JPS6217745A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the defects such as the devitrification of the titled material due to an addition of an antistatic agent, and to improve the anti-adhesive and the antistatic properties of the titled material by providing at least one layer of hydrophilic colloid layers added the prescribed dispersoid to a substrate. CONSTITUTION:The dispersoid of a polymer latex is mainly composed of the following components A and B in the titled material in which at least one layer of the hydrophilic colloid layers added the polymer latex is provided on the substrate. The component A is the polymer forming the particle of the dispersoid. The component B is a block polymer or a graft polymer comprising at least one unit selected from the fluorine unit and the silicon unit and the unit having a compatibility to the polymer A. At least one layer of the photographic sensitive material, preferably, the most outer layer of the prescribed material is formed by adding the hydrophilic binder such as a gelatin or its derivative, and the prescribed additives to the mixture of the polymer A and 0.001-10wt% of the polymer B on the weight basis of the mixture.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a photographic material, and more particularly to a photographic material that has excellent antistatic properties and adhesion resistance without adversely affecting photographic properties.

[Conventional technology]

Generally, the outermost layer of a silver halide photographic light-sensitive material uses a hydrophilic colloid, typified by gelatin, as a binder. Therefore, when the surface of a photosensitive material is in a high-temperature, high-humidity atmosphere, its adhesion or tackiness increases, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between photosensitive materials, or between photosensitive materials and objects in a pond that come into contact with them, often resulting in serious malfunctions. Particularly in color photosensitive materials, adhesiveness has been a major problem since the photographic layer contains many additives such as color couplers. In order to solve this problem, the outermost layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, and calcium carbonate, as well as organic substances such as polymethyl methacrylate, cellulose acetate propionate, and fluororesin, to make photosensitive materials. Methods have been proposed to increase surface roughness, so-called matting, and reduce adhesion. In silver halide color photographic materials, it is necessary to use a large amount of matting agent for the reasons mentioned above. However, since adding a large amount of a matting agent has an adverse effect on photographic image quality, particularly sharpness, there is a limit to the amount of matting agent that can be used. Incidentally, since silver halide photographic materials generally have a support having electrical insulation properties, accumulation of electrostatic charges is a major problem in addition to adhesion. This accumulated electrostatic charge causes many problems, but the most serious problem is that the photosensitive emulsion layer is sensitized by discharging the electrostatic charge accumulated on the processing surface, and the photographic film is processed. In some cases, dot-like spots or dendritic or feather-like density spots occur. This is what is called a static mark, and it significantly reduces the commercial value of photographic film, and in some cases causes it to disappear completely. This phenomenon becomes apparent only after development, and is a very troublesome problem. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or uneven coating. The best way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be quickly dissipated before the accumulated charge is discharged. Therefore, methods of improving the conductivity of supports and various coated surface layers of photosensitive materials have been considered, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, surfactants, polymers, and the like. Examples of these include, for example, U.S. Pat.
No. 76, No. 3,454゜625, JP-A-55-776
2, US Pat. No. 56-43636, US Pat. No. 56-114944, etc., such as US Pat. 999, JP-A No. 56-78834, JP-A No. 57-204540, JP-A No. 57-179837, JP-A No. 5
There are polymers described in No. 8-82242 and the like. However, it is extremely difficult to prevent static electricity on a hydrophilic colloid layer, and known antistatic means often do not reduce the surface resistance sufficiently at low humidity, or often cause adhesive failure of photosensitive materials at high temperature and high humidity. . Moreover, if the hydrophilic colloid layer contains a necessary amount of antistatic agent (such as the fluorine-containing surfactant described in Japanese Patent Publication No. 56-44411) to obtain a sufficient antistatic effect, It may adversely affect the physical properties of the film or leak into the developing solution, causing sludge. JP-A No. 54-38110 describes an antistatic means in which a photosensitive material contains a latex of a polymer derived from fluoroalkyl acrylate, but this method does not require the necessary amount of antistatic material to obtain a sufficient antistatic effect. If the amount is contained, the membrane may devitrify or the cost may increase, which is not preferable.

[Purpose of the invention]

An object of the present invention is to provide a photographic material which has improved the above-mentioned drawbacks caused by the addition of an antistatic agent and has excellent adhesion resistance and antistatic properties.

[Structure of the invention]

An object of the present invention is to provide a photographic material having at least one hydrophilic colloid layer formed by adding a polymer latex on a support, in which the dispersoids of the polymer latex mainly consist of the following (A) and (B). This is achieved by a photographic material characterized by: (A) Polymer (B) forming the particles of the above dispersoid
Block polymer or graft polymer having at least one selected from fluorine units and silicon units and a unit compatible with the polymer (A) The present invention will be described in detail below. The polymer (A) that forms the particles that are the dispersoid of the polymer latex of the present invention is particularly restricted if it forms particles in a dispersion medium and is substantially free of the fluorine units and silicon units described below. There isn't. Here, "substantially free" means that these units may be present as long as they do not impede the purpose of the present invention. Specifically, fluorine units and silicon units are 100% in total. % or less. Polymer (A) preferably has a glass transition temperature (T g)
is in the range of 40 to 150°C. Preferred polymers as the above particle-forming polymer (A) include acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and glycidyl acrylate; methacrylic esters such as methyl acrylate, ethyl methacrylate, hydroxyquimethafrylate, and glycidyl acrylate; N% Acrylic acid amide derivatives such as N-trimethylacrylamide and N,N-diethylacrylamide, methacrylic acid amide derivatives such as N,N-dimethylmethacrylamide, vinyl esters such as vinyl acetate, vinyl halides, vinylidene halides, and styrene derivatives. Homo or copolymers of butadiene, isoprene, acrylonitrile, etc. can be mentioned. Particularly preferred is a homo- or copolymer styrene formed by polymerizing at least one selected from acrylic esters, methacrylic esters, vinyl halides, vinylidene halides, vinyl acetate, butadiene, and styrene. Methods for producing these latexes are well known and can be easily produced by those skilled in the art. Production methods include an emulsion polymerization method and a method in which a polymer synthesized by solution polymerization or bulk polymerization is dissolved in a water-insoluble solvent and dispersed in water (abbreviated as redispersion method), but emulsion polymerization is preferred. The monomer used to form the fluorine unit is preferably a compound represented by the following general formula (r) or (II). General formula (1) General formula [■] R, R. II CN 2 = CCI (2 = C COORr, OR4゜In the formula, R1 and R7 each represent a hydrogen atom or a methyl group which may be substituted with a fluorine atom, and Rrl and Rr are each substituted with a fluorine atom. Represents a straight-chain, branched or cyclic alkyl group, preferably having 1 carbon atom.
~10, and may be substituted with groups or atoms other than fluorine atoms, such as hydroxy groups, halogen atoms (e.g. C12,1
3r, etc.). Further, this alkyl group may have a linking group such as an oxo group or a thio group interposed between the carbon chains. Among the fluorine-based vinyl monomers represented by the general formula CI), typical examples of those preferably used in the present invention are shown below. C11', = C11 COOCIIy(CFz)n! I n = integer from 2 to 9 (ill CI+2 = C COOCIIt (CFt) nF n = integer from 2 to 9 C1 + 2 = C COOCIl, CI, 0 (CF,) nFn = integer from 2 to 8 CH, = C11 C00CIIaCII(CF2)nF n =
Integer from 2 to 8 cut = CH C00CI1. ClICl1ffi(CF,)nFOf
I n=integer from 2 to 8 -8CH3 C11,=CF-9 CI+3 C112= CCI+3 CI+3 C1f2=C COO(CF2)-nF n=integer from 2 to 8 CF3 C1f2=C COOCII, (CF2)nHn= 2 ~9 integer C1
2=C11-0-CH2-(CF2)nll n=2
-8, the silicon unit in the polymer (B) is a polysiloxane atomic group in the polymer molecule, for example -(R,5iO)n-1-(R2SiO)nsiOR3
(Here, R represents a substituent (for example, an alkyl group, an aryl group, etc.), and n represents an integer of 2 or more.). Note that n is preferably 5 or more and 1000 or less, more preferably 10 or more and 500 or less. The unit in the polymer B that is compatible with the polymer (A) is a polymer chain, and a polymer (
C) is compatible with polymer (A). Preferably, the difference in solubility parameters between polymer (C) and polymer (A) is within ±2, more preferably within ±1. Examples of monomers from which units compatible with the polymer (A) are derived include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and cyclohexyl acrylate; methyl methacrylate;
Methacrylic acid esters such as ethyl methacrylate, cyclohexyl methacrylate, and sulfopropyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; and vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone. styrenes such as styrene, methylstyrene, chloromethylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride,
Examples include butadiene and isoprene. The content of fluorine units and silicon units in the polymer (B) of the present invention is appropriately such that the fluorine unit is a fluorine atom, the silicon unit is SiO, and the total of fluorine atoms and SiO is in the range of 1 to 90% by weight, 5-80% by weight
A range of is preferred. When the content of fluorine atoms and/or SiO is 1% by weight or more, sufficient antistatic properties and adhesion resistance can be obtained; when the content exceeds 90% by weight, the solubility in organic solvents becomes poor and handling becomes difficult. The resulting polymer is expensive. The content of units compatible with polymer (A) in polymer (B) is suitably in the range of 10 to 99% by weight, preferably in the range of 20 to 95% by weight. In addition to fluorine units, silicon units, and units compatible with hydrophilic colloids, the polymers of the present invention contain various linking groups (for example, thio groups, oxy groups, carbonyl oxyne groups, etc.) and terminal groups introduced during synthesis. Furthermore, it may contain a component derived from a monomer copolymerizable with the macromonomer from which the above-mentioned unit is derived, as long as it does not impede the object of the present invention. The fluorine content in the polymer (B) of the present invention is N
It can be determined by MR, and the silicon unit can be determined as 5iOa by firing a polymer. The molecular weight of the polymer (B) of the present invention is suitably in the range of 2,000 to 200,000 in terms of styrene-equivalent number average molecular weight using gel permeability chromatography (hereinafter referred to as GPC), and 200,000 when it does not contain silicon units.
When the range of 00 to 100,000 does not include a fluorine unit, the range of 3,000 to 2QQ (IQQ is preferable). The following combinations of commercially available polymers (A) and (B) of the present invention can be used. A combination of Aron G (registered trademark, Toagosei Kagaku Co., Ltd.) and Modiper F (registered trademark, Nippon Oil & Fats Co., Ltd.) as the polymer (A) and as the polymethyl methacrylate polymer (B). Fluorine unit and polymer of the present invention Synthesis methods for graft polymers having units compatible with (Δ) include conventionally known chain transfer methods, radiation grafting methods, mechanical or organic chemical reaction methods, polymer initiator methods, and prepolymer methods. Either the bonding method or the macromonomer method can be preferably used, but the most effective graft polymer for the purpose of the present invention can be obtained by synthesis by the macromonomer method. Synthesis method of the above-mentioned fluorine-based graft polymer When the polymer (A) to be combined is, for example, polymethyl methacrylate, for example, methyl methacrylate is radically polymerized in the coexistence of thioglycolic acid to obtain a one-terminated carboxylic acid prepolymer with a molecular fi of 300 to 10,000, and this is mixed with methacrylic acid. A macromonomer having a methacrylic acid ester type terminal group is obtained by reacting with Greennor.A fluorine-based vinyl monomer such as fluoroacrylate (CF3+ CF2)-C11, CIl, 0COCII is added as a copolymerization component to this macromonomer.
= C11,), a graft polymer is obtained in which the trunk is a fluorine unit and the branches are part of an anchor of polyhydroquinoedyl methacrylate. On the other hand, a graft polymer in which the trunk is polymethyl methacrylate and the branches are fluorine units can be easily obtained. Methods for synthesizing the block polymer having the fluorine-based units of the present invention and units compatible with the polymer (Δ) include conventionally known anionic living polymerization methods, cationic living polymerization methods, and both anionic and cationic living polymerization methods. Any of the following methods can be preferably used: connection of , terminal functional group method, condensation method, etc. Vinyl monomers such as methyl methacrylate are radically polymerized in the coexistence of thioglycolic acid to obtain one-end carboxylic acid polymers with a molecular weight of 300 to 10,000, and fluorine-based vinyl monomers such as fluoroacryle-1-(CF, (-CF2-) -2(C11, CI
1,0COCII=C11,) in the coexistence of mercaptoethanol, and the same molecular weight was 1000 to 1.
0000 one-terminated hydroquine polymer is obtained. By condensing this one-end carboxylic acid polymer and one-end hydroquine polymer, the desired fluorine-based block polymer can be obtained. Methods for synthesizing graft polymers having units compatible with the silicon unit of the present invention and polymer (A) are described, for example, in Japanese Patent Publication No. 32-6896, Japanese Patent Publication No. 47-16199, Japanese Patent Publication No. 48-28389, etc. As described in Japanese Patent Publication No. 46-9355, an active group is formed by abstracting hydrogen from a lower argylene group bonded to the silicon atom of silicone, and an organic polymer is grafted onto the active group. A method of reacting a silicone having a group with a living polymer obtained by anionic polymerization,
As seen in Japanese Patent Publication No. 52-135391, a polysiloxane polyester containing maleic acid in the main chain is synthesized, and maleic acid and an electron-donating monomer that easily forms a charge transfer complex are mixed and polymerized. Method: 0.2 per mole of α,ω-dihydroxydimethylpolysiloxane
A method of radical copolymerization of an acrylic modified silicone obtained by condensing 5 to 1 mole of γ-methacryloquinebropylmethyldichlorosilane and a vinyl monomer having radical polymerization ability (abbreviated as the acrylic modified silicone method)
Among these, graft polymers obtained by the acrylic modified silicone method have particularly high performance. The Noricon-based graft polymer thus obtained is a graft polymer having silicon units as branches and a polymer obtained from a vinyl monomer as a trunk. As vinyl monomers having radical polymerization ability, all hydrophilic vinyl monomers and other copolymerizable vinyl monomers that can be used when synthesizing a fluorine-based graft polymer can be mentioned. Examples of the method for synthesizing the block polymer having a unit compatible with the silicon unit of the present invention and the polymer (A) include a method of reacting licone with a living polymer obtained by anionic polymerization, a condensation method, and the like. The block polymer of the present invention can be obtained by condensing a one-terminal carboxylic acid obtained by polymerizing a vinyl polymer such as methyl methacrylate in the presence of diglycolic acid with α,ω-dihydroxydimethylpolysiloxane. When synthesizing by emulsion polymerization, for example, 5% by weight of a surfactant (for example, anionic,
nonionic, cationic) 0.3% by weight of water-soluble initiators (e.g. peroxides, azo compounds), 20% by weight relative to water
The desired latex can be obtained by polymerizing the monomers while stirring. The amount and type of surfactant are determined depending on the type of monomer, compatibility with hydrophilic colloid, influence on photographic performance, etc., but preferably 1 to 20% by weight. The reaction temperature depends on the type of initiator used, but if a thermal initiator is used,
0-120℃, 40-60℃ for redox initiator
C is appropriate. As a method for containing the graft polymer (A) and polymer (B) of the present invention in the form of polymer latex,
After dissolving the polymer (B) in the monomer from which the polymer (A) is derived during emulsion polymerization, the polymer (A) and the polymer (B) are simultaneously dissolved and dispersed using a polymerization method or a redispersion method. There are methods etc. The polymers contained in the latex particles of the present invention are mainly composed of the above-mentioned polymer (A) and polymer (B), and polymers other than these may also be present as long as they do not impede the purpose of the present invention. However, polymer (A
) and polymer (B), and most preferably consists only of both of these polymers. Specifically, the total ratio of polymer (A) and polymer (B) to the polymers contained in the latex particles is 9.
It is preferably 0% by weight or more. In the latex particles of the present invention, the polymer (A) and the polymer (B) are present in a mixed state as a so-called polymer blend. The mixing ratio of both polymers is that polymer (B) is polymer (A)
A suitable amount is 0.001-10% by weight, particularly preferably 0.01-5% by weight. It is sufficient to use the polymer (B) in an amount sufficient to coat the surface of the latex particles, and therefore, the preferred amount also depends on the particle size of the latex particles. The latex particles of the present invention have compounding agents (
For example, a plasticizer such as dioctyl phthalate, a fluorine-based surfactant, etc.) can be contained. The photographic light-sensitive material of the present invention has a photosensitive layer on a support, and at least one of the layers (photographic constituent layers) coated on the support is a hydrophilic colloid layer. The particle size of the dispersoid of the polymer latex of the present invention is 0.01
A range of 5.0 μm, particularly 0.05 to 1.0 μm is preferred. In the photographic light-sensitive material of the present invention, the hydrophilic colloid layer to which the polymer latex of the present invention is added may be a photosensitive layer (for example, a light-sensitive silver halide emulsion layer) or a non-photosensitive layer (for example, a protective layer, an intermediate layer, a back layer). etc.), but it is preferably the outermost layer. The above-mentioned outermost layer refers to the layer located farthest from the support among the hydrophilic colloid layers that are coated and dried on the support in the finished product or intermediate product of the 4 types of photosensitive materials, and is the photosensitive layer. It may be either the side or the back layer side. The outermost layer is, for example, a surface protective layer, a back layer consisting of one layer, a non-photosensitive intermediate layer which is the outermost layer of an intermediate product in a multilayer photosensitive material coated in multiple layers, and the like. Examples of the hydrophilic colloid binder used in the photographic material of the present invention include gelatin, gelatin derivatives (eg, acetylated gelatin, phthalated gelatin, etc.), albumin, and collodion, with gelatin being particularly preferred. Furthermore, in the present invention, if necessary, a hardening agent, a smoothing agent,
Various additives such as surfactants, antistatic agents, thickeners, etc. can be included. Examples of hardening agents include aldehyde compounds, halogen-containing compounds such as 2-hydroxy-4,6-dichloro-1,3,5-triazine, vinylsulfone compounds, N-methylol compounds, and mucochloric acid. Halogen carboxaldehyde compounds and the like can be used. As the smoothing agent, for example, liquid paraffin, waxes, polyfluorinated hydrocarbons, silicones, etc. can be used. Examples of surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxides, cationic surfactants such as higher alkylamines and quaternary ammonium salts, and acidic groups such as carboxylic acids and sulfonic acids. Any anionic surfactant containing the following can be used. As the antistatic agent, the above-mentioned surfactant,
Alkali metal salts such as the fluorosurfactant styrene-maleic acid copolymer and acrylonitrile-acrylic acid copolymer described in U.S. Pat. No. 3,754.924, and U.S. Pat. No. 3,206.312, Same No. 3,428
, 451 can be contained. In the present invention, known matting agents such as alkali-insoluble matting agents such as silicon dioxide, polymethacrylate, polytetrafluoroethylene, MMA/MAA, and EMA are used.
An alkali-soluble matting agent consisting of /MAA can be used in combination. When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material, the silver halide emulsion used therein can be prepared by any one of the usual single jet method, double jet method, acid method, ammonia method, neutral method, etc. There are no particular restrictions on the shape, size, or size distribution of the silver halide grains. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. Hydrophilic colloid binders used in silver halide emulsions include gelatin, modified gelatin, gelatin derivatives, carboxyl methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, poly-N-pyrrolidone, polyacrylic acid copolymer, polyacrylamide, etc. These may be used alone or in combination of two or more. Further, the photographic constituent layer coated on the support of the photographic light-sensitive material according to the present invention may contain a latex-like water-dispersed vinyl compound other than the polymer latex of the present invention. As such a latex, homo or copolymers of alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. are used. The silver halide emulsion in the present invention can be chemically sensitized by conventional methods. For example, U.S. Patent No. 2.399,0
83, US Pat. No. 2,597,856, salts of noble metals such as platinum, palladium, rhodium, and iridium, US Pat.
Chemical sensitization can be carried out using the sulfur compounds shown in the specifications such as No. 689 and No. 3,501,313, other stannous salts, amines, and the like. A stabilizer or an antifoggant can be added to the silver halide emulsion in the present invention. For example, 4-hydroxy-6-methyl-1,3,3a,7
-titrazaindene, 3-methyl-penzothiazole,
Including l-phenyl-5-mercaptotetrazole,
Many heterocyclic compounds, mercury-containing compounds, mercapto compounds2
Many compounds such as compounds, metal salts, etc. can be used. Furthermore, various spectral sensitizing dyes such as merocyanine dyes, carbocyanine dyes, cyanine dyes, etc. can be used in the silver halide emulsion in the present invention depending on the purpose. In the present invention, the color couplers include a 4-equivalent methylene yellow coupler, a 2-equivalent m-type noketomethylene yellow coupler, a 4-equivalent or 2-equivalent pyrazolone magenta coupler, an indashilon magenta coupler, an α-naphthol cyan coupler, and a 2-equivalent methylene yellow coupler. Phenolic cyan couplers can be used. Also, the so-called DIR
Couplers and polymer couplers can be used. Furthermore, the photographic constituent layer of the photographic material of the present invention may contain dyes, ultraviolet absorbers, hardeners as described above, surfactants, and polymer latex. As the support for the photographic light-sensitive material, any film commonly used in the art, such as cellulose acetate film, polyethylene terephthalate film, baryta paper, or paper coated with α-olefin polymer, may be used. It's coming. The photographic constituent layers of the photographic light-sensitive materials of the present invention can be coated one layer at a time or in multiple layers simultaneously using pure methods such as di-tube coating, air knife coating, curtain coating, extra-noon coating, etc. . For information on the various additives, vehicles, supports, coating methods, etc. that can be used in the present invention, please refer to the Product Licensing Index.
sing Index) Vol. 92, pp. 107-110 (1
December 971) No. 1; Self, li! can be used as a reference. The exposure light source for the photographic light-sensitive material of the present invention is not particularly limited, and can range from low illuminance to high illuminance, with exposure times ranging from several tens of seconds to 104' seconds. You can use it. Silver halide photosensitive materials to which the present invention can be applied include black and white photographic materials, color photographic materials, and silver halide photographic materials for general use, printing use, X-ray use, radiation use, etc. Specifically, black and white negative film, paper, reversal photographic materials, color negative films, paper, so-called external color photographic materials containing color formers in reversal and processing solutions, and all other halogen Examples include silver oxide photographic materials. The present invention is also applicable to other photographic materials having any type of water-based colloid layer in the outermost layer. In the case of the photographic light-sensitive material of the present invention or a silver halide color light-sensitive material, the development process for forming a dye image after exposure includes at least one color development step according to Hashimoto, and optionally, It includes a hardening process, a neutralization process, a first development (black and white development) process, etc. Said steps and the steps following them (e.g. selected combinations of bleaching, fixing, bleach-fixing, intensification, stabilization, washing, etc.) are 3
The treatment is carried out at 0°C or higher, particularly preferably at 35°C or higher. The color developing solution contains p-phenylenediamines (for example, N5N-diethyl-p-phenylenediamine, N%N-diethyl-3-methyl-p-)22-diamine, 4-amino-3-methyl as a developing agent. -N-ethyl-N-methanesulfonamidoethylaniline, 4-amino-3-
methyl-N-ethyl-N-β-hydroquinoethylaniline, N-ethyl-N-β-hydroquinethyl-p-phenylenediamine) or salts thereof (e.g., hydrochloride,
sulfates, sulfites), U.S. Patent No. 2,193.015, U.S. Pat.
It is possible to use the compounds described in (I).The color-developing liquid may contain salts such as sodium sulfate, PU such as sodium hydroxide, sodium carbonate, sodium phosphate, etc. AI moderators and buffers (e.g. acetic acid,
acids such as boric acid or its salts), phenomenon promoters (e.g.
U.S. Patent No. 2,648,604, U.S. Patent No. 3.671゜2
Various pyrinonium compounds, cationic compounds, potassium sulfate, sodium nitrate, described in specifications such as No. 47, U.S. Patent No. 2,533,990, U.S. Pat.
, 577゜127, British Patent No. 2,950,970, and derivatives thereof, British Patent No. 1,020.032, British Patent No. 1,
Nonionic compounds such as polythioethers as represented by compounds of No. Ii, represented by the compounds described in U.S. Patent No. 3,068,097 Polymer compounds having sulfide esters such as pyridine, ethanolamine, benzyl alcohol, hydrazine, etc.) can be included. The color developing liquid may further contain antifoggants (for example, alkali bromide, alkali iodide, nitropenzimidazoles, penztriazole compounds, mercaptotetrazole compounds, etc.), U.S. Patent No. 3,161,514, British Patent No. 3.161,5
No. 14, British Patent No. 1.144.481, etc., and U.S. Patent No. 3.
536,487, preservatives (eg, sulfites, acid sulfites, hydroxylamine hydrochloride, formaldehyde-alkanolamine sulfide adducts, etc.) may be included. 1iii. The hardening solution used in the r&film process contains aldehydes that harden gelatin, which is used as a hydrophilic colloid in photographic light-sensitive materials, such as U.S. Pat.
Aliphatic aldehydes, formaldehyde, glyoxal, zacunaldehyde, geltaraldehyde, pyruvaldehyde, etc. described in specifications such as No. 232.761), and U.S. Patent Nos. 3,565,632 and 3.6.
An aqueous solution containing one or more aromatic aldehydes described in Patent No. 67.760 and the like can be used. This solution contains inorganic salts such as sodium sulfate, borax, boric acid, acetic acid, sodium acetate, sodium hydroxide, sulfuric acid, etc.
It may contain anti-fogging agents such as heat-setting agents, buffering agents, and alkali halogenides (for example, potassium bromide, etc.). The neutralization tower used in the neutralization process contains hydroquinamine,
In addition to aldehyde removing agents such as L-ascorbic acid, inorganic salts, ptI regulators, buffers, etc. may be added. In the first development step of the color reversal film, hydroquinone, I-phenyl-3-pyrazolidone, N-methyl-p
- An alkaline aqueous solution containing one or more phenomenon agents such as aminophenol can be used, as well as inorganic salts such as sodium sulfate, and p+-1 regulators such as borax, boric acid, sodium hydroxide, and sodium carbonate. It may also contain buffering agents, alkali halides (eg, potassium bromide), and other developer fog inhibitors. The various additives and amounts added in the above processing steps are well known in color photographic processing methods. Bleaching agents used in bleaching baths and bleach-fixing baths include known compounds such as ferinoanates, dichromates, water-soluble iron ([11) salts, water-soluble cobalt (III) salts, water-soluble steel (II) salts]. ) salt, water-soluble quinones, 2) Rosophenol, iron (III), cobalt ([[), copper (II)
), complex salts of polyvalent cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-
Aminopolycarboxylic acids such as hydroxyethyl ethylenediamine triacetic acid, metal complex salts such as malonic acid, hydric acid, malic acid, diglycolic acid, notothioglycolic acid, and 2.
6-Novicolinic acid class complex salts, peracids such as alkyl peracids, persulfates, permanganates, hydrogen peroxide, etc., hypochlorites, chlorine, bromine, salts, etc. alone or in appropriate combinations. Can be used. In addition to these baths, bleaching accelerators as described in U.S. Patent No. 3,042,520, U.S. Pat. I also take it. A known fixing solution can be used for fixing. That is, as fixing agents, ammonium, sodium, and potassium salts of thiosulfate are used in an amount of 50 to 200 g/Q, and in addition, stabilizers such as sulfites and isomeric bisulfites, and hardening agents such as potassium alum are used. agents, plJ buffers such as acetates, borates, and the like. As for the bleaching agent, fixing agent, and bleach-fixing bath, the techniques described in US Pat. No. 3,582,322 and the like can be applied. Examples of hli liquids include a method using Go(III) salt, a method using hydrogen peroxide, and a method using chlorous acid.
Li horn liquid can be used. For image stabilizing baths, see U.S. Patent No. 2,515,121.
No. 3,140,177, etc. can be used. Next, in order to explain the present invention more specifically, synthesis examples, examples, and comparative examples are given. Note that the percentages listed in each column represent weight percent in total.・Synthesis Example 1 (1) Synthesis of terminal methacrylate type hydrogyshadyl methacrylate macromonomer Hydroxyethyl methacrylate (hereinafter referred to as M abbreviated) and acetone-toluene (175%: 82.5%) mixed solvent 83
After degassing with N2 gas for 1 hour, azobisisobutyronitrile (hereinafter referred to as AIBN) was added as a polymerization initiator under reflux.
(abbreviated as )) and 0.32 g of thioglycolic acid as a chain transfer agent were added to initiate polymerization. then 4.5
90 g of MMA was added dropwise every 30 minutes, and 2.88 g of thioglycolic acid was dissolved in 7 g of toluene.
Add 1.5 g of A [B N
．． The mixture was added in three portions every 5 hours, and reflux was continued for 2 hours to obtain a polymer having the following structural formula (1). A part of the reaction solution was reprecipitated with n-hexane and dried, and the acid value was measured and found to be 0.340 mg equivalent/g. CI). 113 11(CH,-C)-nS-CIl, COO110OC
IL Next, after distilling off part of the acetone from the above reaction solution, 0.5% of triethylamine as a catalyst and 200 ppm of hydroquinone monomethyl ether as a polymerization inhibitor were added, and glisonol was added at an amount of 1.2 times the acid value. Methacrylate was added and reacted under reflux (approximately 110°C) for 11 hours. The reaction rate determined from the decrease in oxidation was 96%. The reaction solution was poured into 10 times the volume of n-hexane and precipitated. After, 80
It was dried under reduced pressure at °C to obtain 90 g of a macromonomer having the following structural formula (n). The number average molecular weight of the polystyrene equivalent molecular weight determined by GPC was 2,900. Moreover, the hydroxyl value was 0.350 equivalent/g. (II) CIl,
CI+3+1(C112-C)-nS
-CIl, Coo -C11, -CIl -CIl2-
0CO-C= C112COOCH30H (2) Synthesis of fluorine-based graft polymer by macromonomer method 70 g of macromonomer of structural formula (V) and fluoroalkyl acrylate CI+, = C11-COO-CIItCtlt(-c
Fz) nCF3 (n=4-12 mixture average n
= 7) 30g, trifluorotoluene (C,ll,
CF,) and 0.35 g of A I B N were mixed and polymerized under reflux (about 100° C.) for 5 hours. After the reaction was completed, the reaction solution was poured into 10 times the amount of methanol to precipitate it, and dried under reduced pressure at 80°C to obtain the graft polymer (
+) 67g was obtained. This product showed a single peak by GPC, and the number average molecular weight was 10,000. In addition, trifluorotoluene was added as an internal standard substance, 'H-NMR spectrum was measured in CDCf2s solvent, and grafting was determined from the peak area ratio of H of trifluorotoluene and H of MMA unit -〇-CIL in the polymer. Calculate the content of MMA units in the polymer.
It was 0%. The remaining fluorine content is 40%. Therefore, the same reaction was carried out by changing the amount of fluoroalkyl acrylate charged, to obtain graft polymers (2) and (3) with fluorine contents of 20% and 60%. The number average molecular weights were all about 10.000.・Synthesis Example 2 220 g (0.1 mol) of α,ω-dihydroquine dimethylpolysiloxane C11° Cll0(SiO) nll n=30] and 9.49 g (0.12 mol) of C11° pyridine were mixed with diethyl ether. 12.06 g of γ-methacryloxypropylmethyldichlorosilane (0,0
A 10% noethyl ether solution (5 mol) was gradually added dropwise over 20 minutes at room temperature. After dropping, add 1 more time at room temperature.
The mixture was stirred for an hour and pyridine hydrochloride crystals were removed by filtration. Next, put this filtrate into a branch funnel and add 500 m of water.
Q was added, shaken well, and washed with water. After washing with water, the separatory funnel was left standing to separate the upper ether layer and the lower aqueous layer, and the obtained ether layer was dehydrated with anhydrous sodium sulfate overnight. Thereafter, Glauber's salt was removed by filtration, and ether was distilled off under reduced pressure from the resulting filtrate to obtain 225 g of a colorless and transparent acrylic-modified silicone. This acrylic modified silicone 50g5HE M A 5
0g. Azobisisobutyronicalyl log and toluene 300
g were mixed and polymerized for 24 hours at 80° C. in N gas. After the reaction, toluene and unreacted HEMA were removed under reduced pressure,
The obtained solid was extracted with n-hexane and dried under reduced pressure to obtain 81 g of white powdery graft polymer (4). The amount of silicone in this graft polymer was 40% as dimethylborisiloxane, and the molecular weight determined by GPC was number average molecule fll 11n = 90,000. To determine the amount of silicone, put about 0.2g of graft polymer into a platinum crucible, add 3ml of concentrated sulfuric acid, and put it in an electric furnace for 70 minutes.
It was heated at 0° C. for 2 hours, and the silicone was determined as Sin. Next, production examples of typical matting agents used in the present invention will be shown. Production Example I Add surfactant Cal+ to water Iσ degassed with N2 gas, ○
-0(IV,CH20)-ff(cII2)3sOJa
Mix 10g and heat to 80'C. Next, 0.75 g of ammonium persulfate was added, and while stirring, edyl acrylate 2 in which 2.5 g of graft polymer (1) had been dissolved was added.
Add 50g dropwise over 1 hour. After finishing the dripping, 1 more
The desired latex (+) can be obtained by reacting for a period of time and steam distilling for 1 hour to remove some residual monomer. Production Example 2 80 g of prepolymerized polyethyl acrylate and 0.8 g of graft polymer (1) were mixed with ethyl acetate and ten-butanol (
1: I) Dissolved in 190g. Also, add 1.5 g of sodium dodenlebenzene sulfonate to 40 g of water. og was dissolved. Add 40g of gelatin to a 500m12 beaker, add 320g of water, and let rise for 30 minutes! After incubation, it was lysed at 60'C. Next, the dissolved gelatin solution and the aqueous sodium dodenlebenzene sulfonate solution were placed in a three-bottle flask with an internal volume of 1.5 mm, and the flask was heated to 35°C. The above pre-dissolved solution was added thereto and stirred for 20 minutes at a speed of 1000 revolutions per minute to obtain latex (1). Production Example 3 Graft polymer (4) was used instead of graft polymer (1).
) was treated in the same manner as in Production Example 1 to obtain (2). Production Example 4 Modiva F-100 instead of graft polymer (1)
(manufactured by Nippon Oil & Fats Co., Ltd.) in the same manner as in Production Example I to obtain 3). Production Example 5 Graft polymer (4) instead of graft polymer (1)
) was treated in the same manner as in Production Example 2 to obtain latex (2'). Production Example 6 Modiper F-10 instead of graft polymer (1)
Latex (3') was obtained by processing in the same manner as in Production Example 2 using 0 (manufactured by Nippon Oil & Fats Co., Ltd.). [Example] Example 1 Containing 300 g of gelatin per mole of silver halide, and containing α-pivaloyl-α-(
2.5 l-benzylimidazolidin-2,4-dion-3-yl)-2-chloro-5(7-(2,4-tert-aminophenoxy)butylamidoacetanilide)
Color blue-sensitive silver iodobromide (silver iodide 7 mol %) containing 10-2 mol of
The emulsion was prepared. In addition, latex (1) of the present invention, (
2), (3), (B), (2') and (3') and comparative polyethylene acrylate latex (A) and polyhexafluoroisopropylacrylate latex (manufacturing example of JP-A-54-3.8110) Items listed in 1)
(B): A gelatin solution containing a hardening agent and a coating aid in the amounts shown in Table 1 was applied to the slide hopper at the coating amount shown in Table 1, and was applied onto a cellulose triacetate film support having a subbing layer. An emulsion layer and a protective layer were applied in order from the support side to samples (1), (2), (3) (1'), (2'
) (3'), (A) and (B) were obtained. The dry thickness of the protective layer was 1.5 μm. Appendix Table I For each sample, 2
Cut out each piece, making sure that they do not touch each other.
After storing for one day in an atmosphere of 80% RH at 40°C, two protective layers of the same sample were brought into contact with each other, a load of 800 g was applied, and the sample was stored at 40°C in an atmosphere of 80% Rr-1. After that, the sample was peeled off and the area of the adhesive part was measured.
Adhesion resistance was measured. Note that the evaluation criteria are as follows. Rank Area of adhesive part A 0-20% 8 21-40% C41-60% D 61% or more The results are shown in Table 2. From the results in Table 2, it can be seen that the adhesive resistance of the samples using the polymer latex of the present invention is superior to that of the conventional one. Example 2 Samples (1), (2), (3) (1') (2') of the present invention
) and (3') and comparative samples (A) and (B), the antistatic property and devitrification property were investigated by the following method. After conditioning the unexposed sample at 25°C and 25% RH for 2 hours, the emulsion side of the sample was rubbed with a neoprene rubber roller in a dark room under the same air conditioning conditions, and then developed, bleached, fixed, and After washing with water and stabilization, the degree of static mark occurrence was examined. Processing process Humidity Processing time (1) Development...38℃ 3 minutes 15 seconds (2)
Bleaching... 38℃ 4 minutes 30 seconds (3) constant
Arrival: 38℃ 4 minutes 20 seconds (4) Washing: 38℃ 3 minutes 15 seconds (5) Stabilization
... 38° C. 1 minute 5 seconds The compositions of the developer, bleaching solution, fixing bath, and stabilizing bath are as follows. Phenomenon solution (1) tl = lQ, Q5) Add 2.5 g of hydroxylamine sulfate, 4 g of sodium sulfite sulfite, and
Let it be Q. Bleach bath (pI (= 5.70) Ammonium bromide 173g'E
Add 27g of DTA water to make 112. Fixing bath (l (= 6.50) ammonium diosulfate 800m12
L Sodium bisulfite 5.0g Add water to make IQ. Stable bath (+) I-1 = 7.30) 40% formalin 6.6 mQ L Alcohol 0, 6 m
Add Q water to make 112. Devitrification was determined visually. Table 3 shows the test results of antistatic properties and devitrification properties of these samples.
Shown below. In the table, the evaluation of the degree of static mark occurrence is A: No static marks observed at all) B: Some static marks observed C: //
Fairly acceptable D, //
It was divided into 4 stages depending on whether it was completely recognized. As is clear from Table 3, the sample antistatic using the polymer latex of the present invention has an excellent antistatic effect with almost no static marks, but there is no devitrification of the film. [Effects] The photographic material of the present invention has excellent adhesion resistance and antistatic properties, and can be used without the use of conventional antistatic agents. Disadvantages (antistatic effect is insufficient at low humidity, adhesion failure may occur at high temperature and high humidity, and if a sufficient amount is used for antistatic purposes, the physical properties of the film may deteriorate or the developing processing solution Slack generation in the membrane and devitrification of the membrane are improved. The fluorine-based and graft polymers and block polymers of the present invention consist of a portion having fluorine or silicone units and an anchor portion that is compatible with the latex-forming polymer, and the presence of the anchor portion causes the graft to migrate and concentrate on the latex particle surface. The polymer and block polymer are easily separated and do not flow out into the developing solution, improving adhesion and charging properties. Applicant: Konishiroku Photo Industry Co., Ltd. Procedure corrector: October 31, 1985

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one hydrophilic colloid layer formed by adding a polymer latex on a support, in which the dispersoid of the polymer latex contains the following (A) and (
A photographic light-sensitive material mainly consisting of B). (A) A polymer forming particles of the above dispersoid (B) A block polymer or graft polymer having at least one selected from fluorine units and silicon units and a unit compatible with the polymer of (A) above.