JPH08201949A - Photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain a silver halide photographic sensitive material not causing coating trouble having improved physical properties of a film such as trailing trouble, transparency and scratch resistance without deteriorating photographic characteristics such as sensitivity. CONSTITUTION: This photographic sensitive material contains a composite polymer consisting of particles of at least one kind of inorg. material and a hydrophilic molecular compd. and contains the composite polymer and particles of at least one kind of inorg. material in at least one layer on the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved film physical properties (scratch, static) without impairing photographic characteristics.

[0002]

2. Description of the Related Art Generally, each constituent layer of a photographic light-sensitive material, such as an undercoat layer or a hydrophilic colloid layer, does not have a bad influence on the photographic light-sensitive property, and also has a physical property such as an adhesive strength before and after development. Predetermined strength is also required in terms of dimensional stability before and after development, dimensional stability against heat and humidity, flexibility, pressure resistance, and dryness. 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 obtained by polymerizing various monomers in the hydrophilic colloid layer or Various attempts have been made to improve the physical properties of a hydrophilic colloid film formed by containing colloidal silica, such as dimensional stability, scratching strength, flexibility, pressure resistance and drying property.

From this point of view, US Pat. No. 2,376,005
Use of vinyl acetate polymer latex in U.S. Pat. No. 3,325,286, use of alkyl acrylate polymer latex in U.S. Pat. No. 3,325,286, and n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate in JP-B-45-5331. ,
The use of a polymer latex such as acrylonitrile, the use of a polymer latex of alkyl acrylate, acrylic acid, and sulfoalkyl acrylate in JP-B-46-22506, and 2-acrylamide-2 in JP-A-51-130217. -Use of polymer latex of methyl propane sulfonic acid, etc.
No. 0723, JP-A-61-140939, it is possible to use colloidal silica, JP-A-61-236544, JP-A-1-1177033, it is possible to use a composite latex containing acrylic acid ester and colloidal silica. Proposed. However, these polymer latices and colloidal silica have poor compatibility with hydrophilic colloids and cannot be added in a large amount, or the adhesive strength between layers decreases and scratch resistance deteriorates. There is a problem that the quality of the photographic light-sensitive material is remarkably deteriorated because the material is cracked or the photographic performance is deteriorated.

Further, even when the composite latex described in JP-A 1-177033 is used, the occurrence of cracks can be moderated, but it cannot be said to be sufficient, and the compatibility with hydrophilic colloid is not improved and a large amount is obtained. However, there is a problem that the scratch resistance at the time of development is deteriorated and the photographic performance is deteriorated.

[0005]

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

[0006]

The above object of the present invention can be achieved by the following constitutions.

1) A photographic light-sensitive material containing a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound.

2) The photographic light-sensitive material as described in 1 above, wherein the composite polymer is a composite polymer obtained by polymerizing a hydrophilic monomer in the presence of at least one kind of inorganic particles.

3) The photographic light-sensitive material as described in 1 or 2 above, which is a hydrophilic polymer compound of a composite polymer containing at least one kind of hydroxyl group-containing monomer.

4) The composite polymer contains a composite polymer obtained by polymerizing a hydrophilic monomer in the presence of at least one metal alkoxide compound.
The photographic light-sensitive material as described in 2 or 3.

5) The photographic light-sensitive material as described in any one of 1 to 4 above, wherein the inorganic particles of the composite polymer are metal oxides.

6) The composite polymer is a composite polymer containing composite particles obtained by polymerizing a hydrophilic monomer in the presence of at least one water-soluble polymer and at least one inorganic particle. 6. The photographic light-sensitive material as described in any one of 1 to 5 above, which is characterized.

7) The photographic light-sensitive material as described in any one of 1 to 6 above, wherein the composite polymer is hydrophilic particles.

8) The amount of gelatin coated on one surface of the support is 2.5 g / m ² or less, and at least one of the composite polymers described in any one of 1 to 7 above is contained. A photographic light-sensitive material characterized by being.

9) A photographic light-sensitive material characterized in that at least one layer on a support contains a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound, and at least one kind of inorganic particles. .

10) A photographic light-sensitive material characterized in that at least one layer on a support contains a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound, and a latex.

11) A photographic light-sensitive material characterized in that at least one layer on a support contains a water-soluble polymer and a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound.

Examples of the inorganic particles used in the present invention include metal oxides, nitrides, sulfides, etc. Among them, metal oxides are preferable. As the metal oxide, Na, K,
Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, M
n, Ga, V, Nb, Tu, Ag, Bi, B, Si, Mo, Ce, Cd, M
Single or complex oxide particles of metals such as g, Be and Pb are preferable, and particularly preferable are Y, Sn, Ti, Al, V, Sb, In,
Single or complex oxide particles of Mn, Ce, B and Si are particularly preferable from the viewpoint of compatibility with the emulsion.

Such metal oxide particles can be preferably used in either crystalline or amorphous form, but amorphous metal oxide particles are particularly preferable.

The average particle size of the metal oxide particles used in the present invention is preferably 0.5 nm to 3000 nm, particularly preferably
It is 3 nm to 1000 nm. Such metal oxide particles are preferably dispersed in water and / or a water-soluble solvent, and particularly preferably water and alcohols such as methanol, ethanol and isopropanol.

The addition amount of the metal oxide of the present invention is preferably 1 to 1000% by weight, particularly preferably 30 to 300% by weight, based on the hydrophilic polymer.

Examples of preferable metal oxides are shown below.

[0023]

[Table 1]

Examples of the monomer forming the composite polymer of the present invention include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate, and alkylene oxide-containing monomer. body,
Although acrylamides, methacrylamides, sulfonic acid group monomers, amino group-containing monomers and the like can be preferably used, hydroxyl group-containing monomer, carboxyl group-containing monomer, amide group-containing monomer, sulfone It is particularly preferable to include a group-containing monomer. If such a hydrophilic monomer is small, it becomes hydrophobic, so that it is preferably about 30 wt% to 100 wt%, and particularly preferably 40 wt% to 80 wt%.

In the hydrophilic polymer compound forming the composite polymer of the present invention, it is preferable to copolymerize a hydrophobic monomer in addition to the hydrophilic monomer. As such a hydrophobic monomer, , For example, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes,
Crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles,
Examples of the hydrophobic monomer include one kind or a combination of two or more kinds selected from various unsaturated acids. Preferably,
Acrylic acid esters and / or methacrylic acid esters, and styrenes, and it is particularly preferable that the ester group has 6 or more carbon atoms. It is also preferable to use a hydrophobic monomer having a glycidyl group for these hydrophobic monomers, at least 1.0 to 20% by weight, particularly preferably 20% by weight.
~ 70wt%.

The composite polymer of the present invention can be selected, for example, from a carboxyl group, a glycidyl group, an amino group, an amide group, an N-methylol group, etc. by selecting the kind of the above hydrophobic monomer and / or hydrophilic monomer. By using the hydrophobic monomer having a cross-linking group, a composite polymer having a cross-linking group can be obtained.

The composite polymer of the present invention preferably contains at least two copolymerizable ethylenically unsaturated monomers and is in the form of particles. Examples of such a monomer include those having two vinyl groups such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, and N, N-methylenebisacrylamide, and trivinyl. Those having three vinyl groups such as cyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol trimethacrylate, and vinyl groups such as pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.
Although the thing which has an individual can be mentioned, it is not limited to these.

When the composite polymer of the present invention is in the form of particles, the weight average particle diameter is particularly preferably 0.01 to 0.8 μm, and any weight average particle diameter of 0.005 to 3.0 μm is preferably used. it can.

The method for polymerizing the composite polymer of the present invention includes:
Examples thereof include emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method and radiation polymerization method.

In solution polymerization, a mixture of monomers having a suitable concentration in a solvent (usually 40% by weight or less, preferably 10 to 25% by weight of the solvent) is added in an amount of about 10% in the presence of an initiator. ~
It can be obtained by carrying out the polymerization at a temperature of 200 ° C., preferably 30 to 120 ° C. for about 0.5 to 48 hours, preferably 2 to 20 hours.

Any initiator may be used as long as it is soluble in a polymerization solvent, and examples thereof include organic solvent initiators such as benzoyl peroxide, azobisisobutyronitrile (AIBN) and ditertiary butyl peroxide. Water-soluble initiators such as ammonium sulphate (APS), potassium persulfate and 2,2'-azobis- (2-amidinopropane) -hydrochloride, combined with reducing agents such as Fe ²⁺ salts and sodium bisulfite A redox type polymerization initiator etc. can be mentioned.

Any solvent may be used as long as it can dissolve a mixture of monomers, and examples thereof include water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more of these. be able to. After completion of the polymerization, the reaction mixture can be separated and removed by pouring the reaction mixture into a medium in which the produced polymer is not dissolved, allowing the product to settle, and then drying.

In the emulsion polymerization method, water is used as a dispersion medium, 10 to 50% by weight of a monomer with respect to water, 0.05 to 5% by weight of a polymerization initiator with respect to the monomer, and 0.1 to 20% by weight of a monomer. About 3 with dispersant
It can be obtained by polymerizing with stirring at 0 to 100 ° C, preferably 60 to 90 ° C for 3 to 8 hours. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time, etc. can be changed widely and easily.

Although a water-soluble polymer is used as the dispersant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

Examples of the water-soluble polymer include synthetic polymers and natural water-soluble polymers, both of which can be preferably used in the present invention. Among them, 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, nonionic Examples thereof include those having a 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, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base and a tertiary amino group.

As the natural water-soluble polymer, for example, those having a nonionic group, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group in the molecular structure, Examples thereof include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

As the water-soluble polymer, whether it is a synthetic water-soluble polymer or natural water-soluble polymer, those having an anionic group and those having a nonionic group and an anionic group can be preferably used.

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

Examples of the synthetic water-soluble polymer include those containing the repeating unit represented by the following general formula (1) and / or (2) in an amount of 10 to 100 mol% in one molecule of the polymer.

[0040]

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In the formula, R ₁ represents a hydrogen atom, an alkyl group, a halogen atom or a —CH ₂ COOM group, preferably an alkyl group having 1 to 4 carbon atoms. L ₁ represents a divalent linking group, for example -CONH -, - NHCO -, - COO -, - OCO
-, -CO-, -O- and the like can be mentioned. J ₁ represents an alkylene group, an arylene group, or an oxyalkylene group. Q ₁ is -OM, -NH ₂ , -SO ₃ M, -COOM, or

[0042]

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Representing a hydrogen atom, --COOM and --SO ₃ M are preferred, and --SO ₃ M is particularly preferred. M represents a hydrogen atom or a cation (for example, an alkali metal ion, an ammonium ion), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R _8, R _9, R ₁₀ represents an alkyl group having a carbon number of 1 to 20, X represents an anion, and m ₁ and n ₁ each represents 0 or 1.

Y is a hydrogen atom or-(L ₂ ) m _2- (J ₂ ) n ₂ -Q ₂
And L ₂ , J ₂ , Q ₂ , m ₂ and n ₂ are respectively L ₁ and
It is synonymous with J ₁ , Q ₁ , m ₁ and n ₁ .

[0045]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R
₂₆ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or --SO ₃ X, wherein X is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or ammonium. A group or an amino group, R ₂₁ ,
At least one of R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ is —SO.
₃ X.

The synthetic water-soluble polymer having the repeating unit represented by the general formula (1) and / or (2) is a homopolymer of the unit represented by the general formula (1) and / or (2). It may be present or may contain other ingredients.

Other components include, for example, acrylic acid esters, methacrylic acid esters, vinyl esters,
Olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, allyl compounds, vinyl ethers,
Examples thereof include one or a combination of two or more selected from vinyl ketones, glycidyl esters, and unsaturated nitriles, and preferably acrylic acid esters, methacrylic acid esters, and styrenes.

Next, specific examples of the synthetic water-soluble polymer represented by the general formulas (1) and (2) will be given.

[0050]

[Chemical 4]

[0051]

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[0052]

[Chemical 6]

Examples of the natural water-soluble polymer include those described in detail in the comprehensive technical data collection of water-soluble polymer water-dispersed resin (Management Development Center), preferably lignin, starch, pullulan, and cellulose. , Dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran 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 preferred are glucose, gelatin, dextran, cellulose, pullulan, glucomannan, dextrin, gellan gum, locust bean gum, xanthan gum and derivatives thereof.

When polymerizing the composite polymer of the present invention, it is preferable to allow a metal alkoxide compound to be present. Some metal alkoxide compounds are also called coupling agents, such as silane coupling agents, titanium coupling agents,
Various types of aluminum coupling agents, zirconium coupling agents and the like are commercially available, but silane coupling agents and titanium coupling agents are preferable.

Examples of preferable metal alkoxide compounds relating to the present invention will be given below.

[0056]

[Chemical 7]

[0057]

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[0058]

[Chemical 9]

[0059]

[Chemical 10]

The composite polymer of the present invention can be contained in the photographic constituent layer as it is or after being dissolved or dispersed in water. As the dispersion method, ultrasonic waves, a ball mill, an attritor, a pearl mill, a three-roll mill, a high speed grind device and the like can be preferably used.

The content of the polymer of the present invention is preferably 5 to 300% by weight based on the binder of the photographic constituent layer,
It is particularly preferably 10 to 150% by weight.

The place of addition may be a photosensitive layer or a non-photosensitive layer.

Next, an example of a method for producing the composite polymer of the present invention will be described.

(Production Method of Composite Polymer) Production Example 1 (Synthesis of PL-1) A 1,000 ml four-necked flask was provided with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, and nitrogen gas was supplied. While deoxidizing the mixture, 50 cc of distilled water and 45 g of 30 wt% silica sol were added and heated until the internal temperature reached 80 ° C. The following structure of the surfactant SF-1 pC ₉ H ₁₉ as a dispersing agent _{- (C 6 H 4) -O} (CH 2 CH 2 O) 6 (CH 2) 3 SO 3 and Na 4.5 g was added, further initiator As a solution, 0.45 g of ammonium persulfate is added, and then 30 g of hydroxyethyl acrylate and 15 g of acrylic acid are added dropwise with a dropping funnel over about 1 hour. After the dropping was completed, the reaction was continued for 5 hours. After cooling, adjust the pH to 6 with ammonia water and adjust the composite polymer PL-
Get one.

Production Example 2 (Synthesis of PL-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, and nitrogen gas was introduced to perform deoxidation. Distilled water 125cc, 10wt% tin oxide sol 225
g was added and heated until the internal temperature reached 80 ° C. Further, 4.5 g of hydroxypropyl cellulose and 1 g of dodecylbenzenesulfonic acid were added. Further, 0.45 g of ammonium persulfate was added as an initiator, and then 35 g of hydroxyethyl methacrylate and 10 g of ethylene glycol dimethacrylate were added dropwise with a dropping funnel over about 1 hour. After the dropping was completed, the reaction was continued for 5 hours, then cooled and adjusted to pH 6 with aqueous ammonia to obtain a composite polymer PL-2.

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

[0067]

[Chemical 11]

[0068]

[Chemical 12]

[0069]

[Chemical 13]

As the binder for the silver halide emulsion layer, it is advantageous to use gelatin or a gelatin derivative.

Examples of gelatin include lime-processed gelatin, Bulletin of the Society of Scientific Photography of Japan (Bull. Soc. Sci. Phot. Japan) No. 16, p. 30. (1966)
The acid-treated gelatin as described in 1. may be used, and a hydrolyzate or an oxygen hydrolyzate of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples are U.S. Pat.Nos. 2,614,928 and 3,13
2,945, 3,186,846, 3,312,553, UK Patent 86
1,414, 1,033,189, 1,005,784, Japanese Patent Publication No.42-2
No. 6845.

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, the silver halide grains may be those having a uniform silver halide composition distribution within the grain, or may be core / shell grains having a different silver halide composition between the inside of the grain and the surface layer, Further, the particles may be such that the latent image is mainly formed on the surface, or the particles are mainly formed inside the particles.

The silver halide grains used in the silver halide emulsion used in the present invention may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have a spherical or plate shape. Although it may have an irregular crystal form, it may have a flat crystal. Here, the tabular grains have a ratio (aspect ratio As) of a diameter R of a circle having an area equal to the projected area of the tabular grains and an average thickness t of the tabular grains of 3.
Say 0 or more. Particularly preferably, the aspect ratio As is 4
That is all.

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
The thickness is preferably 5 μm or less, and 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) may be used alone or in combination of several kinds. 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 sensitization method,
A selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compound can be used alone or in combination. It is preferably used in combination with a selenium-sensitized silver halide emulsion.

A color light-sensitive material may be prepared by containing a dye-forming coupler in the silver halide emulsion layer. Color sensitizers generally include a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, and at least one green having at least one magenta dye-forming coupler. A magenta dye image-forming constituent unit comprising a sensitive silver halide emulsion layer and a yellow dye image-forming constituent 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 consists of the material applied to the body.

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

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 forming a colorless dye, which is called a so-called competing coupler, can be contained.

The silver halide emulsion layer contains a so-called DIR which releases a development inhibitor or its precursor in addition to the coupler.
A substance such as 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 these compounds used in the color photographic light-sensitive material are, for example, Research Disclosure 17643 (1978) p25 "VII Color m.
ate-rials ”and the like.

The silver halide photographic light-sensitive material of the present invention is specifically applied to, for example, an X-ray light-sensitive material, a lith light-sensitive material, a black and white photographic light-sensitive material, a color negative light-sensitive material, a color reversal light-sensitive material, a 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-colored 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.

[0089]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. (Preparation of silver halide emulsion coating solution Em1) Temperature 40 ° C, pH
The silver potential EAg was adjusted to 17 with 1N NaCl under a nitric acid acidic atmosphere of 3.0.
The solution B and the solution C were mixed with the following solution A by the controlled double jet method for 11 minutes, maintaining at 0 mV.

Solution A Gelatin 5.6 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O) mH (however n + m = 6) 10% ethanol solution 0.56 ml sodium chloride 0.12 g Concentrated nitric acid 0.43 ml Distilled water 440 ml Solution B Silver nitrate 60 g Concentrated nitric acid 0.208 ml Distilled water 85.2 ml Solution C Gelatin 3.0 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O ) mH (however n + m = 6) 10% ethanol solution 0.3 ml sodium chloride 20.2 g Na ₃ (RhCl ₆ ) 1% aqueous solution 3.0 ml distilled water 86.4 ml solution D gelatin 1.4 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O) mH (however n + m = 6) 10% ethanol solution 0.14 ml distilled water 48.8 ml The obtained silver halide grains have an average grain size of 0.12 μm and a monodispersity degree. Was 8 to 15%. Solution D was added to the emulsion thus prepared, the pH was adjusted to 6.0 with sodium carbonate, and then 200 mg of 4-hydroxy-6-methyl-1,3,3a, 7 tetrazaindene was added. Thereafter, each silver halide emulsion was washed with water and desalted in a conventional manner, and Solution E was added as a preservative.

Solution E 2-Methyl-5-chloroisothiazol-3-one 15 mg Pure water 0.3 ml 4-hydroxy-6-methyl-1,3,3 as a stabilizer in the above emulsion
200 mg of a, 7 tetrazaindene and 8.6 g of gelatin were added.

Further, the following coating additives were added, and pure water was adjusted so that the total amount of the coating liquid was 303 ml to prepare a silver halide emulsion coating liquid Em1.

Saponin 33% (W / V) aqueous solution 2.2 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 2.2 ml 1-decyl-2- (3-isopentyl) succinate-2-sulfonate sodium 4% ( W / V) aqueous solution 0.3 ml Citric acid 7% (W / V) aqueous solution 0.4 ml

[0094]

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2-Mercaptohypoxanthine 0.5% Alkaline aqueous solution 4 ml Sodium ethylenediaminetetraacetate 5% aqueous solution 10 ml Spirobis (3,3-dimethyl-5,6-dihydroxyindane) 1.5 ml 5% methanol solution Hydroquinone 20% aqueous solution 2.5 ml Styrene sulfone Acid-maleic acid water-soluble copolymer 4% aqueous solution 4 ml 2-methyl-5-chloroisothiazol-3-one 5% aqueous solution 0.1 ml (Preparation of coating liquid M1 for intermediate layer) The following additives were added and mixed to give a total amount of 1414 ml. Was adjusted with pure water to prepare an intermediate layer coating solution M1.

Gelatin 12% (W / V) aqueous solution 250 ml Saponin 33% (W / V) aqueous solution 12.3 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 12.3 ml Citric acid 7% (W / V) aqueous solution 3 ml Dimezone S 2% (W / V) methanol solution 20ml Resorcin 20% (W / V) aqueous solution 40ml Garlic acid propyl ester 10% (W / V) methanol solution 60ml Dye E 2% (W / V) aqueous solution 700ml Water-soluble copolymer of styrene sulfonic acid and maleic acid 4% (W / V) aqueous solution 22.7 ml 2-Bromo-2-nitro-1,3-propanediol 0.1% (W / V) aqueous solution 6 ml Fine particle dispersant Bu described later
250 ml

[0097]

[Chemical 15]

(Preparation of Coating Liquid P1 for Protective Film) The coating liquid P1 for protective layer was prepared by adding and mixing the following additives and adjusting with pure water so that the total amount was 1414 ml.

Gelatin 12% (W / V) aqueous solution 250 ml 1-decyl-2- (3-isopentyl) succinate-2-sulfonic acid 50 ml NaCl 10% (W / V) aqueous solution 22 ml Amorphous silica (average particle size 3.5 μm ) Amorphous silica (average particle size 6μm)

[0100]

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Citric acid 7% (W / V) aqueous solution 5.1l Dimezone S 2% (W / V) methanol solution 20ml Dye E 2% (W / V) aqueous solution 700ml Styrenesulfonic acid and maleic acid water-soluble Copolymer 22.7 ml 4% (W / V) aqueous solution 2-Bulmo-2-nitro-1,3-propanediol 0.1% (W / V) aqueous solution 6 ml Fine particle dispersant Bu 250 ml described below (preparation of dye dispersion Bu) The following dyes Disperse a solution in which Se is applied in an amount of 100 g / m ² dissolved in 200 ml of ethyl acetate, 30 g of gelatin, 400 mg of isopropylnaphthalene sulfonic acid, and 400 g of phenol in 250 ml of pure water with a PD disperser. After that, remove ethyl acetate while heating under reduced pressure, finish with pure water to 250 ml, and set by cooling to obtain an average dye particle size of 0.2.
A 0 μm dye dispersion was prepared.

[0102]

[Chemical 17]

(Preparation of Hardener Solution MH1 for In-Line Addition to Intermediate Layer) The following additives were mixed to prepare 300 ml of a hardener solution MH1 to be mixed and added in-line to the intermediate layer coating solution immediately before coating.

Hardeners 10% (w / v) aqueous solution of H1 below 260 ml Pure water 40 ml (Preparation of hardener liquid PH1 for in-line addition of protective layer) The following additives are mixed and immediately before coating to the coating liquid for protective layer 300 ml of the hardener solution PH1 to be mixed and added in-line to was prepared.

Hardener 2.5% (w / v) aqueous solution of H2 below 187 ml Pure water 113 ml

[0106]

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(Preparation of Backing Layer Coating Liquid BC1) After the following additives were added and mixed, the total amount was adjusted to 895 ml with pure water to prepare a backing layer coating liquid BC1.

Gelatin 32.4 g Pure water 695 ml Dye C 6% (W / V) aqueous solution 64 ml Dye D 5% (W / V) aqueous solution 24 ml Saponin 33% (W / V) aqueous solution 6.6 ml Polymer latex 20% (W / V) Emulsion liquid 33.6ml (cyclohexyl-methacrylate, isononyl acrylate, copolymer of glycidyl-acrylate and styrene-isopropylene sulfonic acid with an average particle size of 0.10μm) Zinc oxide 10% (W / V ) solid fine particle dispersion (average particle size _{^{0.15μm) 10ml Co 3+ {H 2}} N-C (= NH) -NH-C (= NH) -NH 2} 3 (BPh 4 -) 3 of solid fine particle dispersion 10 ml (average particle size 0.1 μm) Citric acid 7% (W / V) aqueous solution 3.8 ml Sodium styrenesulfonate 4% (W / V) aqueous solution 23 ml

[0109]

[Chemical 19]

(Preparation of Backing Protective Layer Coating Solution BP1)
After the following additives were added and mixed, the total amount was adjusted to 711 ml with pure water to prepare a backing protective layer coating liquid BP1.

Gelatin 24.9 g Pure water 605 ml Methyl methacrylate (2% (W / V) dispersion having an average particle size of 7 μm 72 ml 1-decyl-2- (3-isopentyl) succinate-2-sulfonic acid 11 ml Sodium 4% ( W / V) Aqueous solution Glyoxal 4% (W / V) aqueous solution 4 ml Preparation of hardener liquid BH1 for backing layer in-line addition Pure water 27.22 ml Methanol 1.5 ml Hardener BH-1 1.28 ml NaCl 0.005 g

[0112]

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30 ml of a hardener BH1 was prepared by mixing the above additives and adding them inline to the protective layer coating solution by mixing inline immediately before coating.

(Preparation of Samples No. 1 to No. 15) One side of a 100 μm-thick polyethylene terephthalate transparent support, which had been subjected to undercoating in advance, was coated with the above silver halide emulsion coating solution Em 1 from one side closer to the support. Immediately before coating, the hardener MH1 for in-line addition of the intermediate layer and the hardener PH1 for in-line addition of the protective layer were applied at the above-mentioned finishing ratio so that the dry weight was 1.0 g / m ² and the amount of silver was 3.5 g / m ^2. While mixing, coating liquid M1
The so that the gelatin dry weight 0.3 g / m ^2, were simultaneously coated a protective layer coating liquid P1 so that the intermediate layer Gelatin dry weight 0.3 g / m ^2. At that time, the compound of the present invention was added as shown in Table 1.

At the same time, the backing layer coating solution BC1 was applied to the opposite side of the support from the backing layer in-line addition hardener solution BH1.
And the coating ratio BP1 for the backing protective layer is coated in multiple layers while mixing just before coating with the above-mentioned finishing ratio so that the dry weight of gelatin is 1.8 g / m ² and the dry weight of gelatin is 0.5 g / m ^2. did. After coating all coating liquids at a coating liquid temperature of 35 ° C, treat them with cold air at 5 ° C for 6 seconds and set, and control the conditions to keep the dry-bulb temperature below 35 ° C and the film surface temperature below 20 ° C in sequence. The coated layer is dried for 2 minutes, and within 20 seconds after the completion of drying, the dry-bulb temperature is 50 ° C and the dew point is -5 ° C.
It processed for 50 seconds and created sample No1-No12. The following evaluation was performed using the sample thus obtained, and the obtained results are shown in Table 1.

(Evaluation method) <Coating finish> The sample after coating is 100 cm ² with a 100 times magnifying glass.
It was observed and the number of failures in it was visually counted to obtain a coating finish.

<Photographic performance> Meitou room, manufactured by Dainippon Screen Co., Ltd.
Using a UV printer P-627FA, 50% of 100 μm thickness as the original
Hard dot halftone transmissive film The original logarithm of the reciprocal of the exposure time, which is 50% after processing under the following processing conditions, using a sample original while exposing the emulsion layer coating side to the original while suction-adhering to the original. Is the sensitivity and the same day sensitivity of the control sample
The specific sensitivity is set to 100.

Processing conditions Development conditions 34 ° C. for 12 seconds Fixing conditions 32 ° C. for 12 seconds Washing conditions at room temperature for 10 seconds Drying conditions for 40 ° C. for 10 seconds Developer formulation Pure water 205.7 ml Diethylenetriamine-5-acetic acid 3.63 g Sodium sulfite 52.58 g Boric acid 8.0 g KBr 4.0g Potassium carbonate 49% (W / V) aqueous solution 112.24g 2-Mercaptohypoxanthine 0.07g Diethylene glycol 40g Benzotriazole 0.21g Hydroquinone 20g Dimezone S 0.85g 1-Phenyl-5-mercaptotetrazole 0.03g Potassium hydroxide 48.55% (W / V) When 14 ml of aqueous solution was used, water was added to make 1 liter, and it was set in an automatic processor and used. The pH was 10.4.

Fixer formulation Ammonium thiosulfate 70% (W / V) aqueous solution 262g Pure water 79ml Sodium sulfite 22g Boric acid 9.78g Sodium acetate 38.5g Acetic acid 90% (W / V) aqueous solution 13.28g Tartaric acid 90% (W / V) aqueous solution 7.27 g Aluminum sulphate (Al ₂ O ₃ equivalent content was 8.1% (W / V) 26.5 g of aqueous solution was used, and water was added to make 1 liter, and it was set in an automatic processor and used. PH was 4.85.

<Haze Test> The haze of an unexposed sample treated in the above-mentioned treatment step was measured by using a turbidimeter T-2600DA (manufactured by Tokyo Koden Co., Ltd.) and shown in%.

<Scratch Test> Development in the above processing step,
After fixing and washing with water, re-immerse in developing solution for 30 seconds at the specified development temperature and move the sapphire needle pressure continuously in the range of 0-200g while moving parallel on the film surface with the sapphire needle of radius 0.3mm. At the very least, obtain the minimum load that causes scratches on the film surface of the sample as the scratch strength.

The results are summarized in Table 2.

[0123]

[Table 2]

From the results shown in Table 2, the photographic properties (sensitivity), the physical properties of the film [haze (turbidity, transparency), coating finish (tailing coating failure due to solidification), scratches, scratches, and scratches were observed in all cases using the compound of the present invention. (Scratch) strength] is excellent.

Example 2 An emulsion layer (coating gelatin amount: 1.7 g / coating amount: 1.7 g / g) was prepared by using the following coating solution for emulsion layer and emulsion protective film layer coating solution on a sublimed blue-colored polyethylene lephthalate support (thickness 180 μm). m
² ) and an emulsion protective layer (coating gelatin amount 1.0 g / m ² )
Light-sensitive material samples 21 to 37 were prepared by simultaneously coating four layers on the support undercoat layer and drying.

[Preparation of Silver Halide Emulsion Coating Solution] The following emulsion was kept at 55 ° C., and 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 mol of silver halide 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-triphenylphosphorus Aluminum chloride 50mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 4g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 15mg 1,1-Dimethylol-1-bromo-1-nitromethane
10 mg

[0127]

[Chemical 21]

Then, the compound of the present invention was added as shown in Table 2 to prepare an emulsion coating solution.

(Preparation of emulsion) 60 ° C., pAg = 8, pH = 2.
Average particle size by double jet method while controlling to 0
A silver iodobromide monodisperse cubic emulsion containing 0.3 μm of silver iodide 2 mol% was obtained. From the electron micrograph of this emulsion, the incidence of twins was 1% or less in number. Then a solution containing protected gelatin kept at 40 ° C and optionally ammonia 8.
5 liters were added and the 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, pH and EAg are pA
A layer having a silver iodide content of 35 mol% was formed by controlling g to 7.3 and pH to 9.7, and the pH was changed from 9 to 8 until the grain size reached 95%.
Ag was kept at 9.0 and grown. Then, a potassium bromide solution was added with a nozzle over 8 minutes, pAg was lowered to 11.0, and mixing was completed 3 minutes after the addition of the potassium bromide was completed. This emulsion had an average grain size of 0.55 μm and the silver iodide content of the entire grain was about 2.2 mol%. Next, in order to remove the excess soluble salt of this reaction solution, the reaction solution was kept at 40 ° C., and Kao Atlas Demol Na was used.
An aqueous solution of 5 g / Ag 1 mol and MgSO ₄ of 8 g / Ag 1 mol were added, and the mixture was stirred for 5 minutes and then left to stand. After that, the supernatant liquid was discharged to a liquid volume of 200 ml per mol of Ag. Then 40
C. Pure water (1.8 liter / Ag 1 mol) was added and stirred for 5 minutes. Next, 20 g / Ag of 1 mol of MgSO ₄ was added, and the mixture was allowed to stand with stirring in the same manner as above, the supernatant was removed and desalting was carried out. The solution was then stirred and gelatin was added to redisperse the silver halide and adjust the emulsion.

(Preparation of coating liquid for emulsion protective film) The following compounds were added. (Addition amount is per 1 liter of coating solution) Gelatin 70g Sodium-i-amyl-n-decylsulfosuccinate 0.3g Polymethylmethacrylate (average particle size 3.5μ) 1.1g C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0131]

[Chemical formula 22]

Further, the compound of the present invention shown in Table 2, 0.4 g of glyoxal and 0.2 g of formalin were added to prepare a coating solution for protective layer.

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

The development is performed by the automatic processor SRX-501 (Konica
(Manufactured by Co., Ltd.) using the following developer and fixer at a developing temperature of 35 ° C.
The fixing temperature was 33 ° C., and the washing water was supplied at 3.5 ° C./min at a temperature of 18 ° C., and the entire treatment process was performed at 45 ° C. for 45 seconds.

<Treatment Process> Process Treatment temperature (° C) Treatment time (sec) Replenishment amount Insertion 1.2 Development + crossover 35 14.6 15cc / 4 cuts Fixing / crossover 33 8.2 30cc / 4 cuts Water washing + crossover 18 7.2 3.5l / Min Squeeze 40 5.7 Dry 45 8.1 Total 45.0 (Developer) Potassium sulfite 70 g Hydroxyethylethylenediamine-trisodium triacetate 8 g 1,4-Dihydroxybenzene 28 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1-Phenyl-5-mercaptotetrazole 0.01 g Sodium metabisulfite 5g Acetic acid (90wt%) 13g Triethylene glycol 15g 1-Phenyl-3-pyrazolidone 1.2g 5-Nitroindazole 0.2g Glutaraldehyde 4g Potassium bromide 4g 5-Nitrobenzimidazole 1g Make an aqueous solution of 1l and water The solution was adjusted to pH 10.5 with sodium oxide.

(Fixer) Sodium thiosulfate-5-hydrate 4.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Aluminum sulfate 10-18 hydrate 10 g Sulfuric acid (50 wt%) 5 g Citric acid 1 g A solution of boric acid (7 g), glacial acetic acid (5 g, 1 l) was made into an aqueous solution, and glacial acetic acid was used to obtain a solution having a pH of 4.2.

(Evaluation Method) <Photographic Performance> The exposed sample processed in the above-mentioned processing step was measured with a Konica sensitometer KS-1 type. 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 is faced downward on a rubber sheet, and after pressure bonding with a rubber roll from above, a static mark is generated by peeling, and after development processing, static marks are generated. The degree of mark generation was visually evaluated in the following 5 grades.

A: Generation of static marks is not recognized.

B: Static marks are slightly generated.

C: Static marks are considerably generated.

D: Static marks are remarkably generated.

E: Static marks were generated on the entire surface.

<Crack Resistance> The unexposed light-sensitive material was placed in a desiccator containing a silica gel desiccant and left at 55 ° C. for 24 hours. The degree of cracking of this sample was observed with a 100 times magnifying glass, and the degree was visually evaluated in the following 5 grades.

A: No cracks were found. B: Some cracks were found. C: Cracks were found considerably. D: Cracks were found significantly. E: Cracks were found all over the surface.

Evaluations other than the above were carried out by the method described in Example 1. The results are shown in Table 3.

[0147]

[Table 3]

From the results shown in Table 3, the photographic properties (sensitivity, pressure fog), film physical properties [coating finish (tail coating failure due to solidification), scratch (scratch) strength], It can be seen that static performance and crack resistance are excellent.

[0149]

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 defects without impairing photographic characteristics.

Claims (11)

[Claims] 1. A photographic light-sensitive material comprising at least one inorganic particle and a composite polymer comprising a hydrophilic polymer compound. 2. The photographic light-sensitive material according to claim 1, wherein the composite polymer is a composite polymer obtained by polymerizing a hydrophilic monomer in the presence of at least one kind of inorganic particles. 3. The photographic light-sensitive material according to claim 1, wherein the composite polymer is a hydrophilic polymer compound containing at least one kind of hydroxyl group-containing monomer. 4. The photograph according to claim 1, wherein the composite polymer is a composite polymer obtained by polymerizing a hydrophilic monomer in the presence of at least one metal alkoxide compound. Photosensitive material. 5. The inorganic particle of the composite polymer is a metal oxide, according to any one of claims 1 to 4.
The photographic light-sensitive material as described in the above item. 6. The composite polymer is a composite polymer containing composite particles obtained by polymerizing a hydrophilic monomer in the presence of at least one water-soluble polymer and at least one inorganic particle. The photographic light-sensitive material according to any one of claims 1 to 5, which is characterized. 7. The photosensitive material according to claim 1, wherein the composite polymer is hydrophilic particles. 8. The amount of gelatin coated on one surface of the support is 2.5 g / m ² or less, and at least one of the composite polymers according to claim 1 is used. A photographic light-sensitive material characterized by containing. 9. A photographic light-sensitive material characterized in that at least one layer on a support contains a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound, and at least one kind of inorganic particles. . 10. A photographic light-sensitive material characterized in that at least one layer on a support contains a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound, and latex. 11. A photographic light-sensitive material characterized in that at least one layer on a support contains a composite polymer comprising at least one kind of inorganic particles and a hydrophilic polymer compound, and a water-soluble polymer.