JPH0132972B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material, and particularly to a photographic material with improved antistatic properties. Photographic materials generally consist of an electrically insulating support and a photographic layer, so during the manufacturing process of the photographic material and during use, it is subject to contact friction or peeling with surfaces of the same or different materials. Electrostatic charge often builds up. This accumulated electrostatic charge causes many problems, but
The most serious problem is that the photosensitive emulsion layer is exposed to light due to the discharge of electrostatic charges accumulated before processing, resulting in dots or dendritic or feather-like streaks when the photographic film is processed. It is something that happens. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, or in some cases completely destroys it. For example, if it appears in medical or industrial X-ray film, it will be easily recognized that it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. Furthermore, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly. As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials. This occurs due to peeling between the support surface and the emulsion surface, etc. Alternatively, it may occur due to contact peeling between the X-ray film and a mechanical part or fluorescent intensifying screen in an automatic camera. It can also occur due to contact with other packaging materials. Static marks on photographic materials induced by such electrostatic charge accumulation become more noticeable as the sensitivity of photographic materials increases and the processing speed increases. Particularly in recent years, static marks are more likely to occur due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. There is. In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, antistatic agents that can be used in photographic light-sensitive materials should not only have excellent antistatic properties, but also have no adverse effects on the photographic light-sensitive materials, such as their sensitivity, fog, graininess, sharpness, etc. It does not adversely affect the film strength of the photographic material (i.e., it does not become easily damaged by friction or scratching);
It should not have an adverse effect on the adhesion resistance (that is, the surface of the photographic light-sensitive material should not easily stick to the surface of the photographic light-sensitive material or the surface of other substances), it should not cause the processing solution of the photographic light-sensitive material to fatigue quickly, and each of the photographic light-sensitive materials Application of antistatic agents to photographic materials is subject to numerous restrictions, as performance such as not reducing the adhesive strength between constituent layers is required. One way to eliminate the problems caused by static electricity is to increase the electrical conductivity of the surface of the photosensitive material so that the static charges can be dissipated in a short period of time before the accumulated charges are discharged. Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, and certain surfactants. Ta. For example, US Patent No. 2882157, US Patent No. 2972535, US Patent No. 3062785,
No. 3262807, No. 3514291, No. 3615531,
3753716, 3938999, etc., for example, U.S. Pat.
No. 3428456, No. 3457076, No. 3454625, No. 3454625, No. 3457076, No. 3454625, No.
Surfactants such as those described in US Pat. No. 3,062,700 and US Pat.
Metal oxides, colloidal silica, and the like described in No. 3245833 and No. 3525621 are known. However, many of these materials exhibit specificity depending on the type of film support and photographic composition, giving good results with some film supports, photographic emulsions, and other photographic components, but not with others. Vine film supports and photographic components are not only completely useless in preventing static electricity, but may also have an adverse effect on photographic properties. On the other hand, although it has an extremely excellent antistatic effect, it is often unusable because it adversely affects photographic properties such as sensitivity, fog, graininess, and sharpness of photographic emulsions. For example, polyethylene oxide compounds are generally known to have an antistatic effect, but they often have adverse effects on photographic properties such as increased fog, desensitization, and deterioration of graininess. In particular, it is difficult to establish a technology that effectively imparts antistatic properties without adversely affecting the photographic properties of photosensitive materials in which photographic emulsions are coated on both sides of the support, such as direct X-ray photosensitive materials for medical use. It was difficult. As described above, it is very difficult to apply antistatic agents to photographic materials, and the scope of their use is often limited. Another method for eliminating problems caused by static electricity in photographic light-sensitive materials is to adjust the charging voltage on the surface of the light-sensitive material to reduce the generation of static electricity due to friction or contact as described above. For example, British Patent No. 1330359, British Patent No. 1524631,
U.S. Patent No. 3666478, U.S. Patent No. 3589906, Special Publication No. 1977-
Attempts have been made to utilize fluorine-containing surfactants such as those shown in Japanese Patent Application Laid-open Nos. 26687, 49-46733, and 51-32322 for this purpose in photographic materials. However, the electrostatic properties of photographic light-sensitive materials containing these fluorine-containing surfactants utilize the properties of the surfactants, such as monomolecular film formation, and therefore may vary depending on the process conditions used to manufacture these photographic light-sensitive materials. It is extremely difficult to stably produce a uniform product with constant electrostatic properties, for example, the temperature and humidity of the process of coating the constituent layers of the photographic material on the support, and the temperature and humidity after coating. The electrostatic properties of the product change greatly depending on the temperature, humidity, drying time, etc. of the drying process. This was a serious problem in terms of quality control. Additionally, these fluorine-containing surfactants also have the disadvantage that even if they have good electrostatic properties immediately after production, their properties deteriorate over time and they no longer have good electrostatic properties by the time the product is used. was. In order to overcome the problems of fluorine-containing surfactants, attempts have been made to utilize fluorine-containing polymers in photographic materials. For example, UK patent no.
No. 1497256 discloses a polymer emulsion (latex) obtained by homopolymerizing or copolymerizing an acrylic ester or methacrylic ester monomer of a fluorine-containing alcohol with JP-A-158222-1497.
JP-A-52-129520 discloses polymers obtained by copolymerizing the above-mentioned fluorine-containing monomers and monomers having polyethylene oxide chains, and JP-A-52-129520 discloses copolymerizations of the above-mentioned fluorine-containing monomers, vinyl esters of fluorine-containing carboxylic acids, fluorine-containing vinyl ethers, and fluorine-substituted monomers. A polymer obtained by copolymerizing a fluorine-containing monomer such as an olefin with a monomer having quaternary nitrogen, and a ternary copolymer of a maleic ester of a fluorine-containing alcohol, maleic acid, and other monomers, is also disclosed in Japanese Patent Publication No. 49-23828. A method for utilizing each polymerized polymer in a photographic material (particularly in its surface layer) is described. When these fluorine-containing polymers are used in photographic materials, the electrostatic charge on the surface of the photographic material can be adjusted to a certain extent, and the generation of static electricity due to friction and contact as described above can be reduced to a certain extent. In addition, the above-mentioned drawbacks of the fluorine-containing surfactant, namely, that the electrostatic properties are largely dependent on process conditions and deteriorate over time, are overcome to some extent. However, photographic materials containing these fluorine-containing polymers are insufficient in terms of the above-mentioned charging properties, and also have various drawbacks in terms of photographic properties and film properties that are important for photographic materials. However, these drawbacks significantly impair commercial value, and practically these polymers cannot be used in photographic materials. For example, a layer of a photographic light-sensitive material containing a fluorine-containing polymer emulsion described in British Patent No. 1497256 has high adhesiveness, and the emulsion surfaces of the photographic light-sensitive material do not come into contact with each other or between the emulsion surface and the back surface. On the other hand, these surfaces tend to adhere to each other and cannot be separated from each other or leave easily visible adhesive marks after separation, and layers of photographic materials containing these polymers can be easily bonded to other substances. The photosensitive material is easily damaged by friction or scratching, which significantly reduces the commercial value of the photographic material. On the other hand, the fluorine-containing polymers described in JP-A-54-158222, JP-A-52-129520, and JP-B-49-23828 have the ability to adjust the charging voltage when incorporated into photographic light-sensitive materials. This is significantly inferior, and to compensate for this, it is necessary to include a large amount in the photographic material. This not only increases product costs, but also has negative effects on photographic properties such as decreased sensitivity, decreased density, and fogging, as well as physical properties of the film such as easy adhesion and scratching. Due to the above-mentioned adverse effects, it has been impossible to utilize these polymers in photographic materials. A first object of the present invention is to provide an antistatic photographic material that generates less static electricity. A second object of the present invention is to provide an antistatic photographic material with good adhesion resistance. A third object of the present invention is to provide an antistatic photographic material that has high film strength and is resistant to scratches. A fourth object of the present invention is to provide a photographic material whose electrostatic properties are not easily changed by manufacturing process conditions and can be stably produced with uniform quality. A fifth object of the present invention is to provide a photographic material of stable quality whose electrostatic properties do not change over time after manufacture. A sixth object of the present invention is to provide a photographic light-sensitive material that is antistatic and has no adverse effects on photographic properties such as sensitivity, fog, graininess, etc. A seventh object of the present invention is to provide an antistatic agent for photographic materials that has an effective antistatic ability even when added in a small amount. An eighth object of the present invention is to provide an antistatic agent for photographic materials that is easy to manufacture and inexpensive. The purpose of these is to produce a fluorine-containing polymer having a styrene monomer having a fluorine-containing substituent as a polymerization unit as shown in the following general formula (), and at 20℃ 100℃.
This can be achieved by incorporating a water-soluble polymer having a solubility of 0.1 g or more per g of water into at least one of the constituent layers of the photographic light-sensitive material. General formula () In the formula, A represents a monomer unit copolymerized with a copolymerizable monomer having an ethylenically unsaturated group. R ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. R ² represents a monovalent substituent, and R ² may be linked to each other to form a ring. R ^f represents an alkyl group, aralkyl group, aryl group, or alkylaryl group having 4 to 30 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom. Q is a general formula; - (R) _p
-L- represents a divalent linking group, where R represents an alkylene group, an arylene group, or an aralkylene group, and L represents an oxy group, a thioxy group,
imino group, carbonyl group, carboxyl group, carbothoxyl group, carboxamide group, oxycarbonyl group, carbamoyl group, sulfone group, sulfonamide group, N-alkylsulfonamide group,
It represents a sulfamoyl group, a sulfoxyl group or a phosphate group, and p is 0 or 1. l is 0~
is an integer of 4, m is an integer of 0 to 3, and n is an integer of 1 to 5. x is 0.1 to 50 mol%,
y is 50 to 99.9 mol%. Among the polymers represented by the general formula (), particularly preferred are the polymers represented by the following general formula (). General formula () In the formula, A ¹ is a copolymerizable monomer having an ethylenically unsaturated group, and per 100 g of water.
Represents a monomer unit copolymerized with a water-soluble monomer having a solubility of 10 g or more. B represents a monomer unit obtained by copolymerizing a copolymerizable monomer having an ethylenically unsaturated group and having a solubility of less than 10 g in 100 g of water. R ¹ , R ² , R ^f , Q, l, m, and n have the same meanings as in the general formula (). x is 0.1 to 50 mol%, _y1 is 20 to 99.9 mol%, and z is 0 to 79.9 mol%. Preferred polymers of the present invention are shown below. A ¹ is a copolymerizable monomer having an ethylenically unsaturated group, and represents a monomer unit copolymerized with a water-soluble monomer having a solubility of 10 g or more in 100 g of water; examples of this monomer include: Acrolein, acrylamide, methacrylamide, N
-Methylolacrylamide, N,N-dimethylaminoethyl acrylamide, N,N-dimethylaminopropylacrylamide, hydroxyethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, poly(ethyloxy)acrylate, Poly(ethyloxy)methacrylate, 2
- Nonionic monomers represented by vinylpyridine, 4-vinylpyridine, 1-vinyl-2-pyrrolidone, 1-vinylimidazole, 1-vinyl-2-methylimidazole, etc., vinylbenzyltrimethylammonium salt, vinylbenzyltriethyl Cations represented by ammonium salt, vinylbenzyltripropylammonium salt, benylbenzyldimethylamine hydrochloride, methacryloxyethyltrimethylammonium salt, methacryloxyethyldimethylethylammonium salt, N,N-dimethylaminoethyl methacrylate hydrochloride, etc. Examples include, but are not limited to, anionic monomers such as acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc., or salts thereof. It is not something that will be done. Among these monomers, nonionic monomers are particularly preferred. B represents a monomer unit copolymerized with a copolymerizable monomer having an ethylenically unsaturated group and having a solubility of less than 10 g in 100 g of water; examples of this monomer include ethylene,
Olefins such as propylene and 1-butene, styrene or α-methylstyrene, vinyltoluene, chloromethylstyrene, styrene derivatives such as divinylbenzene, ethylenically unsaturated esters of organic acids such as vinyl acetate and allyl acetate, methyl acrylate , methyl methacrylate, n-butyl acrylate, n-butyl methacrylate,
Esters of ethylenically unsaturated carboxylic acids such as benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, amides of ethylenically unsaturated carboxylic acids such as N-butylacrylamide and N-amyl acrylamide, butadiene, Examples include, but are not limited to, dienes such as isoprene, acrylonitrile, vinyl chloride, maleic anhydride, and the like. Among these monomers, B is particularly preferably styrene or styrene derivatives. Examples of A ¹ or B are further illustrated by, for example, J.Brandrup.E.
It is described in Polymer Handbook, 2nd edition, edited by H. Immergut (John Wiley & Sons, 1975) - pages 1 to 11. R ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is particularly preferred. R ² represents a monovalent substituent, such as a halogen atom, a nitro group, an amino group, an alkylamino group, a carboxyl group, a sulfonic acid group, a carboxylic acid ester group, a sulfonic acid ester group, a carbamoyl group, a sulfamoyl group, and an alkylsulfonyl group. group, alkoxyl group, thioalkoxyl group, alkyl group, aryl group, etc., and these examples are further described in "Chemical Handbook Basic Edition" revised 2 edited by the Chemical Society of Japan.
Edition (Publisher: Maruzen Co., Ltd.) pages 1012-1013,
Acta Chim.Sinica Volume 32 (Acta Chim.Sinica)
32) Described on page 107 (1966). ^R2
is preferably a halogen atom, a nitro group, an alkyl group, etc. R ₂ may be linked to each other to form a ring, and this ring can be, for example, a benzene ring. R ^f has 4 to 30 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom,
It preferably represents an alkyl group, aralkyl group, aryl group, or alkylaryl group having 4 to 20 carbon atoms, and among these, perfluorohexyl group, perfluorooctyl group, 2,2,
3,3-tetrafluoropropyl group, 2,2,
3,3,4,4,5,5-octafluoroamyl group, 2,2,3,3,4,4,5,5,6,6,
7,7-dodecafluoroheptyl group, 2,2,2
-trifluoroethyl group, 2,2,3,3,4,
4,4-heptafluorobutyl group, 1,1,1,
3,3,3-hexafluoro-2-propyl group,
1,1,1,3,3,3-hexafluoro-2-
Hydroxy-2-propyl group, 1,1,2,2,
-tetrafluoro-2-hydroxyethyl group, p
-fluorophenyl group, p-trifluoromethylphenyl group, 2,3,4,5,6-pentatrifluoromethylphenyl group, etc. are preferred. Q represents a divalent linking group represented by the general formula: -(R) _p -L-, where R represents an alkylene group, an alkylene group, an arylene group, or an aralkyl group,
L is an oxy group, a thioxy group, an imino group, a carbonyl group, a carboxyl group, a carbothyoxyl group, a carbamide group, an oxycarbonyl group, a carbamoyl group, a sulfone group, a sulfonamide group, an N-alkylsulfonamide group, a sulfamoyl group, a sulfoxyl group, or represents a phosphate group, p is 0
Or 1. l is an integer of 0 to 4, preferably an integer of 0 to 2, m is an integer of 0 to 3, preferably 0 or 1, n is an integer of 1 to 5, especially 1 Or 2 is preferable. x is 0.1~
50 mol%, preferably 0.5-20 mol%, y ¹
is 50 to 99.9 mol%, preferably 20 to 99.5 mol%, and z is 0 to 79.9 mol%, preferably 0 to 49.5 mol%. The polymer represented by the general formula () of the present invention includes a fluorine-containing monomer represented by the following general formula (), a monomer represented by A ¹ in the general formula (), and, if necessary, a monomer represented by B in the general formula (). It can be obtained by copolymerizing with monomers. At this time, two or more types of fluorine-containing monomers may be used, and two or more types of monomers ^A1 or B may also be used. general formula Here, R ¹ , R ² , R ^f , Q, l, m, and n are as described above. The polymer of the present invention can be produced by various polymerization methods such as solution polymerization, emulsion polymerization, inverse emulsion polymerization, precipitation polymerization,
This is done by suspension polymerization, bulk polymerization, etc. Also,
The polymerization initiation method is a method using a radical initiator,
There are methods such as irradiation with light or radiation, thermal polymerization, cationic polymerization, and anionic polymerization. These polymerization methods and polymerization initiation methods are described, for example, in Teiji Tsuruta's "Polymer Synthesis Reactions" revised edition (published by Nikkan Kogyo Shimbun, Inc.,
(1971). Among the above polymerization methods, the solution polymerization method is particularly preferred, and the solvent used at that time is, for example, N,N
-Dimethylformamide, N,N-dimethylacetamide, dimethyl sulfide, methanol, ethanol, 1-propanol, 2-propanol, acetone, and other highly polar organic solvents are preferred. On the other hand, the polymer represented by the general formula () of the present invention is a homopolymer of a non-fluorine styrene monomer having a functional group or a copolymer with the monomer A ¹ represented by the general formula () and, if necessary, a monomer B. It can also be obtained by reacting a fluorine compound having a functional group with the coalescence. In this case, the non-fluorine styrene monomer having a functional group is, for example, hydroxymethylstyrene, aminomethylstyrene, aminostyrene, hydroxystyrene, carboxystyrene,
Mercaptomethylstyrene, chloromethylstyrene, vinylbenzoic acid chloride, etc., while fluorine compounds having functional groups are, for example, R ^f -COCl, R ^f
--OH, R ^f --NH ₂ , R ^f --SO ₂ Cl, etc. (R ^f is as already stated in the general formula ()). Alternatively, a copolymer of a fluorine-containing monomer represented by the general formula () and monomer B represented in the general formula () may be subjected to hydrolysis or other reactions to obtain a water-soluble polymer represented by the general formula (). You can also do it. Similarly, the polymer represented by the general formula () is also composed of the monomer represented by the general formula () and the general formula ().
It is synthesized in the same manner from monomer A shown therein. Examples of the fluorine-containing monomer of the present invention represented by the general formula () are described below. Monomer example Examples of the polymers of the present invention are shown below. Polymer example Next, synthesis examples of the polymer according to the present invention and the monomer that is the raw material thereof will be described. Synthesis example 1 Monomer example (M-1) 2, 2, 3, 3, 4,
4,5,5,6,6,7,7-dodecafluoro-
Synthesis of n-heptanoic acid vinylbenzyl ester 2, 2, 3, 3,
289.3 g (0.836 mol) of 4,4,5,5,6,6,7,7-dodecafluoro-n-heptanoic acid was added, and the mixture was cooled with ice water. 149.2 g (0.836 x 1.5 mol) of thionyl chloride was slowly poured into the solution while stirring. Furthermore, 3.3g of pyridine (0.836×0.05
mol) was slowly added dropwise. After dropping, reduce the external temperature to 100
℃ and continued stirring for 4 hours. After cooling, the precipitated needle crystals and pale yellow solidified material were separated, and the remaining thionyl chloride was distilled off, and the resulting fluorocarboxylic acid chloride was purified by atmospheric distillation. Thus 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7,
7-dodecafluoro-n-heptanoic acid chloride
280.3g (yield 92.0% bp=131-133°C) was obtained. In a 300 ml three-necked flask equipped with a stirrer, reflux condenser, and calcium chloride drying tube, add 100 ml of diethyl ether, vinylbenzyl alcohol (from chloromethylstyrene (meta: para = about 6: about 4)).
It was synthesized by the method described in Polymer 14 330 (1973). bp=69-73℃/0.4mmHg) 40.2g (0.3mol),
30.3 g (0.3 mol) of triethylamine and 2,
0.5 g of 6-di-t-butylphenol was added and cooled on ice. 2, 2, 3, 3, 4, 4, synthesized earlier
5,5,6,6,7,7-dodecafluoro-n-
109.4 g (0.3 mol) of heptanoyl chloride was cooled on ice,
It was added dropwise while stirring. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours, and then stirred under reflux for an additional hour. After cooling, the precipitated triethylamine hydrochloride was separated, washed twice with water, further washed with an aqueous sodium carbonate solution, and dried over anhydrous sodium carbonate. When purified by two distillations, 2, 2, 3,
3,4,4,5,5,6,6,7-dodecafluoro-n-heptanoic acid vinylbenzyl ester 61.0
g (yield 44.0% bp=106-116℃/0.9mmHg d
= 1.47) was obtained. Synthesis example 2 Monomer example (M-4) 2, 2, 3, 3, 4,
Synthesis of 4,5,5,6,6,7,7-dodecafluoro-n-heptanoic acid vinylbenzylamide 500 equipped with stirrer and calcium chloride drying tube
300 ml of acetonitrile in a 3-neck flask, vinylbenzylamine (chloromethylstyrene (meta: para = about 6: about 4)), Proceedings of the Society of Polymer Science 26
It was synthesized by the method described in Vol. p834 (G3 C-07) (1977). bp=82℃/1.5mmHg) 33.9g (0.3mol), triethylamine 30.3g (0.3mol) and 2,6
-0.5 g of di-t-butylphenol was added and cooled on ice. 2, 2, 3, 3, 4, synthesized in Synthesis Example 1
4,5,5,6,6,7,7-dodecafluoro-
109.5 g (0.3 mol) of n-heptanoyl chloride was added dropwise with stirring under ice cooling. After completing the dropping, 1 at room temperature.
After stirring for a certain period of time, the precipitated triethylamine hydrochloride was separated. After the solvent acetonitrile was distilled off under reduced pressure, 200 ml of ethyl acetate was added and dissolved, and at this time some white insoluble matter was separated. After concentrating by distillation under reduced pressure, 300 ml of n-hexane was added and cooled. After removing the precipitated white crystals,
It was dried under vacuum at room temperature. Thus, 2, 2, 3,
3,4,4,5,5,6,6,7,7-dodecafluoro-n-heptanoic acid vinylbenzylamide
90.1g (yield 65.2% mp=53-57°C) was obtained. Synthesis example 3 Synthesis of polymer example (P-1) Monomer example (M
-4) 20g (0.043mol), acrylamide 80g
(1.13 mol), N,N-dimethylformamide 80ml
Then, 2.85 g (0.012 mol) of benzoyl peroxide were added thereto, and the tube was degassed and sealed. This was heated in an oil bath at 60°C for 72 hours to polymerize. The polymer solidified by polymerization was taken out from the reactor, placed in 500 ml of water, and left for 72 hours to dissolve the variable components. After separating the insoluble materials, the mixture was poured into methanol (No. 2) for reprecipitation, dissolved in 300 ml of water, and dialyzed overnight. Fluorine-containing polymer aqueous solution 540 with a solid content of 6.5wt%
I got g. The copolymerization ratio x:y is based on the elemental analysis value.
It was determined to be 2.1:97.9. Synthesis example 4 Synthesis of polymer example (P-6) Monomer example (M-
4) 1.15g (2.5 mmol), acrylic acid 7.0g
(0.0975 mol), N,N-dimethylformamide 20
ml and 0.24 g (1.0 mmol) of benzoyl peroxide, and the tube was degassed and sealed. This was heated in an oil bath at 770°C for 64 hours to polymerize. The polymerized polymer solution was poured into 100 ml of ethyl acetate for reprecipitation, dissolved in 100 ml of water, and dialyzed overnight. 120 g of a fluorine-containing polymer aqueous solution having a solid content of 3.6 wt% was obtained. The copolymerization ratio x:y was determined to be 2.0:98.0 by PH titration. The amount of the polymer of the present invention having a repeating unit represented by the general formula () varies depending on the type, form, coating method, etc. of the photographic material used. However, in general, the amount used may be 0.001 to 0.5 g per m ² of the photographic material, and preferably 0.001 to 0.1 g. The method of applying the polymer of the present invention of the general formula () into a layer of a photographic light-sensitive material includes water, an organic solvent (e.g.
methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dioxane, dimethylformamide, formamide, dimethyl sulfoxide, methyl cellosolve, ethyl cellosolve, etc.) or a mixed solvent thereof,
After dissolving, a photosensitive emulsion layer, a non-photosensitive auxiliary layer (e.g. bucking layer, antihalation layer,
(intermediate layer, protective layer, etc.), or it may be sprayed or coated on the surface of the photographic light-sensitive material, or it may be immersed in the solution and dried. Further, it may be used together with a binder such as gelatin, polyvinyl alcohol, cellulose acetate, cellulose acetate phthalate, polyvinyl formal, or polyvinyl butyral to form an antistatic layer. It is also possible to use another antistatic agent in the layer containing the polymer represented by the general formula () of the present invention or in other layers, and by doing so, a more preferable antistatic effect can be obtained. Such antistatic agents include, for example, U.S. Pat. No. 2,882,157;
No. 2972535, No. 3062785, No. 3262807, No.
No. 3514291, No. 3615531, No. 3753716, No.
No. 3938999, No. 4070189, No. 4147550, German Patent No. 2800466, Japanese Unexamined Patent Publication No. 48-91165, No. 48-
No. 94433, No. 49-46733, No. 50-54672, No. 50
-94053, US Pat. No. 52-129520, etc., for example, US Pat. No. 2,982,651, US Pat.
No. 3428456, No. 3457076, No. 3454625, No. 3454625, No. 3457076, No. 3454625, No.
Surfactants such as those described in US Pat. No. 3,062,700 and US Pat.
So-called metal oxides, colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica, powdered silica, etc. as described in Nos. 3245833 and 3525621, etc. Mention may be made of matting agents. Examples of the layer containing the polymer of the present invention include an emulsion layer, an undercoat layer on the same side as the emulsion layer, an intermediate layer, a surface protective layer, an overcoat layer, and a back layer on the opposite side to the emulsion layer. Among these, outermost layers such as a surface protective layer, an overcoat layer, and a back layer are particularly preferred. Supports to which the polymer of the present invention can be applied include, for example, polyolefins such as polyethylene, polystyrene, cellulose derivatives such as cellulose triacetate, films such as cellulose esters such as polyethylene terephthalate, baryta paper, synthetic paper, or paper. This includes supports made of sheets coated on both sides with these polymer films, and similar materials thereof. The support used in the present invention can also be provided with an antihalation layer. For this purpose carbon black or various dyes, e.g.
Examples include oxole dyes, azo dyes, arythene dyes, styryl dyes, anthraquinone dyes, merocyanine dyes, and tri(or di)allylmethane dyes. As a binder for carbon black dye, cellulose acetate (di or mono),
polyvinyl alcohol, polyvinyl butyral,
polyvinyl acetal, polyvinyl formal,
Polymethacrylic ester, polyacrylic ester, polystyrene, styrene/maleic anhydride copolymer, polyvinyl acetate, vinyl acetate/maleic anhydride copolymer, methyl vinyl ether/maleic anhydride copolymer, polyvinylidene chloride, and Derivatives thereof can be used. The light-sensitive material according to the present invention includes ordinary black-and-white silver halide light-sensitive materials (for example, black-and-white light-sensitive materials for photography,
Examples include various photosensitive materials such as black-and-white photosensitive materials for X-ray, black-and-white photosensitive materials for printing, etc.), ordinary multilayer color photosensitive materials (e.g., color reversal film, color negative film, color positive film, etc.) can. It is particularly effective for silver halide light-sensitive materials for high-temperature rapid processing and high-sensitivity silver halide light-sensitive materials. Below, the photographic layer of the silver halide photosensitive material according to the present invention will be briefly described. As a binder for the photographic layer, proteins such as gelatin and casein; carboxymethyl cellulose,
Cellulose compounds such as hydroxyethylcellulose; sugar derivatives such as agar, sodium alginate, starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacid copolymers, polyacrylamide or derivatives thereof and partial hydrolysis It is also possible to use other items together. Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. In addition to being able to replace part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, that is, groups that can react with amino groups, imino groups, hydroxy groups, or carboxyl groups as functional groups contained in the molecule, can be replaced with one or more gelatin derivatives. It may be replaced with a material treated or modified with a specific reagent, or a graft polymer in which molecular chains of a polymeric substance are bonded. The silver halide emulsion layer of the photographic light-sensitive material of the present invention,
Types of silver halide used in surface protective layers, manufacturing methods, chemical sensitization methods, antifoggants, stabilizers,
There are no particular restrictions on hardeners, antistatic agents, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes, color couplers, etc.
Licensing, Vol. 92, pp. 107-110 (December 1971) and Research
Disclosure) Vol. 176, pages 22-31 (December 1978) can be referred to. In particular, antifoggants and stabilizers include 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene-3-methyl-benzothiazole,
A large number of compounds such as 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercanto compounds, and metal salts are used as hardening agents, such as mucochloric acid, mucobromic acid, and mucophenoxychloric acid. , mucophenoxybromic acid, formaldehyde, dimethylol urea,
Trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy-
1,4-dioxane, 2,3-dihydroxy-5
-Methyl-1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran,
Aldehyde compounds such as glutaraldehyde;
Divinyl sulfone, methylene bismaleimide, 5
-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,
3,5-trivinylsulfonyl-hexahydro-
s-triazine bis(vinylsulfonylmethyl)
Active vinyl compounds such as ether, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane; 2,4-dichloro-6-hydroxy-s-
Triazine sodium salt, 2,4-dichloro-
6-methoxy-s-triazine, 2,4-dichloro-6-(4-sulfoanilino)-s-triazine sodium salt, 2,4-dichloro-6-(2
-sulfoethylamino)-s-triazine, N,
Active halogen compounds such as N'-bis(2-chloroethylcarbamyl)piperazine; bis(2,
3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis(2',3'-epoxypropyloxy)butane, 1,
3,5-triglycidyl isocyanurate, 1,
3-diglycidyl-5-(γ-acetoxy-β-
Epoxy compounds such as oxypropyl isocyanurate; 2,4,6-triethyleneimino-
s-triazine, 1,6-hexamethylene-N,
Ethyleneimino compounds such as N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di(methanesulfonoxy)ethane, 1,4-di(methanesulfonoxy)butane, 1,5- Examples include methanesulfonic acid ester compounds such as di(methanesulfoneoxy)pentane; furthermore, carbodiimide compounds; isoxazole compounds; and inorganic compounds such as chromium alum. Known surfactants may be added alone or in combination to the photographic constituent layer of the present invention. Examples of surfactants that can be used include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles. cationic surfactants such as phosphoniums or sulfoniums; anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters;
Examples include amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols. In addition, the photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411,911, U.S. Pat.
The alkyl acrylate latex described in No. 5331 and the like can be included. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 (1) Preparation of sample: A silver halide emulsion layer with the following composition was coated on a polyethylene terephthalate film support with a thickness of 180 μm that had been undercoated, and a protective layer with the following composition was further coated on top of the silver halide emulsion layer. The mixture was dried to prepare a black and white silver halide photographic material. The polymer of the present invention or a known antistatic agent was added to the protective layer. (Emulsion layer) Thickness: Approximately 5 μ Composition and coating amount Gelatin 2.5 g/m ² Silver iodobromide (1.5 mol% silver iodide) 5 g/m ² 1-Phenyl-5-mercaptotetrazole
25mg/m ² (protective layer) Thickness: approx. 1μ Composition and coating amount Gelatin 1.7g/m ² 2,6-dichloro-6-hydroxy-1,3,
5-triazine sodium salt 10 mg/m ² Sodium N-oleyl-N-methyltaurate 7 mg/m ² Polymer of the present invention or fluorine-containing compound for comparison below Γ Comparative compound-1 HC ₆ F ₁₂ COONa Γ Comparative compound-2 ( Polymer described in British Patent No. 1497256 Synthesis Example-1) Γ Comparative compound-3 (Copolymerization example [10] described in JP-A-52-129520) Γ Comparison compound-4 (Polymer of synthesis example (1) of Japanese Patent Publication No. 49-23828) Γ Comparison compound-5 (Compound example-1 described in JP-A-54-158222) (2) Test method: (1) Electrostatic voltage measurement method: The above sample is placed 30cm in length and width.
It was cut into 40 cm rectangles, and the two pieces of each were pasted together with double-sided tape so that the protective layers were on the outside of each other. These samples were heated to 25℃25
After conditioning the humidity for 5 hours under %RH conditions, two rotating white neoprene rubber rollers (roller diameter 12 cm, width 1 cm, pressure between the rollers 6 kg)
The ^sample was passed through a linear rotation speed of 320 m/min) and placed in a Faraday cage, and the charged voltage was measured using an electrometer. Aging test method: After conditioning the above sample and white high-quality paper at 25°C and 70% RH for 1 hour, the high-quality paper was heated so that the surface of the emulsion layer side of each sample was in contact with both sides of the high-quality paper. These were placed in a polyethylene laminate bag and sealed. These samples were aged at room temperature for one week under a load of 4 g weight/cm ² . Thereafter, the charging voltage was measured according to the charging voltage measuring method described above, and compared with that before aging. (Part 2) Photographic property test: After exposing the above sample to tungsten lamp light through Fujifilm filter SP-14, it was developed with a developer of the following composition (35°C, 30 seconds), fixed, and washed with water. The photographic characteristics were investigated after processing. Developer composition temperature Water 800ml Sodium tetrapolyphosphate 2.0g Anhydrous sodium sulfite 50g Hydroquinone 10g Sodium carbonate (monohydrate) 40g 1-phenyl-3-pyrazolidone 0.3g Potassium bromide 2.0g Add water to make the whole 1000ml (Part 3) ) Membrane strength test: Place the sample in water at 25℃ for 5 minutes.
Soaked for minutes. A needle with a steel ball with a radius of 0.4 mm at the tip was crimped onto the emulsion side surface of the sample, and the load applied to the needle was continuously varied in the range of 0 to 200 g while moving parallel on the surface at a speed of 5 mm per second. , the load at which damage to the sample surface began to occur was measured. (Part 4) Adhesion resistance test: The sample was cut into squares of 4 cm x 4 cm, and after conditioning the humidity at 25°C and 70% RH for 2 days, the surfaces of the two emulsion layers were glued together and a load of 800 g was applied. 50℃70%
It was left for one day under RH conditions. The sample was peeled off, the area of the bonded part was measured, and evaluated according to the following criteria. Rank A Adhesive area area is 0 to 40% B 41 to 60 C 61 to 80 D 81 to 100 (3) Test results The results are shown in Table 1. [Table] As is clear from the results in Table 1, the sample to which no antistatic agent was added (sample No. 1) had a large charge, but the samples containing an appropriate amount of the polymer of the present invention (sample No. 3,
6, 8, 9, 10) substantially does not occur and this performance does not substantially change over time. On the other hand, it can be seen that the sample containing an appropriate amount of Comparative Compound-1 (fluorine-containing surfactant) (Sample 12) did not become electrostatically charged before aging, but significantly increased after aging. It is also found that Comparative Compounds -2, -3, -4 and -5, which are known fluorine-containing polymers, require addition in large amounts in order to adjust the charging voltage. It was revealed that the antistatic performance of the polymer of the present invention is extremely good, and that there is no deterioration of the antistatic performance over time unlike that of fluorine-containing surfactants. Furthermore, although the polymer of the present invention does not have any adverse effects on photographic performance, Comparative Compounds -3 and -4, which are known fluoropolymers, have adverse effects such as increased fog and decreased maximum density. Compound-5 showed a decrease in sensitivity. Further, it can be seen that although the polymer of the present invention does not cause a decrease in membrane strength, the membrane strength of Comparative Compounds -2, -3 and 4 is significantly impaired. In addition, the adhesion resistance of the samples using Comparative Compounds -2, -3, and 4 was significantly inferior, but the adhesion resistance of the samples using the polymer of the present invention was not inferior to, or even improved, compared to the blank. It can be seen that Example 2 A photosensitive material was prepared using the polymers of the present invention shown in Table 2 instead of the polymers of the present invention used in the protective layer of the black and white silver halide photosensitive material of Example 1. Next, tests were conducted in the same manner as in Example 1, and the results shown in Table 2 were obtained. All had excellent performance. [Table] Preferred Embodiment 1 of the Invention A photographic material as claimed in the claims, which contains a polymer having a repeating unit represented by the general formula () in the outermost layer. 2. A photographic light-sensitive material according to the claims, in which a polymer having a repeating unit represented by the general formula () is used in combination with another antistatic agent. 3. The photographic material according to the preferred embodiment 2, wherein the other antistatic agent is an antistatic agent shown in US Pat. No. 4,070,189. 4 In the above preferred embodiment 2, the other antistatic agent is JP-A-48-91165, JP-A-48-94433,
No. 54-159222, No. 55-7763 or U.S. Patent No.
A photographic light-sensitive material which is an antistatic agent shown in No. 4126467. 5. A photographic light-sensitive material containing, on the outermost layer, a soluble polymer represented by the general formula () having a repeating unit and having a solubility of 0.1 g or more in 100 g of water at 20°C. 6. The photographic material according to Embodiment-5, wherein the water-soluble monomer represented by A ₁ in the general formula () is nonionic. 7. The photographic material according to Embodiment 5, wherein the water-soluble monomer is acrylamide or methacrylamide in the above-mentioned preferred embodiment 6. 8. A photographic light-sensitive material as claimed in the claims, wherein the photographic light-sensitive material is particularly a silver halide photographic light-sensitive material.

Claims (1)

[Scope of Claims] 1 A polymer having a repeating unit represented by the following general formula () in at least one of the constituent layers of a photographic light-sensitive material, and at least 0.1g per 100g of water at 20°C. 1. A photographic material comprising a water-soluble polymer having a solubility of . General formula () In the formula, A represents a monomer unit copolymerized with a copolymerizable monomer having at least one ethylenically unsaturated group. R ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms.
R ² represents a monovalent substituent, and R ² may be linked to each other to form a ring. R ^f is a carbon atom in which at least one hydrogen atom is replaced with a fluorine atom.
Represents an alkyl group, aralkyl group, aryl group, or alkylaryl group having 30 groups. Q represents a divalent linking group represented by the general formula -(R) _p -L-, where R represents an alkylene group, arylene group, or aralkylene group, and L represents an oxy group, thioxy group, or imino group. , carbonyl group, carboxyl group, carbothoxyl group, carboxamide group, oxycarbonyl group, carbamoyl group, sulfone group, sulfonamide group, N-alkyl-sulfonamide group, sulfamoyl group,
represents a sulfoxyl group or a phosphate group, p
is 0 or 1. l is an integer from 0 to 4, m
is an integer of 0 to 3, and n is an integer of 1 to 5. X is 0.1-50 mol%, and y is 50-99.9 mol%.