JPS60260038A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the adhesion resistance and antistatic property by using a matting agent made of a copolymer constituting a monomer contg. fluorine and methacrylic acid or acrylic acid as copolymerizable components. CONSTITUTION:When a silver halide photosensitive material contg. a matting agent in the top layer is manufactured, the matting agent is made of a copolymer constituting a monomer contg. fluorine and methacrylic acid or acrylic acid as copolymerizable components. The monomer contg. fluorine is a compound represented by the formula (where R is H, methyl or F preferably substituted methyl, Rf is F substituted straight chain, branched or cyclic alkyl, preferably 1-10C alkyl, and a group such as hydroxy or other atom such as Cl or Br may be used in place of F in Rf). The resulting silver halide photosensitive material has superior adhesion resistance and a satisfactory antistatic property, and when the material is processed, a high quality image with high transparency is formed.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a photographic material having excellent antistatic properties and adhesive resistance without adversely affecting photographic properties, etc. It is related to f(--e-≠←4Je4-photosensitive materials).

[Prior art]

Generally, the outermost layer (uppermost layer or back layer) of a silver halide photographic light-sensitive material (hereinafter simply referred to as light-sensitive material) uses a hydrophilic colloid typified by gelatin as a binder. Therefore, when the surface of a photosensitive material is in a high temperature and high humidity atmosphere, its adhesion or tackiness increases, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between photosensitive materials or between photosensitive materials and objects in a pond that come into contact with them during manufacturing, storage, and photographing.
This often resulted in serious failures. Particularly in color photosensitive materials, adhesiveness has been a major problem because the photographic layer contains many additives such as color couplers.

To solve this problem, the top layer or back layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, and calcium carbonate, and organic substances such as polymethyl methacrylate, cellulose acetate propionate, and fluorine resin. A method has been proposed in which the roughness of the surface of the photosensitive material is increased to create a so-called matte appearance and to reduce adhesiveness. In color light-sensitive materials, it is necessary to use a large amount of matting agent for the reasons mentioned above.

However, the above-mentioned matting agent is insoluble in the alkaline processing solution and remains in the photosensitive material even after processing, so if a large amount of the matting agent is used, it may adversely affect the transparency of the formed painter or the image quality. There are drawbacks that can damage the

In order to avoid such problems, matting agents have been proposed that are insoluble in neutral or acidic solutions and soluble in alkaline 11-based solutions. For example, U.S. Patent No. 2.992.101
In this issue, methyl methacrylate (hereinafter referred to as
It is proposed to use a copolymer with a molar ratio of MMA (hereinafter referred to as "MAA")/methacrylic acid (hereinafter referred to as "MAA") of 1/1. Another drawback is that a large amount of the matting agent dissolves, especially in the coating process during the production of photosensitive materials in which a matting agent-containing coating solution is coated and dried. In order to improve this drawback, U.S. Patent No. 3.76
In No. 7.448, MMA/MAA=1/1 (molar ratio)
When using a matting agent, a technique using demineralized gelatin or deionized gelatin is disclosed. Here, the matting agent made of a copolymer with free carboxyl groups dissolves during the coating process because the calcium ions contained in gelatin and the matting agent form a salt, and therefore the gelatin is deionized or deashed. It is said that it needs to be processed. However, gelatin treated in this way generally lacks coating suitability and may cause coagulum or so-called "Ii-shiki", and gelatin processing also increases costs, making it impractical. do not have.

On the other hand, in Special Publication No. 57-9054, MMA/MA
A matting agent is disclosed in which A is about 674 to 9/1 (molar ratio). When the ratio of MMA/MAA is within this range, sufficient matting properties can be obtained without the matting agent being dissolved during the coating process, but if a mixture of butanol or a solvent containing butanol as a main component is used as a solvent. However, since a large amount of butanol remains without being completely removed even after washing the dispersion, it has the disadvantage of emitting an unpleasant odor.
A copolymer of ethyl methacrylate (hereinafter abbreviated as DMA) and MAA (MAA) is used as a matting agent that dissolves in ethyl acetate.
A one-piece agent using (containing (2) weight percent) has been proposed. However, EMA/MAA copolymer is MM
Compared to the A/MAA copolymer, the glass transition point (hereinafter referred to as Tg
It has the disadvantage that it is difficult to obtain sufficient matte properties due to the low matteness.

Incidentally, silver halide photographic materials generally consist of a support having electrical insulation properties, and therefore, in addition to adhesion, accumulation of electrostatic charges also poses a major problem.

This accumulated electrostatic charge causes a number of problems, but the most important one is that the photosensitive emulsion layer is sensitized by the discharge of the accumulated electrostatic charge before processing, which makes the photographic film visible. When treated, it produces punctate spots or dendritic or feather-like streaks. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, and in some cases completely destroys it.This phenomenon only becomes apparent after it is developed, and is one of the most troublesome problems. It is one. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or inability to apply uniformly.

The best way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be quickly dissipated before the accumulated charge is discharged.

Therefore, methods of improving the conductivity of supports and various coated surface layers of photosensitive materials have been considered, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, surfactants, polymers, and the like. Examples of these include, for example, U.S. Patent No. 2.982.651, U.S. Patent No. 3.428.456, U.S. Pat.
No. 55-7762, 56-43636, 5
6-114944, etc., for example, US Pat. No. 782.882.157, US Pat.
062,785, 3.938.999, JP 56-78834, JP 57-204540, JP 57-1
79837, No. 58-82242, etc. [Object of the Invention] The object of the present invention is to solve the above-mentioned disadvantages associated with matting due to a matting agent for reducing adhesion, and disadvantages caused by addition of an antistatic agent. It is an object of the present invention to provide a photographic photosensitive material with improved properties and excellent adhesion resistance and anti-edge resistance.

An object of the present invention is to provide a silver halide photographic material containing a matting agent in at least one outermost layer, in which the matting agent is substantially made of a copolymer containing the following (n and) as copolymer components. - Achieved by ±≠7P photographic light-sensitive materials.

(5) Fluorine-containing monomer (B) At least one fluorine-containing monomer selected from the group consisting of methacrylic acid and acrylic acid (A is a compound represented by the following general formula [■]).

General formula [I] CH, == C OORf In the formula, R represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom, and Rf is a linear, branched or cyclic alkyl group substituted with a fluorine atom. This alkyl group preferably has 1 to 10 carbon atoms and may be substituted with groups or atoms other than fluorine atoms, such as hydroxy groups, halogen atoms (e.g. CIJ , Br, etc.). In addition, this alkyl group may have a linking group such as an oxo group or a thio group interposed between the carbon chains.

The copolymer (hereinafter referred to as the copolymer of the present invention) comprising the above (5) and (2) as copolymerization components is a fluorine-containing monomer (4) of lO to closed molti, methacrylate of 10 to (a) molti of at least one monomer selected from the group consisting of acid and acrylic acid), as well as a compound having a vinyl group that can be copolymerized with It is preferable that there be.

Among the fluorine-containing monomers represented by the general formula [I], representative examples of those preferably used in the present invention are shown below. integer (II)
-2 CI4゜CH,=C C00CH2(CF,)nHn = integer from 2 to 9 (f
f)-a CH.

CH,=　Cn　=　Integer from 2 to H ■ C00CH,CH,0(CF,)nF (II)-4 (n)-5 (n)-6 CH=CH C00CH,CH7(CF,)nF n = integer from 2 to 8 (n)-7 CH, -CH (n)-8 H8 CH,=C C00CHCFHCF.

C,H.

(n)-9 CH3 (Q is a monomer and a compound having a vinyl group that can be copolymerized with (B), such as acrylic esters such as methyl acrylate, ethyl acrylate, 'butyl acrylate, cyclohexyl acrylate, methyl Methacrylic acid esters such as methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and sulfoglopyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; methyl vinyl ketone; Examples include vinyl ketones such as ethyl vinyl ketone, styrenes such as styrene, methylstyrene, and chloromethylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, and imprene.

Two or more types of each of the above (4), (B) and (Q) can be used.

Specific examples of the copolymer used as the matting agent of the present invention will be given below.

1゜ 6.0H.

7.0H.

ridge 8.CH.

13, CH3 1 14.CH.

15, CHs 16, CHs 17.CH 20, CH.

Shiri υshi 1-1. ni", L;F'HυF, L;tJ
LJL:l-1,L:LJ(JM22゜23゜24゜25゜26゜28゜29゜30゜32゜The copolymer of the present invention can be produced by conventionally known solution polymerization, bulk polymerization,
0, which can be easily synthesized by methods such as suspension weighting.
For example, in solution polymerization, a mixture of two or three monomers at an appropriate concentration (usually 40% or less relative to the solvent, preferably ' ilO~25 heavy forging #stable 2
or a mixture of three monomers) in the presence of a polymerization initiator (e.g. benzoyl peroxide, azobisisobutyronitrile, etc.) at a suitable temperature (e.g. 40-120°C, preferably 50-100°C). ), a copolymerization reaction is carried out. Thereafter, the reaction mixture is poured into a medium such as water, the product is precipitated, and the unreacted mixture is separated and removed by drying.The copolymer used as the matting agent of the present invention has a molecular weight of 25"C. Intrinsic viscosity in ethanol 0.04-0.40 m17.9
Preferably the sail is 08 to 0.25 rnl/l/.

The matting agent according to the present invention consists essentially of the copolymer of the present invention, but here, "substantially" means that it does not interfere with the effects of the present invention. This means that there is no problem even if it contains substances.

The matting agent of the present invention is finely dispersed and contained in the outermost layer of the photosensitive material. ), butanol-containing methanol (less than 50% by weight of butanol), etc., by dispersing a solution of the copolymer in an aqueous gelatin solution under rapid stirring. The size of the matting agent of the present invention can vary in free VC within a considerable range, but in the present invention a range of 0.2 to 10 .mu.m, particularly 0.5 to 5 .mu.m is preferred. The aqueous gelatin solution containing the matting agent obtained above can be applied as the outermost layer of the light-sensitive phase material by any method known in the photographic field.

In the present invention, the outermost layer refers to, for example, a surface reinforcing layer, a back layer, a non-photosensitive intermediate layer of a final product in a multilayer photosensitive material coated with a multilayer coating, or all of them. It is preferable that the protective layer contains a matting agent.

The matting agent of the present invention is applied to the outermost layer at a rate of 50 to 50 s per square meter.
It is preferable to contain o om9, especially 100 to 400 ++I&.

In the present invention, examples of the hydrophilic colloid binder constituting the outermost layer include gelatin, gelatin derivatives (
Examples include acetyl gelatin, phthalated gelatin, albumin, and collodion, with gelatin being particularly preferred.

Furthermore, in the present invention, the outermost layer may contain various additives such as a hardening agent, a smoothing agent, a surfactant, an antistatic agent, a thickener, and a polymer latex, if necessary.

Examples of hardening agents include aldehyde compounds, active halogen fM compounds such as 2-hydroxy-4,6-dichloro-1,3,5-to-11azine, vinyl sulfone compounds, N-methylol compounds, and mucochlor. A halogen carboxaldehyde formulation such as an acid can be used. As the smoothing agent, for example, fluidized rosette in, waxes, polyfluorinated hydrocarbons, silicones, etc. can be used. Examples of surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxides, cationic surfactants such as higher alkylamines and quaternary ammonium salts, and acidic groups such as carboxylic acids and sulfonic acids. Any anionic surfactant containing the following can be used. Examples of antistatic agents include the above-mentioned surfactants, alkali metal salts such as styrene-maleic acid copolymers and acrylonide-11-acrylic acid copolymers, and U.S. Pat. ．．
The antistatic agent described in No. 428,451 may be included.

In the present invention, a well-known matting agent such as an alkali-insoluble matting agent made of silicon diacid, polymethacrylate, etc. or MMA/MAAXF! An alkali-soluble matting agent consisting of MA/MAA can be used in combination. However, since the known alkali-insoluble matting agents remain in the photographic material after processing, it is preferable to use them in smaller amounts than the matting agents of the present invention, for example, at a concentration of 501n9 m/m2.

The halomonosilver emulsion used in the light-sensitive material of the present invention can be produced by any method such as the usual single-jet method, double-jet method, acidic method, ammonia method, or neutral method. There are no particular restrictions on the shape, size and size distribution of the particles. As the silver halogen, silver chloride, silver chloride, silver iodobromide, silver chloride iodobromide, etc. can be used.

Hydrophilic colloid binders used in halomono-silver emulsions include gelatin, modified gelatin, seratin derivatives, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, poly(N-pyro-11 tons), and polyacrylic acid. Examples include polymers, polyacrylamide, etc., and these may be used alone or in combination of two or more.

Further, a latex-like water-dispersed vinyl compound can also be contained in the photographic constituent layer of the light-sensitive material according to the present invention. Such latexes include alkyl acrylates,
Alkyl acrylate, acrylic acid, methacrylic acid,
Homo or copolymers of glycidyl acrylate, styrene, vinyl chloride, dichloride and vinylidene are used.

The silver halide emulsion in the present invention can be chemically sensitized by conventional methods7, for example, U.S. Pat.
No. 83, No. 2,597.856, etc., as well as salts of noble metals such as platinum, palladium, rhodium, and i1), U.S. Patent No. 2,410.
Chemical sensitization can be carried out using sulfur compounds, their sulfur tin salts, amines, etc., as shown in the specifications of Pat.

A stabilizer or an anticapri agent can be added to the silver halide emulsion in the present invention. For example, 4-hydroxy-6-methy”-1+3+38+7-titrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercagut complexes, Many compounds such as metal salts can be used.

Furthermore, various spectral sensitizing dyes such as merocyanine dyes, carbocyanine dyes, cyanine dyes, etc. can be used in the halomono-silver emulsion of the present invention depending on the purpose.

In the present invention, the color quadrants include a 4-equivalent methylene yellow coupler, a 2-equivalent diketomethylene yellow coupler, a 4-equivalent or 2-equivalent pyrazolone magenta coupler, an indashilon magenta coupler, and an α-naphthol cyan coupler. or a phenolic cyan coupler can be used. Also, the so-called DIR
Couplers and polymer couplers can also be used.

Further, the photographic constituent layers of the light-sensitive material of the present invention may contain dyes, ultraviolet absorbers, hardeners as described above, surfactants, and polymer latex.

As a support for the photosensitive material of the present invention, any support commonly used in the art may be used, such as cellulose acetate film, polyethylene terephthalate film, baryta paper (t+), paper coated with α-olefin polymer, etc.

The photographic constituent layers of the light-sensitive material of the present invention can be applied one by one or in multiple layers simultaneously using various methods such as dip coating, air knife coating, curtain coating, and extrusion boat.

For information on various additives, vehicles, supports, coating methods, etc. used in the present invention, please refer to the Product Licensing Index.
The exposure light source for the photosensitive material of the present invention is not particularly limited, and may be from low to high illuminance. , and the exposure time is several tens of seconds ~
Any of these can be used over a range of about 10-6 seconds.

The photosensitive material applicable to the present invention may be a black-and-white photographic material, a color photographic material, or a material for general use, for printing, for Xa, for radiation, etc. Specifically, black and white negative film, paper, reverse The present invention can be applied to all types of photographic materials such as photographic materials, color negative films, papers, reversals, and so-called external color photographic materials containing color formers in processing solutions.

When the light-sensitive material of the present invention is a color light-sensitive material, after exposure, it is subjected to development processing to form a dye image. Here, the current treatment basically includes at least one color development liquid, and may include a predural process, a neutralization process, and a -first phenomenon (black and white phenomenon) process. Including etc. Said steps and subsequent steps (e.g. bleaching, fixing, bleach-fixing, intensifying, stabilizing, washing, etc. in selected combinations)
The treatment is carried out at a temperature of .degree. C. or higher, particularly preferably 35.degree. C. or higher.

A coloring agent is a compound whose oxidation product reacts with a coloring agent (color coupler) to form a coloring product.
N, N-diethyl-p-phenylenediamine, N,
N-diethyl-3-methyl-p-phenylenediamine,
4-amino-3-methyl-N-ethyl-N-methanesulfonamidoethylaniline, 4-amino-3-methyl-
N-ethyl-N-β-hydroxyethylaniline, N-
ethyl-N-β-hydroxyethyl-p-phenylenediamine) or fc is an alkaline aqueous solution (pH 8 or higher, preferably pH 9 to 12) containing these salts (e.g., hydrochloride, sulfate, sulfite). As the main drug, U.S. Patent No. 2.193,015, U.S. Patent No. 2.592.364
Compounds described in the specifications of JP-A-48-64933 and the like can be used. The color developer also contains salts such as sodium sulfate, sodium hydroxide, and sodium carbonate.
pH adjusters and buffers (e.g., acids such as acetic acid and boric acid or their salts), development accelerators (e.g., U.S. Pat. No. 2,648.604, U.S. Pat. Various pyridinium compounds, cationic compounds, sulfuric acid power described in specifications such as No. 3.671.247 1) Rum, sodium nitrate, U.S. Patent No. 2.533.9
No. 90, No. 2.577.127, No. 2.950.
Polyethylene glycol condensates and derivatives thereof described in specifications such as No. 970, British Patent No. 1.020.0
No. 32, nonionic compounds such as polythioethers as typified by the compounds described in US Pat. No. 1,020,033, US Pat. No. 3,068,097, US Pat.
Polymer compounds with sulfide esters such as those typified by the compounds listed in '6, organic amines such as pyridine and ethanolamine, benzyl alcohol, hydrazine, etc. Inhibitors (e.g. alkali bromide, alkali iodine, nitrobenzimidazoles, benztriazole complexes, mercaptotetrazole compounds, etc.), U.S. Patent No. 3.161.514, British Patent No. 3,161
, No. 514, British Patent No. 1,144,481 and other specifications, and U.S. Patent No. 3.
, 536.487;
Processing solutions prior to the development step, which may also include preservatives (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride, formaldehyde-alkanolamine sulfide adducts, etc.), typically include a pre-hardening bath. , aldehydes that react with and harden gelatin, which is a constituent factor in photographic emulsions, such as aliphatic aldehydes, formaldahytes, and glyoxal described in U.S. Pat. No. 3,232, 761 Keimei series. ,
succinic aldehyde, geltaraldehyde, pyruvaldehyde, etc.), and U.S. Patent No. 3.565.632
An aqueous solution containing one or more aromatic aldehydes described in the specification, such as No. 3,667,760, is used. This liquid contains inorganic salts such as sodium sulfate, borax,
Contains current antifoggants such as boric acid, acetic acid, sodium acetate (1) rum, hydroxide, pH adjusters and buffers such as sulfuric acid, and alkali halides (for example, Shinsaku potassium). .

Generally, a neutralization bath is provided for the purpose of preventing aldehydes used in the pre-hardening process from being carried into the development process. An aldehyde removing agent such as hydroxylamine or L-ascorbic acid is added to the neutralization bath, and inorganic salts, a pH adjusting agent, and a buffering agent are also added.

The first reaction solution for color reversal film is also a process that precedes the color development process, and contains liquids such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-p-aminophenol, etc.
An alkaline aqueous solution containing one or more herbal medicines is used, and the pond contains inorganic salts such as sodium sulfate, borax, boric acid, hydroxide, carbonate, etc.
These include H modifiers and buffering agents, alkali halides (eg, potassium bromide), and other current anti-capri agents.

The various additives and amounts added in the above processing steps are well known in color photographic processing methods.

After the color development event, the color photographic material is usually bleached and fixed, although bleaching and fixing can also be combined into a bleach-fix bath. Many compounds are used as whitening agents, among them ferricyanates, dichromates, water-soluble iron (III) salts, water-soluble cobalt (■) salts, and water-soluble steel (I).
I) Salts, water-soluble quinones, nitrosophenols, iron (■
), complex salts of polyvalent cations such as cobalt (■), copper (II), and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, Metal complex salts such as malonic acid, hydric acid, malic acid, diglycolic acid, dithioglycolic acid, 2,6-dipicolinate steel complex salts, peracids, alkyl peracids, persulfates, permanganates, etc. Hydrogen peroxide, hypochlorite, chlorine, bromine, saran powder, etc. are commonly used alone or in appropriate combinations, and other U.S. Pat. Nos. 3,042,520 and 3.2.
No. 41.966, Special Publication No. 45-8506, No. 45-8
Bleaching accelerators as described in the specification of No. 836 and the like can also be added.

Any conventionally known fixing solution can be used for fixing. That is, as fixing agents, ammonium, sodium, and potassium salts of thiosulfate are used in amounts of 50 to 200 g/l, and in addition, stabilizers such as sulfites and isomeric bisulfites, and hardeners such as potassium alum are used. A membrane agent, a pH buffering agent such as an acetate, a borate, etc. can be included.

Bleach agents, fixing agents, and bleach-fixing baths are described in U.S. Pat. No. 3,582,322 and elsewhere.

As the intensification liquid, intensification liquids using a method using Co(III) salt, a method using hydrogen peroxide, and a method using chlorous acid can be used.

For image stabilizing baths, U.S. Patent No. 2.515.121
No. 3.140.177, etc. can be used.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 (Exemplary Compound A10) CH.

book C00CR, CF.

M A A 43.0 g (0.50 mol), α, α'
-Azobisin butyronitrile (AIBN)
2.0! ! Three 500 ml portions of ethanol and 500 ml of ethanol were placed in a flask, and the mixture was refluxed for 10 hours fc7.Then, the reaction solution was poured into a large amount of water with vigorous stirring to allow the reaction product to stagnate. Next, the precipitate was filtered, washed with water, and dried in air at 60°C to obtain a copolymer exemplified compound AIO according to the present invention. The yield is 116.6 II (
NMR, elemental analysis, etc. confirmed that this material had the composition of Compound Example A10. Intrinsic viscosity in ethanol at 25°C is 0.11
M/,? Met.

Synthesis Example 2 (Exemplary Compound A6) CH.

CH,=C-C00CH(CF3),94.4,F
(0.40 mol), acrylic acid (hereinafter abbreviated as AA)
43.2 # (0.60 mol) AIB, N2.0.9
was reacted and treated in the same manner as in Synthesis Example 1 to obtain copolymer exemplified compound A6 according to the present invention. The yield is 129.3 #
(yield: 94 cm), and it was confirmed by NMR, elemental analysis, etc. that this substance had the composition of compound example A6, fc,
The intrinsic viscosity in ethanol at 25°C is 0.1514! /g
Met.

Synthesis Example 3 (Exemplary Compound A18) 'i'1・cH,=C-C00CH,CF, 76.89 (0
, 40 mol), MMA 20.0.9 (0.20 mol), AA, 28.8II (0.40 mol), A I B
V 2.0.9 was reacted and treated in the same manner as in Synthesis Example 1 to obtain copolymer exemplified hardware 18 according to the present invention. The yield was 115.6 F (yield 92 F), NMR,
It was confirmed by elemental analysis etc. that this substance had the composition of Compound Example A18.

The intrinsic viscosity in ethanol at 5°C was 0.12 co/gte.

Synthesis Example 4 (Exemplary Compound A23) CH.

cH,=C-C00CH,CF,57.6.9 (0
, 30 mol), M M A 30.0 g (0.30 mol), MAA 34.4.9 (0.40 mol), A I
B N 2.0.17 was reacted in the same manner as in Synthesis Example 1 to obtain copolymer exemplified compound A23 according to the present invention. The yield was 115.911 (95% yield), and it was confirmed by NMR, elemental analysis, etc. that this substance had the composition of Compound Example A23. , the intrinsic viscosity in 25°C ethanol was 0.17 m1/11 n Synthesis Example 5 (Exemplary Compound A26) CH3 Cl (, = C-C00CH, CF, 76.8.9 (
0.40 mol), M A A 50.7.9 (0.6
0 mol), A I B N 2. O! ! was reacted and treated in the same manner as in Synthesis Example 1 to obtain a copolymer exemplified compound according to the present invention. This substance is compound example 26
It was confirmed that it had the following composition. , the intrinsic viscosity in ethanol at 25 °C was 13WLt/77.

Next, production examples of typical matting agents used in the present invention will be shown.

Production Example 1 80 g of copolymer A 10 obtained in Synthesis Example 1 was dissolved in a mixed solvent of ethyl acetate 19"0.9 and n-butanol 60 g at 40°C. Dodecylbenzene was dissolved in 40 g of water. Sodium sulfonate was dissolved in 1.o and p.Additionally, 40g of gelatin was added to a 500m beaker and 320g of water was dissolved.
I! was added and allowed to swell for 30 minutes, and then dissolved at 60°C. Next, the dissolved gelatin solution and the aqueous sodium dodecylbenzenesulfonate solution were placed in a three-bottle flask having an internal volume of 1 mm, and the flask was heated to 35°C. A pre-dissolved solution of copolymer AIO was added thereto, and the
The emulsion was stirred at a rotating speed for 20 minutes and the resulting emulsion was observed under an optical microscope, and as a result, polymer oil droplets of 2 to 5 μm in size were observed. This emulsion is 10010
The solvent was removed by drying under reduced pressure at 45°C. After that, a matting agent with a particle size of 2 to 5 μm (
10) was obtained.

Production Example 2 Copolymer A6 obtained in Synthesis Example 2 was treated in the same manner as in Production Example 1 to attack the matting agent (6) having a particle size of 2 to 4 μm.

Production Example 3 Copolymer M18 obtained in Synthesis Example 3 was treated in the same manner as in Production Example 1 to obtain a matting agent (18) with a particle size of 2 to 4 μm.

Production Example 4 Copolymer A23 obtained in Synthesis Example 4 was treated in the same manner as in Production Example 1 to obtain a matting agent (23) with a particle size of 2 to 4 μm.

Production Example 5 Copolymer A26 obtained in Synthesis Example 5 was treated in the same manner as in Production Example 1 to obtain a matting agent (26) with a particle size of 2 to 5 μm.

Example 1 Hao) Contains 300 g of gelatin per mole of silver ionide, and as a yellow coupler, α-pivaloyl-
α-(1-benzyl-2,4-dioximidacillin-
3-yl)-2-chloro-5[γ-(2,4-tert
-aminophenoxy)butyramide]acetanilide at 2.5XtG"! Mol and hardener t, 1", 1
+' 2-bis(vinylsulfonyl)ethane 0.02.
A blue-sensitive silver iodobromide (silver iodide 7 molt) emulsion for color containing F/1.9 gelatin was prepared, and together with this emulsion, matting agent (10) of the present invention and matting agent (6) were used for a protective layer. ) and a matting agent with a particle size of 2 to 4 μm having a composition of MMA/MAA = 6/4 for comparison were placed in a slide hopper method so that the gelatin solution containing a coating aid had the composition shown in Table 1 below. An emulsion layer and a protective layer were coated in order from the support onto a cellulose triacetate film support having a subbing layer, and matting agents (10), (6) and matting agent (5) were coated without dissolving during coating. , Sample (1), Sample (2) and sample surface were obtained, respectively. A sample (C1) containing no matting agent was also prepared. The dry film thickness of the protective layer was 1.5 μm.

Table 1 For each of the above samples, two pieces were cut into 5 crrL square pieces and each was heated at 23°C to avoid contact with each other.
After being stored in an atmosphere of 80SR, H, for one day, two protective layers of the same sample were brought into contact with each other, and 800I!
After applying a load of
Adhesion was measured.

The evaluation criteria are as follows.

Rank: Area of adhesive part A　O~20chi B 21~40 yen 0 41-60% D 61 inches or more The above results are shown in Table 2.

Table 2 From the results in Table 2, it can be seen that the adhesion resistance of the matting agent of the present invention is superior to that of the conventional matting agent.

Example 2 A blue-sensitive silver iodobromide emulsion for color was prepared in the same manner as in Example 1, and the matting agent (18) of the present invention and the matting agent (
23), matting agent (26) and EMA/MA for comparison
A matting agent (B) having a particle size of 2 to 4 μm and having a composition (molar ratio) of A = 6 g/40 was coated on a cellulose triacetate film support to form samples (3) and (4), respectively.
, Sample (5) and Sample (B) were obtained.

In these samples (3), (4), (5) and (B), matting agents (3L (4),
(5) and ■) were not dissolved. The dry film thickness of the protective layer of each of these samples was 1.6 μm. The same evaluation as in Example 1 was performed for each of the above samples.

The results are shown in Table 3.

Table 3 Example 3 Samples (1), (2), (3), (4) and (5) of the present invention
) was investigated for antistatic properties using the following method.

After conditioning the unexposed sample at 25°C and 25mm RH for 2 hours, the emulsion side of the sample was rubbed with a neoprene rubber roller in a dark room under the same air conditioning conditions, and then developed with the following processing solution.
After washing, bleaching, fixing, washing and stabilization, the degree of static mark formation was examined.

Processing process Temperature Processing time (1) Developer 38603 minutes 15 seconds (2)
Bleaching: 38°C, 4 minutes and seconds (3) Fixing: 38°C, 4 minutes and seconds (4) Washing with water...
...38℃ 3 minutes 15 seconds (5) Stabilization...3
8° C. 1 minute 5 seconds The compositions of the developing solution, bleaching solution, fixing bath, and stabilizing bath are as follows.

Current liquid (pH=10.05) Add water to make 11.

Bleach bath (pH=5.70) Add water to make 11.

Fixing bath (pH=6.50) Add water to make 11. Stable bath (pH=7.30) Add water to make 11.

The antistatic test results of these samples are shown in Thorn 4.

In the table, the evaluation of the degree of static mark occurrence is as follows: A: No static marks observed at all B: Some static marks observed C: Considerable D: Appeared on almost the entire surface 4 I divided it into stages.

Table 4 Static mark generation was #1 for samples that were antistatic.
It has an excellent antistatic effect that is rarely recognized.

Example 4 Samples (1), (2), (3), (4) and (
5) and the following comparative samples were examined for sharpness using the following method fC.

After conventional wedge exposure of the unexposed sample of the present invention with a tungsten lung, the current iron treatment of Example 3 was performed, and M T
F (Modulatjon Transfer F
unc) was measured. Spatial frequency is 10 lines/mm
The two comparison samples that compared the MTF values at the values of
A sample (D) was prepared using the same amount of MMA homopolymer.

The results are shown in Table 5.

Table 5 As is clear from Table 5, even when the matting agent of the present invention is used, sharpness does not deteriorate.

〔Effect of the invention〕

The halogenated photographic material of the present invention has excellent adhesion resistance and antistatic properties, and the images obtained by processing have good transparency and image quality. Moreover, in the manufacturing process, there is no dissolution of the matting agent during the coating process, and no coagulation or repellency occurs.

Claims (1)

[Claims] At least one of the outermost layers contains a matting agent.
4. A 4-edge photographic material, characterized in that the matting agent consists essentially of a copolymer containing the following (5) and (B) as copolymer components. Fluorine-containing 7-mer (B) At least one selected from the group consisting of methacrylic acid and acrylic acid