JPS6162033A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To form a photosensitive silver halide material having a satisfactory antistatic effect by incorporating a specified cross-linked polymer into at least one layer other than emulsion layers. CONSTITUTION:A cross-linked polymer represented by the formula is incorpo rated into at lest one layer other than emulsion layers. In the formula, A is a monomeric unit obtd. by copolymerizing a copolymerizable ethylenic unsatd. monomer, B is a monomeric unit obtd. by copolymerizing a copolymerizable and cross-linkable monomer having at least two copolymerizable ethylenic unsatd. groups, M<+> is a cation, w=10-95mol%, x=3-88mol%, y=0-50mol%, and z=2-30mol%. A satisfactory antistatic effect is produced even at low humidity.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic light-sensitive material, and particularly to a photographic light-sensitive material with improved antistatic properties.

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so they are subject to contact friction or peeling with surfaces of the same or different materials during the manufacturing process and during use. This often causes electrostatic charges to accumulate. This accumulated electrostatic charge causes many problems, but the most serious one is that the photosensitive emulsion layer is exposed to light due to the discharge of the accumulated electrostatic charge before processing, and when the photographic film is processed. It is the appearance of dot-like spots or dendritic or feather-like streaks on the skin. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, or in some cases completely destroys it. For example, it will be easily recognized that if it appears in a medical or industrial X-ray film, it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. These accumulated electrostatic charges can cause secondary failures such as dust adhesion to the film surface and uneven coating.

As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials. This occurs due to peeling between the support surface and the emulsion surface, etc. Alternatively, this may occur due to contact peeling between the X-ray film and a mechanical part or fluorescent intensifying screen in an automatic camera. It can also occur due to contact with other packaging materials. Static marks on photographic materials induced by such accumulation of electrostatic charges become more noticeable as the sensitivity of photographic materials increases and processing speed increases. Particularly in recent years, single-layer static marks are more likely to occur due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. .

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, in addition to having excellent antistatic properties, antistatic agents that can be used in photographic light-sensitive materials do not have any negative effects on photographic properties such as sensitivity, fog, graininess, sharpness, etc. of photographic light-sensitive materials. In other words, R is the film strength of photographic light-sensitive materials.
1) have no adverse effect on the adhesion resistance (i.e., do not easily scratch against the surfaces of photographic materials or other substances); Application of antistatic agents to photographic materials requires performance such as not causing premature fatigue of processing solutions for photographic materials, and not reducing adhesive strength between constituent layers of photographic materials. This is subject to many restrictions.

One way to eliminate the problems caused by static electricity is to increase the electrical conductivity of the surface of the photosensitive material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged.

Therefore, methods of improving the electrical conductivity of supports and various coated surface layers of photographic light-sensitive materials have been considered, and one of these methods has been the use of ionic polymers. for example,
Special public service No. 17-43jtrt, No. j7-1137j,
German patent No. 1,7 μj.

J- oti, special public Shohiru Turco 3t27, same j! - Hari i
S issue, same! ! -1!247, JP-A Show μr-t Tata 72
No., U.S. Patent No. 27, ≠IO, No. 3.7/
, No. 131, and Kotori No. 37 discloses an attempt to utilize a (anionic) polymer having a carboxyl group for antistatic purposes in photographic light-sensitive materials. However, these polymers are water-soluble, and when a silver halide photographic light-sensitive material to which these polymers are added is processed, these polymers are eluted into the (aqueous) processing solution and are dissolved in the processing solution. It accumulates and contaminates the silver halide photographic light-sensitive material that is subsequently developed. It leaves minute elution marks on the surface of the silver halide photographic light-sensitive material, causing cloudiness on the silver halide photographic light-sensitive material. There was a problem. In addition, these polymers also have the problem that these polymers diffuse from the layer of the silver halide photographic light-sensitive material to which they are added into other layers, resulting in a significant decrease in antistatic performance. Ta. In order to further solve this problem, an attempt to form a polymer of acrylic acid or meth-l-acrylic acid into a crosslinked latex is described in US Pat. No. 44.30/, No. 2μQ. This crosslinked polymer of acrylic acid or methacrylic acid was able to solve the above-mentioned problems of the non-crosslinked polymer having carboxyl groups.

However, although this cross-linked polymer of acrylic acid or methacrylic acid has sufficient antistatic power at normal humidity to high humidity, it does not have sufficient antistatic power at low humidity, causing static marks on photographic materials. It was virtually impossible to prevent this. We have conducted extensive research aimed at developing an antistatic agent that takes advantage of the features of crosslinked polymers and has sufficient antistatic power even at low humidity, and as a result, we have achieved the present invention. A major feature of the crosslinked polymer of the present invention is that it has a monomer represented by the general formula (ltl) as a copolymer component.

Here, R2, R3, R4 and n are as shown above.

(Object of the Invention) An object of the present invention is to provide a silver halide photographic material which is sufficiently prevented from charging.

A third object of the present invention is to provide a silver halide photographic material which is sufficiently prevented from charging even at low humidity.

A third object of the present invention is to provide a silver halide photographic material which is antistatic and does not generate scum during development.

A fourth object of the present invention is to provide a silver halide photographic material which is antistatic and does not become cloudy during development.

(Structure of the Invention) These objects are based on the following general formula (I) in at least one layer other than the halogenated emulsion layer of a silver halide photographic light-sensitive material.
This could be achieved by incorporating a crosslinked polymer represented by:

General formula (I) In the formula, Ro and R2 represent a hydrogen atom or an alkyl group, and R3 is a hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an aryl group or an acyl group, and R4 represents a hydrogen atom or an alkyl group. R3 and R4 may be linked to each other to form a ring. Further, these groups Ro, R2, R3, and R4 may be unsubstituted or substituted.

L represents a divalent, trivalent or valent linking group. l represents O or l, m represents an integer of 7 to 3, and ntj:/-10. A represents one monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. B represents one mono-termer unit copolymerized with a copolymerizable crosslinking monomer having at least one copolymerizable ethylenically unsaturated group. M (9 represents a cation. W is l
O~rijmolti, X is 3~tIrmolti, y is ONjθ
Molti, 2 is greater than 1 to 30 moles.

The crosslinked polymer of the present invention will be explained in detail below.

Examples of R□ and R2 include a hydrogen atom, an unsubstituted alkyl group such as a methyl group, an ethyl group, and an n-propyl group, and a substituted alkyl group such as a carboxymethyl group. Among these, a hydrogen atom, a methyl group, or a carboxymethyl group is preferred.

R3 is a hydrogen atom or a methyl group, ethyl group, n-propyl group, 1-propyl group, n-butyl group, i-butyl group,
Unsubstituted alkyl groups such as n-hexyl group and n-dodecyl group, substituted alkyl groups such as benzyl group, phenethyl group and cochloroethyl group, cycloalkyl group such as cyclohexyl group, phenyl group, p-methylphenyl group, p - unsubstituted or substituted aryl groups such as chlorophenyl group, unsubstituted or substituted acyl groups such as acetyl group, benzoyl group, p-methoxybenzoyl group, among which lower groups having 1 to 7 carbon atoms; is preferred. Examples of It4 include a hydrogen atom or an unsubstituted or substituted alkyl group such as a methyl group, an ethyl group, an n-propyl group, a chloromethyl group, and among these, a hydrogen atom or a methyl group is preferable. When R3 and R4 are connected to each other to form a ring, an example of the ring is a tetrahydrofuran ring.

L is a divalent, trivalent or μ-valent linking group, -Q in the case of a co-valent linking group, % is a linking group in the field of a trivalent linking group, examples of which are alkylene groups (e.g. methylene group,
ethylene group, trimethylene group), arylene group C example, t
(phenylene group), -C-0-X- (wherein, X represents an alkylene group having 1 to about 6 carbon atoms or an arylene group. 1/J- can be done.

l is O or l.

m is an integer of 1 to 3, preferably l or .

n is an integer of 7 to io, preferably an integer of /-j.

Examples of Natsuma-A include ethylene, propylene, norpuran, isopran, styrene, alpha-methylstyrene, vinyltoluene, ethylenically unsaturated esters of fatty acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated carboxylic acids. esters (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate,
benzyl methacrylate, n-butyl acrylate, n
-hexyl acrylate, coethylhexyl acrylate), monoethylenically unsaturated compounds (eg acrylonitrile) or gels (eg butadiene, isoprene), etc.

Examples of Shitsummer B include divinylbenzene, trivinylcyclohexane, ethylene glycol dimethacrylate,
Examples include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and pentaerythritol tetraacrylate.

Examples of M include monovalent cations such as hydrogen ions, sodium ions, potassium ions, lithium ions, cesium ions, and ammonium ions, as well as polyvalent cations such as calcium ions, barium ions, and aluminum ions. . Among these, heptavalent cations are preferred.

W is 10~ri! Molch, preferably 30 to 70 mol%,
X is 3 to tt mol%, preferably 70 to 60 mol%, y
is 0~! Theta mole, preferably 0 to 30 moles, 2 is co-30 moles, preferably ia-j-20 moles.

The method for synthesizing the crosslinked polymer of the present invention is shown below, but the present invention is not limited thereto. First, the general formula (I
Monomers represented by I), monomers represented by general formula (III), monomers represented by A in general formula (1), and monomers represented by B in general formula (I), for example, according to Research Disclosure ( R
As in the method described in Vol. lt/Section 2 of E5earch Disclosure), a method of directly emulsion copolymerizing in water and then neutralizing with an alkali if necessary is exemplified.

General formula (TI) where R,, L% l and m are as already shown.

General formula (II[) where 几2, R'1, R4 and n are as already shown.

Second, the 7mer represented by the above general formula (III)
After emulsion copolymerizing the monomer represented by A in the general formula (T) and the monomer represented by B in the general formula (I) in water to obtain a crosslinked polymer dispersion represented by the general formula (fV), for example, US Patent No.≠, JO/, 2
An example of this method is saponification with an alkali in the same manner as the method described in μθ.

General formula (IV) where 'fL2, TL3, R4, n, A, BXw,
x.

ylz is as already shown.

Thirdly, monomers represented by general formula (II), monomers represented by general formula (ill), general formula (I)
The monomer represented by A in formula (I) and the monomer represented by B in general formula (I) are subjected to inverse emulsion copolymerization in the same manner as described in U.S. Patent No. μ, 30/, JaO. A method of redispersing the crosslinked polymer in water and further neutralizing it with an alkali if necessary can be mentioned. Among these methods, a preferred method is selected depending on the type of each monomer and the copolymerization ratio.

Examples of the crosslinked polymer of the present invention are shown below.

l 7- QcfJ flash O medium Q-Q-Q=Oli. Ql
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! Work 8 Q 1I k Po ≠ 乍 Q Korea 1 Chu 0 <1゛'= 1 ~ Jiketsu-8 '-1 Work... Q x Q-○-Q=Q Work 2 - Work... Work \Q
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1" Q.

1v1; ... (1) GeQ 1 = N A synthesis example of the crosslinked polymer dispersion of the present invention is also shown below.

Synthesis Example 1 Synthesis of Crosslinked Polymer Example 1 A stirrer, a reflux condenser, and a thermometer were installed. 21 In a Mitsuro flask, add distilled water urOxl and an emulsifier (commercially available from Sanyo Kasei under the trade name BL) 1. the law of nature!
2 and methoxyethyl acrylate 1017. A mixed solution of jf and divinylbenzene A4.01 was added, and the mixture was stirred at 0°C and ztorpm under a nitrogen stream. After replacing the air in the container with nitrogen, add potassium persulfate o, spy
Emulsion polymerization was started by adding a solution prepared by dissolving Jll) in distilled water. The mixture was heated and stirred at OoC for 1.5 hours to obtain a cloudy crosslinked polymer dispersion (latex). Further, a solution of potassium persulfate (o) and os4At@distilled water (10@l) was added, and the mixture was heated and stirred for 30 minutes, and then cooled to room temperature. Separate some aggregates into the furnace and determine the solid content concentration! 2.7
Wt- crosslinked polymer dispersion (latex) 6 kota, jf
I got it. The crosslinked polymer particle diameter determined by dynamic light scattering method is o,
It was 1r4tμ.

The above crosslinked polymer dispersion (latex) was placed in another 34-meter flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and potassium hydroxide was added while stirring at 30θrpm at room temperature. A solution dissolved in distilled water/r j ml was added dropwise over 1 hour. After further stirring at room temperature for 2 hours, the mixture was heated to 0°C to 0°C and stirred for 1.5 hours. Next, potassium hydroxide 7,≠jf was added to distilled water 113
After dropping the solution dissolved in m1 over 30 minutes, det-?
The mixture was heated and stirred at P'c for 3 and a half hours. Furthermore, a solution of potassium hydroxide, 2s, ty dissolved in 4 J ml of distilled water was added dropwise over 3Q minutes, and the mixture was heated and stirred at 0C for 12 hours. The mixture was cooled to room temperature, purified by dialysis, and then concentrated to obtain a dispersion of crosslinked polymer example 1/2J7ff. Solid content concentration bar,
77Wt9b, the saponification rate determined by acid-base titration is 7,
j%, the crosslinked polymer particle diameter determined by dynamic light scattering method is O1
It was ≠31μ.

Synthesis Example 2 Synthesis of Crosslinked Polymer Example t Add distilled water, 11 emulsifier (same as the emulsifier used in Synthesis Example 1) p, and 4Iry to an fcJ11 Mitsuro flask equipped with a stirrer, reflux condenser, temperature needle, and constant flow rate dropping pump. Then tag under a nitrogen stream.

, 2! The mixture was stirred at Orpm. After sufficiently replacing the air in the container with element 9, (I) a mixed solution of acrylic acid o, oy, methoxyethyl acrylic V-) JJ, jl and pentaerythritol tetraacrylate sr, tt, (2) potassium persulfate, , if solution dissolved in 1 ml of distilled water, (3) Sodium bisulfite / , + f 81 m ferrous hydride 0. ! Three solutions of TFF dissolved in 10 ml of distilled water were simultaneously added dropwise over 7 and a half hours. After the dropwise addition was completed, the mixture was heated and stirred for 11 minutes, and then a solution of potassium persulfate, 12, and sodium sulfite λ, tf dissolved in 11 AOme of distilled water was added, and the mixture was further heated and stirred for 1 hour and 1j minutes. Next, add sodium hydroxide ao, oy to distilled water 200117
A solution dissolved in was slowly poured into the solution to neutralize it, and then cooled to room temperature. Some aggregates were separated from each other to obtain a crosslinked polymer dispersion/7j/f'i. Solid concentration is //, 0w
t%, frame-2 determined by dynamic light scattering method! - The bridge polymer particle size was O, Kokota μ.

The amount of the crosslinked polymer represented by the general formula (I) varies depending on the type, form, coating method, etc. of the photographic material used. However, in general, the amount used is O07 to Nooy per 1m of photographic light-sensitive material.
Ko, r~j ri is desirable.

The method of applying the crosslinked polymer represented by general formula (I) to the antistatic layer of a photographic light-sensitive material includes water, an organic solvent (e.g.
Methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dioxane, dimethylformamide, formamide, dimethyl sulfoxide, methyl sesol, ethyl sesol, etc. (especially methanol and ethanol are preferred) or a mixed solvent thereof is added and dispersed. Afterwards, it may be sprayed, coated, or immersed in the solution and dried.

Further, it may be used together with a binder such as gelatin, polyvinyl alcohol, cellulose acetate, cellulose acetate phthalate, polyvinyl formal, polyvinyl butyral alcohol, etc. to form an antistatic layer.

Particularly favorable effects can be obtained when a fluorine-containing surfactant and a matting agent are used in combination in the layer containing the crosslinked polymer represented by the general formula (T) of the present invention.In particular, when a fluorine-containing surfactant is used in combination, Great for preventing static marks.

Furthermore, the above layer may contain additives for various purposes such as a curing agent, a slip agent, and an antihalation dye.

Examples of matting agents that can be used in combination with the crosslinked polymer represented by the general formula (I) of the present invention to obtain preferable effects include barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, powdered silica, oxidized There are titanium etc. The particle size of the matting agent is /-10μ,
In particular, /-jμ is preferable. The amount of the matting agent to be used is preferably from 10 to 300 cm/-/m of the photosensitive material.

A fluorine-containing surfactant particularly preferably used in combination with the crosslinked polymer of the present invention is represented by the following general formula.

General formula (V) f-A-X In the formula, Rf represents a partially or fully fluorinated substituted or unsubstituted alkyl group, alkenyl group, or aryl group containing at least three fluorine atoms. A represents a divalent linking group, and X represents a water-soluble group.

A preferably represents an alkyl group, an aryl group, or an alkylaryl group, which is a divalent substituted or unsubstituted linking group interrupted by a heteroatom such as oxygen, an ester group, an amide group, a sulfonyl group, or sulfur. It's okay.

X is a hydrophilic group, for example, a polyoxyalkylene group of the general formula (-B-0)n, R (where B is -CH2CH2-1 -CH, CH2CH2- or the average degree of polymerization of the lyoxyalkylene group) represents l~30
is the number of In addition, a nonionic group represented by "1B represents a substituted or unsubstituted alkyl group or aryl group", a hydrophilic betaine group, such as a lower alkylene group such as methylene, ethylene,
Zoropyrene and butylene are represented, R□4 and R15 are substituted or unsubstituted alkyl groups, aryl groups with carbon number/-ff,
(for example, methyl group, ethyl group, benzyl group, etc.) and hydrophilic cationic groups (in the formula, R, , ) 1 , R
□6 has 141% the same meaning as R14, and Ye represents an anion. )-1 and preferably a hydrophilic anionic group such as -8
03M, -0803M, -COOM.

-01-0-P(O, etc.). Here, M represents an inorganic or organic cation.

Specific examples of typical fluorine-containing surfactants of the present invention are shown below.

Compound example [-1 07F1sCOOH [-J H(-OF + CHCOONH4[-J C, F17803■-μ fJ-z I-1+CF2+6COOC)I2C■]2CH2SO
3Na-r p: average ≠ ■-ta p: average! -2l - ■-10 08F, CH2C) 120+CH2CH2Osu, Hn
5: / Co[-// n5:// '[1-12 ■-73 1-/4L The amount of the fluorine-containing surfactant used in the present invention is generally 0.000. 001~/f is fine, especially! ~JOO■ is preferred.

Examples of the antistatic layer containing the crosslinked polymer of the present invention include an undercoat layer on the same side as the emulsion layer, an intermediate layer, a surface protective layer, an overcoat layer, and a pack layer on the opposite side to the emulsion layer. Among these, the outermost layer such as a surface protective layer, overcoat layer, or pack layer or a layer adjacent thereto is particularly preferable.

Supports to which the crosslinked polymer of the present invention can be applied include, for example,
Polyolefins such as polyethylene, polystyrene,
cellulose derivatives, such as cellulose triacetate,
Included are supports made of films of cellulose esters such as polyethylene terephthalate, or sheets of baryta paper, synthetic paper, or paper coated on both sides with these polymer films, and the like.

The support used in the present invention can also be provided with an antihalation layer. For this purpose, carbon black or various dyes such as oxole dyes, azo dyes, aryl tin dyes, styryl dyes, anthraquinone dyes, Examples include merocyanine dyes and tri(di)allylmethane dyes. As a binder for carbon black dye, cellulose acetate (di or mono)
, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, polymethacrylic ester, polyacrylic ester, polystyrene, Styrene V/maleic anhydride copolymer, polyvinyl acetate, vinyl acetate/maleic anhydride copolymer, methyl Vinyl ether/maleic anhydride copolymers, polyvinylidene chloride, and derivatives thereof can be used.

The photographic material according to the present invention may be a conventional black-and-white silver halide photographic material (for example, black-and-white photographic material, X-r
black-and-white photosensitive materials for ay, black-and-white photosensitive materials for printing, etc.), ordinary multilayer color photographic materials (e.g., color reversal films, color negative films, color positive films, etc.), and various photographic materials. .

It is particularly effective for silver halide photographic materials for -3 goo high temperature rapid processing and high-sensitivity silver halide photographic materials.

Other components that can be used in the photographic material of the present invention, such as the type and manufacturing method of silver halide emulsions, chemical sensitizers, spectral sensitizers, antifoggants, stabilizers, color couplers, binders such as gelatin, There are no particular limitations on the hardening agent, polymer latex, coating aid, coating agent, antistatic agent other than the antistatic agent of the present invention, and the exposure and development method of the photographic light-sensitive material of the present invention.
rchDisclosure magazine/volume 77 here ~ 3/page (
You can refer to the description in December 2007).

For example, as the gelatin, acid-treated gelatin or lime-treated gelatin can be preferably used.

As a hardening agent, an active vinyl compound having a vinyl sulfone group or the like (≠dichloro-t-hydroxy-s-)
Active SO-generating compounds such as riazine are preferably used.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 (I) Preparation of sample: A silver halide emulsion layer having the following composition was coated on an undercoated polyethylene terephthalate film support having a thickness of iroμ, and a protective layer having the following composition was further applied thereon. A black and white silver halide photosensitive material was prepared by coating and drying.

(Emulsion layer) Thickness: approx. j μ Composition and coating amount Lime-treated gelatin, j 'i/m
2 silver iodobromide (silver iodide/J momol) If/m”6■
/m2 /-Phenyl-j-mercaptotetrazole 2Jmg/m2 (protective layer) Thickness: Approximately lμ Composition and coating amount Lime-treated gelatin /, 7 f/m
2λ, t-dichloro-μm hydroxy/, J, j-) riazine sodium salt IQ■/m2 □N-oleyl sodium N-methyltaurate 7~/m2 Sample JFk
/ consists of only the above composition, and Sample Coat T has the composition of Sample A/ plus the polymer of the present invention or comparative polymer / in the protective trowel layer.
, 7 f/m2 equivalent was added.

More sample shop~/! t(0, I
(equivalent to sf/ln2) was created.

(2) Method for determining antistatic property: Antistatic property was determined by measuring surface resistivity and static mark generation. ■Surface resistivity is measured by measuring the test piece of the sample with an electrode spacing of 0. /1Aax, length 10 (II) with a brass electrode (the part in contact with the test piece is made of stainless steel), and measure the value for 7 minutes with a Takeda Riken insulation meter T1%ft!/ type.■
In the static mark generation test, static marks were generated by placing an unexposed photosensitive material on a rubber sheet with the antistatic agent-containing surface facing downward, pressure-bonding the material with a rubber roller from above, and then peeling it off.

For each measurement condition, the surface resistivity is 1.2J 'C, JjFR
The static mark generation test was carried out at Jj'CX 2j'16H and Koj''c, 10もRH.The humidity of the sample test piece was adjusted under the above conditions. So I went there for two days and nights.

In order to evaluate the degree of static mark generation, each sample was developed at -200C for 5 minutes using a developer having the following composition.

Developer composition N-methyl-p-aminophenol sulfate ay anhydrous sulfite 60?3 t-hydroquinone ioy soda carbonate (/hydrate) 332 potassium bromide
-257 Add water to make /l.

The evaluation of static marks followed the following j-level criteria.

A: No markings were observed.

B: Some static marks occur.

C: A static mark occurs.

D = Significant occurrence of tick marks.

E: Static marks appear on the entire surface.

The results are shown in Table 1.

-3ter comparative polymer A (-CH-CH2-) w:y:z=7A:/4:f (mol%) (U.S. Patent No.
, 30/, 2≠θ (Synthesized according to Example R Modification t-Co) As is clear from Table 1, the black and white silver halide photographic light-sensitive material added to the protective layer of Comparative Polymer A-i was Jj 'CJj
%RH, it is sufficiently prevented from charging, but at COS OC10
It can be seen that at low humidity of %RH, static marks are not sufficiently prevented and static marks are significantly generated.

On the other hand, black-and-white photo materials containing the polymer of the present invention added to the protective layer (1,2 s 'C, 2, t c
It can be seen that not only s RJH but also Jj 'C101RH is sufficiently prevented from charging even at low humidity, and almost no static marks are observed.

Example 2 A multilayer color photosensitive material was prepared, which consisted of a back layer on one side of a cellulose triacetate film-covered body and each layer on the opposite side of the back layer.

[Back layer]

7th layer coating amount Cf/m)
Binder: Gelatin i3≠≠゛ coating
Agent: Sulfoconophosphate dioctyl ester sodium salt 0. jKS Thickener: Sodium polystyrene sulfonate o, o here, 2 Fm Binder: Gelatin 4. oθ Coating agent: Sulfoconomonolilic acid dioctyl ester sodium salt 1.72j Hardening agent: J,7-dichloro-l-hydroxy-/, J,j-)riazine sodium salt 0.043 Pack protective layer (third layer) Binder: Gelatin 0.612 Matting agent: Polymethyl methacrylate (average particle size 3, jμ) O, here! Coating agent: Sulfosuccinic acid dioctyl ester sodium salt NO, TIY Fluorine-containing surfactant: Compound example 11-4! o, oos hardener:
J, B-dichlor-1≠-Hydroxy/,! ,! -) Riazine sodium salt 0. II/ [Color photosensitive layer] 1st layer; antihalation layer; gelatin layer 4A containing black colloidal silver; J-th layer; intermediate layer; 3rd gelatin layer containing an emulsified dispersion of j-di-t-octylhydroquinone; Layer: 7th red-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide:! Morch)...
...Silver coating amount 1.79 f/m" Sensitizing dye I......70 moles per mole of silver Sensitizing dye ■... ...for 1 mole of silver / , jXl O mole Casolar A ... old ... o for 7 moles of silver,
op molkazolar〇-/・・・・・・0.00 per 7 moles of silver
Nojmol Kabra-C-1...0.00 per mole of silver
11 mole 12- D... old... o for 7 moles of silver
, ooo≦molar μth layer: @Red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: molar %)・・・・・・・・・
...-l μ- Silver coating amount /, 4Af! /m2 Sensitizing dye■・・・・・・・・・J×10 for 7 moles of silver 5 moles Sensitizing dye■・・・・・・・・・・・・For 7 moles of silver te l, Jxlo Molar coupler A......0.02 mole for 7 moles of silver Coupler C-/...o, oo for 1 mole of silver
or mol Casolar C-co... o, oo per mole of silver
or mole j! @: Same layer as the first intermediate layer: 7th green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 24' molar preponderance)...
...Amount of coated silver / , j f / m "Sensitizing dye■ ......Jxl per mole of silver
o Molar sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・／×10 for 1 mole of silver Molar coupler B・・・・・・・・・・・・O, OS molar coupler for 7 moles of silver M-/・・・o, oo per mole of silver
r mole coupler D...0.00/j mole per mole of silver 7th layer: 1st night-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 1 mol% )・・・・・・・・・
・・・Amount of coated silver /, At/m2 Sensitizing dye■・・・・・・・・・・・・Co, jX10' moles per 1 mole of silver Sensitizing dye■・・・・・・・・・...0, Ixlo% per mole of silver Coupler B...0.02 mole per mole of silver Coupler M-/...7 mole of silver 0.00 against
3 mole coupler D...0.0003 mole per mole of silver J layer: yellow filter single layer Yellow colloidal silver and 2.0 mole in gelatin aqueous solution. ! -G-t-
and a gelatin layer comprising an emulsified dispersion of octylhydroquinone.

Second layer: First evening-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%)...
...Amount of coated silver /, 197m" Coupler~Y-/...0.2j per mole of silver
Mole 7th Q layer: Blue-sensitive emulsion layer silver iodobromide (silver iodide = t mole)...
・Amount of silver coated / , / 17m" Turnip 2-Y-/...0.01 per mole of silver
Mol layer II: protective layer polymethyl methacrylate particles (diameter approx. l.

! μ) Sodium dodecylbenzenesulfonate (ioo
■/m @ Sho) coated with a gelatin layer.

In addition to the above composition, each layer contains a gelatin hardener and 4C7- Surfactant was added.

Compound sensitizing dye I used to prepare the sample: Anhydro J No. I'-dichloro-3.3
1-di(r-sulfopropyl)-terethyl-thiacarbocyanine hydroxide-pyridinium salt sensitized color in: anhydroterethyl-3.3/-diCr-sulfopropyl)-Hiro・j-11/j' -Shihenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye■:Anhydrotorethyl-!・! I-Zikuo 3a! '-Cr-sulfosolovir) oxacarbocyanine-sodium salt sensitizing dye ■: Anhydro!・T-! 'Fist 4/-Tetrachloro7al/-Diethyl-3,3/-C[β-[β-Cr-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt t- Coupler B COOC, 6H33 Coupler C -2 Coupler D H3 Coupler M-/α Coupler Y-/1! l- Sample shop consists of only the above composition, sample shop, 2λ ~
In addition to the composition of sample A-7, the core has the second layer of the back layer,
A polymer of the present invention or a comparative polymer.

1397m was added, and samples A J r ~ J J i
j, co.

It was created by adding 4617m2. Note that when the present polymer or comparative polymer was added, a considerable amount of gelatin was reduced.

The antistatic properties were evaluated in the same manner as in Example 1. However, development was carried out using Fuji Film ■ ON-/4 processing.

The results are shown in Table 2.

As is clear from Table J-1, the silver halide color photographic light-sensitive material added to the comparative polymer Ai pack layer had Jj'C
1t R and H have sufficient anti-static properties, but t'
It can be seen that static marks are significantly generated at low humidity of 10% RH. On the other hand, the silver halogenide photographic light-sensitive material containing the polymer of the present invention added to the pack layer was
It can be seen that charging is sufficiently prevented even at low humidity of H, and no static marks are observed.

Preferred embodiments of the present invention are shown below.

t Silver halide in which the layer containing the crosslinked polymer represented by general formula (I) in the claims is the outermost layer such as a surface protective layer, overcoat layer, pack layer, etc. or a layer adjacent thereto. Photographic material.

2. A silver halide photographic material in which the layer containing the crosslinked polymer represented by formula (I) is a layer adjacent to a silver halide emulsion layer.

3. In the claims, l in general formula (I)
is O, and m is l.

Hiroshi A 710 silver-genide photosensitive material according to the claims, wherein the cross-linked polymer has a particle size of 0.01-/μ in water.

A silver halide photographic light-sensitive material characterized in that the crosslinked polymer represented by the general formula (I) is contained in at least one layer other than the trout silver halide emulsion layer of the silver halide photographic light-sensitive material. Method for preventing static electricity of materials.

Patent applicant: Fuji Photo Film Co., Ltd.
month end i day

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer, which contains a crosslinked polymer represented by the following general formula (I) in at least one layer other than the emulsion layer. General formula (I) for silver halide photographic materials characterized by ▲Mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 represent a hydrogen atom or an alkyl group, and R_3 represents a hydrogen atom, an alkyl group, or a cycloalkyl group. group, aryl group or acyl group, and R_4 represents a hydrogen atom or an alkyl group. R_3 and R_4 may be connected to each other to form a ring. Also, R_1, R_2,
These groups R_3 and R_4 may be unsubstituted or substituted. L represents a divalent, trivalent or tetravalent linking group. l is 0 or 1, m is an integer from 1 to 3, and n
represents an integer from 1 to 10. A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. B represents a monomer unit obtained by copolymerizing a copolymerizable crosslinking monomer having at least two copolymerizable ethylenically unsaturated groups. M^■ represents a cation. w is 10~
95 mol%, x is 3 to 88 mol%, y is 0 to 50 mol%
, z are 2 to 30 mol%.