JPS61223736A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain good antistatic characteristics, to improve antitackiness, and to prevent scum in development processing by arranging a layer contg. a specified polymer on a silver halide emulsion layer. CONSTITUTION:The layer to be arranged on the photosensitive silver halide emultion layer formed on the support of a photographic sensitive material, contains as an antistatic agent a polymer represented by the formula shown on the right in which A is a monomer unit obtained by copolymerizing a comonomer having at least 2 ethylenically unsatd. groups; B is a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsatd. monomer; R1 is H or 1-6 C lower alkyl; L is -CH2O-, -CH2NR6-, or the like; R6 is H or aralkyl; M is 1-12 C divalent group; R2-R4 are each 1-20 C alkyl, 7-20 C aralkyl, or they may combine with each other to form a ring; R5 is 1-20 C alkyl, acyl, amide, or the like; X<-> is an anion; x is 0-10, y is 0-90, and z is 10-100 mol%; and n is 0, 1, or 2. Such a photosensitive material has high sensitivity and high effect when used for high-temp. high-speed processing, and it is used for an ordinary black-and white photograph and a multilayer color photograph.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic material,
In particular, it relates to an antistatic photographic material comprising at least one light-sensitive silver halide emulsion layer and at least one antistatic layer.

(Prior Art) During the manufacture and use of photographic materials, static electricity tends to accumulate, and this accumulation of static electricity causes many problems. This charging occurs, for example, at the contact point between the photographic light-sensitive material and the roller in the manufacturing process, or at the friction between the support surface and the emulsion surface during the winding and unwinding process of the photographic light-sensitive material.
Also, peeling occurs between the support and the emulsion surface when the photosensitive material is exposed to high humidity that causes adhesion during use, and automatic development of movie cameras and X-ray films. This also occurs when the following is used. When these accumulated N72 static electricity is discharged, the photosensitive material is exposed to light, and after the development process, irregular static marks such as spots, branches, and feathers are formed, which reduces the commercial value of the photographic material. This is a significant loss. The existence of these static marks is not known until they are developed, so
This is one of the most troublesome problems, and the accumulated electricity causes dust to adhere to the surface of the photosensitive material.
This may cause secondary failures such as uneven coating failures. Furthermore, since all photosensitive material supports are hydrophobic, they accumulate a large amount of static electricity, so the occurrence of static marks increases as processing speed and emulsion sensitivity increase.
It will have a significant negative impact.

Conventionally, various substances have been used to prevent charging of photographic materials. These substances are ionic conductive substances or hygroscopic substances, and a method is often used to impart conductivity to the photosensitive material and quickly dissipate the charge before discharge occurs due to charge accumulation. 1! ! friend.

When used, these substances may be used alone or in combination. In order to directly impart antistatic properties to the support of photographic light-sensitive materials, it is known that such substances are directly blended into the polymeric material that is the support, or coated on the surface of the support. There is. In the latter case, use an antistatic agent alone or use gelatin, polyvinyl alcohol, cellulose acetate, polyvinyl formal,
A method of mixing and coating with a polymeric substance such as polyvinyl butyral is used. In addition to the photosensitive emulsion layer provided on the support, the antistatic agent can also be added to non-photosensitive layers (for example, backing layer, antihalation layer, intermediate layer, protective layer, etc.). can. Alternatively, there is a method of coating the developed photosensitive material to prevent dust from adhering to the developed photosensitive material during handling. However, among the conventionally known antistatic agents, in the case of photosensitive materials having a highly sensitive emulsion layer, there are few that exhibit a satisfactory antistatic effect, especially under low humidity conditions, or the antistatic effect decreases over time, or when high temperature However, it is often accompanied by adhesion failure under high humidity conditions, and may have an adverse effect on photographic properties, making it difficult to apply it to photographic light-sensitive materials. , 726 and British Patent Nos. 1 and 4
Some polymers whose polymerized units are acrylic or methacrylic esters with μ-class ammonium groups, such as those shown in Af≠, rtr, have fairly good antistatic properties, but these polymers The coated layer is sticky and easily adheres to the surface of the substrate, and it also has poor resistance to aqueous development compounds, which inevitably causes scum to form in the photosensitive material. there were.

On the other hand, when a crosslinked polymer having vinylbenzyl μ-class ammonium as a polymerization unit as shown in JP-A No. 3-μ 23/ is used, conversely, the generation of scum in the contact-resistant layer and during the development process is Although it is good in this respect, it is impossible to sufficiently achieve the objective in terms of the antistatic properties essential for an antistatic agent.

(Objects of the Invention) The first object of the present invention is to provide an antistatic N72 silver halide photosensitive material having extremely low surface electrical resistance. A second object of the present invention is to provide a silver halide photosensitive material that has good adhesion resistance and is antistatic. A third object of the present invention is to provide a silver halide photosensitive material which is antistatic and does not generate scum during development.

A fourth object of the present invention is to provide an antistatic silver halide photosensitive material that does not adversely affect photographic properties.

Elaborate means for solving problem C) The present inventors synthesized polymer dispersions having units represented by general formula (I) and used them as antistatic agents. It was discovered that the above-mentioned objectives can be achieved in succession, with performance far exceeding expectations.

General Formula (I) In the formula, A represents one unit of a monomer obtained by copolymerizing a copolymerizable monomer containing at least two ethylenically unsaturated groups.

B represents one monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer.

R1 represents a hydrogen atom or a lower alkyl group having 1 to about 6 carbon atoms.

L is -CH20-, -CH2N(R,S -CH20C
−.

-CN(R'-), (wherein R, , 16 is a hydrogen atom or an alkyl group);

M represents a divalent group having from 1 to about 72 carbon atoms.

R, R, and R4 each represent the same or different alkyl group having from I to about 20 carbon atoms or an aralkyl group having from 7 to about 0 carbon atoms, and R2, R3t
R4 may be interconnected to form a cyclic structure together with the nitrogen atom.

Xo represents an anion;
Tatamol%.

In the preferred polymer dispersion of the present invention, examples of copolymerizable heptamers having at least two ethylenically unsaturated groups represented by A in the above general formula include divinylbenzene,
These include ethylene glycol dimethacrylate, isopropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol diacrylate, and tetramethylene glycol dimethacrylate, among which divinylbenzene and ethylene glycol dimethacrylate are particularly preferred.

B is one monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer, and examples of the ethylenically unsaturated monomer are ethylene, propylene, /-butene, isobutyne,
Styrene, α-methylstyrene, vinyltoluene, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-hexyl methacrylate, n-octyl acrylate, benzyl acrylate, cyclohexyl methacrylate, coethylhexyl acrylate and acrylonitrile, among which styrene, methyl methacrylate, ethyl methacrylate, n-butyl Particularly preferred are methacrylate, cyclohexyl methacrylate, etc. Bfl may contain two or more of the above monomer units.

R1 is a hydrogen atom or a carbon number/4 lower alkyl group (e.g. methyl group, ethyl group, n-propyl group, n-
7'thyl group, n-amyl group, n-hexyl group), and among these, a hydrogen atom or a methyl group is particularly preferred.

L represents a linking group such as -CH20-, -CH2N(R6)-t hydrogen atom or an alkyl group), and among these, -CH20-, -CH2N(R5)- (for example -C
H2NH-, -CH2N-).

CH3 -CH2QC- is preferred.

Mfl, a divalent group having from 1 to about 1 carbon atoms, examples of which are alkylene (e.g. methylene, ethylene, trimethylene, -(:HCHCH2)-alkylene having from 11 to about 1 carbon atoms; , -CHCHOCHCH
-1-CH2CH2NHCH2CH2- and the like are preferred.

RR and R4 are each the same or different l to about 20
or an aralkyl group having from 7 to about 20 carbon atoms, including substituted alkyl and aralkyl groups.

R2, R3 and R4H may be interconnected to form a cyclic structure together with the nitrogen atom.

Examples of the alkyl group include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-aryl group,
Isoamyl group, n-hexyl group, cyclohexyl group, n
-heptyl group, n-octyl group, coethylhexyl J
Ln-/nyl group, n-decyl group, n-dodecyl group, etc.; the alkyl group preferably has 79 carbon atoms.

Examples of substituted alkyl groups include alkoxyalkyl groups (e.g., methoxymethyl group, methoxyethyl group, methoxybutyl group, ethoxyethyl group, ethoxypropyl group,
ethoxybutyl group, butoxyethyl group, butoxypropyl group, butoxybutyl group, vinyloxyethyl group), cyanoalkyl group (e.g. 2-cyanoethyl group, 3-cyanopropyl group, μm cyanobutyl group), halogenated alkyl group (e.g. 2-cyanopropyl group, μm cyanobutyl group), Examples include a fluoroethyl group, a cochloroethyl group, a J-fluoropropyl group), an alkoxycarbonyl alkyl group (for example, an ethoxycarbonylmethyl group), an allyl group, a coptenyl group, and a propargyl group.

Examples of the aralkyl group include unsubstituted aralkyl groups such as benzyl group, phenethyl group, diphenylmethyl group, and naphthylmethyl group; substituted aralkyl groups such as (alkylaralkyl group such as μm methylbenzyl group, Improbil benzyl group, alkoxyaralkyl group, such as μm methoxybenzyl group,
l-ethoxybenzyl group, "-Cμm methoxyphenyl)benzyl group, cyanoaralkyl group, such as ≠-cyanobenzyl group, ≠-(Hiro-cyanophenyl)benzyl group,
Non-fluoroalkoxyaralkyl groups, such as ≠-antafluoropropoxybenzyl group, μm undecafluorohexyloxybenzyl group, halogenated aralkyl groups, such as μm chlorobenzyl group, ≠-bromobenzyl group,
There are 3-chlorobenzyl group, μ-Cμm chlorophenyl)indyl group, and 4′-(4′-bromophenyl)benzyl group fxt. The number of carbon atoms in the aralkyl group is preferably 7 to 7.
There are I-m pieces.

An example in which R2, R3, and R4 are interconnected to form a cyclic structure together with a nitrogen atom is that R2, R3 represents a cyclic structure (for example, a number, and R4 and Xo are the same as shown above. %R2, R3, and R4 form a cyclic structure (for example, Q and Xe are the same as shown above).

Xo represents an anion, such as a halogen ion (e.g. chloride ion, bromide ion, iodine ion), an alkyl sulfate ion (e.g. methyl sulfate ion, ethyl sulfate ion), an alkyl or aryl sulfone ion (e.g. methanesulfonic acid, ethanesulfone). Examples include benzenesulfonic acid, p-toluenesulfonic acid), acetate ion, and sulfate ion, with chloride ion being particularly preferred.

X is about 0.2% to about 10% by mole, preferably about 7%.
O to about 5.0 mol%, y is O to about 0 mol%, preferably O to about 0 mol%, and 2 is about i
o to about 22 mol%, preferably about go to about 2
P mole %, particularly preferably about 10 to Tata mole %.

The polymer dispersion represented by the general formula (I) of the present invention generally comprises a copolymerizable monomer containing at least two of the above ethylenically unsaturated groups, an ethylenically unsaturated monomer and the following general formula (n). (However, R□, L, and MlX are the same as those shown above.)
After emulsion polymerization with chloromethylanilinomethylstyrene, λ-chloroethoxymethylstyrene, etc.), R2-N
Tertiary amines having the structure -R3 (e.g. trimethylamine, triethylamine,) di-n-butylamine,
It can be obtained by quaternization with tri-n-hexylamine, pyridine, H-methylpyridine, etc.).

Further, the polymer dispersion represented by the general formula (I) of the present invention comprises a copolymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer and the following general formula (III). ) (However, R1, R2, R3, L%M
is emulsion polymerization with an unsaturated monomer (e.g., 2-dimethylamineethoxymethylstyrene, 2-dimethylaminoethylaminomethylstyrene, dimethylaminemethylphenoxymethylstyrene, etc.) represented by t″L7?: shown above. An alkylating agent or an aralkylating agent having the structure &, R, -X (wherein R4,
is the same as shown above) (alkylating agent, e.g.
Jf, p-) methyl luenesulfonate, dimethyl sulfate, diethyl sulfate, ethyl bromide, n-propyl bromide, allyl chloride, n-butyl bromide, chloro-coptene, ethyl chloroacetate, n-hexyl bromide, n-octyl bromide; Aralkylating agents such as benzyl chloride, benzyl prolide, p-nitrobenzyl chloride% p-chlorobenzyl chloride, p-methylbenzyl chloride, p-
Good IL, <t! , p-) methyl luenesulfonate, dimethyl sulfate, diethyl sulfate, benzyl chloride)
It can also be obtained by quaternizing it.

The above emulsion polymerization is generally carried out using anionic surfactants (such as those commercially available from Rohm & Haus under the name Triton 7700), cationic surfactants (such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride), and nonionic surfactants. (for example, polyvinyl alcohol) and a radical initiator (for example, a combination of potassium persulfate and potassium bisulfite).

The above quaternization reaction is generally carried out at a temperature of 06C to about 1000C, with temperatures of 0C to 70C being particularly preferred.

The polymer dispersion and antistatic agent of the present invention can be manufactured in a single container, and are extremely easy to manufacture, and there is no need to use a large amount of solvent.

Examples of the polymer dispersion of the present invention are shown below. (Each of the exemplified polymers contains the following repeating units in the following proportions.) (/) CH3+L; H- to H2' CHα0 x:y:z=j:J:ri3 +CH-CH2± x :y:z=4c: dat:art 1,000CH-CH2÷(μ) c, eCH3 x:y:z=4c:≠f:IAI (j) CH3 ■ x: y: z=μ”, at : μt (Otsu) CH3 Authentic product α03 X: y: Z=J: J: Ri+CH-CH2
÷ x: y: z=j: J: ri2 (j) z:y:z==j:j:ri2 (ri) α x:y:z=μ:4! r: μt z : y : z=41- : 4Af : ut(
ti) CH3 0+C-CH2÷ ■ CH3 C4H9(n) +CH2-CH÷2 c, eCH・x:y:z=j:j: Tata H3 Surprise x:y:z=Hiroshi: ψt:μr General formula (I ) The amount of the dispersion of the present invention to be used differs depending on the type, form, coating method, etc. of the photographic material used. However, in general, the amount used is about o, oi ~ solid content per m2 of photographic light-sensitive material.
t, op may be used, especially 0.03 to 0. Da I is preferable.

The polymer dispersion of the present invention represented by the general formula (I) can be used as it is or in water,
Organic solvents (e.g. methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile,
Dioxane, dimethylformamide, formamide, dimethyl sulfoxide, methyl cellosolve, methyl cellosolve, etc. (methanol, ethanol, acetone are particularly preferred) or a mixed solvent thereof are added thereto, and then the photosensitive emulsion layer on the support and the non-photosensitive auxiliary layer are added. The solution may be sprayed or applied onto the surface of a layer (eg, backing layer, anti-ration layer, intermediate layer, protective layer, etc.) or support, 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 hetatalate, polyvinyl formal, or polyvinyl butyral to form an antistatic layer.

Particularly favorable effects can be obtained when a fluorine-containing surfactant and a matting agent are used in combination with the surface layer containing the compound of the general formula (I) of the present invention.In particular, when a fluorine-containing surfactant is used in combination, static marks can be prevented. Great effect. Furthermore, the surface 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 compound of general formula (I) of the present invention to obtain preferable effects include silver halide, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica, and powder. There are silica etc.

Furthermore, examples of the following compounds can be cited as fluorosurfactants that can provide a combined effect.

For example, British Patent/, 330. Jet issue, US Patent J,
ttA, atr issue, same 3. There are fluorine-based surfactants described in JR9,904 and the like.

Typical examples of compounds include, for example, N + , e
+Fluorooctylsulfonyl-N-propylcridine potassium salt % J -(N-perfluorooctylsulfonyl-N-dithylamino)ethylphos 7-ether), N
-(4'-(perfluorononenyloxy)benzyl)
-N, N-dimethylammonioacetate, N-
(3-(N',N',N'-)limethylammonio)propyl), e-fluorooctylsulfonamide iodide, and N-<polyoxyetherenyl)-N-7'ropyl/safluorooctyl Sulfamide (C8F□7SO2N(C3H7)(CH2CH2
0) n-)gaagerarel.

Layers containing the polymer dispersion of the present invention include an undercoat layer, a protective layer, an overcoat layer on the same side as the emulsion layer, a back layer on the opposite side to the emulsion layer, and the like.

Supports I/C that can be used with the compounds of the present invention 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, laminated paper, or paper coated on both sides with these polymer films, and the like.

The support VC used in the present invention can also be provided with an anti-nolation layer. For this purpose, carbon black or various dyes such as oxole dyes,
Azo dyes, aryl tin dyes, styryl dyes, anthraquinone dyes, merocyanine beam side and tri(or di)allylmethane dyes, etc. are available. Carbon black dyes include cellulose acetate (di or mono), polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, polymethacrylate, polyacrylate, polystyrene, styrene/maleic anhydride copolymer. , polyvinyl acetate, vinyl acetate/maleic anhydride copolymer, methyl vinyl ether/maleic anhydride copolymer, polyvinylidene chloride, and derivatives thereof.

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

It is particularly effective for silver halide light-sensitive materials for high-temperature rapid processing and high-sensitivity silver halide light-sensitive materials.

There are no particular restrictions on other additives used in the silver halide photosensitive material of the present invention, such as chemical sensitizers, spectral sensitizing dyes, hardeners, surfactants, color couplers, etc. Reference may be made to the description in Veri Search, Disclosure, Volume 174, pages 22-31 (December 127F).

Further, regarding the exposure and development method of the silver halide photosensitive material of the present invention, the descriptions in the above-mentioned Research and Disclosure magazines can be referred to.

The present invention will be described below with reference to Examples, but it is not limited thereto.

Synthesis Example 1 Synthesis of O-hydroxymethylphenoxymethylstyrene O-hydroxybenzyl alcohol Tata, Jli (o,
Add 200rnl of methanol to 200rnl of sodium methoxide (2tmol) and add 2t% methanol solution l of sodium methoxide.
6 g mol) is added. 122II (0.

t mol) was added dropwise. Stir under reflux for about μ hours. Cool to room temperature and filter off the 7't Na formed.

Methanol is distilled off from the filtrate, and the filtrate is thoroughly washed repeatedly with hexane until the raw material chloromethylstyrene and by-products are removed. After adding and dissolving chloroform OOd, wash with distilled water 2 to 3 times.

The chloroform phase is separated, dried over Glauber's salt, and then the chloroform is distilled off. 123 g of light yellow liquid is obtained (yield ≦4A%
). This product was the target product and was confirmed to be a high purity product (more than 1%) by TLC and GLC.

Elemental analysis C%) C H Calculated value 10,00 4.47 Actual value 7
Synthesis of 0-chloromethylphenoxymethylstyrene O-hydroxymethylphenoxymethylstyrene 0
Add 4.7.4 cp (0.A mol) of pyridine to a solution of 9 (0.7 mol) and 200 d of chloroform. Add thionyl chloride'yi while stirring under water cooling. 4L
g (o.t mol) is added dropwise while maintaining the temperature at 3 to 10C. After stirring at the same temperature for 1 hour, stir at 306C for another 1 hour. After washing with water, drying with sodium sulfate and distilling off chloroform under reduced pressure, the desired product as a yellow liquid was obtained.

Confirm that it is a high purity product (more than 1%) by TLC and GLC.

Elemental analysis %CHct calculated value 74! , j j, f /J, 7 actual value 74C1/ 4.0 /u, /Synthesis Example 3 Synthesis stirring device for intermediate latex [poly(divinylbenzene-co-methacrylate-2-0-chloromethylphenoxymethylstyrene)], 1 with cooling pipe, thermometer, and nitrogen gas introduction pipe
Nira Santrax H-u in a 00m1 four-roof flask
3;, io% aqueous solution (sulfuric acid ester-sodium salt of ethylene oxide adduct of octylphenol, NOF ff) 4.9% distilled water degassed with nitrogen gas 210ml
．． Potassium persulfate 0.3, sodium bisulfite o
, txg, sodium bicarbonate i, and iag were dissolved in distilled water tzttt.
While heating and stirring, a mixture of O-chloromethylphenoxymethylstyrene 2r, rtg, methacrylic acid O, divinylbenzene O, and yrI obtained in Synthesis Example 1 was added dropwise over about 30 minutes. Potassium persulfate 00-2
9, sodium bisulfite 0°///l, sodium bicarbonate/l, 0.1 da9 were dissolved in distilled water/jd and a constant solution was added. Stir at 60°C for 3 hours under a nitrogen stream. Cool to room temperature and filter to determine solid content //,
90 Synthesis Example: Synthesis of Illustrative Polymer Dispersion 1 Poly[divinylbenzene-co-methacrylic acid-=r-N
-11 (4cm vinylbenzyloxy)-indyl-N
, N, N-trimethylammonium chloride] The intermediate Utexcoda 01i (solid content 1/, 3%) obtained in Synthesis Example 3 above was mixed with a stirrer, a cooling pipe, a thermometer, and a four-port SOOW equipped with a dropping funnel. Add 30% trimethylamine aqueous solution, l/l, to a flask and stir at room temperature.
/l was added dropwise and heated to -20 io"c and stirred for 30 minutes (once formed, the aggregates were redispersed). Next, tOo
Stirring was continued at C for 3 hours. The mixture was cooled to room temperature and filtered to obtain 2 to 5 g of latex with a solid content concentration of 2.2%. The quaternization rate was 0%.

In addition, in order to obtain the methanol dispersion, the water dispersion must be approximately
The aqueous dispersion was injected into twice the volume of acetone with stirring to precipitate it, and then the precipitate was removed by suction filtration and redispersed in methanol.

Synthesis example! Synthesis of intermediate latex [poly(divinyl-cyclohexyl methacrylate-N,N-diethylaminoethoxymethylstyrene)] L with stirring device, cooling tube, thermometer, and nitrogen gas inlet tube
! Sanded BL4'j% water fg- in a four-bottle flask.
1eL (Dodecyl-di-phenyl ether-genedium sulfonate, manufactured by Sanyo Chemical) 10°01s Degassed with nitrogen gas t Distilled water Corog Potassium persulfate o, e4
cg Sodium bisulfite 0.17g in distilled water 10ml
7g of cyclohexyl methacrylate JJ while heating and stirring under a nitrogen stream.
, N, N-diethylaminoethoxymethylstyrene u!
, Ir1s divinylbenzene 2.09% was added dropwise over about 1 hour. Stirring was continued for about 1 hour after the dropping was completed. A solution prepared by dissolving 0.114 ml of potassium persulfate and 0.1777 ml of sodium bisulfite in distilled water/Qo was added again, and stirring was continued at 6 o 0 C for z hours.

The mixture was cooled to room temperature and filtered to obtain a polymerization dispersion having a solid content concentration of .twt%.

Synthesis Example 6 Synthesis of exemplified polymer dispersion (I2) Poly[divinylbenzene-cocyclohexyl methacrylate-co-N-(≠-vinylbenzyloxyethyl)
-N,N-diethyl-N-benzylammonium chloride] 37.4 CM of distilled water of latex jO1O11 obtained in combination example j was placed in a reaction vessel, cooled to about 20'C, and benzyl chloride! , 5i! After stirring for another 20 minutes, the reaction temperature was set to tooc and stirring was continued for 1 hour. Cooled to room temperature and filtered to obtain a polymer of the exemplified compound (/J) having a solid content concentration/jwt%. A series of polymer dispersions were also obtained in Release Example 3. μ,! , it bottomed out in the same way as Otsu.

Example 1 Preparation of samples For each of the exemplary compounds (I) to (L) of the dispersion of the present invention and the following dispersions (A) and (B) for comparison,
T as solid content! Ii, diacetylated cellulose (binder) 309 with 55% acetone and 4! Dispersion liquid dispersed in a mixed solvent containing t% methanol (solid content concentration 1
．． 1%). Each of these dispersions was coated on a cellulose triacetate film to a thickness of 0 to 1/2 m'', and then dried.The other side of the film base coated on one side was coated with 2% by weight of gelatin and silver halide. % by weight of indirect radiographic emulsion was coated.

Samples using the dispersion of the present invention/-4 were sample A/-, respectively.
4, and the sample using the comparative dispersion (A) was used as the sample muff.

Further, as a blank, only the emulsion layer was coated and nothing was coated on the other side, and a sample AI was used.

Comparative dispersion (A): Polymer dispersion expressed by the following formula + CH - CH2 ÷ Method for determining antistatic ability: Antistatic ability is determined by measuring surface resistivity and static generation.

(I) Surface resistivity is the distance between the electrodes of the sample specimen, Q, /4c
α, sandwiched between brass electrodes with a length of 10 crn (the part in contact with the test piece is made of stainless steel), and the Takeda Riken insulation meter TRI
&r Measure the value for 1 minute with a mold. (2) Static mark generation test is a method in which static marks are generated by placing an unexposed photosensitive material on a rubber sheet with the antistatic agent-containing surface facing downward, pressing it with a rubber roller from above, and then peeling it off. Yes.

Each measurement condition is: surface resistivity is 21'C, JO%RH
The static mark generation test was measured at 2!0C, 3
Perform at 0% RH. Note that the humidity of the sample test piece was adjusted under the above conditions all day and night.

To evaluate the degree of static mark generation, each sample was developed for 3 minutes at Co00C using the following developer solution.

Developer solution N-methyl-p-aminophenol sulfate Anhydrous sodium sulfite tog Hydroquinone
iog carbonate soda (l hydrate)
Evening 39 Potassium Bromide 2
Add 5g of water! shall be.

The evaluation of static marks was based on the following J-level criteria: A: No static marks were observed.

B: Some static marks occur.

C: Static marks occur considerably.

D: Significant static marks occur.

E: Static marks appear on the entire surface.

Measurement results: The measurement results of the surface resistivity and static mark generation on the film pack surface of each sample are shown in Table 1.

As can be seen from Table 1, the comparison between the polymer dispersion according to the present invention and the comparative dispersion clearly shows that the sample (A/ It can be seen that -4) has a lower surface resistivity and fewer static marks than the comparative dispersion (&7).

Preparation of Example Samples For each of the exemplary compounds (I) to (6) of the dispersion of the present invention and the dispersion (A) for comparison, the solid content was 7.39 diacetylated cellulose (binder)/
ill! ! % aceto/toda! A dispersion liquid (solid, form concentration/, f%) is prepared using a mixed solvent containing % methanol. Each of these dispersions was coated on a cellulose triacetate film to give j OImp/m 2 and then dried. In this way, one side of the coated film base was coated with an indirect X-ray film containing % by weight of gelatin and 2% by weight of silver halide.
Using the comparative dispersion (A) as ~/j, the sample was designated as sample J.
It was set to i/4. Sample 417 was used as a blank sample in which only the emulsion layer was coated and nothing was coated on the opposite side.

The antistatic performance was evaluated in the same manner as in Example-1.
o The evaluation results are shown in Table 2.

From Table 2, it can be seen that as the ratio of the polymer dispersion to the amount of the binder used increases, the antistatic ability becomes even better.

In Example 1, polymer dispersion/binder=0°2! and the example is 0. It is j. The coating amount of the polymer dispersion was the same as in Example. The binder is necessary for the abrasion resistance and scratch resistance of the antistatic layer.

A comparison between the polymer dispersion of the present invention and the comparative dispersion shows that, as in Example 1, the polymer dispersion of the present invention is clearly superior.

Example 3 Preparation of Sample Two examples of the dispersion of the present invention, A and a photographic emulsion were coated on cellulose triacetate in the same manner as in Example 1. These samples are respectively referred to as samples A/~t. Separately, for comparison, a sample prepared by applying the same amount of compound (B) was designated as sample I67.

Compound (B) here is a polymer represented by the following formula.

Comparative Compound (B) H3 These samples were J, jcFffX J,
The sample was cut to a size of J(m), and an adhesion test was conducted by overlapping the emulsion side and the pack side.

Evaluation method for adhesive resistance performance After the film was wetted for a time at %RH (relative humidity) and 3z0c, the emulsion side and the pack side were overlapped and a poop load was applied, and the film was left for a time under the same conditions. (I) Peel off both the emulsion side and the pack side, and measure the adhesive marks left on the pack side on the emulsion side. are different, and the adhesive traces can be clearly identified by reflected light. The adhesion area ratio is shown in Table 3.

Table 3: Test shop Antistatic agent Adhesive resistance 1
Example of dispersion of the present invention (I) A2
(-A j (J) B4C
(Ri A! (j) A'(
A) B 7 Comparative Compound @ D Here, the adhesion area ratio to A is 0 to 30% B 31 to 60 C61 to jO 1) 11% or more or the adhesion is too strong to be removed.

represents something.

As is clear from Table 3, the sample plate having an antistatic layer (back layer) made of the polymer dispersion according to the present invention is shown in Table 3.
Sample A with back layer taken from comparative compound (C)
It can be seen that, compared to Sample No. 7, it is difficult to bond the emulsion layer and the back layer.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, comprising a layer containing a polymer dispersion having units represented by the following general formula (I). A silver halide photographic material having at least one layer. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable monomer containing at least two ethylenically unsaturated groups. B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R_1 represents a hydrogen atom or a lower alkyl group having 1 to about 6 carbon atoms. L is -CH_2O-, -CH_2N(R_5)-, ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_5 and R_6 are hydrogen atoms or alkyl groups). M represents a divalent group having 1 to 12 carbon atoms. R_2, R_3 and R_4 each represent the same or different alkyl group having 1 to about 20 carbon atoms, or an aralkyl group having 7 to about 20 carbon atoms, and R_2, R_3 and R_4 are interconnected; may form a cyclic structure together with the nitrogen atom. X^■ represents an anion. x is approximately 0.25 to 10
mol%, y is 0 to about 90 mol%, and z is about 1
It is 0 to 99 mol%.