JPH0330131B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic material containing a polymer latex treated with electrodialysis. Polymer latexes are used in various layers of photographic materials, including subbing layers, intermediate layers, dye image donor-containing layers, scavenger layers, protective layers, auxiliary layers, and back layers. layer, image receiving layer, timing layer, barrier layer, release layer, antistatic layer, antihalation layer, etc. In terms of its functions, polymer latex is used, for example, as a mordant, an antistatic agent, a coloring agent, an ultraviolet absorber, an adhesion improver, a film quality improver, etc. In addition, it is used as a coupler, an ultraviolet absorber,
Antioxidants, brighteners, development inhibitors, development accelerators,
It has also been proposed to use it as a dispersion medium for filling or adsorbing photographic additives such as dye image donors. For information on how to use these latexes, specific latex agents, literature, etc., please refer to Research
Disclosure (Research Disclosure)
Outlined in Journal No. 19551 (1980). Generally, when a polymer latex is incorporated into a photographic light-sensitive material, it is added to a coating solution and coated to produce a photographic light-sensitive material or a film unit.
It is known that certain components penetrating into polymeric latexes can have an adverse effect on photographic performance. For example, in synthesizing a polymer latex containing a quaternary ammonium salt, a monomer having a halogenated alkyl group, a monomer having at least two ethylenically unsaturated groups, as described in U.S. Pat. No. 3,958,995, A method is known in which a monomer and a monomer having an α,β-ethylenically unsaturated group are emulsion polymerized and then reacted with a tertiary amine. However, according to this method, unreacted tertiary amine remains, which is undesirable because it causes "repellent" development during coating and adversely affects photographic performance.
-Described in No. 142339. For this reason, great efforts are being made to study synthesis conditions, search for new monomers, and study synthesis methods in order to reduce the amount of components that adversely affect photographic performance. This also poses limitations or increases manufacturing costs. The present inventors, including the search for new monomers,
Although we have repeatedly investigated synthesis conditions and methods, we have found that there are limits to the synthesis approach alone in order to dramatically improve photographic performance. Therefore, in order to dramatically improve photographic performance, the present inventors tackled the new problem of exploring approaches other than synthesis methods. Therefore, an object of the present invention is to provide a photographic material containing a polymer latex with improved photographic performance. The present inventors have attempted to purify the aqueous polymer latex, for example, by simple dialysis, ion exchange, or simple membrane filtration using a microfilter or fiber, or by blowing steam or ozone into the remaining monomer, or by using a catalyst. I tried various methods, but none of them were able to achieve the desired purpose. In the end, it has been found that the above object can be effectively achieved by using electrodialyzed polymeric aqueous latex in photographic materials. By the way, the electrodialysis method itself has been made popular by the Chemistry Encyclopedia (Kyoritsu Publishing), Iwanami Physical and Chemical Dictionary, "Ion Exchange Membrane" by Shimizu and Kosaka (Kyoritsu Publishing), and "Ion Exchange Resin Membrane" by Yamabe and Senoo (Gihodo). well known. Furthermore, it has been common knowledge in the art to use polymer latex without refining it, since refining it deteriorates its stability and gives a negative photographic effect. This is why there is no literature on the use of purified polymer latex for photography. However, the electrodialyzed polymer latex was unexpectedly stable. In the end, we were able to improve photographic performance using a stable polymer latex without any synthetic limitations. The unexpected improvement in photographic performance of the electrodialyzed polymer latex of the present invention is due to the fact that even a trace amount of a component can sometimes have a large effect on the photographic performance of photographic light-sensitive materials. It is presumed that this is due to the special characteristics of The minor components are in some cases the polymerization initiator used during latex synthesis and/or its decomposition products, in some cases the remaining monomers, and in other cases the emulsifier used in large amounts, and in other cases, the polymerization initiator used during latex synthesis and/or its decomposition products. When used in a reaction, it is a reaction reagent and/or a reaction product, and is used as a silver halide emulsion, coupler, dye, dye image donor, etc. during and/or after production and processing of a photographic light-sensitive material. It is estimated that this will have an adverse effect on the body. In particular, in the synthesis of certain mordants or antistatic latexes, monomers with active halogen atoms such as chloromethylstyrene, monomers with tertiary amino groups, monomers with quaternary ammonium salts, and as reaction reagents for active halogens. When using amines, etc., water-soluble or hydrophilic salts such as excess halogen ions generated by hydrolysis of active halogens, residual monomers, amines, quaternary ammonium salts made by reacting residual monomers containing halogen with tertiary amines, etc. It is estimated that low molecular weight components have a particularly negative effect. Polymer latex that undergoes electrodialysis treatment includes:
For example, the aforementioned Research Disclosure magazine No. 19551 (1980
A variety of latexes such as those described in 1999, which can be used in various layers of photographic materials, such as certain electrodialyzed polymer latexes, may be mixed with the silver halide photographic emulsion. A preferred polymer latex is a vinyl polymer latex. More specifically, it is a cationic polymer latex such as a mordant latex or an antistatic latex. Particularly preferred is a crosslinked quaternary ammonium salt (or phosphonium salt) polymer latex represented by the following general formula () and used as a dyeing agent or an antistatic agent. In the formula, A represents a copolymerizable monomer unit having at least two ethylenically unsaturated groups. B
represents an ethylenically unsaturated monomer unit copolymerizable with component A, etc. R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and L represents a divalent group having 1 to about 12 carbon atoms. R ₂ , R ₃ and
R ₄ represents the same or different alkyl group having 1 to about 20 carbon atoms, or an aralkyl group having 7 to about 20 carbon atoms, R ₂ ,
R ₃ and R ₄ may be interconnected to form a cyclic structure together with Q. Q is N or P, and
represents an anion. x is 0.2 to about 15 mol%;
y is 0 to about 90 mol% and z is 5 to about 99 mol%. Regarding the preferred polymer latex of the present invention, monomers having at least two or more (preferably 2 to 4) ethylenically unsaturated groups corresponding to the monomer unit of A in the general formula () include esters, amides, etc. , olefins, aryl compounds, etc. Examples of copolymerizable monomers having at least two ethylenically unsaturated groups are, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neopentyglycol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate. Methacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl phthalate, methylenebisacrylamide, methylenebismethacrylamide, trivinylcyclohexane , divinylbenzene, N,N-bis(vinylbenzyl)-N,N-
Dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxyethyl)-N-
(vinylbenzyl)ammonium chloride N,
N,N',N'-tetraethyl-N,N'-bis(vinylbenzyl)-p-xylylene diammonium dichloride, N,N'-bis(vinylbenzyl)-
triethylenediammonium dichloride, N,
Examples include N,N',N'-tetrabutyl-N,N'-bis(vinylbenzyl)-ethylenediammonium dichloride. Among these, divinylbenzene and trivinylcyclohexane are particularly preferred from the viewpoint of hydrophobicity, alkali resistance, and the like. A may contain two or more of the above monomers. Examples of the ethylenically unsaturated monomer B include olefins (e.g., ethylene, propylene, 1-butene, vinyl chloride, vinylidene chloride,
isobutene, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chloroprene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, vinyl propionate, vinyl butyrate,
esters of ethylenically unsaturated acids (e.g. methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, octyl methacrylate, amyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate) , maleic acid dibutyl ester, fumaric acid diethyl ester, ethyl crotonate, methylene malonic acid dibutyl ester, etc.), styrenes (e.g., styrene, α-methylstyrene, vinyltoluene, chloromethylstyrene, chlorstyrene, dichlorostyrene, bromine) styrene, etc.)
There are unsaturated nitriles (eg acrylonitrile, methacrylonitrile, allyl cyanide, crotonitrile, etc.). Among these, emulsion polymerizable,
From the viewpoint of hydrophobicity, styrenes and methacrylic acid esters are particularly preferred. B may contain two or more of the above monomers. B ₁ is preferably a hydrogen atom or a methyl group from the viewpoint of polymerization reactivity. L is especially

【formula】

【formula】

A divalent group represented by the formula is preferable, from the viewpoint of alkali resistance etc.

【formula】

[Formula] is more preferable, especially from the viewpoint of emulsion polymerization and mordant properties.

[Formula] is preferred. In the above formula, R ₅ represents alkylene (e.g. methylene, ethylene, trimethylene, tetramethylene, etc.), arylene, aralkylene (e.g.

[Formula] However, R ₇ represents an alkylene having 0 to about 6 carbon atoms, and R ₆ represents a hydrogen atom or R ₂ . n is an integer of 1 or 2. Q is preferably N in view of the toxicity of the raw material. Examples of X include halogen ions (e.g. chloride ions, bromide ions, iodide ions, etc.),
Alkyl sulfate ions (e.g. methyl sulfate ion, ethyl sulfate ion, etc.), alkyl or aryl sulfonate ions (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid,
p-toluenesulfonic acid, etc.), acetate ion, sulfate ion, etc. Among these, chloride ions, alkyl sulfate ions, and arylsulfonate ions are particularly preferred. The alkyl groups and aralkyl groups of R ₂ , R ₃ and R ₄ include substituted alkyl groups and substituted aralkyl groups. Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, hexyl, cyclohexyl, 2-ethylhexyl, and dodecyl; substituted alkyl groups such as alkoxyalkyl; groups (for example, methoxymethyl group, methoxybutyl group, ethoxyethyl group, butoxyethyl group,
vinyloxyethyl group, etc.), cyanoalkyl group (e.g. 2-cyanoethyl group, 3-cyanopropyl group, etc.), halogenated alkyl group (e.g.
(2-fluoroethyl group, 2-chloroethyl group, perfluoropropyl group, etc.), alkoxycarbonyl alkyl group (for example, ethoxycarbonylmethyl group, etc.), allyl group, 2-butenyl group, propargyl group, etc. As the aralkyl group, unsubstituted aralkyl group,
Substituted aralkyl groups such as benzyl, phenethyl, diphenylmethyl, and naphthylmethyl groups, such as alkylaralkyl groups (e.g., 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropylbenzyl, 4- octylbenzyl group, etc.), alkoxyaralkyl group (e.g., 4-methoxybenzyl group, 4-pentafluoropenyloxybenzyl group, 4-ethoxybenzyl group, etc.), cyanoaralkyl group (e.g., 4-cyanobenzyl group, 4-( (4-cyanophenyl)benzyl group, etc.), halogenated aralkyl group (e.g., 4-chlorobenzyl group, 3-chlorobenzyl group, 4-bromobenzyl group, 4-
(4-chlorophenyl)benzyl group, etc.). The alkyl group preferably has 1 to 12 carbon atoms, and the aralkyl group preferably has 7 to 14 carbon atoms. Examples of R ₂ , R ₃ and R ₄ interconnected to form a cyclic structure with Q include the following.

[Formula] (W ₁ represents an atomic group necessary to form an aliphatic heterocycle together with Q) Examples of an aliphatic heterocycle include, for example:

[Formula] (R ₈ represents a hydrogen atom or R _4. n is an integer from 2 to 12),

[Formula] (a+b=2~7 integer),

[Formula] (R ₉ and R ₁₀ each represent a hydrogen atom and a lower alkyl group having 1 to 6 carbon atoms.)

[Formula] etc. others,

[Formula] (W ₂ is absent or represents an atomic group required to form a benzene ring),

【formula】

[Formula] (R ₁₁ is a hydrogen atom,

【formula】

[Formula] and R ₂ are represented. When there are two R ₂ s, they may be the same or different. ) etc. Among these ring structures,

[Formula] (n is an integer from 4 to 6) call

[Formula] is preferred. In the above example, R ₂ , R ₄ , R ₆ , Q and X have the same meaning in the general formula (). It may be a mixture of two or more components as well as two components. x is preferably 1.0 to 10 mol%, y is preferably 20 to 60 mol%, and z is preferably 20
The amount is preferably from 30 to 80 mol%, particularly preferably from 30 to 70 mol%. The aqueous polymer latex represented by the general formula () generally includes a monomer having at least two ethylenically unsaturated groups as described above, an ethylenically unsaturated monomer (this may be omitted) and a general formula ().
After emulsion polymerization of the monomer represented by

It can be obtained by reacting and quaternizing the compound represented by the formula. In the formula, L, X, and R ₁ are the same as those shown in the general formula (). Also

Examples of the compound represented by the formula (R ₂ , R ₃ , R ₄ and Q have the same meanings as those of the general formula ()) include N-methylaziridine, N-methylazetidine, N-methyl Pyrrolidine, N-ethylpyrrolidine, N-methylpyrrolidine, N-benzylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-benzylpiperidine, N-p-chlorobenzylpiperidine, N
-p-isopropylbenzylpiperidine, N-p
-Pentafluoropropenyloxybenzylpiperidine, N-methylhexamethyleneimine, N-benzylhexamethyleneimine, N-methyldodecamethyleneimine, N-benzyldodecamethyleneimine, trimethylamine, triethylamine, tributylamine, dimethylpropylamine, dimethylbenzylamine , tributylfuosphine,
Trihexylamine, dimethyl-p-chlorobenzylamine, azabicyclooctane, N-methylimidazole, N-methyl-2-methylimidazole, N-methylpyrazole, pyridine, 3,5
-Lutidine, methylpyridine, etc. When synthesizing the aqueous polymer latex represented by the general formula () of the present invention by this method,

[Formula] (L, X and R ₁ are synonymous with general formula ()) and

It is customary to contain repeating units represented by the formula: 0 to about 10 mol%, usually 0 to about 5 mol%. In addition, the aqueous polymer latex represented by the general formula () includes a monomer having at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer (this may be omitted), and an unsaturated polymer represented by the general formula (). After emulsion polymerization with saturated monomer,
It can also be obtained by quaternization by reaction with an alkylating agent, alkenylating agent or aralkylating agent represented by R ₄ -X. R ₁ , L, Q, R ₂ and R ₃ have the same meanings as in the general formula (). Examples of monomers represented by the general formula () include N-vinylbenzylpyrrolidine, N-vinylbenzylpyrroline, N-vinylbenzylpiperidine, N-vinylbenzylhexamethyleneimine, N-vinylbenzyldodecamethyleneimine, N-dimethylaminopropyl methacrylate, N-N-diethylaminoethyl methacrylate, N-N-dimethylaminopropyl methacrylamide, N-(N'-N'-dimethylaminomethylphenyl)acrylamide, N-(N'-
Examples include N'-dihexylaminomethyl) methacrylamide. Among these, N-vinylbenzylpiperidine, N-vinylbenzylhexamethylimine, and N-(N',N'-dimethylaminomethylphenyl)acrylamide are particularly preferred. Examples of R ₄ -X (R ₄ , , ethyl chloroacetate, n-hexyl bromide, benzyl chloride, p-chlorobenzyl chloride, p-methylbenzyl chloride, p-isopropylbenzyl chloride,
Examples include p-pentafluoropropenyloxybenzyl chloride. Among these, benzyl chloride, p-chlorobenzyl chloride, p-
Methyl toluenesulfonate, dimethyl sulfate, and diethyl sulfate are preferred. Furthermore, the aqueous polymer latex represented by the general formula () includes a monomer having at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer (this may be omitted), and an unsaturated monomer represented by the general formula (). It can also be obtained by emulsion polymerization with monomers. R ₁ , R ₂ , R ₃ , R ₄ , L, Q, and X have the same meanings as in the general formula (). Examples of monomers represented by the general formula () include N-benzyl-N-vinylbenzylpiperidinium chloride, N-benzyl-N-vinylbenzylperhydroazenium chloride, N-benzyl-N-vinylbenzylperhydroazenium chloride,
-(4-chlorobenzyl)-N-vinylbenzylperhydroazepinium-p-toluenesulfonate, N-methyl-N-vinylbenzyldecamethyleneiminium chloride, N-benzyl-N'-vinylbenzylimidazolium chloride , 1-hexyl-2-methyl-3-vinylbenzylimidazolium chloride, 1-butyl-2-phenyl-3
-vinylbenzylimidazolium chloride, 1-
Octyl-2-isopropyl-3-vinylbenzylimidazolium chloride, N-vinylbenzyl-p-phenylpyridium chloride, N-vinylbenzyl-p-benzylpyridinium-p-toluenesulfonate, N-vinylbenzyl-p-phenylpyridium chloride enylpropylpyridinium chloride, N-benzyl-N'-vinylbenzylbenzimidazolium chloride, N-(N',N'-diethyl-N'-(p
-isopropylbenzyl)ammoniomethylphenyl)acrylamide chloride, N-methacryloyloxyethyl-N-N-diethyl-N-p-
Chlorbenzylammonium chloride, N-methacrylamidopropyl-N-N-dimethyl-N-
p-octylbenzylammonium chloride, N
-vinylbenzyl-N,N,N-trihexylammonium chloride, N-vinylbenzyl-N,
N,N-tributylammonium-p-toluenesulfonate, N-vinylbenzyl-N,N-dibutyl-N-benzylammonium chloride, N
-vinylbenzyl-N,N-diethyl-N-p-
Examples include isopropylbenzylammonium chloride. For the synthesis of the aqueous polymer latex used in the present invention,
No. 48-76593, No. 48-92022, No. 49-21134,
49-120634, Japanese Patent Application Publication No. 53-72622, British Patent No. 1211039, 961395, U.S. Patent No. 2795564
No. 2914499, No. 3033833, No.
No. 3547899, No. 3227672, No. 3290417, No. 3262919, No. 3245932, No. 2681897,
No. 3230275, Canadian Patent No. 704778, Jiyoung, Shi, Petropoulos, et al.
Digest” (John C. Petropoulos etal:
Official, Digest) 33 , 719-736 (1961), "Introduction to Emulsions" by Takuo Hayashi (1970), "Chemistry of Polymer Latex" by Soichi Muroi (1970), "Vinyl Emulsion" by Takuhiko Motoyama (1965) , "Journal of Science, Polymer Chemistry Edition" by Mike, Sheider, Jiyuang et al.
(Mike Shi-der Juaug etal; Journal of
Polymer Science, Polymer Chemistry
It is convenient to perform this by referring to the method described in, for example , 14 , 2089-2107 (1976). It goes without saying that the polymerization initiator, concentration, polymerization temperature, reaction time, etc. can be varied widely and easily depending on the purpose. For example, polymerization is generally carried out at 20-180°C, preferably 40-120°C. The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and, if necessary, 0.1 to 10% by weight of an emulsifier, based on the monomers to be polymerized. Examples of polymerization initiators include azobis compounds, peroxides, hydroperoxides, redox catalysts, etc., such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, and 2,4-dichlorobenzoyl peroxide. oxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, 2-2'-azobis(2-amidinopropane) hydrochloride, and the like. Examples of emulsifiers include anionic, cationic, amphoteric, and nonionic surfactants as well as water-soluble polymers. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium lauryl phosphate, polyoxyethylene nonyl phenyl ether , polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, an emulsifier described in Japanese Patent Publication No. 53-6190, and water-soluble polymers. The above quaternization reaction is generally carried out at -10°C to about 100°C.
The temperature is preferably 20°C to 80°C. The entire manufacturing process of the aqueous polymer latex used in the present invention can be carried out in one container;
In addition, it is not necessary to use a water-miscible organic solvent during the quaternization reaction, and therefore the latex is stable without causing aggregation or destabilization when an organic solvent is added, and it has the characteristics of being easy to manufacture. have Next, examples of the aqueous polymer latex used in the present invention will be shown. When carrying out electrodialysis treatment, it is appropriate to use a 1% aqueous solution of Na ₂ SO ₄ as the concentrate and electrode solution, and carry out the treatment at a limiting current density of 0.3 to 1 mA/cm ² equivalent, preferably 0.3. ~0.5 mA/cm ² equivalent.
Increasing the current can increase the throughput per unit membrane area, but if it is too large,
The amount of water transferred from the liquid to the membrane surface cannot keep up with the amount that should be transferred electrically, and electrolysis of water occurs, which not only causes a pH change in the liquid and significantly reduces current efficiency, but also causes scale formation, which impedes operation. Undesirable. The chemical composition of the electrodialysis membrane is a styrene/divinylbenzene copolymer film with a sulfone group introduced as an exchange group for the cation exchange membrane, and a quaternary ammonia base introduced for the anion exchange membrane. suitable, more preferably fourth
It is preferable not to use CH ₃ I when introducing the class ammonia base, so that there is no I in the film. The particle size of the polymer latex to be electrodialyzed is generally about 0.01 to 0.1 μm, but preferably 0.03 to 0.3 μm from the viewpoint of stability. The appropriate concentration of solid particles in the polymer latex is about 1 to 80% by weight (the same applies hereinafter), but in consideration of stability and pressure loss when passing through an electrodialysis tank, it is preferably 2 to 40%, especially 2 to 80% by weight.
~30% is preferred. The degree of electrodialysis treatment varies depending on the type, composition, counterion type, purpose, application, stability, etc. of the latex used, so it cannot be said in general, but it is determined by the electrical conductivity after electrodialysis treatment and depends on the use. It is preferable to adjust. The preferred electrical conductivity when used as a mordant is 400μ when converted to a latex concentration of 1% by weight.
/cm or less, particularly preferably 25μ/cm or less. Pretreatment can also be performed to prevent the polymer latex from changing during storage and adversely affecting photographic performance. For example, 40
Heat at a temperature of ℃ to 95℃ for about 30 minutes to 24 hours, or add acids such as hydrochloric acid and sulfuric acid; alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate; ammonia; amines, etc. Examples of methods include heating the mixture after heating it. Furthermore, as described in JP-A-57-202539, a hydrophobic substance can be adsorbed or filled into a polymer latex and then subjected to electrodialysis treatment. Furthermore, after adding an ionic substance such as an acid, an alkali, or a salt, it is also possible to partially replace the counter ion of the ionic group by electrodialysis treatment. Even after electrodialyzing the polymer latex, it is possible to adsorb or fill the latex with hydrophobic substances, or it is possible to replenish the emulsifier that was partially removed during the electrodialysis process, if necessary. . The photographic light-sensitive material used in the present invention can be applied to both black-and-white photography and color photography, and silver halide or other light-sensitive materials can be used as the light-sensitive material. Even if silver halide photographic emulsions are “negative” emulsions,
It may also be a "positive" emulsion. The silver halide color photography method may be, for example, a coupler type photography method or a photography method in which an image is formed using diffusion transfer of a dye or its precursor. The most typical photographic method of the latter image forming method is the "color diffusion transfer method", which will be described below, but is not limited to this photographic method or mode. When the photographic light-sensitive material of the present invention is used as a photographic film unit, that is, a film unit that can be processed by passing the film unit between a pair of juxtaposed pressing members, the following elements are required: Consisting of 1 photosensitive element; 2 image-receiving element; 3 processing element; comprising means for releasing an alkaline processing composition within the film unit, such as a rupturable container, optionally containing a silver halide developer; Good too. 4. At least one support In one embodiment of this film unit,
After exposure, a light-sensitive element comprising one or more silver halide emulsion layers coated on a support is superposed face-to-face with an image-receiving element having at least one layer comprising a mordant on the support. The alkaline treatment composition is spread between the two elements and treated. Preferably, the film unit is shielded from light on both sides of the photosensitive element or the film unit when taken out from the camera. In this case, the image receiving element may be peeled off after transfer, or as described in U.S. Pat. No. 3,415,645,
The image may be viewed without peeling off. In another embodiment, the support, the image receiving element and the photosensitive element in the film unit are arranged integrally. For example, Belgian patent no.
757960, a transparent support with an image-receiving layer (containing a mordant) and a substantially mud-free transparent light-reflecting layer (e.g. _two TiO layers and a carbon black layer).
Also effective are those coated with a single photosensitive layer or a fat photosensitive layer. After exposure of the photosensitive layer, it is placed face-to-face with an opaque cover sheet and a processing composition is spread between the two. Another embodiment of the overlapping and integrated type to which the present invention can be applied is the Belgian patent.
No. 757959. According to this aspect,
On a transparent support, an image-receiving layer (containing a mordant),
applying a substantially opaque light-reflecting layer (e.g. as described above) and a single or fatty photosensitive layer;
Furthermore, a transparent cover sheet is placed on both sides. A rupturable container containing an alkaline processing composition including an opacifying agent (eg, carbon black) is placed adjacent the top layer of the photosensitive layer and the transparent cover sheet. Such a film unit is exposed to light through a transparent cover sheet, and when taken out from the camera, the container is ruptured by a pressing member, and the processing composition (including the opacifying agent) is transferred between the photosensitive layer and the cover sheet. It spreads over a whole area in between. This blocks the film unit from light.
Development progresses. The transferred image can be viewed through the transparent support on the side opposite to the exposed side. Examples of the present invention will be described below. Department,
% indicates weight basis. Example 1 (i) Preparation of polymer latex and electrodialysis treatment In a polymerization tank equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 73.4 parts of water, 2 parts of sodium polyoxyethylene alkyl sulfonate, and 0.1 part of styrene were added.
of potassium persulfate as a polymerization initiator.
Add 0.5 part of % aqueous solution at about 90℃, perform initial polymerization for 1 hour while stirring, and then continue stirring to lower the liquid temperature.
While maintaining the temperature at 60°C, a mixed solution of 12 parts of a 22% potassium persulfate aqueous solution, 5 parts of chloromethylstyrene, 3 parts of styrene, and 1 part of divinylbenzene was added dropwise over 4 hours to carry out emulsion polymerization. After the dropwise addition was completed, 3 parts of N-methylpiperidine as a neutralizing agent was added at 30°C, and the mixture was heated at 70°C for 1 hour to obtain a polymer latex with a solid content of 13.5% and a pH of 7.7. Add 100 parts of this latex to sodium bicarbonate.
Pretreated by adding a mixture of 0.3 parts and 12.5 parts of deionized water, solids content 13.5%, pH 7.0, electrical conductivity
13300μ/cm, residual amine 2.12%/g polymer, chloride ion 3.0×10 ^-3 equivalent/g polymer, sodium ion 470ppm, potassium ion 490ppm, ash content
A polymer latex containing 0.5% styrene and 40 ppm (GC method) was obtained. 8 kg of this latex was
Electrodialysis membrane that does not use (Tokuyama Soda Co., Ltd. anion exchange membrane ACH-45T/cation exchange membrane C66-
5T) While circulating 12 pairs at a speed of 4/min,
Electrodialysis was performed under constant voltage control with a bath voltage of 10V.
The treatment was completed 4 hours after the start of operation. The resulting polymer latex had a solids concentration of 11.3.
%, PH5.3, electrical conductivity 1500μ/cm, residual amine
0.47wt%, chloride ion 1.5×10 ^-3 equivalent/polymer g, sodium ion 12ppm, potassium ion
5ppm, ash 0.02%, styrene not detected (GC method)
It was found that a product of extremely high purity was obtained. (ii) Preparation of photosensitive material (sheet) On a polyethylene terephthalate transparent support,
A photosensitive sheet was prepared by coating each layer as follows. (1) According to (i) above, the electrodialyzed mordant latex was mixed with a solid content of 3 g/m ² and gelatin 3 g/m 2 .
m ² and as a coating aid an image-receiving layer containing (2) Titanium dioxide 20g/m ² , gelatin 2.0g/m ²
A white reflective layer containing. (3) Carbon black 2.0g/ ^m2 and gelatin 1.5
A light shielding layer containing g/m ² . (4) The following cyan dye-releasing redox compound 0.44
g/m ² , tricyclohexyl phosphate 0.09
g/m ² , 2,5-di-t-pentadecylhydroquinone 0.008 g/m ² , and gelatin 0.8 g/m 2
layer containing m ² . (5) Red-sensitive latent type direct positive silver bromide emulsion (depending on the amount of silver)
1.03g/m ² , gelatin 1.2g/m ² , nucleating agent below 0.04mg/m ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.13
g/ ^m2 ). (6) 2,5-di-t-pentadecylhydroquinone 0.43g/m ² , trihexyl phosphate 0.1
g/m ² and a layer containing 0.4 g/m ² of gelatin. (7) Magenta dye-releasing redox compound having the following structural formula (0.21 g/m ² ), magenta dye-releasing redox compound having the structural formula (0.11 g/m ² ), tricyclohexyl phosphate (0.08 g/m ² ),
A layer containing 2,5-di-t-pentadecylhydroquinone (0.009 g/m ² ) and gelatin (0.9 g/m ² ). (8) Green-sensitive latent type direct positive silver bromide emulsion (depending on the amount of silver)
0.82 g/m ² , gelatin (0.9 g/m ² ), the same nucleating agent as layer (5) (0.03 mg/m ² ) and 2-sulfo-5
- A green-sensitive emulsion layer consisting of n-pentadecylhydroquinone sodium salt (0.08 g/m ² ). (9) Same layer as (6). (10) Yellow dye-releasing redox compound with the following structure (0.53 g/m ² ), tricyclohexyl phosphate (0.13 g/m ² ), 2,5-di-t-pentadecylhydroquinone (0.014 g/m ² ), and a layer containing gelatin (0.7 g/m ² ). (11) Blue-sensitive latent type direct positive silver bromide emulsion (depending on the amount of silver)
1.09 g/m ² , gelatin (1.1 g/m ² ), the same nucleating agent as layer (5) (0.04 mg/m ² ), and 2-sulfo-
A blue-sensitive emulsion layer consisting of 5-n-pentadecylhydroquinone sodium salt (0.07 g/m ² ). (12) Layer containing 1.09 g/m ² of gelatin. As a comparative example, the same photosensitive sheet was prepared except that the mordant latex of layer (1), but untreated, was applied. In addition, a cover sheet was made as follows. Cover Sheet A cover sheet was prepared by sequentially coating the following layers (1') to (3') on a transparent polyethylene terephthalate support. (1′) 80:20 acrylic acid and butyl acrylate
(weight ratio) copolymer with 5 mol% of acrylic acid groups
acid polymer (11.5 g/m ² ) neutralized with sodium hydroxide and 1,4-bis(2,3-
Layer containing epoxypropoxy)-butane (0.22 g/ ^m2 . (2') Acetylcellulose (100g of acetylcellulose is hydrolyzed to yield 36.8g of acetyl groups) (4.2g/ ^m2 ) and a methanol-opened product (0.23 g/m ² ) of a 60:40 (weight ratio) copolymer of styrene and maleic anhydride (molecular weight approximately 50,000) and 5-(2-cyano-1-methylethylthio). - Layer containing 1-phenyltetrazole (0.154 g/m ² ). (3') Styrene-n-butyl acrylate-acrylic acid-N-methylol acrylamide layer.
49.7:42.3:3:5 copolymer latex and 93:4:3 (weight ratio) of methyl methacrylate-acrylic acid-N-methylolacrylamide
Copolymer latex is mixed in a solids ratio of 6:4 and coated in a 2μ thick layer. After exposing the photosensitive sheet to light through a color test chart, the cover sheet was placed on top of the other, and the following processing solution was spread between both sheets to a thickness of 85μ (spreading was done with the help of a pressure roller). ivy). The treatment was carried out at 15°C and the results shown in Table 1 were obtained. Treatment liquid 1-p-tolyl-4-hydroxy methyl-4-methyl-3-pyrazolidone 6.9g Methylhydroquinone 0.3g 5-methylbenzotriazole 3.5g Sodium sulfate (anhydrous) 0.2g Carboxymethylcellulose Na salt 58g Hydroxide Potassium (28% aqueous solution) 200c.c. Benzyl alcohol 1.5cc Carbon black 150g Water 685c.c.

[Table] From the results in Table 1, it can be seen that the photosensitive sheet of the present invention using the electrodialyzed mordant has a higher maximum density of the transferred image than the photosensitive sheet using the untreated one. Example 2 The photosensitive sheet of Example 1 was subjected to a forced storage test under the conditions listed in Table 2, and then a processing solution was developed at 25° C. in the same manner as in Example 1. From the results in Table 2, it can be seen that the photosensitive sheet of the present invention using an electrodialyzed mordant is excellent with less decrease in maximum density even under high temperature and high humidity conditions.

【table】

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing an aqueous polymer latex, characterized in that the latex is an electrodialyzed polymer latex represented by the general formula (). photosensitive material. In the formula, A represents a copolymerizable monomer unit having at least two ethylenically unsaturated groups. B
represents an ethylenically unsaturated monomer unit copolymerizable with component A, etc. R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and L represents a divalent group having 1 to 12 carbon atoms. R ₂ , R ₃ and R ₄
each represents the same or different alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ₂ , R ₃ and
R ₄ may be interconnected to form a cyclic structure together with Q. Q is N or P, and X represents an anion. x is 0.2 to 15 mol%, y is 0
~90 mol%, z from 5 to 99 mol%.