JP2002082415A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in coatability, transparency and film sticking without requiring troublesome temperature control of a body to be coated and pretreatment of the body to be coated in a producing process. SOLUTION: The silver halide photographic sensitive material has at least one hydrophilic colloidal layer formed by applying and drying a coating liquid for the hydrophilic colloidal layer on a base. The coating liquid has 200-3,000 mPa.s dynamic viscosity coefficient at 20 deg.C when the temperature is lowered from 35 deg.C at 1 deg.C/min rate while continuously applying vibration with 10 rad/see frequency and 10% strain.

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 material, and more particularly, to a conventional silver halide photographic material (conventional silver halide photographic material).

[0002]

2. Description of the Related Art Ordinary silver halide photographic materials are prepared by subjecting a support to a so-called hydrophilic colloid coating solution containing a hydrophilic binder, photosensitive silver halide particles, and various additives by an extrusion coating method. Slide coating method,
It is composed of at least one layer applied by an application method such as a curtain application method. As a method for producing these conventional silver halide photographic materials, a hydrophilic colloid coating solution containing photosensitive silver halide particles and various additives is coated on a support, and then the coated hydrophilic colloid is coated. In order to prevent the colloid coating solution from flowing, it is rapidly cooled and set, and then dried while gradually increasing the temperature. When these hydrophilic colloid coating solutions are coated on a support, the method of applying the hydrophilic colloid coating solution differs depending on the type of silver halide photographic material. For example, in the case of medical or printing photographic materials. Is applied to both sides, and in the case of a general color film, it is applied to one side.

[0003] As a method for producing a photographic light-sensitive material coated on both sides, generally, after one side is coated, it is cooled and set immediately. It is manufactured by drying. In addition, as a method of manufacturing a photographic material having a multi-layered coating on one side, when it is difficult to apply the multi-layer coating at one time, a method of dividing and coating is adopted, but in this case, after drying, the upper layer is coated. It is manufactured by repeating it.

[0004] As a problem at the time of production, when a photographic light-sensitive material coated on both sides is manufactured, since the other side is coated immediately after the cooling step, the temperature of the object to be coated may be reduced. When the application is performed at a temperature lower than the temperature, or when the layers are divided and applied, the upper layer is applied immediately after the drying step, so the temperature of the object to be applied is higher than the temperature of the application liquid. Is applied. When the temperature difference between the object to be coated and the coating liquid is large, the temperature of the coating liquid rapidly changes at the moment the coating liquid comes into contact with the object to be coated. In some cases, unevenness may occur, the transparency of the coating film may deteriorate, and the film may deteriorate.

In order to prevent such occurrence, the viscosity, surface tension, and temperature of the coating solution are repeatedly determined by trial and error in accordance with the manufacturing process conditions for each coating. Further, in the manufacturing process conditions, the coating is performed while changing the cooling conditions and the drying conditions for each coating liquid so that the temperature difference between the object to be coated and the coating liquid does not increase. For this reason, the production efficiency is low, and the cost of the process management is high, and the coating and drying equipment for the process are currently applied at an unnecessary cost. There is a demand for a photographic light-sensitive material which has no coating, has good transparency of a coating film, and has good film formation.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to eliminate the need to control the temperature of an object to be coated and the viscosity and surface tension of the coating solution, which are complicated in the manufacturing process, and to improve the applicability, transparency and film quality. An object of the present invention is to provide a silver halide photographic light-sensitive material having excellent durability.

[0007]

According to the present invention, there is provided a silver halide photographic light-sensitive material excellent in coatability, transparency of a coating film and film formation in a wide temperature range of a support during coating. As a result of intensive studies focusing on the physical properties of the coating solution,
By controlling the dynamic viscosity and dynamic surface tension of the coating liquid within a certain range, it was found that the occurrence of coating unevenness, transparency of the coating film, and film adhesion can be improved without changing the production process. . Specific means for achieving the present invention will be described below.

1) The dynamic viscosity is 10 rad / sec.
35 ° C to 1 ° C while continuously applying 10% strain vibration at c
/ Min at a rate of 200-300 at 20 ° C
A silver halide photographic material comprising at least one hydrophilic colloid layer obtained by applying and drying a coating liquid for a hydrophilic colloid layer having a pressure of 0 mPa · s on a support.

2) The dynamic surface tension is 40 × 10 ^-3 to 70 ×
A silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer obtained by applying and drying a coating liquid for a hydrophilic colloid layer of 10 ^-3 N / m on a support.

3) Dynamic table of coating liquid for hydrophilic colloid layer
Surface tension is 50 × 10^-3~ 65 × 10 ^-3N / m
2. The silver halide photographic material as described in 2) above.

4) When the dynamic viscosity of the coating solution for the hydrophilic colloid layer is lowered at a rate of 1 ° C./min from 35 ° C. while continuously applying a vibration with a frequency of 10 rad / sec and a strain of 10%, The silver halide photographic light-sensitive material according to 2) or 3), which has a temperature of 200 to 3000 mPa · s at ℃.

5) When the dynamic viscosity of the coating liquid for the hydrophilic colloid layer is lowered at a rate of 1 ° C./min from 35 ° C. while continuously applying a vibration with a frequency of 10 rad / sec and a strain of 10%, The silver halide photographic light-sensitive material according to 1), 3) or 4), which has a temperature of 300 to 2000 mPa · s at ℃.

(6) The silver halide photographic material as described in any one of (1) to (5) above, wherein the temperature of the support during coating is 15 ° C. or lower.

7) The surface energy of the support is 55 × 10
^The silver halide photographic material according to any one of 1) to 6), wherein the silver halide photographic material is ^-3 N / m or more.

8) A conductive composition prepared by mixing a polymer fine particle having a functional group and a water-soluble polymer having a group capable of reacting with the functional group in a coating liquid for a hydrophilic colloid layer, followed by heat treatment. The silver halide photographic material as described in any one of 1) to 7) above, wherein

Hereinafter, the present invention will be described in detail. The dynamic viscosity of the coating solution for the hydrophilic colloid layer of the present invention is 200
3,000 mPa · s is preferable, and 30 is more preferable.
0 to 2000 mPa · s. When the viscosity is less than 200 mPa · s, any of the coating properties, transparency and film formation deteriorates, which is not preferable. As a method for controlling the dynamic viscosity, a commonly used method can be used. For example, a method of controlling the particle size and aspect ratio of the contained solid fine particles, a method of designing the molecular weight of the thickener, a method of changing the concentration of the coating solution, a method of changing the pH of the coating solution, and the like can be used. Any device may be used for the method for measuring the dynamic viscosity in the present invention. For example, Rheometric Scientific
An ARES viscoelasticity measurement system of F.E.

The dynamic surface tension of the coating liquid for the hydrophilic colloid layer of the present invention is ^{40 × 10 -3 ~70 × 10 -3} N / m, preferably 50 × 10 ^-3 ~65 × 10 ^{- 3} N / m. When it is less than 40 × 10 ⁻³ N / m, applicability, transparency,
70 × 1
It is not preferable to exceed 0 ^-3 N / m because the same state is obtained. As a method for controlling the dynamic surface tension, a commonly used method can be used. For example, selection of a binder, addition of a surfactant, and the like can be used. The measurement of the dynamic surface tension of the present invention is based on the journal of fluid mechanism (J. Fluid).
Mech. (1981), vol. 112. p443
To 458).

The surface energy of the support of the present invention is 55 ×
It is preferably at least 10 ⁻³ N / m. Further preferred surface energy is 55 × 10 ^{−3 to} 100 × 10 ⁻³ N / m. 5
If it is less than 5 × 10 ⁻³ N / m, the coatability is undesirably deteriorated.

In the present invention, the surface energy of the support can be controlled by providing an undercoat layer, or by performing corona discharge, ultraviolet irradiation, plasma irradiation, or the like.

The surface energy in the present invention is a value obtained by measuring a contact angle by a droplet method (using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.) and obtaining the following equation. Surface energy [gamma] s = [gamma] d + [gamma] p + [gamma] h, where [gamma] d represents the dispersion component surface energy, [gamma] p represents the polar component surface energy, and [gamma] h represents the hydrogen bond component surface energy.

Next, the conductive composition used in the present invention will be described. First, the polymer fine particles having a functional group required for producing a conductive composition are fine particles of a water-insoluble resin having a particle size of 0.03 to 10 microns, preferably 0.05 to 0.5 microns. And polymer fine particles having a functional group capable of reacting with the conductive water-soluble polymer. It is a group having a carboxyl group, a hydroxyl group, an epoxy group, or active methylene as a functional group, and is a polymer fine particle having at least one of these groups. These functional groups may contain two or more kinds. The content of these functional groups is 5 as monomer units.
-100% by mass, but preferably 10-6% by mass.
0% by mass. If the amount is less than 5% by mass, it is difficult to obtain a conductive effect, which is not preferable.

Examples of the method for forming the fine particles include an emulsion polymerization method, a suspension polymerization method, and a dispersion of a resin, and the emulsion polymerization method is preferred from the viewpoint of achieving the target particle diameter.

The structure of the polymer of the polymer fine particles having a functional group in the present invention is particularly preferably one represented by the general formula (1).

Formula (1)-(A) _x- (B) _y- (C) _z-wherein A is derived from an ethylenically unsaturated monomer having a functional group represented by the following formula (2): B represents a methacrylate, an acrylate having a glass transition temperature of 35 ° C. or lower of a homopolymer,
It represents a repeating unit derived from an ethylenically unsaturated monomer selected from maleic esters, and C represents a repeating unit derived from an ethylenically unsaturated monomer other than A and B. Here, x, y, and z represent the mass percentage ratio of each component in the polymer latex, and 10 ≦ x ≦ 6, respectively.
0, 5 ≦ y ≦ 90, and x + y + z = 100.

[0025]

Embedded image

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X represents a monovalent group including any of a carboxyl group, a hydroxyl group, an epoxy group, and a group having active methylene.

Here, the group having active methylene includes
Specifically, an acetoacetoxy group, an acetoacetamide group,
Cyanoacetoxy group, ethoxycarbonylacetyl group,
Examples include a cyanoacetamide group and an acetoacetyl group.

Preferred examples of the ethylenically unsaturated monomer having a functional group represented by A in the polymer represented by the general formula (1) are shown below, but the invention is not limited thereto. MN-1 2-acetoacetoxyethyl methacrylate MN-2 2-acetoacetoxyethyl acrylate MN-3 2-acetoacetoxypropyl methacrylate MN-4 2-acetoacetoxypropyl acrylate MN-5 2-acetoacetamidoethyl methacrylate MN-6 2- Acetoacetamidoethyl acrylate MN-7 2-cyanoacetoxyethyl methacrylate MN-8 2-cyanoacetoxyethyl acrylate MN-9 N- (2-cyanoacetoxyethyl) acrylamide MN-10 2-propionylacetoxyethyl acrylate MN-11 N- ( 2-propionylacetoxyethyl) methacrylamide MN-12 N-4- (acetoacetoxybenzyl) phenylacrylamide MN-13 ethylacryl Loyl acetate MN-14 Acryloyl methyl acetate MN-15 N-Methacryloyloxymethyl acetoacetamide MN-16 Ethyl methacryloyl acetoacetate MN-17 N-Allyl cyanoacetamide MN-18 Methyl acryloylacetoacetate MN-19 N- (2-methacryloyl Methyl)
Cyanoacetamide MN-20 p- (2-acetoacetyl) ethylstyrene MN-21 4-acetoacetyl-1-methacryloylpiperazine MN-22 ethyl-α-acetoacetoxymethacrylate MN-23 N-butyl-N-acryloyloxyethyl acetoate Acetamide MN-24 p- (2-acetoacetoxy) ethylstyrene MN-25 Methacrylic acid and / or alkali salt thereof MN-26 Acrylic acid and / or alkali salt thereof MN-27 Maleic acid and / or alkali salt thereof MN-28 Hydroxyethyl methacrylate MN-29 Hydroxyethyl acrylate MN-30 Glycidyl methacrylate The ethylenically unsaturated monomer giving the repeating unit represented by B in the general formula (1) is a glass transition of a homopolymer thereof. It is a monomer having a temperature of 35 ° C. or lower, specifically, an alkyl acrylate (for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, iso-nonyl) Acrylate, n-dodecyl acrylate, etc.), alkyl methacrylate (for example, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, iso-nonyl methacrylate, n-
Dodecyl methacrylate), dienes (eg, butadiene, isoprene) and the like. These monomers may be used alone or in combination as the B component.

More preferred monomers are those having a homopolymer having a glass transition temperature of 10 ° C. or lower, such alkyl acrylates having an alkyl side chain having 2 or more carbon atoms (eg, ethyl acrylate, n -Butyl acrylate, 2-ethylhexyl acrylate, iso-nonyl acrylate, etc.), alkyl methacrylates having an alkyl side chain having 6 or more carbon atoms (e.g., n-hexyl methacrylate, 2-ethylhexyl methacrylate, etc.), dienes (e.g., butadiene, Isoprene).

The value of the glass transition temperature of the above-mentioned polymer is described in J. Am. Brandrup, E .; H. Imberg
ut co-edited "Polymer Handbook" 3rd edition (John Wily & Sons, 1989) VI
/ 209-VI / 277.

The repeating unit represented by C in the general formula (1) is a repeating unit other than B, that is, a repeating unit derived from a monomer whose homopolymer has a glass transition temperature exceeding 35 ° C. preferable. These monomers are B
A single component or a plurality of components may be used, and components necessary for improving the dispersion stability described below may be counted as the C component.

Specifically, acrylic esters (for example, t-butyl acrylate, phenyl acrylate,
2-naphthyl acrylate, etc.), methacrylates (for example, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate) , Ethylene glycol dimethacrylate, glycidyl methacrylate, etc.), vinyl esters (eg, vinyl benzoate, pivaloyloxyethylene, etc.), acrylamides (eg, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert- Butyl acrylamide, cyclohexyl acrylamide,
Benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, diacetoneacrylamide, etc.), methacrylamides (for example, methacrylamide, methylmethacrylamide, ethyl) Methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide,
Phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, etc.), styrenes (for example, styrene,
Methyl styrene, dimethyl styrene, trimethylene styrene, ethyl styrene, isopropyl styrene, chloro styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoate methyl ester), divinyl benzene, acrylonitrile, meta Acrylonitrile, N-vinylpyrrolidone, N-vinyloxazolidone, vinylidene chloride, phenyl vinyl ketone and the like can be mentioned.

The polymers represented by the general formula (1) are described in JP-B-60-15935 and JP-B-45-3.
Nos. 822 and 53-28086, U.S. Pat.
A monomer having an anionic functional group (for example, a carboxyl group or a sulfonic acid group) as described in Japanese Patent No. 0,456 may be copolymerized for the purpose of improving the stability of the latex.

The following compounds can be mentioned as such monomers. Acrylic acid; methacrylic acid;
Monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate; citraconic acid; styrene sulfonic acid; vinylbenzyl sulfonic acid; Vinylsulfonic acid; acryloyloxyalkylsulfonic acid,
For example, acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc .; methacryloyloxyalkylsulfonic acid, for example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc .; acrylamidoalkyl Sulfonic acid, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-
2-methylpropanesulfonic acid, 2-acrylamide-
2-methylbutanesulfonic acid and the like; methacrylamide alkylsulfonic acid, for example, 2-methacrylamide-2
-Methylethanesulfonic acid, 2-methacrylamide-2
-Methylpropanesulfonic acid, 2-methacrylamide-
These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

The above-mentioned monomer having an anionic functional group can be used as required, for example, for imparting stability to latex, irrespective of the glass transition temperature of the homopolymer. If so, the preferred amount is 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the total weight of the polymer.

In the general formula (1), x, y, and z represent the mass percentage ratio of each component in the polymer latex. x, y,
z is 5 ≦ x ≦ 60, 5 ≦ y ≦ 90, x + y + z, respectively.
= 100.

The polymer latex having a functional group is preferably prepared by an emulsion polymerization method. The dispersed particle size is not particularly limited, but the preferred range is 0.05 to
0.5 μm. In the emulsion polymerization method of the present invention, a water-soluble polymer may be used as at least one type of emulsifier. The monomer is emulsified in water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.), and is generally treated at 30 ° C. to about 100 ° C., preferably 40 ° C. with a radical polymerization initiator. ° C
To a temperature of about 90 ° C. The amount of the organic solvent that is miscible with water is 0 to 100% by volume relative to water, and more preferably 0 to 50%.

The polymerization reaction is usually carried out using 0.05 to 5% by mass of a radical mass initiator and optionally 0.1 to 10% by mass of an emulsifier with respect to the monomer to be polymerized. As the polymerization initiator, azobis compounds, peroxides,
Hydroperoxide, redox solvent and the like, for example, potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl-carbonate, 2,4-dichlorobenzyl peroxide, methyl ethyl ketone peroxide,
Cumene hydroperoxide, dicumyl peroxide, 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) hydrochloride,
There are combinations of potassium sulfite and sodium bisulfite.

As an emulsifier, an anionic, cationic, amphoteric or nonionic surfactant can be used. Examples of the surfactant include sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium dodecylnaphthalenesulfonate, sodium dodecylbenzenesulfonate, sodium dodecylphosphate, cetyl Trimethyl ammonium chloride, dodecyl trimethylene ammonium chloride, N-2-
Examples include ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, and polyoxyethylene sorbitan laurate ester.

When emulsion polymerizing a polymer latex having a functional group, it is preferable to use a water-soluble polymer. As the water-soluble polymer, most of water-soluble natural polymers and water-soluble synthetic polymers having a water-soluble anionic group, a cationic group, and a nonionic group in a molecular structure can be used. Or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof,
The cationic group is preferably a tertiary amine or ammonium salt, the nonionic group is preferably a hydroxyl group, an amide group or a methoxy group, the alkylene oxide group is preferably an oxyethylene group, and the heteroatom ring is preferably a pyrrolidone group. Among the water-soluble synthetic polymers, anionic or nonionic polymers are preferred, and anionic polymers are particularly preferred. More preferably, a polymer having a sulfonate is used, and a polymer containing a polystyrene sulfonate or a conjugated diene sulfonate is more preferable.
Further, two or more water-soluble polymers may be used in combination. Further, the water-soluble polymer may be the same as a water-soluble polymer having a group capable of reacting with a functional group which is a component of the present invention.

The water-soluble polymer used as an emulsifier when the polymer latex having active methylene is subjected to emulsion polymerization includes a natural polymer or a semi-synthetic water-soluble polymer, and examples thereof include alginic acid or a salt thereof, and dextran. Dextran sulfate, glycogen, gum arabic, albumin, agar, starch derivatives, carboxymethylcellulose or salts thereof, hydroxycellulose, cellulose sulfate, and the like, and these derivatives can also be used.

The water-soluble polymer used when the polymer latex of the present invention is emulsion-polymerized is exemplified below, but is not limited thereto.

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

In the emulsion polymerization, depending on the purpose,
Wide range of polymerization initiator, concentration, polymerization temperature, reaction time, etc.
Needless to say, it can be easily changed. Also,
The emulsion polymerization reaction may be carried out by putting the monomer, the surfactant, the water-soluble polymer, and the medium in advance in a container, and adding the initiator, or dropping a part or the whole amount of each component as necessary. The polymerization may be carried out while performing the polymerization.

The Tg of the polymer is, for example, as described in “J.
rup, E.R. H. Co-authored by Immergut, Polyme
r Handbook, 2nd Edition, II
I-139 to III-192 (1975) ". In the case of a copolymer, it can be determined by the following formula.

[0051]

(Equation 1)

The content of the polymer fine particles having a functional group in the layer coated on the image forming material of the conductive composition is preferably 10 to 90% by mass as solid content.

The water-soluble polymer having a group capable of reacting with the functional group of the fine particles of the present invention will be described. The water-soluble polymer is a polymer substance that dissolves in an amount of 1 g or more per 100 g of water at 23 ° C., and is not particularly limited as long as it has a group that reacts with a functional group of polymer fine particles used in combination. Are preferred. A particularly preferred polymer structure is represented by the general formula (3).

Formula (3)-(D) _a- (E) _b- (F) _c-wherein D represents an ethylenically unsaturated monomer unit having a sulfonic acid group, and E has a carboxyl group. 1 shows an ethylenically unsaturated monomer unit. F is D, E
Represents an ethylenically unsaturated monomer unit other than a,
b and c represent the molar fraction of each unit in the water-soluble polymer, 10 ≦ a ≦ 90, 10 ≦ b ≦ 90, a + b + c = 1
Represents 00. Preferred molar fractions are 40 ≦ a ≦ 90,
0 ≦ b ≦ 60 and c ≦ 20.

The monomer unit of D is styrenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid,
Acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfone, 2-acrylamide-2-methylethanesulfonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl Butanesulfonic acid and the like can be mentioned. These sulfonic acids may be introduced into the polymer by polymerizing a monomer unit having a sulfonic acid group, or may be obtained by introducing a sulfonic acid group after polymer polymerization. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Preferred examples include styrene sulfonic acid.

Examples of the monomer unit of E include acrylic acid, methacrylic acid, itaconic acid and maleic acid. These acids may also be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. A preferred example is maleic acid.

Hereinafter, examples of the water-soluble polymer having a group capable of reacting with the functional group of the fine particles will be described.

[0058]

Embedded image

[0059]

Embedded image

Next, the production of the conductive composition of the present invention will be described. The conductive composition can be manufactured by mixing the polymer fine particles and the water-soluble polymer and performing a heat treatment. Next, mixing and heat treatment will be described.

The polymer fine particles having a functional group and the water-soluble polymer having a group capable of reacting with the functional group are mixed in an aqueous medium, and the mixing ratio can be arbitrarily set depending on the required conductivity level and film strength. However, assuming that the polymer fine particles in the mass ratio of solids is 1, the water-soluble polymer may be mixed at a ratio of about 0.1 to 10, preferably,
It is a mixing ratio of a ratio of 0.5 to 3. The mixing method is not particularly limited as long as the whole can be uniformly mixed. The heat treatment is
To maintain the mixed solution of the aqueous medium at a temperature of 50 ° C. or more for 10 minutes or more. Preferably, a temperature of 60 ° C. or more and 90 ° C. or less is maintained for 1 hour to 6 hours. In addition to the polymer fine particles and the water-soluble polymer, a material used as a component of the conductive composition may be added to the mixed solution in advance, and may be subjected to a heat treatment. For example, a physical property improving agent for a coating film such as a surfactant, a viscosity modifier, a crosslinking agent, and a wax for improving the coating property may be added as necessary. After the heat treatment,
What is necessary is just to store at 30 degreeC or less.

The content of the polymer fine particles having a functional group and the water-soluble polymer having a group capable of reacting with the functional group in the conductive composition may be 60% by mass or more. It may contain fine particles, various thickeners, inorganic fillers, polymer emulsions other than the present invention, crosslinking agents, thermosetting polymers, film forming aids, plasticizers, dispersants, wetting agents, defoamers , An organic solvent and the like may be mixed and used.

The method of applying the coating liquid for a hydrophilic colloid layer of the present invention on a support may be any method such as a simultaneous multi-layer coating method and a single-layer coating method. Research Disclosure (hereinafter also referred to as RD) 176, pages 27-28, "Coating Produce" (Coating pr
oders) may be used. For example, dip coating, roller coating, curtain coating, extrusion coating, slide
A hopper method or the like can be used.

When the coating solution for a hydrophilic colloid layer of the present invention is coated on a support, the temperature of the support is preferably 15 ° C. or lower. A more preferred temperature of the support is 15 to 5 ° C. 1
When the temperature exceeds 5 ° C., it is not preferable because a load is applied to drying after coating. If the temperature is lower than 5 ° C., the temperature difference from the coating temperature of the coating liquid becomes large, and the coating property is unfavorably deteriorated. Fifteen
In order to reduce the temperature to below ° C, it is sufficient to pass through a cooling step before coating, and the temperature of the support can be controlled by controlling the temperature in the cooling step. Any device may be used for measuring the temperature. For example, you may measure using a surface thermometer.

The support used in the present invention is not particularly limited as long as it is a support generally used for a photographic material.
For example, preferred supports include polyethylene terephthalate (hereinafter also referred to as PET), polyethylene naphthalate, polycarbonate, polyethersulfone, polyarylate, polyetheretherketone, polysulfone, polyimide, polyetherimide, polyamide, and polystyrene (hereinafter PS). ), And a polymer film such as syndiotactic polystyrene (hereinafter, also referred to as SPS). These polymers may form a film by themselves, or may be a copolymer or a polymer blend containing a main component of the polymer. The term “main component” as used herein refers to a component in which one of the constituent components has a copolymerization ratio or a blend ratio of 50% by mass or more.

The thickness of the support used is not particularly limited, and may be set so as to have a necessary strength according to the purpose of use. In particular, when used for medical or printing photographic materials, the thickness is preferably 50 to 300 μm, and more preferably 70 to 200 μm. The width of the support used is not particularly limited, and the necessary width may be set according to the purpose of use.

As the binder used in the coating liquid for the hydrophilic colloid layer of the present invention, gelatin is preferably used, but other hydrophilic colloids can be used. For example, proteins such as albumin and casein hydroxyethylcellulose, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, dextran, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, Polyacrylic acid,
Various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Photo. J
apan. No. 16 (1966), p. 30 as well as gelatin derivatives such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkane sultones, vinylsulfonamides, etc. Products obtained by reacting various compounds such as maleimide compounds, polyalkylene oxides, and epoxy compounds).

In the silver halide photographic light-sensitive material of the present invention, the total amount of the coated binder is not particularly limited, but is preferably 1.0 to 4.5 g / m ² per one surface. Moreover, 1.2-3.6 g / m < ² > is especially preferable.

Next, the ordinary silver halide photographic light-sensitive material of the present invention will be described. A preferred silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is (100)
An emulsion consisting of silver chloride-based tabular grains having a major surface as the surface,
Preferably, (a) a step of introducing nuclei by introducing a silver salt and a halide salt into a dispersion medium under a condition of not less than 30 mol% of chloride, (b) following the nucleation, (10)
0) a step of performing Ostwald ripening under conditions that maintain the main plane, (c) a desired particle size and a silver chloride content,
It is prepared by a step of performing grain growth. As a method of reacting a silver salt and a halide salt during nucleation, it is preferable to use a double jet method. It is preferable to use the double jet method also during grain growth, and to keep pAg in a liquid phase in which silver halide is generated constant,
That is, a so-called controlled double jet method can be used. The silver halide emulsion may be formed by supplying fine silver halide grains during part or all of the steps during grain formation. Since the particle size of the fine particles governs the supply rate of halide ions, it depends on the size and composition of the silver halide grains to be formed, but the preferred size is approximately 0.3 μm or less in terms of the average equivalent sphere diameter, and more preferably 0 μm or less. .1 μm or less. In order for the fine particles to be stacked on the grown particles by recrystallization, the fine particle size is desirably smaller than the sphere equivalent diameter of the grown particles,
More preferably, it is 1/10 or less of the sphere equivalent diameter of the growth particles.

The silver halide emulsion according to the present invention may be subjected to a noodle washing method, a flocculation sedimentation method or the like in order to remove soluble salts after completion of the growth of silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a polymer flocculant described in JP-A-2-7037 can be used. A desalting method using certain exemplified compounds G-3, G-8 and the like can be mentioned. RD102 volume, 1
0208 (October 1972) and 131, 1312
2 (May 1975) may be used for desalting. The silver halide emulsion may be spectrally sensitized with a cyanine dye or the like.

The silver halide photographic light-sensitive material of the present invention includes
RD-17643 and 18716 (November 1979) were used before and after physical ripening or chemical ripening of a silver halide emulsion.
), 308119 (December 1989) and the like.

The silver halide photographic light-sensitive material of the present invention includes
In addition to the silver halide emulsion layer, if necessary, an ultraviolet absorbing layer, an antihalation layer, an intermediate layer, a filter layer, a protective layer and the like can be provided. In some cases, a crossover light cut layer may be provided.

The processing solutions usable for the development processing of the silver halide photographic light-sensitive material of the present invention are described in the above-mentioned RD-176.
43 and 308119 can be used. Developers used for black and white photography include dihydroxybenzenes (hydroquinone, etc.),
3-pyrazolidones (1-phenyl-3-pyrazolidone); aminophenols (N-methyl-aminophenol); and the like.
An alkali agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like can be added. In the fixing solution, a fixing agent such as thiosulfate and thiocyanate is used, and a water-soluble aluminum salt (aluminum sulfate, potassium alum, etc.) as a hardening agent, a preservative, a pH adjuster,
It may contain a water softener or the like.

The silver halide photographic light-sensitive material of the present invention is suitable for rapid processing. In particular, it is preferable that the Dryto Dry processing time be within 60 seconds. More preferably 45
Within seconds, more preferably within 38 seconds. Also 25
Ultra-rapid processing such as within a second can be performed, and processing can be performed with a low replenishment amount of a developing solution or a fixing solution of 200 ml or less per 1 m ² of the photosensitive material.

[0076]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 [Preparation of Sample Coated with Emulsion Layer] (Preparation of Subbed Substrate) Corona discharge of 8 W / m ² · min. On both sides of a biaxially stretched and heat-fixed PET film having a thickness of 100 μm. After applying the treatment, one surface of
-1 is applied so as to have a dry film thickness of 0.8 μm, and dried to obtain a photosensitive layer side undercoat layer A-1. It was applied so as to have a thickness of 8 μm, and was dried to obtain a back surface undercoat layer B-1.

<< Undercoating Underlayer Coating Solution a-1 >> A copolymer latex solution containing 30% by mass of butyl acrylate, 20% by mass of t-butyl acrylate, 25% by mass of styrene and 25% by mass of 2-hydroxyethyl acrylate (solid content: 30% by mass) %) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish to 1 L with water.

<< Undercoating Underlayer Coating Solution b-1 >> A copolymer latex liquid of 10% by mass of butyl acrylate, 30% by mass of acetoacetoxyethyl methacrylate, 20% by mass of styrene and 40% by mass of glycidyl methacrylate (solid content: 30% ) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 L with water.

<Coating of Undercoating Upper Layer A-2>
1 was subjected to a corona discharge of 8 W / m ² · min, and the following undercoating upper layer liquid a-2 was applied at 10 ml / m ² ,
It was dried for a minute to obtain a lower draw upper layer A-2.

<< Underdrawing upper layer liquid a-2 >> Gelatin 10 g (C-1) Surfactant 0.2 g (C-2) Surfactant 0.2 g (C-3) Hardener 0.1 g (C- F) Fungicide 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Finished to 1 L with water. <Application of antistatic layer B-2> On the undercoat layer B-1,
8 W / m ² · min of corona discharge, antistatic liquid b-2
Is applied with a combination of a roll coater and a wire bar so that the dry film thickness becomes 1.0 μm,
It dried at 1 degreeC for 1 minute, and was set as the antistatic layer B-2. << Preparation of antistatic liquid b-2 >> Conductive composition 90 g in terms of solid content Silica particles having an average particle diameter of 3 μm 0.1 g (C-1) Surfactant 0.1 g (C-4) Fungicide 12 g With water Finish to 1.5L.

The method for synthesizing the conductive composition is shown below. (Synthesis of Conductive Composition) Polymer fine particles having a functional group and an aqueous solution polymer having a group capable of reacting with the functional group were stirred and mixed, and then heat-treated to synthesize a conductive composition. The synthesis conditions are shown below.

Polymer fine particles having a functional group: sodium dodecylbenzenesulfonate, SP-
Poly (styrene / glycidyl methacrylate / butyl acrylate = 4/4/2) latex having a solid content of 30% obtained by emulsion polymerization using No. 23.

Water-soluble polymer: ASP1 mixing ratio (polymer fine particles / water-soluble polymer) = 1/1 Heat treatment condition: 75 ° C., 2 hours

[0085]

Embedded image

(Coating of Emulsion Layer) <Coating Solution of Emulsion Layer> Subbing upper layer A of subbed support sample
-2, a silver halide emulsion having a silver content of 2.9 g / m ² and a gelatin content of 1.2 g was prepared as the emulsion layer shown below.
/ M ² and dried.

<< Composition of Emulsion Layer Coating Solution >> The composition excluding the amounts of silver and gelatin is shown below.

(C-5) Sensitizing dye 0.6 mg / m ² (H-7) Hydrazine compound 30 mg / m ² (C-6) Amino compound 50 mg / m ² (C-7) Surfactant 100 mg / m ² (C-8) Latex polymer 1.0 mg / m ² (C-9) Hardener 30 mg / m ² Sodium-isoamyl-n-decylsulfosuccinate 0.7 mg / m ² 2-mercapto-6-hydroxypurine 10 mg / m ² EDTA 50 mg / m ² (Preparation of Evaluation Samples 1-1 to 1-6) On the antistatic layer B-2 of the sample coated with the emulsion layer, the dynamic viscosity shown in Table 1 was obtained. The hydrophilic colloid layer coating solution having the following formula 1 in which the amount of pure water was adjusted was applied and dried, and the evaluation sample 1-1 shown in Table 1 was obtained.
~ 1-6 were produced. During coating, the temperature of the support is 18 ° C
And the surface energy was 52 × 10 ⁻³ N / m.

[0089]

[Table 1]

<< Formulation 1, Composition of Coating Solution for Hydrophilic Colloid Layer >> Gelatin 1.5 g / m ² (SP-13) Water-soluble polymer 40 mg / m ² Colloidal silica (average particle size 12 nm) 0.3 g / m ² ( C-8) Latex polymer 2.0 mg / m ² Dihexyl sulfosuccinate (DHS) 0.0 mg / m ² (C-7) Activator 100 mg / m ² (C-12) Hardener 100 mg / m ²

[0091]

Embedded image

[0092]

Embedded image

The silver halide photographic light-sensitive material of the present invention was processed with a developer and a fixer under the following formulation and conditions. << Developer Composition >> Amount per 1 L of each used solution Diethyltriamine pentaacetic acid / pentasodium salt 3 g Sodium sulfite 50 g Potassium carbonate 40 g Hydroquinone 21 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0 0.9 g Potassium bromide 5 g Benzotriazole 0.2 g 5-Methyl-benzotriazole 0.13 g Boric acid 8 g Diethylene glycol 40 g 2-Mercapto-6-hydroxypurine 0.06 g Water and potassium hydroxide are added to make 1 L, pH = 10. 2
Adjust to. << Fixing solution composition >> Amount per 1 L of working solution Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate ( (27% aqueous solution) 25 ml The pH of the working solution was 4.9.

<< Development Processing Conditions >> (Step) (Temperature) (Time) Development 38 ° C. for 12 seconds Fixing 35 ° C. for 10 seconds Rinse at 40 ° C. for 10 seconds Drying at 50 ° C. for 12 seconds Total of 44 seconds (Evaluation method) << Coatability >> Unexposed Of the hydrophilic colloid layers of Samples 1-1 to 1-6 were visually evaluated on a scale of 1 to 5 according to the following evaluation criteria.

5: Good finish without uneven coating and streaks 4: Very slight uneven coating and streaks 3: Some uneven coating and streaks 2: Uniform coating and streaks 1 : The coating unevenness and streaks are severely generated, and the finish is very poor. << Transparency >> The transparency of Samples 1-1 to 1-6 was visually evaluated in five steps according to the following evaluation criteria.

5: Very high transparency, clear film 4: Very slightly milky white, but not significantly reduced in transparency 3: Slightly milky white, slightly less transparent than 2: Transparency Slightly bad 1: The film is milky white and has little transparency. <With film> For each of Samples 1-1 to 1-6 before the development treatment, a cellophane adhesive tape was pressed on the hydrophilic colloid layer, and the film was rapidly peeled off to obtain a peeled area of the emulsion layer. Therefore, it was evaluated.

Evaluation Criteria 3. Adhesion is very strong, peel area less than 5% 2. The adhesive strength is strong, and the peeled area is 5% or more and less than 20%. 1. The peeled area is 20% or more and less than 50%. Peeling area is 50% or more and less than 100% The adhesion was very weak, and the emulsion layer was completely peeled off.

[0098]

[Table 2]

As is clear from Table 2, the sample N of the present invention
o. 1-2 to 1-5 improve coatability, transparency and film formation.

Example 2 Antistatic Layer B of Sample Coated with Emulsion Layer Prepared in Example 1
-2, a hydrophilic colloid layer in which the dynamic surface tension was changed by changing the addition amount of DHS as shown in Table 3 in the composition of the hydrophilic colloid layer coating solution of formulation 1 used in Example 1. The coating liquid for application was applied and dried to produce evaluation samples 2-1 to 2-6 shown in Table 3.

Further, of the composition of the hydrophilic colloid layer coating solution of Formulation 1 used in Example 1, a water-soluble polymer SP-13 was added as shown in Table 3, and the amount of pure water was adjusted. A hydrophilic colloid layer having a changed dynamic viscosity shown in Table 3 was applied and dried, and evaluation samples 2-7 to 2-1 shown in Table 3 were obtained.
0 was produced. The temperature of the support at the time of coating was 18 ° C., and the surface energy was 52 × 10 ⁻³ N / m.

Each of the evaluation samples 2-1 to 2-10 was treated with a developing solution and a fixing solution in the same manner as in Example 1, and evaluated for coatability, transparency and film formation according to the same evaluation method as in Example 1. Table 4 shows the results.

[0103]

[Table 3]

[0104]

[Table 4]

As is clear from Table 4, the sample N of the present invention
o. 2-2 to 2-5 and 2-7 to 2-10 improve coatability, transparency and film formation.

Example 3 Samples 3-1 and 3-2 shown in Table 5 were prepared by changing the temperature of the support when preparing Sample 1-3 of Example 1.
The temperature of the support is a value measured using a handy type digital temperature indicator (manufactured by Shinko Technos Co., Ltd.).

Samples 3-1 and 3-2 were treated with the same developing solution and fixing solution as in Example 1, and were evaluated for coatability, transparency and film formation according to the same evaluation method as in Example 1. Table 5 shows the results.

[0108]

[Table 5]

As is clear from Table 5, the sample N of the present invention
o. 1-3, 3-1 and 3-2 confirmed that there was no problem in applicability, transparency and film formation.

Example 4 Samples 4-1 and 4-2 shown in Table 6 were prepared by changing the surface energy of the support when preparing Sample 2-4 of Example 2. The surface energy of the support is determined by the antistatic layer B-
2 was subjected to corona discharge and controlled. The surface energy was measured by a contact angle measurement (using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.). The treatment was carried out using the same developing solution and fixing solution as in Example 1, and the applicability, transparency and film formation were evaluated according to the same evaluation methods as in Example 1.

[0111]

[Table 6]

As is clear from Table 6, the sample N of the present invention
o. 2-4, 4-1 and 4-2 all confirmed that there was no problem in applicability, transparency and film formation.

Example 5 Antistatic layer B of the sample coated with the emulsion layer prepared in Example 1
-2, the addition amount of DHS and SP-13 was changed as shown in Table 7 among the hydrophilic colloid back layer coating solution composition of Formula 2 below and the protective layer coating solution composition of Formula 4 below. A hydrophilic colloid back layer coating solution and a protective layer coating solution each having an adjusted amount of pure water so as to have a dynamic viscosity and a dynamic surface tension of 8 were simultaneously coated and dried, and the evaluation sample 5 shown in Table 8 was obtained.
-1 to 5-6 were produced. The temperature of the support during coating is 8 ° C
And the surface energy was 65 × 10 ⁻³ N / m.

[0114]

[Table 7]

[0115]

[Table 8]

<< Formulation 2, Composition of Coating Solution for Hydrophilic Colloid Back Layer >> Gelatin 1.5 g / m ² (SP-13) Water-soluble polymer (Amount shown in Table 5) Colloidal silica (average particle size: 12 nm) 3 g / m ² (C-8) latex polymer 2.0 mg / m ² dihexyl sulfosuccinate (DHS) (amount described in Table 5) (C-7) activator 100 mg / m ² (C-12) hardening 100 mg / m ² << Prescription 4, Composition of Coating Solution for Back Protective Layer >> Gelatin 1.0 g / m ² (SP-13) Water-soluble polymer (Amount shown in Table 5) Matting agent: Monodisperse having an average particle size of 5 μm Polymethyl methacrylate 30 mg / m ² Sodium-di- (2-ethylhexyl) sulfosuccinate 10 mg / m ² (C-13) dye 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² (C-10) Hardener 15 mg / m ² Polysiloxane 0.7 g / m ² Dihexyl sulfosuccinate (DHS) (Amount shown in Table 5) For the above Samples 5-1 to 5-6, Example 1 And treated with a developing solution and a fixing solution in the same manner as described in Example 1. According to the method described in Example 1, applicability, transparency, and evaluation of film formation were performed.
Table 9 shows the results.

[0117]

[Table 9]

As is clear from Table 9, the sample N of the present invention
o. 5-2 to 5-6 improve coatability, transparency and film formation.

[0119]

By controlling the dynamic viscosity and the dynamic surface tension of the coating liquid for the hydrophilic colloid layer within a certain range, complicated temperature control in the coating and drying process, and the viscosity and surface tension of the coating liquid can be controlled. A silver halide photographic light-sensitive material excellent in coatability, transparency and film formation can be provided without requiring management.

Claims (8)

[Claims] 1. The dynamic viscosity is a frequency of 10 rad / sec.
From 35 ° C to 1 ° C /
When the temperature is lowered at a rate of 20 minutes,
A silver halide photographic material comprising at least one hydrophilic colloid layer obtained by applying and drying a coating liquid for a hydrophilic colloid layer having a mPa · s on a support. 2. The dynamic surface tension is 40 × 10 ⁻³ to 70 × 1.
A silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer obtained by applying and drying a coating liquid for a hydrophilic colloid layer of 0 ^-3 N / m on a support. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the dynamic surface tension of the coating liquid for the hydrophilic colloid layer is 50 × 10 ^{−3 to} 65 × 10 ⁻³ N / m. material. 4. When the temperature of the coating solution for the hydrophilic colloid layer is lowered at a rate of 1 ° C./min from 35 ° C. while continuously applying a vibration having a dynamic viscosity of 10 rad / sec and a strain of 10%. 4. The silver halide photographic light-sensitive material according to claim 2, wherein the photographic material has a temperature of 200 to 3000 mPa.s. 5. When the temperature of the coating liquid for the hydrophilic colloid layer is lowered at a rate of 1 ° C./min from 35 ° C. while continuously applying a vibration having a dynamic viscosity of 10 rad / sec and a strain of 10%. 5. The silver halide photographic material according to claim 1, wherein the temperature is 300 to 2000 mPa.s. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the temperature of the support during coating is 15 ° C. or lower. 7. The support has a surface energy of 55 × 10 ^−3.
The silver halide photographic material according to any one of claims 1 to 6, wherein the photographic material is at least N / m. 8. A conductive composition produced by mixing a polymer fine particle having a functional group and a water-soluble polymer having a group capable of reacting with the functional group in a coating liquid for a hydrophilic colloid layer, followed by heat treatment. The silver halide photographic light-sensitive material according to any one of claims 1 to 7, wherein the photographic light-sensitive material contains a substance.