JPS6355543A - Silver halide photographic sensitive material preventing sweating phenomenon and formation of static mark - Google Patents

Abstract

PURPOSE:To prevent the formation of static marks without causing a sweating phenomenon by using a polymer derived from repeating units of a specified monomer. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on the support and contains a polymer derived from repeating units of a monomer represented by formula I (where R1 is H, 1-4C alkyl or halogen, X is -CONH-, -COO- or phenylene, A is 1-20C alkylene or 6-20C arylene, U is -COO-, -OCO- or the like, m=0 of 1, n=0 or 1 and Q is a UV absorbing group).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material (hereinafter referred to as a "photographic material"), and in particular, the present invention relates to a silver halide photographic material (hereinafter referred to as a "photographic material"). This invention relates to a photographic material that has no adverse effects and has improved static marks.

[Background of the Invention] Photographic materials are made by coating a light-sensitive photographic emulsion on a support with relatively high electrical insulation, such as polyethylene terephthalate film or laminated paper coated with polyethylene. During the manufacturing process, during use, etc., the accumulation of electrostatic charge causes sparks to be generated due to air discharge, and after the development process, various image defects such as dendritic marks, so-called static marks, are produced, which reduces the product value. may cause significant damage.

Conventionally, ultraviolet absorbers have been used, especially in the range of 300 to 40 Gno+
Attempts have been made to prevent the generation of static marks by blocking ultraviolet light.

We have used U.S. Pat. No. 3,417.
Although we tried adding the compound described in No. 082, we found that the static prevention effect was insufficient and that a sweating phenomenon occurred in which an oily substance or powdery crystalline substance appeared on the surface of the photographic light-sensitive material.

[Object of the Invention] An object of the present invention is to provide a photographic material that does not cause the sweating phenomenon and prevents the generation of static marks.

[Structure of the Invention] The present inventors have achieved the above object (as a result of intensive research), in a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the following general formula [ It has been found that the above object can be achieved by a silver halide photographic material containing a polymer derived from the repeating unit of Kurumatsu body shown in [I].

General formula [I] Direct CR2-C-X-(A)V(Ll) "R1 in the Q formula
is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, X is 100NH-1-COO- or a phenylene group, and A is an alkylene group having 1 to 20 carbon atoms or a carbon W16
~20 arylene Mtr, u is -coo-1-OCO
-1-CONH-1-NHCO-1-8O2NH=,N
HS O2-1-302 or -〇-, 刱 and n each represent O or 1, and Q represents an ultraviolet absorbing group represented by the following general formula [I[].

General formula I ,
Represents a cyano group, acylamino group, carbamoyl group, acyl group, sulfonyl group, sulfamoyl group, sulfonamido group, acyloxy group or oxycarbonyl group, R
15 and R17 each represent a hydrogen atom, an alkyl group, or an aryl group, R+s represents a hydrogen atom, an alkyl group, or an aryl group, and at least one of Ra1 to R46 is bonded to a polymerizable group. However, when R++~Rn is CR2'' C-X-(A), --(Ll)7V-, R1 is a hydrogen atom or a methyl group, and X is 100NH
- or -COO-1 and ta -n =Ote.

When R1 is a hydrogen atom or a methyl group, X is -CON
H- or -C00-1 and not I -n -0, R1 is a hydrogen atom or a methyl group, and X is -CO
O-1g+-n-1, A is an alkyl group, and U is never 10-.

[Specific Structure of the Invention] The silver halide photographic material of the present invention has the general formula [
It contains a polymer derived from a repeating unit of a monomer represented by I].

In the general formula [I], R1 has 1 to 1 carbon atoms;
Examples of the alkyl group (4) include methyl, ethyl, n-propyl, and isopropyl, and examples of the halogen atom include fluorine, chlorine, and the like.

Examples of the alkylene group having 1 to 20 carbon atoms represented by A include groups such as methylene, ethylene, trimethylene, 2-hydroxytrimethylene, hexamethylene, and 3-oxapentamethylene. An example of an arylene group is a phenylene group.゛In the above general formula [I[], examples of the halogen atoms represented by Rn to R14 include fluorine, chlorine, bromine, etc. Examples include methyl, ethyl, n-
Examples of the aryl group (the same applies to the aryl groups represented by R15 to R17) include phenyl, tolylmesityl, and aryl groups. Examples of groups such as lophenyl, alkoxy groups include methoxy, ethoxy, octyloxy, 2-
Groups such as ethylhexyloxy and methoxyethoxy; examples of aryloxy groups include phenoxy and 4-methylphenoxy; examples of alkylthio groups include methylthio and propylthio; examples of arylthio groups include Examples of phenylthio groups and alkylamino groups include methylamine, dimethylamino, ethylamino, benzylamino, diacrylamino, and cyanoethylamino groups; examples of arylamino groups include anilino, anisidine, toluidino, diphenylamino, etc. Examples of acylamino groups include acetylamino and benzoylamino groups; examples of carbamoyl groups include methylcarbamoyl and dimethylcarbamoyl; examples of acyl groups include acetyl and benzoyl; Examples of sulfonyl groups include methylsulfonyl and phenylsulfonyl; examples of sulfamoyl groups include ethylsulfamoyl and dimethylsulfamoyl; examples of sulfonamide groups include methanesulfonamide and benzenesulfonamide. Examples of the allyloxy group include acetoxy and benzoyloxy, and examples of the oxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, and phenoxycarbonyl.

The polymer of the present invention may be a homopolymer of a monomer having an ultraviolet absorbing group, a copolymer of two or more of the monomers, or a combination of the monomer and a monomer having no ultraviolet absorbing group. A copolymer may also be used.

In the case of a copolymer, the comonomer having no ultraviolet absorbing group includes, for example, acrylic acid, α-lyroacrylic acid, α-alacrylic II (preferably an ester derived from acrylic acids such as methacrylic acid) , lower alkyl esters and amides such as acrylamide, methacrylamide, t-butylacrylamide, methyl acrylate, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and lauryl methacrylate, methylenebisacrylamide, etc.), vinyl esters ( (e.g. vinyl acetate and vinyl laurate, etc.), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene and styrene sulfinic acid, etc.), itaconic acid, citraconic acid , crotonic acid, vinylidene chloride, vinyl alkyl ether (such as vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, and the like.

Among these, acrylic esters, methacrylic esters, and aromatic vinyl compounds are particularly preferred.

Two or more of the above comonomer compounds can also be used together.

Specific examples of the monomer represented by the general formula [I] of the present invention are shown below.

CH3 ■ Hs Hs CH3 CH.

CH3 CH.

CH3 C.HS Specific examples of the polymer of the present invention are shown below.

Exemplary polymers P-1 to P-15: Examples! Homopolymer copolymer of 11 bodies 1 to 15 Monomer molar ratio P-1
6 Exemplary monomer 1: HHA 6:4P-17 Exemplary monomer 4: BA 5:5P-18 Exemplary monomer 2: BA 6:4P-19 Exemplary monomer 3: EA 7:3P-20 monomer 6
: ST: HHA 6:1:3P-21 Exemplary Monomer 9: HHA:AA 6:3.9:0. I
P-22 exemplified monomer 12: ST:APS
6:3: IP-23 Exemplary Monomer 10: HHA
5:5P-24 Exemplary Monomer 13 2VA:BA
6:1:3P-25 Exemplary Monomer 15:HA
6:4HHA-methyl methacrylate, BA=n-butyl acrylate ST=styrene, AA=acrylic acid, APS=
2-acrylamido-1-propanesulfonic acid Na VA-vinyl acetate, HA-methyl acrylate Specific synthesis examples are shown below.

Synthesis Example-1 Synthesis of Exemplified Monomer-2 Trahydrofuran 500. Dissolve in Q, add 350 H3, and slowly add 10% sodium hydroxide 50Q dropwise while keeping at 0-5°C. After the addition was completed, the reaction was continued for another 2 hours, and the resulting salt was filtered with O and poured into ice water.

After extraction with ethyl acetate, the precipitated crystals were recrystallized from ethanol to obtain 6 g of the desired product.

The structure was confirmed by IR and NMR.

Synthesis Example 2 Synthesis of Exemplified Monomer-3 40 g of exemplified monomer-3 was added to 3001 (l) of acetonitrile and 1512 of pyridine, stirred, and a 100i12 acetonitrile solution of 13 g of methacrylic acid chloride was added dropwise at 40°C. After cooling, the resulting solid was collected and recrystallized from acetonitrile to obtain the desired product.The structure was [
Confirmed by R, NMR.

Synthesis Example 3 Synthesis of Exemplified Monomer 9 Add 33 (l
of H3 is added, and the mixture is allowed to react at 40°C or lower for 2 hours. Pour the reaction solution into ice water, take the resulting precipitate [1], and recrystallize it from acetonitrile to obtain the desired product 25 (J).

It was confirmed by IR and NMR that it was the desired product.

Synthesis Example-4 Polymer P-2 Synthesis 109 500142 aqueous solution was heated through a nitrogen stream.
Heat to 80°C under oxygen. A 201e aqueous solution containing 350 mg of potassium persulfate was added to this aqueous solution. Next, Exemplified Monomer-250 (l) was dissolved in 200 ml of ethanol and added. Stirring was continued for 1 hour after the addition, and 10 ml of potassium persulfate 15011 (l) was added.

picture. React for 1 hour. After the reaction was completed, ethanol was distilled off as an azeotrope of water and diluted with 0.1N* sodium oxide.
) After adjusting H to 6.0, it was filtered with O. The polymer concentration of the latex was 8.5%.

Synthesis Example-5 Synthesis of Polymer P-5 Exemplified Monomer-5 instead of Exemplified Monomer-2 in Synthesis Example-4
The desired product was obtained in the same manner as Synthesis Example 4 except that .

The polymer concentration of the latex was 8.4%.

Synthesis Example-6 Synthesis of Polymer P-19 Sodium dodecylbenzenesulfonate 10 (5001 l)
The Q aqueous solution was heated to 80°C while passing 1152°C of oxygen through a nitrogen stream.
Heat to ℃. Add 350ml of potassium persulfate to this aqueous solution.
g of 201i2 aqueous solution was added. Next, exemplified monomer-3
459 and ethyl acrylate 5g ethanol 150
The mixture was heated and dissolved in b) and added. Rough stirring was continued for 1 hour after the addition, 250 m9 of potassium persulfate in 10tj2 aqueous solution was added, and after further reaction for 1 hour, ethanol and unreacted monomers were distilled off as an azeotrope of water, and 0. IN
After adjusting the pH to 6.0 with sodium hydroxide, it was passed through the mouth.

The polymer concentration of the latex was 8.0%, and the example monomer-3
The content of units was 70 mol%.

Synthesis Example 7 Synthesis of Polymer P-21 45g of Exemplified Monomer-3 in Synthesis Example 6 was added to 50 units of Exemplified Monomer-9, 5 units of ethyl acrylate, 89 units of methyl methacrylate, and 1 unit of acrylic acid. The pond was the same as Synthesis Example 6 to obtain Polymer P-20. The polymer concentration of the latex was 6.8%, and the content of exemplary monomer units was 60 mol%.

Synthesis Example 8 Synthesis of Polymer P-12 Exemplified monomer-12 of 500 was converted into dioxane 1501! IN
2,2′-Azobis(2,4
- After adding >270 mg of dimethylvaleronitrile,
The reaction took place for 4 hours. After the reaction is complete! After cooling to room temperature, the reaction solution was poured into 2 tons of ice water, and the precipitated solid was taken out.

A latex was produced using this polymer as follows.

5 g of polymer are dissolved in 201 g of ethyl acetate at 38° C. and a 70% by weight methanol solution of sodium dodecylbenzenesulfonate is added. Next, this was mixed with 70 g of a 10% by weight aqueous solution of gelatin, separated into layers using a double cylindrical decomposer, and then ethyl acetate and methanol were distilled off at reduced volume to produce latex.

Synthesis Example 9 Synthesis of Polymer P-13 Synthesis was carried out in the same manner as Synthesis Example-8 except that Exemplified Monomer-13 was used instead of Exemplified Monomer-12 in Synthesis Example-8, and latex was added. I made it.

Synthesis Example-10 Synthesis of Polymer P-15 Exemplified Monomer-1 in place of Exemplified Monomer-12 of Synthesis Example-8
Synthesis was carried out in the same manner as in Synthesis Example 8 except that No. 15 was used, and latex was also produced.

The polymer of the present invention is preferably added to the silver halide photographic material as a latex.

To add it as a latex, the above polymer may be polymerized by an emulsion polymerization method, or a lipophilic polymer obtained by another polymerization method is dissolved in an organic solvent and dispersed in an aqueous gelatin solution in the form of a latex. You can also make it by

Examples of initiators and their action are given by F. A. Bovey [Emulsion polyIIlerlZati
onJ InterSCienCeP ubl 1s
Heslnc New'/ork, 1955, pages 59-93.

As the emulsifier used in emulsion polymerization, a compound having surface activity is used, and preferred examples include soaps, sulfonates, sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects can be found in the selgische chem
ische t industry vol. 28 no. 16~
20 (1963).

Hereinafter referred to as ``6-p''; - When dispersing the polymer of Rikiki's invention in the form of a latex in a gelatin aqueous solution, the specific solvent used to dissolve the polymer of the present invention is used to apply the dispersion. It is removed during evaporation before or (less preferably) during drying of the applied dispersion.

The proportion of the monomer having an ultraviolet absorber moiety in the polymer of the present invention is generally preferably 5 to 100% by weight, but 35 to 100% by weight is particularly preferable from the viewpoint of film thickness and stability.

The polymer of the present invention is used by being added to a hydrophilic colloid layer such as a surface protective layer, an intermediate layer, or a silver halide emulsion layer of a silver halide photographic light-sensitive material. Preferably, it is used in the sex colloid layer.

There is no particular restriction on the amount of the polymer of the present invention used, but 1
10-300h+g per square meter, especially 50-20
Preferably it is 001Q.

Examples of the silver halide photographic material of the present invention include color negative film, color reversal film, X-ray film, color paper, and color diffusion transfer method sensitive material.

In the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide used in ordinary silver halide emulsions, such as silver iodobromide and silver chlorobromide, can be used. The silver oxide particles may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Further, it may have a regular crystal shape, or it may have an irregular crystal shape such as a spherical shape or a plate shape.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye. The sensitizing dyes may be used alone or in combination of two or more.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography. The couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, one yellow coupler for the blue-sensitive emulsion layer and one yellow coupler for the green-sensitive emulsion layer. A magenta coupler is used in the red-sensitive emulsion layer, and a cyan coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These couplers may be either 4-equivalent or 2-equivalent. Coupling with a colored coupler that has a color correction effect and an oxidized form of a developing agent produces development inhibitors, development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, and hardeners. film agent, fogging agent, antifogging agent,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers are included.

Although a coupling reaction is performed with the oxidized product of the aromatic primary amine developer, a colorless coupler (also referred to as an 8-coupler coupler) which does not form a dye can also be used in combination.

As the yellow coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

As the cyan coupler, phenol or naphthol couplers are generally used.

Among couplers, DIR compounds, double-image stabilizers, fluorescent brighteners, etc. that do not need to be adsorbed on the surface of fine silver halide products, hydrophobic compounds can be dispersed using solid dispersion methods, latex dispersion methods, and oil-in-water emulsion dispersion methods. Various methods can be used, such as, and can be appropriately selected depending on the chemical structure of the hydrophobic compound.

In addition, when it has an acid group, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution.

A color antifogging agent can be used to prevent color turbidity, deterioration of sharpness, and noticeable graininess caused by the movement of an oxidized product of a developing agent or an electron transfer agent between layers.

The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A formalin scavenger-1 optical brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

In order to obtain a black and white image using the photosensitive material of the present invention, a developing step, a fixing step and/or a stabilizing step may be performed.
After exposure, color photographic processing is performed to obtain a dye image. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. Alternatively, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a monobath process can be carried out using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath. It is also possible to perform a process.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color-developing agent or its arecasa is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in which the monobath process is performed using an activator solution. Beta processing can be applied.

[Example] Next, Examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 A sample was prepared by simultaneously coating a green-sensitive emulsion layer and a protective layer having the following composition on a cellulose triacetate transparent base and drying.

First layer: green-sensitive emulsion layer A green-sensitive silver iodobromide emulsion containing 7 mol % of silver iodide and having an average grain size of 1.2 μm was prepared.

Then, per mole of silver halide, 1-(2,4,6-trichlorophenyl)-3 was added as magenta coupler.
80 g of -[3-(2,4-di-t-amylphenoxyacetamide)penzamide]-5-pyrazolone, 1-(2,4,6-triclophenyl)-4-(1-naphthylazo) as a colored magenta coupler. -3-(2
Weigh out 2.5 g of -chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone, and then 1200 g of tricresyl phosphate. 240% of ethyl acetate was mixed and dissolved by heating, and then a cabler solution prepared by emulsifying and dispersing sodium triisopropylnaphthalene sulfonate 59 and a 7.5% gelatin aqueous solution 550112 was added to the above emulsion.

Further, a gelatin hardener was added to prepare a green-sensitive silver halide coating solution, which was coated to a dry film thickness of 5.5 μm.

2nd layer: Comparative L layer UV absorber and high boiling point ♂ tricresyl phosphate was heated and dissolved in ethyl acetate (twice the weight of the total weight of the UV absorber and tricresyl phosphate). A comparative sample was prepared by adding it to an old gelatin solution containing sodium triisopronaphthalene sulfonate, emulsifying and dispersing it in a colloid mill, and then evaporating off the ethyl acetate, coating, and drying.

On the other hand, samples according to the present invention (see Table 1) were prepared by applying and drying a polymer UV absorber of the present invention in place of the comparative UV absorber and tricresyl phosphate.

The amount of gelatin in the protective layer was 1011 g/100 Cf for both the comparative sample and the sample according to the present invention.

Table 1 After storing one portion of each sample unexposed in an atmosphere of 55°C and 80% RH for 7 days, the surface condition (oil,
The state of appearance of crystals, etc.) was observed.

Evaluation was performed in the following three stages.

A Appearing or no date Appearing C Amount of appearance Also, after conditioning the unexposed sample at 25°C and 20% RH for 6 hours, the emulsion side of the sample was rubbed with a neoprene rubber roller in a dark room under the same air conditioning conditions. After rubbing, the film was developed with the following processing solution, bleached, fixed, washed with water, and stabilized, and the degree of static mark occurrence was examined.

Processing process Temperature Processing time (1) Developer...38℃ 3 minutes 15 seconds (2) Floating
White...38℃ 4 minutes 30 seconds (3) Fixation...
38℃ 4 minutes 20 seconds (4) Washing with water...38℃
3 minutes and 15 seconds (5) Stabilization: 38°C, 1 minute and 05 seconds The compositions of the developer, bleach, fixing bath, and stabilizing bath are as follows.

Developer (1) H=10°05) Hydroxyamine sulfate 2.5g 4-amino-3-methyl-N- (β-hydroxyethyl)aniline sulfate jm 4.56+
It diethylene triamino hexa vinegar Fli 4.7
5! JK2 CO330, 3g Sodium sulfite 49 Add water to make 1t.

Bleach bath (1) H-5,70) Ammonium bromide 173g80%
Acetic acid 20dEDTA F
e NH41030 EDTA 27Q Add water to make 11.

Fixing bath (pH-6,50) Ammonium thiosulfate 800112 Sodium sulfite 4.6 Sodium bisulfite 5.0g Add water to make 12.

Stable bath (DH=7.30) 40% formalin 6.6. p50
% polyoxyethylated uryl alcohol 0.6112 Add water to make 11.

The degree of occurrence of static marks was evaluated on the following four levels A to D.

A: No static marks are observed B: Some static marks are observed C: A considerable amount of static marks are observed D: Static marks are observed almost on the entire surface Shown in the table.

11 Key 4 Table 2 As shown in Table 2, the samples of the present invention are excellent in surface condition and static mark occurrence.

In addition, the samples of the present invention can be further thinned (for example, sample 13.
For 19 and 25, use gelatin 6mr+/IQO
Cf (reduced to 8 mu/100 cf for Samples 14, 15, 20, 21 and 26), there was no deterioration in performance in terms of surface condition or static marks, and it was found that image sharpness could be improved.

Example 2 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a silver halide photographic light-sensitive material for stem color.

α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide]acetanilide at 6.81
113/100cf, blue-sensitive silver chlorobromide emulsion (silver bromide 8
5 mol%) converted to silver is 3.2■C1/100
Cf, di-butyl phthalate 3.511g/100C
f and gelatin were coated to form a coating base of 13.5 mq/100 Cv'.

2nd layer: Intermediate layer 2.5-G t-octylhydroquinone 0.5m
g/100c, z, dibutyl phthalate 0.5
mg/100Cf and gelatin 9.0IIQ/1
00Cv'.

Third layer: green-sensitive silver halide emulsion layer 1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5-tetradecanamidoanilino)-5-pyrazolone is used as a magenta coupler. 2a1g/1
00Cv, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver is 2.5fflO/100Ct', di-butyl phthalate is 3.0110/100Cy',
and 12.0 ffl of gelatin! If/ 100Ct'
It was painted so that

4th layer: Interlayer UV absorber (Table 3), dibutyl phthalate, 2.
5-G t-octylhydroquinone (0,51!1
g/100cf) and gelatin (12,omo/1QO
cf). (Amounts of other materials are shown in Table 3.

) 5th layer: red-sensitive silver halide emulsion layer containing 2-[α-(2,4-G) as a cyan coupler.
4.2 m (J/100 cf
, red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver is 3.0mg/100Cv, tricresyl phosphate is 3.51111J/100Cf, and gelatin is 11.5s9/100cf. I painted it to look like this.

6th layer: Interlayer layer containing gelatin (101 [1/100 cr), ultraviolet absorber (Table 3) and dioctyl phthalate. (Other amounts are shown in Table 3.) 7th layer: Protective layer Gelatin was coated at 8.0 mQ/100 Cv'.

A gelatin hardener was appropriately added to the protective layer.

The test piece of the sample was left unexposed at 55°C and 80% R.
After being stored in an H atmosphere for 3 days, the surface condition was visually observed. The evaluation criteria are the same as in Example-1.

In addition, after humidifying an unexposed sample at 25°C and 20% RH for 6 hours, we tested it in the dark under the same air conditioning conditions. After rubbing the emulsion side of the sample with a neoprene rubber roller in the inside, the sample was developed with the following processing solution, bleached, fixed, washed with water, and stabilized, and the degree of occurrence of static marks was examined. The evaluation criteria are the same as in Example-1.

[Processing process Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Wash with water for 1 minute and 30 seconds at 33℃
Dry for 3 minutes at 50-80°C for 2 minutes The components of each treatment solution are as follows.

[Color developer] Benzyl alcohol 12d diethylene glycol 10 Potassium carbonate
25 (sodium 7 bromide
0.6g, anhydrous sodium sulfite
2.0g hydroxylamine sulfate aMA
2.5.

N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Add water to make 11, and adjust to pi-1-10,2 with NaOH.

[Bleach-fix solution] Ammonium thiosulfate 1209 Sodium metabiite 5A 15 (+Anhydrous sodium sulfite 3g EDTA Secondary ammonium [65 (Add 1 water to make 11, 1, 1) H to 6
．． Adjust to 7-6.8.

The results are shown in Table 3.

From Table 3, it can be seen that the sample R1 of the present invention is inferior to the comparative sample F1 in terms of the surface condition and the degree of occurrence of static marks. Also, in the present invention, samples 53 and 5 (
3, the one with increased amount of No. 6 JF4 is particularly good.
there were. Furthermore, in the samples of the present invention, it was possible to make the ultraviolet absorber layer thinner.

Effects of the present invention J As explained in detail above, by using the polymer of the present invention, it is possible to improve static marks and prevent deterioration of surface condition due to storage under harsh conditions. , it becomes possible to make the film even thinner.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, which is derived from a repeating unit of a monomer represented by the following general formula [I]. A silver halide photographic material containing a polymer. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and X is -CONH-, -COO-, or a phenylene group, A is an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and U is -COO-,
-OCO-, -CONH-, -NHCO-, -SO_2
NH-, -NHSO_2-, -SO_2 or -O-,
m and n each represent 0 or 1, and Q is represented by the following general formula [
II] represents an ultraviolet absorbing group. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1_1 to R_1_4 are hydrogen atoms,
Halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, alkylthio group, arylthio group, amino group, alkylamino group, arylamino group, hydroxy group, cyano group, acylamino group, carbamoyl group, acyl group, sulfonyl group , represents a sulfamoyl group, a sulfonamide group, an acyloxy group, or an oxycarbonyl group, R_1_5 and R_1_7 each represent a hydrogen atom, an alkyl group, or an aryl group, R_1_6 represents a hydrogen atom, an alkyl group, or an aryl group, and at least one of R_1_1 to R_1_6 One is bonded to a polymerizable group. However, when R_1_1 to R_1_4 are ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_1 is a hydrogen atom or a methyl group, and X is -CONH- or -CO
O- and m=n=0. Also, when R_1_6 is ▲There is a mathematical formula, chemical formula, table, etc.▼, R_1 is a hydrogen atom or a methyl group, and X is -CON.
H- or -COO-, and m=n=0, R_1 is a hydrogen atom or a methyl group, and X is -COO
-, m=n=1, A is an alkyl group, and U is -O-
It is never. ]