JPH0534868A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance antistaticness, to attain sufficient drop of surface resistance even under low humidity, and to prevent blocking between the adjacent photosensitive materials under high temperature and high humidity. CONSTITUTION:The photographic sensitive material contains in one of the outermost layers, matting agent particles essentially comprising a polymer A for granulation and an electric charge transfer boron polymer B having N.B atomic complex structure. The polymer A is embodied by polyacrylate, polystyrene, or the like, and the polymer B is represented by formula I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material having excellent antistatic property and adhesion resistance without adversely affecting photographic characteristics.

[0002]

2. Description of the Related Art Generally, the outermost layer of a silver halide photographic light-sensitive material uses a hydrophilic colloid represented by gelatin as a binder. Therefore, the adhesiveness or tackiness of the surface of the photosensitive material increases under high temperature and high humidity atmosphere,
When it comes into contact with other objects, it easily adheres to it.

This adhesion phenomenon occurs between the light-sensitive materials, or between the light-sensitive materials and other objects in contact with the light-sensitive materials during manufacturing, storage, photographing, etc. of the light-sensitive materials, and often causes a serious failure. It was In particular, in a color light-sensitive material, since a photographic layer contains many additives such as color couplers, the adhesiveness has been a serious problem.

In order to solve this problem, the outermost layer is made to contain fine particles of an inorganic substance such as silicon dioxide, magnesium oxide, titanium dioxide and calcium carbonate, and fine particles of an organic substance such as polymethylmethacrylate, cellulose acetate propionate and fluororesin. A method has been proposed in which the surface roughness of the photosensitive material is increased to form a so-called mat and the adhesiveness is reduced.

In the silver halide color photographic light-sensitive material, it is necessary to use a large amount of matting agent for the above reasons. However, the addition of a large amount of matting agent adversely affects the photographic image quality, particularly sharpness, so that the amount of the matting agent used is limited.

By the way, the silver halide photographic light-sensitive material is
Since it generally has a support having an electrical insulation property, accumulation of electrostatic charges is also a serious problem in addition to adhesiveness. This accumulated electrostatic charge causes many obstacles, but the most serious obstacle is that when the photographic film is processed, the photosensitive emulsion is exposed by discharging the accumulated electrostatic charge before development processing. It is to form spots or dendritic or feather-like density spots. This is the so-called static mark, which significantly impairs the commercial value of photographic film and, in some cases, completely loses it.

This phenomenon becomes apparent only after development and is one of the very troublesome problems. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface and non-uniform coating. The best way to eliminate these static failures is to increase the electrical conductivity of the material so that the electrostatic charge can be dissipated in a short time before the stored charge is discharged.

Therefore, conventionally, a method of improving the conductivity of the support of the light-sensitive material and various coated surface layers has been considered, and various hygroscopic substances, water-soluble inorganic salts, surfactants, polymers and the like have been tried to be used. Came.

Examples of these are, for example, US Pat. Nos. 2,982,651, 3,428,456, 3,457,076, 3,454,625 and JP-A-55-55. No. 7762, No. 56-43636, No. 56-
Surfactants such as those described in 114944,
For example, U.S. Pat. Nos. 2,882,157 and 3,06
2,785, 3,938,999, JP-A-56-
No. 78834, No. 57-204540, No. 57-17.
There are polymers described in 9837, 58-82242 and the like.

However, it is extremely difficult to prevent the hydrophilic colloid layer from being charged with static electricity, and in the case where the known antistatic means has a low humidity and the surface resistance is not sufficiently lowered, or the photosensitive material suffers from adhesion failure at high temperature and high humidity. Often. In addition, when the hydrophilic colloid layer contains an antistatic agent (for example, a fluorine-based surfactant described in JP-B-56-44411) in an amount necessary to obtain a sufficient antistatic effect. It may adversely affect the physical properties of the film, or may flow out into the developing solution to cause sludge and the like.

[0011]

An object of the present invention is to provide a photographic light-sensitive material which has a sufficient reduction in surface resistance under low humidity, prevents adhesion between light-sensitive materials under high temperature and high humidity, and has excellent antistatic properties. It is to be.

[0012]

The above object of the present invention is to provide a photographic light-sensitive material containing a matting agent mainly composed of a polymer in at least one of the outermost layers, wherein the polymer forms a matting agent particle and a polymer (A) and a nitrogen atom. It is achieved by a photographic light-sensitive material characterized by mainly comprising at least one kind selected from the charge transfer boron polymer (B) having a boron atom complex structure.

The present invention will be described in detail below. The polymer (A) forming the matting agent particles used in the present invention has a hardness capable of retaining the particle shape at room temperature, and the preferable particle forming polymer (A) includes polyacrylic acid ester and polymethacrylic acid ester. , Polystyrene and the like, but polymethacrylic acid ester (eg, polymethylmethacrylate, polyethylmethacrylate, etc.) is particularly preferable from the viewpoint of the glass transition point and compatibility with the hydrophilic colloid which is the binder of the layer containing the matting agent.

The charge transfer type boron polymer (B) having a nitrogen-boron complex structure (hereinafter referred to as boron polymer (B)) used in the present invention has a structure represented by the following general formula [I]. A reaction product of a polar organic boron polymer and a tertiary amine is preferable, and particularly, the following general formula [II]
Alternatively, a reaction product of a semipolar organic boron polymer having a structure represented by [III] and a tertiary amine is preferable.

[0015]

[Chemical 1]

[In the formula, q is 0 or 1, and when q = 1, A represents _a- (X) _a- (Y) _b- (Z) _c -group.
Here, X and Z each represent an oxygen-containing hydrocarbon group having at least one terminal ether residue and having 100 or less carbon atoms, Y represents an —O—CO—R—CO— group (where R represents a carbon atom). Represents a hydrocarbon group of the number 1 to 82), or-
It represents an O-CO-NH-R'-NHCO- group (wherein R'represents a hydrocarbon group having 1 to 20 carbon atoms). Also,
a, b and c are 0 or 1, respectively. p is 5 to 2
It is 000. ]

[0017]

[Chemical 2]

[In the formula, q is 0 or 1, and when q = 1, B represents _a- (X) _l- (Y) _m- (Z) _n -group.
Here, X and Z each represent an oxygen-containing hydrocarbon group having one terminal ether residue and having a total number of carbon atoms of 200 or less, and Y is —O—CO—R—CO— (where R is Represents a hydrocarbon group having 1 to 82 carbon atoms) or -O
-CO-NH-R'-NHCO- (wherein R'represents a hydrocarbon group having 1 to 20 carbon atoms).

Further, l, m and n are 0 or 1 each independently. R ₁ and R ₂ are each a hydrogen atom or a substituent having 15 or less carbon atoms, and preferably a hydrogen atom. m and n are each an integer of 1 to 3,
When m and n are 2 or more, R ₁ and R ₂ may be the same or different. ]

As the tertiary amine which reacts with the semipolar organic boron polymer, those having 5 to 82 carbon atoms, particularly those having 5 to 30 carbon atoms are preferable. Further, those having at least one hydroxyl group are preferably used.

The charge transfer type boron polymer used as the antistatic agent in the present invention is a reaction between at least one semipolar organic boron polymer represented by the above general formula [I] and at least one tertiary amine. The product (however, the reaction product has a ratio of one boron atom to one basic nitrogen atom).

The semipolar organic boron polymer represented by the above general formula [I] can be produced, for example, by the following method (a) or (b). Method (a): 1 mol or more of one or more compounds represented by the following general formula [IV] in total, and 1 mol of boric acid or a boric acid triester of a lower alcohol having 4 or less carbon atoms. Alternatively, a triester reaction is carried out by reacting 0.5 mol of boric anhydride.

[0023]

[Chemical 3]

[In the formula, q is 0 or 1, and when q = 1, A represents _a- (X) _a- (Y) _b- (Z) _c- group.
However, X and Z each represent an oxygen-containing hydrocarbon group having 100 or less carbon atoms having one terminal ether residue, and Y
Is -O-CO-R-CO- (wherein R is 1 to 1 carbon atoms).
82, preferably a hydrocarbon group of 6 to 82)
Alternatively, -O-CO-NH-R'-NHCO- (however,
R'represents 1 to 20 carbon atoms, preferably 5 to 15
Represents a hydrocarbon group of). a, b and c are each 0 or 1]

Method (b): Poly (etherification) of di (glycerin) -borate or di- (glycerin) -borate containing an intermediate di (glycerin) -borate residue having 206 or less carbon atoms, or one or more diols having 10 to 100 carbon atoms. The reaction is carried out or the number of carbon atoms is 3 to 84, preferably 8 to 1 per 1 mol or more of 1 or 2 or more.
84 dicarboxylic acid (hereinafter referred to as predetermined dicarboxylic acid) or ester of lower alcohol having 4 or less carbon atoms and predetermined dicarboxylic acid, halide of predetermined dicarboxylic acid or 4 to 15 carbon atoms, preferably 8 1 to 2 or more of 15 to 15 diisocyanates (hereinafter, referred to as a predetermined diisocyanate) in total 1
Mole react.

One or more kinds of the semipolar organic boron polymer (hereinafter referred to as a predetermined semipolar organic boron polymer) thus prepared and 5 to 82 carbon atoms having at least one hydroxyl group. , Preferably 5 to 30 tertiary amines (hereinafter, referred to as predetermined tertiary amines), and one or more kinds thereof, so as to have one boric acid atom and one basic nitrogen atom. In proportion
Charged in a closed or open type reactor, under normal pressure, 20 to 20
When the reaction is carried out at 200 ° C., preferably 50 to 150 ° C., the antistatic agent used in the invention (hereinafter referred to as a predetermined charge transfer type boron polymer) is produced. At that time, if a polar solvent such as alcohol, ether, or ketone is made to coexist, the reaction can be carried out more easily.

The raw materials for deriving the predetermined charge transfer type boron polymer used in the present invention and the predetermined semipolar organic boron polymer as an intermediate thereof are as follows. First, as the compound represented by the general formula [IV], which is a raw material of the method (a) leading to a predetermined semipolar organic boron polymer,
For example, diglycerin, di (glycerin) -malonate, di (glycerin) -maleate, di (glycerin)
-Adipate, di (glycerin) -terephthalate, di (glycerin) -dodecanaate, poly (9 mol) oxyethylene-di (glycerin ether), di (glycerin) -tolylene dicarbamate, di (glycerin) -methylenebis (4-) Phenyl carbamate) and the like.

On the other hand, the predetermined dicarboxylic acid in the method (b) is derived from, for example, malonic acid, maleic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, dodecane diacid, linoleic acid. Dimer acid, dodecylmaleic acid, dodecenylmaleic acid, octadecylmaleic acid, octadecenylmaleic acid, maleic acid having a polybutenyl group having an average degree of polymerization of 20 linked thereto and the like. Examples of the isocyanate include ethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate and methylenebis (4-phenylisocyanate).

Next, as the predetermined tertiary amine to be reacted with the predetermined semipolar organic boron polymer, for example, diethyl-hydroxymethylamine, dimethyl-2-hydroxypropylamine, methyldi (2-hydroxyethyl-amine, triethyl) is used. Ethylene oxide of (2-hydroxyethyl) amine, hydroxymethyl-di (2-hydroxyethyl) amine, dibenzyl-2-hydroxypropylamine, cyclohexyl-di (2-hydroxyethyl) amine, di (hexadecyl) amine (1-25 mol ) Adducts, propylene oxide (1-26 mol) adducts of monobutylamine, and the like.

In the context of the present invention, the amine raw material to be reacted with the predetermined semi-polar organic boron polymer is of a type other than the predetermined tertiary amine, that is, a primary or secondary amine is used as the charge transfer type boron polymer. Is not produced successfully, and even if it is produced, it becomes an unstable compound, so that there is a difficulty in developing and maintaining conductivity.

Specific preferred examples of the boron polymer (B) used in the present invention are shown below, but the present invention is not limited to these examples.

[0032]

[Chemical 4]

[0033]

[Chemical 5]

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

Boron polymer (B) used in the present invention
Regarding, for example, “Plastic Age” 1987,
The details are described in February, March, May, JP-A-1-266153, etc., and these can also be used.

The polymer contained in the matting agent particles used in the present invention is mainly composed of the above-mentioned polymer (A) and boron polymer (B), and other polymers are also within the range not impairing the object of the present invention. Although it may exist, it is preferable that the polymer (A) and the boron polymer (B) substantially consist, and it is most preferable that both of these polymers are contained. Specifically, in the polymer contained in the matting agent particles, the total ratio of the polymer (A) and the boron polymer (B) in the polymer is preferably 90% by weight or more.

In the matting agent particles used in the present invention, it is preferable that the polymer (A) and the boron polymer (B) are in a mixed state, that is, a so-called polymer blend. The mixing ratio of both polymers is appropriately 0.001 to 10% by weight, and particularly preferably 0.01 to 5% by weight, of the boron polymer (B) with respect to the polymer (A). It is sufficient that the boron polymer (B) is in an amount enough to coat the surface of the matting agent particles, and therefore, the preferable amount also depends on the particle diameter of the matting agent.

The boron polymer (B) according to the present invention
Of the polymer (A) for forming the matting agent particles does not easily separate the concentrated boron polymer (B) from the matting agent particles and flow out into the developing solution. Is expected to improve. The matting agent particles used in the present invention may contain a compounding agent (for example, a plasticizer such as dioctyl phthalate, a fluorosurfactant, etc.) in addition to the above polymer.

The matting agent used in the present invention is, for example, a polymer (A) and a boron polymer dissolved in a low boiling point organic solvent such as a mixed solvent of ethylene acetate, butanol and ethyl acetate or a mixed solvent of butanol and methanol. It is formed by dispersing the solution with (B) in an aqueous gelatin solution under rapid stirring.

The size of the matting agent used in the present invention is
It can be freely changed within a considerable range, but 0.2 ~
The range is preferably 10 μm, particularly 0.5 to 5 μm. A gelatin aqueous solution containing the matting agent obtained as described above,
It can be coated as the outermost layer of a photographic light-sensitive material by any method known in the photographic field.

The outermost layer in the present invention means the layer farthest from the support in the hydrophilic colloid layer coated and dried on the support in the finished product or intermediate product of the photographic light-sensitive material. It may be either the layer side or the back layer side. The outermost layer is, for example, a surface protective layer, a back layer composed of one layer, a non-photosensitive intermediate layer which is the outermost layer of an intermediate product in a multilayered light-sensitive material subjected to multilayer coating. In the present invention, it is preferable that the polymer (B) used in the present invention is contained in the surface protective layer.

In the present invention, the outermost layer containing the matting agent according to the present invention has the surface of the layer matted or roughened by the matting agent. This matting is performed not only when the protrusions on the outermost layer surface are composed of a matting agent material and the matting agent is exposed on the surface of the protrusions, but the matting agent surface is the outermost layer composition other than the matting agent. By the entrained particles protruding on the surface of the outermost layer,
It also includes the case where the surface of the protrusion is made of the outermost layer material.

In the present invention, the average particle size of the matting agent is preferably 0.1 to 10 μm, more preferably 0.
Although it is 5 to 8 μm, when the matting agent is mixed with the binder of the outermost layer, the particle size of the matting agent may be larger than the dry film thickness (the film thickness of the portion having no protrusion due to the matting agent). From the viewpoint of antistatic effect, it is particularly preferable that the particle size of the matting agent used in the present invention is 2 times or more, more preferably 2.5 times or more, larger than the dry film thickness. The matting agent used in the present invention has an outermost layer of 50 to 500 m per 1 m ² .
g, particularly 100 to 400 mg is preferably contained.

In the present invention, examples of the hydrophilic colloid binder constituting the outermost layer include gelatin, gelatin derivatives (eg acetylated gelatin, phthalated gelatin, etc.), albumin, collodion, etc., among which gelatin is particularly preferable. Further, in the present invention, various additives such as a hardener, a smoothing agent, a surfactant, an antistatic agent, a thickener and a polymer latex can be contained in the outermost layer, if necessary.

Examples of the hardener include aldehyde compounds, 2-hydroxy-4,6-dichloro-1,3,5-
A compound having a halogen such as triazine, a vinyl sulfone compound, an N-methylol compound, a halogen carboxaldehyde compound such as mucochloric acid, and the like can be used. As the leveling agent, for example, liquid paraffin, waxes, polyfluorinated hydrocarbons, silicones and the like can be used.

Examples of the surface active agent include natural surface active agents such as saponin, nonionic surface active agents such as alkylene oxides, higher alkyl amines, cationic surface active agents such as quaternary ammonium salts, carboxylic acids and sulfonic acids. Any of the anionic surfactants containing an acidic group can be used.

As the antistatic agent, the above-mentioned surfactants,
Alkali metal salts such as fluorine-based surfactants, styrene-maleic acid-based copolymers and acrylonitrile-acrylic acid-based copolymers described in US Pat. No. 3,954,924,
Furthermore, US Pat. Nos. 3,206,312 and 3,4
The antistatic agent described in 28,451 specification can be contained.

In the present invention, a known matting agent such as an alkali-insoluble matting agent made of silicon dioxide, polymethylmethacrylate, polytetrafluoroethylene or the like or MMA.
/ MAA and EMA / MAA can be used in combination.

When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material, the silver halide emulsion used in the photographic light-sensitive material can be a normal single jet method, a double jet method,
It can be prepared by any method such as an acidic method, an ammonia method, a neutral method and the like, and there is no particular limitation on the shape, size and size distribution of silver halide grains. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like can be used.

Examples of the hydrophilic colloid binder used in the silver halide emulsion include gelatin, modified gelatin, gelatin derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, poly-N-pyrrolidone, polyacrylic acid copolymer, and polyacrylic acid copolymer. Examples thereof include acrylamide and the like, and these may be used alone or in combination of two or more.

Further, a layer-like water-dispersed vinyl compound may be contained in the layer (photographic constituent layer) coated on the support of the photographic light-sensitive material according to the present invention. As such a latex, a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride or the like is used.

The silver halide emulsion in the present invention can be chemically sensitized by a conventional method. For example, gold compounds as shown in US Pat. Nos. 2,399,083 and 2,597,856, and salts of precious metals such as platinum, palladium, rhodium and iridium, US Pat. No. 410,689, No. 3,501,313, and other sulfur compounds, and other stannous salts,
It can be chemically sensitized with amines and the like.

A stabilizer or an antifoggant can be added to the silver halide emulsion of the present invention. For example, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-
In addition to phenyl-5-mercaptotetrazole, many compounds such as many heterocyclic compounds, mercury-containing compounds, mercapto compounds and metal salts can be used.

Various spectral sensitizing dyes such as merocyanine dyes, carbocyanine dyes and cyanine dyes can be used in the silver halide emulsion of the present invention depending on the purpose. In the present invention, 4-equivalent methylene yellow couplers, 2-equivalent diketomethylene yellow couplers, 4-equivalent or 2-equivalent pyrazolone magenta couplers, indazolone magenta couplers, α-naphthol cyan couplers and phenols are used as color couplers. A cyan coupler can be used. Also, so-called DIR couplers and polymer couplers can be used.

Further, the photographic constituent layer of the photographic light-sensitive material of the present invention may contain a dye, an ultraviolet absorber, the above-mentioned hardener, a surfactant, and further a polymer latex. As the support of the photographic light-sensitive material of the present invention, any of those commonly used in the art such as cellulose acetate film, polyethylene terephthalate film, baryta paper or paper coated with α-olefin polymer can be used.

The photographic constituent layers of the photographic light-sensitive material of the present invention include dip coat, air knife coat, curtain coat,
Various methods such as extrusion coating can be used to apply one layer at a time or multiple layers at the same time. Regarding the above-mentioned various additives, vehicles, supports, coating methods and the like that can be used in the present invention, Product Licensing Index (Product License Index)
g Index, 92, 107-110 (1
The description in Dec. 971) can be referred to.

The exposure light source of the photographic light-sensitive material of the present invention is not particularly limited, and from low illuminance to high illuminance.
Further, as the exposure time, any of several tens of seconds to 10 ⁻⁶ seconds can be used. Examples of the photographic light-sensitive material to which the present invention can be applied include black-and-white photographic light-sensitive materials, color photographic light-sensitive materials, and silver halide photographic light-sensitive materials for general use, printing, X-ray, radiation, etc. Specific examples thereof include all silver halide photographic light-sensitive materials such as black and white negative films, papers, reversal photographic light-sensitive materials and so-called external color photographic light-sensitive materials containing a color former in the processing liquid. In addition, the present invention is effective as long as it is a photographic light-sensitive material having a hydrophilic colloid layer as the outermost layer.

When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material, the developing treatment for forming a dye image after exposure basically includes at least one color developing step, Therefore, the pre-hardening step, the neutralizing step, and the first developing (black and white developing) step are included. The above-mentioned steps and the subsequent steps (for example, bleaching, fixing, bleach-fixing, intensifying, stabilizing,
Selected combinations such as washing with water) are treated at 30 ° C. or higher, particularly preferably 35 ° C. or higher.

The color developer contains p-phenylenediamines (eg, N, N-diethyl-p-phenylenediamine, N, N-diethyl-3-methyl-p-) as a developing agent.
Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-metasulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline, N-ethyl-N-β -Hydroxyethyl-p-phenylenediamine) or salts thereof (eg hydrochloride, sulphate, sulphite) US Pat.
3,015, 2,592,364, JP-A-48.
Compounds described in, for example, -64933 can be used.

The color developing solution may further contain salts such as sodium sulfate, pH adjusting agents such as sodium hydroxide, sodium carbonate, sodium phosphate and the like, buffers (for example, acids such as acetic acid and boric acid or salts thereof), and a developing agent. Accelerator (for example, various pyridinium compounds described in US Pat. Nos. 2,648,604 and 3,671,247, cationic compounds, potassium sulfate, sodium nitrate,
US Pat. Nos. 2,533,990 and 2,577,1
No. 27, No. 2,950,970 and the like, polyethylene glycol condensates and derivatives thereof, British Patent Nos. 1,020,032, 1,020,03.
Nonionic compounds such as polythioethers represented by the compounds described in U.S. Pat.
A polymer compound having a sulfite ester as typified by the compounds described in No. 68,097, other organic amines such as pyridine and ethanolamine, benzyl alcohol, hydrazine and the like) may be included.

The color developer further contains an antifoggant (eg, alkali bromide, alkali iodide, nitrobenzimidazoles, benztriazole compounds, mercaptotetrazole compounds, etc.), US Pat. No. 3,161,51.
4, British Patents 3,161,514 and 1,144
No. 481, etc., stain or sludge inhibitor, multi-layer effect accelerator known in US Pat. No. 3,536,487, preservative (for example, sulfite, acidic sulfite, hydroxylamine hydrochloride). , Formaldehyde-
Alkanolamine sulfite adducts, etc.).

The pre-hardening liquid used in the pre-hardening step is an aldehyde which hardens gelatin used as a hydrophilic colloid in a photographic light-sensitive material (eg, US Pat.
No. 232,761 and other aliphatic aldehydes, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, pyruvaldehyde, etc., and US Pat. Nos. 3,565,632 and 3,3.
An aqueous solution containing one or more of the aromatic aldehydes described in the specification such as 667,760 can be used. This solution has a pH of inorganic salts such as sodium sulfate, borax, boric acid, acetic acid, sodium acetate, sodium hydroxide, sulfuric acid, etc.
An antifoggant such as a regulator, a buffer, and an alkali halide (eg, potassium bromide) can be included.

Into the neutralization bath used in the neutralization step, an inorganic salt, a pH adjusting agent, a buffering agent and the like can be added in addition to the aldehyde removing agent such as hydroxyamine and L-ascorbic acid. In the first development step of the color reversal film, hydroquinone, 1-phenyl-3-pyrazolidone, N-
An alkaline aqueous solution containing one or more developing agents such as methyl-p-aminophenol can be used, and other inorganic salts such as sodium sulfate and pH adjusting agents such as borax, boric acid, sodium hydroxide and sodium carbonate. Or a buffering agent, an alkali halide (eg, potassium bromide, etc.), and other development antifoggants.

The various additives and their addition amounts exemplified in the above processing steps are well known in the color photographic processing method. Known compounds as bleaching agents used in bleaching baths and bleach-fixing baths, such as ferricyanates, dichromates, water-soluble iron (III) salts, water-soluble cobalt (III) salts, water-soluble steel (II) Salt, water-soluble quinones,
Nitrosophenol, iron (III) cobalt (II
I), a complex salt of a polyvalent cation such as copper (II) and an organic acid, for example, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, malonic acid, and tartaric acid. , Malic acid, diglycolic acid, dithiodiglycolic acid and other metal complex salts and 2,6-dipicolinic acid copper complex salt, peracids such as alkyl peracids, persulfates and permanganates,
Hydrogen peroxide, hypochlorite, chlorine, bromine, coconut powder, etc. may be used alone or in an appropriate combination.

These baths also include other US Pat.
No. 2,520, No. 3,241,966 and Japanese Patent Publication No. 45
The bleaching accelerators described in JP-A-8506 and JP-A-45-8836 may be added. A known fixing solution can be used for fixing. That is, as the fixing agent, ammonium, sodium, and potassium salts of thiosulfate are used in an amount of about 50 to 200 g / liter, and in addition, stabilizers such as sulfite and isomeric bisulfite, and hardeners such as potassium alum. PH buffers such as acetate, borate and the like can be included. Bleaching agents, fixing agents and bleach-fixing baths are described in US Pat.
The technique described in the No. 322 specification can be applied.

As the intensifying liquid, an intensifying liquid prepared by a method using a Co (III) salt, a method using hydrogen peroxide, or a method using chlorous acid can be used. Regarding the image stabilizing bath, US Pat. Nos. 2,515,121 and 3,14
The method described in the specification of No. 0,177 can be used.

[0070]

EXAMPLES Next, synthesis examples, examples and comparative examples will be given in order to explain the present invention more specifically, but the examples are not limited to these examples. In addition, all% described in each example represent% by weight.

[Synthesis Example] In a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a gas inlet, 10 g of methyl methacrylate (hereinafter abbreviated as MMA), acetone and toluene (17.5%, 82. 5%) 60g
After being degassed with oxygen gas for 1 hour, 0.5 g of azobis or isobutyrotolyl (hereinafter abbreviated as AIBN) as a polymerization initiator was added under reflux to initiate polymerization. Then 4.
After 5 hours, 10 g of boron polymer (B) dissolved in 90 g of MMA and 20 g of acetone shown in Table 1 was added dropwise.
IBN (1.5 g) was added every 1.5 hours in three times, and the mixture was refluxed for 2 hours to obtain a polymer. Polymers (1) to (3) were obtained as the polymer.

(Production Example 1) 80 g of the polymer (1) obtained in Synthesis Example 1 was dissolved in a mixed solvent of 190 g of ethyl acetate and 60 g of n-butanol at 40 ° C. Further, 1.0 g of sodium dodecylbenzenesulfonate was dissolved in 40 g of water. Further, 40 g of gelatin was placed in a 500 ml beaker, 320 g of water was added, and the mixture was swollen for 30 minutes and then dissolved at 60 ° C.

Next, a gelatin solution and an aqueous solution of sodium dodecylbenzenesulfonate were placed in a three-necked flask having an internal volume of 1 liter, and then heated to 35 ° C.
A solution of the polymer (1) dissolved in advance was put therein and stirred at a speed of 1000 rpm for 20 minutes. As a result of observing the obtained emulsion with an optical microscope, it was 2 to 5 μm.
m polymer oil droplets were observed. 1 this emulsion
The solvent was removed by drying under reduced pressure at 00 mmHg and 45 ° C. Then, the matting agent (1) having a particle size of 2 to 5 μm was obtained by centrifugation.

(Production Example 2) 80 g of the polymer (2) obtained in Synthesis Example 1 was treated in the same manner as in Production Example 1, and the particle size was 2 to 4 μm.
m matting agent (2) was obtained. (Production Example 3) 80 of the polymer (3) obtained in Synthesis Example 1
g was treated in the same manner as in Production Example 1 to obtain a matting agent (3) having a particle size of 2 to 4 μm.

Example 1 300 g gelatin per mol silver halide,
And, as a yellow coupler, α-pivaloyl-α-
(1-Benzylimidazolidine-2,4-dione-3-
Yl) -2-chloro-5 [γ- (2,4-tert-aminophenoxy) butyramide] acetanilide.
Blue-sensitive silver iodobromide for color (containing 7 mol% of silver iodide) containing 5 × 10 ^-2 mol and 0.02 g / 1 g of 1,2-bis (vinylsulfonyl) ethane gelatin as a hardener.
The emulsion was adjusted.

Further, for the protective layer, the matting agents (1) to (3) used in the present invention and the particle size of 2 to 4 μm for comparison.
A matting agent (A) composed of polymethylmethacrylate of m, a hardening agent and a coating aid were added in the amounts shown in Table 1 to provide an undercoat layer by the slide hopper method at the coating amount shown in Table 1. An emulsion layer and a protective layer were coated on a cellulose triacetate film support in this order from the support side to obtain sample (1), sample (2), sample (3) of the present invention and comparative sample (A).

A comparative sample (B) containing no matting agent
Also made. The dry thickness of the protective layer was 1.5 μm. For each sample in Table 1, cut into two pieces each having a size of 5 cm square, and at 23 ° C. and 80 ° C. so as not to contact each other.
After storing the sample in an atmosphere of% RH for 1 day, two protective layers of the same sample were brought into contact with each other, a load of 800 g was applied, the sample was stored in an atmosphere of 40 ° C. and 80% RH, and then the sample was peeled off. The area of the bonded portion was measured to measure the adhesion resistance.

The evaluation criteria are as follows. Rank Area of bonded portion A 0 to 20% B 21 to 40% C 41 to 60% D 61% or more The above results are shown in Table 1.

[0079]

[Table 1]

From the results shown in Table 1, it can be seen that the matting agent used in the present invention is superior in adhesion resistance to the conventional one.

Example 2 The samples (1), (2) and (3) of the present invention and the comparative samples (A) and (B) were examined for antistatic property and devitrification property by the following method. The unexposed sample was conditioned at 25 ° C. and 25% RH for 2 hours, rubbed the emulsion surface side of the sample with a neoprene rubber roller in a dark room under the same air conditioning conditions, and then developed, bleached and fixed with the following processing solution. After washing with water and stabilization, the degree of generation of static marks was examined.

Treatment process Humidity Treatment time (1) Current image 38 ° C. 3 minutes 15 seconds (2) Bleaching 38 ° C. 4 minutes 30 seconds (3) Fixed 38 ° C. 4 minutes 20 seconds (4) Washing with water 38 ° C. 3 minutes 15 seconds (5) Stabilization 38 ° C. 1 minute 5 seconds Each composition of the developing solution, the bleaching solution, the fixing bath and the stabilizing bath is as follows.

[Developer] (pH = 10.05) Hydroxylamine sulfate 2.5 g 4-Amino-3-methyl-N- (β-hydroxyethyl) -aniline sulfate 4.56 g Diethylenetriaminohexaacetic acid 4.75 g Potassium carbonate 30.3 g Sodium sulfite 4 g Water is added to make 1 liter.

[Bleaching bath] (pH = 5.70) Ammonium bromide 173 g 80% acetic acid 20 ml EDTA FeNH ₄ 103 g EDTA 27 g Water is added to make 1 liter.

[Fixing bath] (pH = 6.50) Ammonium thiosulfate 800 ml Sodium sulfite 4.6 g Sodium bisulfite 5.0 g Water is added to make 1 liter.

[Stabilizing bath] (pH = 7.30) 40% formalin 6.6 ml 50% polyoxyethylated lauryl alcohol 0.6 ml Add water to make 1 liter.

The devitrification property was visually evaluated. Table 2 shows the test results of the antistatic property and the devitrification property of these samples. Table 2
The evaluation of the degree of occurrence of static marks is as follows: A: The generation of static marks is not recognized at all. B: Generation of static marks is slightly observed. C: Generation of static marks is considerably recognized. D: Generation of static marks is recognized almost all over the surface. It was carried out in four steps.

[0088]

[Table 2]

As is clear from Table 2, the samples which were antistatic with the matting agent according to the present invention had an excellent antistatic effect in which the generation of static marks was hardly observed, and the devitrification of the film was observed. There is no.

[0090]

In the photographic light-sensitive material of the present invention, the boron polymer (B), which has been transferred to the surface of the matting agent particles of the matting agent particle forming polymer (A) and concentrated, easily separates from the matting agent particles and is contained in the developing solution. It has excellent adhesion resistance and antistatic property because it does not flow out into the air, and the drawbacks of the technology using conventional antistatic agents (the antistatic effect is insufficient at low humidity, and adhesion failure occurs at high temperature and high humidity). In some cases, when used in an amount sufficient for antistatic purposes, the physical properties of the film are reduced, and sludge is generated in the development processing solution, and the film is devitrified.

Claims (1)

Claim: What is claimed is: 1. A photographic light-sensitive material containing a matting agent mainly composed of a polymer in at least one of the outermost layers, wherein the polymer forms a particle of the matting agent and a nitrogen atom-boron. A photographic light-sensitive material, which is mainly composed of at least one kind selected from a charge transfer boron polymer (B) having an atom complex structure.