material sample 25 was prepared in the same manner as Sample 21 above.

(Preparation of Light-Sensitive Material Sample 26) A light-sensitive material sample 26 was prepared in the same manner as in Sample 21, except that 500 mg of Lx-10 was added to the emulsion protective film coating solution as shown in Table 2.

(Preparation of Light-Sensitive Material Sample 27) A light-sensitive material sample was prepared in the same manner as in Sample 21, except that the compound represented by the general formula (I) of the present invention was added to the emulsion coating solution. 27 was produced.

(Preparation of Photosensitive Material Sample 28) Photosensitization was conducted in the same manner as in Sample 21 except that the compound represented by the above general formula (I) was added to the coating liquid for emulsion protective film as shown in Table 2. Material sample 28 was prepared.

(Preparation of Photosensitive Material Sample 29) As shown in Table 2, the compound represented by the above general formula (I) was added to the emulsion coating solution.
A light-sensitive material sample 29 was prepared in the same manner as the sample 22 except that 0 mg was added.

(Preparation of Photosensitive Material Sample 30) In the same manner as in Sample 23 above except that 50 mg of the compound represented by the above general formula (I) was added to the coating solution for emulsion protective film as shown in Table 2. A photosensitive material sample 30 was prepared.

The obtained sample was sandwiched with fluorescent intensifying screen KO-250 (manufactured by Konica Corporation), irradiated with X-ray for 0.05 seconds at a tube voltage of 90 KVP and 20 mA, and a sensitometry curve was prepared by a distance method. did.

For the development, an automatic developing machine SRX-501 (manufactured by Konica Corporation) was used and the developing temperature and the fixing temperature were set to 35.
C., fixing temperature 33.degree. C., washing water was supplied at a temperature of 18.degree.

The processing of the second embodiment will be described below.

[Processing conditions] Process temperature (° C) Time (sec) Insertion of replenishment amount- 1.2 Development + crossover 35 14.6 33 ml / four cuts Fixing / crossover 33 8.2 63 ml / four cuts Water washing + crossover 18 7.2 3.5 l / min Squeeze 40 5.7 Dry 45 8.1 Total-45.0 [Developer formulation] Potassium sulfite
70g 5-Methylbenzotriazole 0.04g 1-Phenyl-5-mercaptotetrazole 0.01g Potassium bromide 4g Triethylene glycol 15g Hydroxyethylethylenediamine triacetic acid trisodium 8g Acetic acid (90% w / w aqueous solution) 13g 5-Nitrobenzimidazole 1g 1-Phenyl-3-pyrazolidone 1.2g 1,4-dihydroxybenzene 28g Boric acid 10g Sodium metabisulfite 5g Glutaraldehyde 4g 5-Nitroindazole 0.2g Mix the above to make 1L aqueous solution and add sodium hydroxide.
The pH was adjusted to 10.5.

[Fixing solution formulation] Ammonium thiosulfate 150 g Ethylenediaminetetraacetic acid disodium 0.5 g Sodium thiosulfate pentahydrate 4.5 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Citric acid 1 g Glacial acetic acid 5 g Sulfuric acid (50% w / w aqueous solution) 5 g Aluminum sulfate 10-18 hydrate 10 g Boric acid 7 g or more were mixed to form a 1 l aqueous solution, and the pH was adjusted to 4.2 with glacial acetic acid.

[Evaluation Method] (Photographic Performance) The exposed sample processed in the above-mentioned processing step was measured with a photometer KS-1 manufactured by Konica Corporation. The fog sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog + 1.0. The results are shown as relative sensitivity when the sensitivity of the control sample is 100.

(Static Mark Generation Test) The protective layer side of the unexposed light-sensitive material was faced downward on a rubber sheet, and after pressure bonding with a rubber roll from above, a static mark was generated by peeling, and after development processing, static marks were generated. The degree of mark generation was visually evaluated in the following 5 grades.

A: No static mark was observed.

B: Some static marks are generated.

C: Static marks are considerably generated.

D: Static marks are remarkably generated.

E: Static marks were generated on the entire surface.

Evaluations other than the above were carried out in the same manner as in the method described in Example 1.

The results are shown in Table 2.

[0153]

[Table 2]

As is clear from the results shown in Table 2, Samples 25 to 30 of the silver halide photographic light-sensitive material of the present invention are all photographic properties (sensitivity, pressure fog), film physical properties [coating finish (tailing coating due to solidification). Failure), scratch (scratch)
Strength], it can be seen that the static performance is excellent.

[0155]

EFFECT OF THE INVENTION It is possible to provide a silver halide photographic light-sensitive material having improved film physical properties and free from coating failure without impairing photographic characteristics.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material characterized in that at least one photographic constituent layer on a support contains at least one compound represented by the following formula (I). Embedded image [Wherein R ₁ is a linear or cyclic alkyl group having 6 to 30 carbon atoms, an alkenyl group or an aralkyl group, and L is an alkylene group having 1 to 5 carbon atoms or a substituted alkylene group. ] 2. The silver halide according to claim 1, wherein at least one photographic constitutional layer on the support contains at least one selected from anionic surfactants and nonionic surfactants. Photographic material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one photographic constituent layer on the support contains at least one water-soluble polymer. 4. A silver halide photograph characterized in that at least one photographic constituent layer on a support contains at least one polymer particle produced in the presence of the compound represented by the general formula (I). Photosensitive material. 5. The silver halide photographic light-sensitive material according to claim 1, wherein at least one photographic constituent layer on the support contains at least one kind of polymer particles.