JPH0115857B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic light-sensitive material with improved physical properties, and in particular, by incorporating a specific polymer compound, the surface properties of the light-sensitive material, such as antistatic performance, scratch resistance, and adhesion (on the front and back surfaces of the light-sensitive material) are improved. The present invention relates to a photographic material characterized by improved adhesion, i.e., sticking, etc.). Photographic materials come into contact with various substances and are subject to friction during manufacturing processes such as coating, drying, and processing, and during handling such as winding, unwinding, and transportation during use such as photographing, developing, printing, and projection. , or contact friction or close contact between photographic light-sensitive materials, such as between the front and back surfaces of the light-sensitive materials, often causing undesirable effects. By increasing the scratch resistance of the photographic constituent layers of a photographic light-sensitive material or by reducing the sliding friction of the photographic light-sensitive material, the photographic material is prevented from being damaged during the manufacturing process, development processing, and printing, and then printed onto photographic paper. Various methods have been proposed in the past for obtaining photographic materials with improved physical properties so as to obtain normal prints without diffused reflection due to scratches. For example, gelatin hardeners are added to photographic constituent layers to increase scratch resistance (see British Patent No. 1270578). ; A method of imparting slipperiness to a photographic light-sensitive material by simultaneously containing dimethyl silicone and a specific surfactant in the photographic emulsion layer or protective layer (see US Pat. No. 3,042,522); Back side of the support of the photographic light-sensitive material A method in which a mixture of dimethyl silicone and diphenyl silicone is coated on a film to impart slipperiness (see U.S. Pat. No. 3,080,317); a photographic light-sensitive material in which methylphenyl silicone with a triphenyl terminal block is included in the protective layer. (see British Patent No. 1143118); A method of imparting slipperiness to photographic materials by incorporating wax-type cetyl palmitate (see German Patent No. 1300015); Aliphatic dicarboxylic acids and a method in which a polyester derived from an aliphatic or cycloaliphatic diol is used as a slip agent in the outermost layer of a photographic constituent layer (see JP-A-51-31217); fatty acids (having 8 to 18 carbon atoms); ) and a styrene, vinyl acetate, acrylic acid metal salt copolymer with an antistatic backing layer (U.S. Patent No.
(See No. 2976148). ; A method of applying a layer consisting of pentaerythritol tetrastearate and tetraacetate as the outermost layer to impart slipperiness (see British Patent No. 1430997); A method of coating a polyester film with vinyl chloride or vinylidene chloride copolymer and unbranched saturated fatty acids, esters of fatty acids and fatty alcohols (e.g. stearyl stearate), esters of fatty acids such as pentaerythritol and stearic acid, diesters of fatty acids such as sutucarose and stearic acid,
Method for improving friction and scratch resistance by providing a layer containing N,N-alkylene bis fatty acid amide (oleamide), glycerol, glycol, montan wax of fatty acid ester of polyethylene glycol ester (see British Patent No. 1321994) ); The upper layer of the antistatic layer or antihalation layer contains polyvinyl alcohol ester of fatty acid having 10 to 20 carbon atoms, glycerin monostearate, ethylene glycol diacetate, sugar rose distearate, and sorbitan monostearate. A method for reducing the friction on the back side of photographic materials by providing a layer (West German Patent No.
See No. 2347301. ); A method of improving slipperiness by incorporating hydrophthalic acid diester into at least one surface layer of a photographic light-sensitive material (Japanese Patent Application Laid-open No.
See No. 54-159221. ); using a phosphate and a transition metal acid compound such as GeO ₃ V ₂ O ₅ , Mo, WO ₃ as a glassy forming substance as an antistatic composition,
A method of impregnating this layer with cellulose acetate as a binder and a lubricant such as carnauba wax to improve mechanical properties, especially the coefficient of friction (Japanese Patent Application Laid-Open No. 1989-1999)
See No. 115291. ); A method of improving slipperiness by allowing a liquid organopolysiloxane having a methyl phase and an alkyl group having 5 or more carbon atoms to exist in at least one photographic photosensitive layer as an organic group bonded to a silicon atom (Japanese Patent Application Laid-Open No. 1989-1999) -117414) are known examples. However, when attempting to improve the slipperiness of photographic light-sensitive materials using these known methods, although the slipperiness is improved before the development process, in many cases the effect is almost completely lost after the development process. .
For this reason, if a large amount is added in an attempt to maintain slipperiness in the developing solution, transparency may be lost (when the surface of a photosensitive material is exposed to high humidity, slipping compounds (compounds that give slipping properties) ), which appears as a white powder on the surface of the photosensitive material, causing the so-called "blooming" phenomenon. As a result, the surface of the photosensitive layer becomes easily scratched. On the other hand, if the back side of the photosensitive material is too slippery, the extremely slippery property may actually worsen transportability during the coating, drying, and processing steps, and the bonding agent may become ineffective when bonding the photosensitive materials. It has any of the following drawbacks: In addition, when photographic materials are stored for a long time under high humidity, the surface on the photosensitive layer side often adheres to the back layer on the non-photosensitive layer side. Fog occurs on the topmost photosensitive layer or on peeled or undeveloped areas.
This fog results in a black color in black-and-white light-sensitive materials, but in photographic light-sensitive materials that are sensitive to blue light, a layer that develops a yellow color through a coupling reaction with a developing agent (paraphenylenediamine type) is used. When the emulsion layer contained is the uppermost layer, it develops a yellow color even without exposure. Although this development has not yet been completely solved scientifically, it occurs when a yellow color develops due to some kind of electrical action caused by the discharge due to the accumulation of static charges or the flow of static electricity that occurs when the adhered photosensitive material is peeled off. It is believed that there is. The following two methods have been proposed as means for preventing undesirable color development or adhesion phenomena caused by such fogging. One method is to reduce the adhesiveness or tackiness of the surface of the photosensitive material to eliminate power generation and reduce the generation of static charges. This is a method of reducing electric charge. The former method involves dispersing what is generally called a matte agent, such as silica or PMMA (polymethyl methacrylate) particles, into a photosensitive material to roughen its surface; Although methods such as the above are known, they are not very effective in preventing fogging, although they reduce adhesiveness. Furthermore, if the amount added is increased in order to overcome this fog using these methods, transparency may be impaired, or agglomeration may occur in the coating solution.
This may impede the coating properties or make the surface more susceptible to scratches due to poor slippage.On the other hand, the sliding friction on the back side of the photosensitive material may decrease too much, making it difficult to transport the material during the coating and packaging processes. It has various drawbacks, such as: In addition, certain types may reduce the sensitivity of the light-sensitive emulsion layer or cause fog, thereby deteriorating photographic properties. In addition to the above methods, methods for preventing the above-mentioned abnormal fog include a method in which an organic fluoro compound is present on the back surface of the support (see JP-A-50-99529); and an organic fluoro compound (see JP-A-50-160034); a method of containing a gelatin derivative and anhydrous silicic acid colloid in the top layer of a photosensitive material (see JP-A-50-141320); ); A method of incorporating an organic fluoro compound into the surface layer of a photosensitive material (see JP-A-50-59025); Containing an organic fluoro compound having a sulfonic acid group, a sulfonate group, or a sulfuric ester group as a hydrophilic group. A method of coating a hydrophilic colloid layer as the outermost layer of a photosensitive material (see JP-A-51-43131); [M: hydrogen atom or alkali metal atom, Y: organic residue having 4 to 24 carbon atoms, R: hydrogen atom or methyl group] A method of incorporating a compound represented by the following into the surface layer of a photosensitive material (Unexamined Japanese Patent Publication No. 1973 (See Japanese Patent Laid-open No. 16224-1983.); and a method of incorporating an alkylpolysiloxane having a polyoxyalkylene chain into at least one surface layer of a photosensitive material (see Japanese Patent Application Laid-open No. 16224-1983). However, even these known methods are hardly effective in eliminating the yellow fog or the fog that occurs in the peeled or undeveloped areas on the back side of the base. In addition, as a method of imparting antistatic properties to photosensitive materials, a method is generally used in which an antistatic agent is added to reduce power generation and charging. This is true, for example, in U.S. Pat.
There are descriptions in No. 3564043, No. 3525621, No. 3457076, No. 3264108, No. 3756828, etc.
Most of the antistatic agents used here are hygroscopic, so yellow fog or fog tends to occur more often on the peeled or undeveloped areas on the back of the base, and these antistatic agents can reduce static electricity. It is very difficult to expect a satisfactory effect just by imparting preventive properties. Therefore, the first object of the present invention is to have a surface layer that does not adhere even under high temperature and high humidity conditions when the surface layer of a photosensitive material comes into contact with another surface, and a surface layer that is not easily scratched. Our objective is to provide photographic materials. A second object of the present invention is to provide a photographic material with almost no fogging. A third object of the present invention is to provide a photographic light-sensitive material in which the back layer does not peel off due to adhesion and the photographic emulsion surface does not suffer from poor development. A fourth object of the present invention is to provide a color photographic material in which abnormal yellowing fog is prevented from occurring in the photographic emulsion layer. A fifth object of the present invention is to provide the following features: during the manufacturing process, during the packaging processing process, during photographing in a photographing device (camera),
The object of the present invention is to provide a photographic material that is resistant to scratches during various handling operations such as post-processing during development and projection. A sixth object of the present invention is to provide a photographic material that does not produce precipitates on the surface or inside, ie, does not cause the "blooming" phenomenon, during the manufacturing process, storage process, etc. A seventh object of the present invention is to provide a photographic light-sensitive material using a polymer compound that is non-diffusible and therefore does not have a negative photographic effect on the light-sensitive layer. Other objects of the invention will become apparent from the following description of the specification. The above-mentioned objects of the present invention are to provide a polymeric compound having 20 wt% or more of repeating units represented by the following general formula [] on at least one surface of a photographic light-sensitive material and which is insoluble in water or a developer (hereinafter referred to as the present invention). This is achieved by a photographic material characterized by having a non-photosensitive layer containing a polymer compound (referred to as a polymer compound). General formula [] [In the formula, R represents a straight chain alkyl group having 12 to 24 carbon atoms. ] According to a preferred embodiment of the present invention, the copolymerization component other than the repeating unit represented by the general formula [ ] of the above-mentioned polymer compound is a radically polymerizable vinyl monomer. Further, the non-photosensitive layer is a back layer. Furthermore, the non-photosensitive layer is a protective layer on the side of the photosensitive layer. That is, the present invention provides a photographic light-sensitive material having at least one (silver halide) photographic emulsion layer on a support. Refers to the top layer of each side with the back layer side. ] is characterized in that at least one layer thereof contains a polymer compound having a repeating unit represented by the above general formula [], and the uppermost layer containing this polymer compound may contain another polymer compound binder. good. Examples of the polymer compound of the present invention include higher fatty acid vinyl ester monomers having 12 to 22 carbon atoms,
For example, vinyl laurate, vinyl mystilate, vinyl palmitate, vinyl stearate,
Examples thereof include vinyl behenate alone or a copolymer, or a polymer obtained by copolymerizing the above monomer with an ethylenically unsaturated monomer that can be copolymerized with these monomers. Examples of monomers that can be copolymerized include (1) olefins such as ethylene and propylene, (2) acrylic acid or methacrylic acid and esters thereof, (3) acrylamide derivatives such as acrylamide and methacrylamide, (4) ) Styrenes such as styrene and α-methylstyrene; (5) acrylonitrile; however, any material that can be copolymerized with the higher fatty acid vinyl ester monomer may be used. below,
The polymer compounds of the present invention which are preferably used are illustrated, but the polymer compounds of the present invention are not limited to these.

【table】

[Table] The above-mentioned polymer compounds can be obtained by conventional radical polymerization. The polymerization form can be selected depending on the purpose and properties, such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc. Synthesis examples will be specifically described below, but the invention is not limited thereto. Synthesis Example 1 (Synthesis of Exemplary Compound (1)) 20 g of vinyl palmitate, 100 ml of benzene, and 0.1 g of benzoyl peroxide were placed in a pressure bottle and left at 80° C. for 5 hours. Add this polymer solution to 1
Dropped into methanol with stirring, melting point 35℃
18 g of polymer powder was obtained. Molecular weight by osmotic pressure
It was 78,000. Synthesis Example 2 (Synthesis of Exemplary Compound (2)) A 500 ml four-headed flask was equipped with a stirring bar, a thermometer, a nitrogen suction tube, and a cooling tube, and 300 ml of water, 1 g of sodium dodecylbenzenesulfonate, and 100 g of vinyl stearate were added. After stirring and emulsifying,
The temperature was raised to 60°C, 0.5 g of potassium persulfate was added thereto, and the temperature was maintained at 60°C for an additional 4 hours. After cooling,
The polymer was precipitated by adding 3 portions of saturated brine and filter-dried to obtain 95 g of the desired product. It had a melting point of 44°C and an osmotic molecular weight of 185,000. Synthesis Example 3 (Synthesis of Exemplified Compound (6)) Attach a stirring bar, a thermometer, a nitrogen suction tube, and a cooling tube to the four-headed flask from 1, and add 600 ml of water, 180 g of vinyl stearate, and 20 g of methylstacrylate.
g, 2 g of benzoyl peroxide, and 5 g of calcium phosphate were added, and the mixture was kept at 70° C. for 10 hours while stirring and blowing nitrogen, and then cooled. After treatment with hydrochloric acid, filtration and drying yielded 180 g of the desired product.
It had a melting point of 40°C and an osmotic molecular weight of 103,000.
The molecular weight of the polymer compound of the present invention is preferably from 10,000 to 1,000,000, more preferably from 10,000 to 500,000. As the solvent for these polymer compounds of the present invention,
Acetone, ethyl acetate, methylene dichloride,
Ethylene dichloride, trichlene, benzene,
Cyclohexane, trichloroethane, trichloromethane, xylene, toluene, carbon tetrachloride, phenol, resorcinol, etc. can be used,
They may be appropriately selected from these and used alone or in combination of two or more. The amount of the polymer compound of the present invention is desirably in the range of about 0.01 to 3 g per 100 ml of the above solvent, more preferably in the range of 0.05 to 1 g, and when coated on a support, the amount is about 5 g per 1 m ² of the support. It is desirable to use the amount up to 100mg. The polymer compounds of the present invention can be used alone or in combination of two or more. When the non-photosensitive layer containing the polymer compound of the present invention is a back layer, this back layer may be one layer or two or more layers. When the back layer consists of two or more layers, the polymer compound of the present invention is contained in the uppermost back layer, but may be contained in different back layers simultaneously. The back layer containing the polymer compound of the present invention preferably contains an antistatic agent and a hydrophobic polymer. According to a preferred embodiment of the invention, the support has at least one light-sensitive silver halide emulsion layer on one side and (i) on the other side (back side) of the support.
at least one layer containing a hydrophobic polymer;
and (ii) it has at least one layer containing the polymer compound of the present invention, and the layer (i) is located closer to the support than the layer (ii). According to a preferred embodiment of the present invention, on the back side of the support, (i) at least one layer containing the high molecular compound of the present invention and a hydrophobic polymer, and (ii) at least one layer containing an antistatic agent. It has one layer, and the layer (ii) is located closer to the support than the layer (i). Furthermore, according to another preferred embodiment of the present invention, at least one compound containing (i) the polymer compound of the present invention and a hydrophobic polymer is provided on the back side of the support.
and (ii) at least one layer containing an antistatic agent and a hydrophobic polymer, and the (ii) layer is located closer to the support than the (i) layer. Furthermore, according to another preferred embodiment of the present invention, on the back side of the support, (i) at least one layer containing the polymeric compound of the present invention, and (ii) an antistatic agent and a hydrophobic polymer. The layer (ii) is located closer to the support than the layer (i). Each of the above preferred embodiments of the present invention describes a case where a non-photosensitive layer containing the polymer compound of the present invention is provided on the back side of the support. This also applies when the non-photosensitive layer containing the polymer compound of the invention is provided as a protective layer etc. on the surface side of the support or on the surface of the immediately photosensitive layer side, and in this case, the above-mentioned preferred embodiments are applied. "The back side of the support" can be read as "the front side of the support". As the antistatic agent used in the present invention, one that can obtain good electrical conductivity and at the same time has excellent film properties by itself or in combination with a suitable binder is effectively used. Such examples include, for example, the copolymer salts of ethylene and ethylene undecanoic acid described in U.S. Pat. No. 3,033,679;
Maleic acid or maleimide resins described in No. 2279410; alkali metal salts of alkylaryl polyether sulfonic acids and alkali metal salts of carboxylic acid polymers described in No. 3525621; alkali metal salts of polycarboxylic acids; polyethylene sulfonic acid described in No. 2735841;
Quaternary salt of polyvinylpyridine described in No. 3072484; 4 described in No. 3479215
graded polyethyleneimine; polyepichlorohydrin described in the same No. 3320317;
Examples include polyquaternized alkylamino acrylates described in JP-A-46-24159, JP-A-50-54672, and JP-A-50.
Examples include various antistatic agents described in Japanese Patent Application No. 51-45453 and Japanese Patent Application No. 51-45458. Furthermore, it is also desirable to use an inorganic oxide containing an electrolyte, especially alumina sol, in addition to the above-mentioned polymer electrolyte as the antistatic agent used in the present invention, and to apply this as a back layer. In general, many of the antistatic agents in polymer electrolytes are hydrophilic, so when applied to silver halide photographic materials in particular, various undesirable phenomena may occur, such as the above-mentioned interaction between silver halide photographic materials at high humidity. Otherwise, the antistatic layer may elute into the processing solution during the development process and combine with other substances present in the processing solution, resulting in turbidity or sludge. may cause loss of antistatic layer. To prevent such undesirable phenomena, a layer located close to the support of the back layer (hereinafter referred to as the first back layer),
A layer coated with alumina sol containing an electrolyte is provided, and the polymer of the present invention is further coated on the first back layer as a second back layer (referring to the back layer located far from the support. The same applies hereinafter). This can be prevented by providing a layer containing a hydrophobic polymer in addition to the compound. By incorporating the polymer compound of the present invention together with the hydrophobic polymer in the second back layer, physical properties such as scratch resistance and slipperiness during the manufacturing process of photographic light-sensitive materials or against cameras, printers, etc. can be better improved. can do. Furthermore, the polymer compound of the present invention exhibits a remarkable effect in preventing abnormal color development failures of color photographic materials without imparting adverse photographic effects (fogging, desensitization, etc.) to the photographic materials. This effect can be applied to unexposed and/or
Another great advantage is that the range of storage or use conditions for undeveloped photographic materials can be widened. In particular, in the case of color photographic light-sensitive materials, the coating is repeated many times during manufacturing and is often rolled up for a long time, so abnormal color development is likely to occur. However, by applying the polymer compound of the present invention, this can be completely eliminated. can be prevented. Furthermore, the polymer compound of the present invention does not cause any blooming phenomenon that occurs when known low-molecular compound photographic slip agents are stored at high humidity. The hydrophobic polymer used in the present invention may be one that is dissolved or dispersed as a coating liquid, forms a thin layer after the coating liquid is applied and dried, and that layer does not dissolve in an acid or alkaline aqueous solution. Specific examples of such hydrophobic polymers include polymers or copolymers such as polymethyl methacrylate, polyethylene, polyvinylidene chloride, polyacrylonitrile and vinyl acetate, cellulose diacetate, cellulose triacetate, cellulose nitrate, ethyl cellulose, cellulose propionate, etc. cellulose derivatives such as
Examples include vinylidene chloride copolymer, vinyl chloride/acrylonitrile copolymer, acrylic acid ester/vinyl chloride/vinyl acetate copolymer, and the like. Further, in the present invention, latexes of these hydrophobic polymers can be used. In particular, it is preferable to use materials that are relatively less likely to generate static electricity, such as cellulose diacetate, polyethylene, and polyvinyl acetal. These hydrophobic polymers may be used alone or mixed with other substances as appropriate. For example, matting agents, plasticizers, antifoaming agents and other auxiliaries can be used in combination. Preferred matting agents include silicon oxide with a particle size of 0.01 to 0.5 μ;
There are aluminum oxide, magnesium oxide, and other oxides, and by adding these, rollers of various materials used in the manufacturing process of photographic light-sensitive materials, photographic equipment, and automatic processors,
In particular, the charge on the rubber roller can be significantly reduced. Next, a method for forming the non-photosensitive layer, particularly the back layer, which is the uppermost surface of the photographic light-sensitive material according to the present invention, will be explained in detail. However, the configuration of the back layer is not limited to these, and more preferred embodiments of the back layer of the present invention will be described. For example, when applying an antistatic agent as a first back layer, it may be first dissolved or dispersed in a suitable solvent, and this solution or dispersion may be applied onto a support and dried. Examples of the solvent for the antistatic agent include methanol, ethanol, acetone, etc., and two or more of these may be used as a mixture.
This liquid may be placed on a support by any coating method such as dip coating, roller coating, or spray coating, and the coated layer may be dried in accordance with a conventional method. The concentration of the antistatic agent in the coating solution is not particularly limited, but a concentration of 0.01 to 10 g per 100 ml of solvent is advantageous for coating and drying. For general use, the coating amount of this antistatic agent is 3 to 300 mg/m ² to provide sufficient antistatic ability. Further, when an inorganic oxide containing an electrolyte, particularly an alumina sol, is used as an antistatic agent, it is preferable that the concentration of the alumina dispersion is in the range of about 0.1 to 1% by weight from the viewpoint of processability and conductivity. In this case, it is preferable that the dispersion medium contains a substance that dissolves or swells the surface of the support to some extent. Specifically, acetone, methanol, ethanol, dimethylformamide, dimethylacetamide, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, benzol, etc. may be used in appropriate combinations, and when the support is a polyethylene terephthalate support, In addition to the above solvents, phenol, methylene chloride,
Ethylene chloride, dioxane, resorcinol,
It may be used by appropriately selecting from catechol and the like. A coating composition may be prepared using these solvents and coated so that the solid content of aluminum oxide in the alumina sol is 5 to 500 mg per 1 m ² of the support. In addition, when a hydrophobic polymer is contained in the first back layer, the hydrophobic polymers of the specific examples described above, particularly cellulose diacetate, cellulose nitrate, ethyl cellulose, cellulose butyrate, and vinylidene chloride/methyl acrylate/acrylate ternary copolymer One or more of the combinations may be added to the alumina sol or polymer electrolyte.
In this case, the amount of the hydrophobic polymer is preferably in the range of 0.05 to 5 g per 1 g of the above-mentioned antistatic agent. Note that when the support is made of polyethylene terephthalate, the first back layer of the present invention is not directly applied to the support, but a subbing layer is first applied, and the first back layer of the present invention is coated on the subbing layer. It is desirable to provide one back layer. This undercoat layer includes polyvinylidene chloride, polyvinylidene chloride/acrylonitrile copolymer,
Vinyl chloride/vinylidene chloride copolymer, vinyl chloride/vinyl acetate copolymer, vinyl chloride/methacrylate copolymer, vinylidene chloride/methacrylate copolymer, polyglycidyl methacrylate, cellulose diacetate, cellulose triacetate, ethyl cellulose and low polymerization polyester Or a modified product of this and other substances, etc. alone or in combination of two or more, dissolved in a solvent by a known method,
It may be applied onto a support and dried. In addition to the above-mentioned cellulose triacetate and polyethylene terephthalate, all hydrophobic films or sheets such as polycarbonate, polystyrene, polyolefin, and polyethylene laminated paper can be used as the support for the photographic material according to the present invention. be. In order to provide the second back layer in the present invention, the polymer compound of the present invention may be provided in the above amount on the first back layer directly or via an intermediate layer; in this case, In order to contain the hydrophobic polymer in this second back layer, the same solvent as in the coating composition containing the polymer compound of the present invention may be used as a solvent, and 0.1 to 1 weight portion of the hydrophobic polymer may be added to the second back layer. % to form a coating composition, and the coating composition is coated on the dried first back layer and dried. The coating method can be the same as the first back layer, such as dip coating, roller coating, or spray coating. Further, the applied layer may be dried according to a conventional method. A photographic light-sensitive material according to the present invention can be obtained by forming a light-sensitive silver halide emulsion layer by a conventional method on the back side (opposite side) of the side coated with the back layer containing the polymer compound of the present invention. can be obtained, and the above object of the present invention can be achieved. In particular, the photographic material is
Not only can it improve physical properties such as scratch resistance and slipperiness, but it also has a remarkable effect on preventing abnormal color development failures of color photographic materials, and it also prevents deterioration of other photographic properties (e.g. sensitivity). (increased fog, gamma fluctuation), etc. will not occur. The present invention will be described in more detail below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A solution having the following composition was applied to one side of a biaxially stretched and crystallized polyethylene terephthalate film having a thickness of 100 μm at a rate of 20 ml/m ² and dried at 120° C. for 10 minutes. Cellulose triacetate 0.3g Ternary copolymer consisting of vinylidene chloride, methyl acrylate, and acrylic acid (weight ratio of 65:35:2)
0.1 g Methylene chloride 20 ml Ethylene chloride 65 ml Resorcinol 15 ml Next, a solution having the composition shown in Table 1 was applied onto this layer at a rate of 25 ml/m ² and dried at 90° C. for 3 minutes to form a back layer.

[Table] The above four bases [1-1], [1-2], [1-
An undercoat layer is provided on the opposite side of the back layer of [3] and [1-4], and a red-sensitive emulsion layer, a gelatin intermediate layer, an edge-sensitive emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer, and a protective layer are formed on the undercoat layer. The corresponding photographic color negative film samples (1-1) and (1) were coated in order.
-2), (1-3) and (1-4) were obtained. These were evaluated for slip performance and scratch resistance on the back side and abnormal yellowing failure test in an atmosphere of 23°C and 55% RH. The test items are (1) dynamic friction coefficient (against steel balls), (2) scratch resistance, and (3) abnormal yellow failure test, as shown below. (1) Dynamic friction coefficient measuring method (using a dynamic friction coefficient measuring device manufactured by Toyo Baldwin Co., Ltd.) A 5 m/mφ steel ball with a load of 20 g is brought into contact with the back surface of the sample. 8cm at a speed of 20cm/min
The resistance value when sliding is detected by the strain gator and automatically recorded on the chart. (2) Scratch resistance measurement method To evaluate scratch resistance, a static load was applied to a saphire needle with a radius of curvature of 0.15 mm, and it was moved over the sample at a constant speed (6.0 cm/sec) until the sample started to scratch. The load was determined and used. (3) Measurement method for abnormal yellow color failure test Cut the sample into 4 cm ² pieces and heat them at 23℃ and 80%
After conditioning the humidity at RH for 2 days, the emulsion side and the back side were overlapped, a load of 20g/cm ² was applied for 2 days, and then heat treatment was performed at 50℃, and it was peeled off without exposure. A normal color film was developed and the area (%) of abnormal yellow color development was evaluated. The results obtained are shown in Table 2.

[Table] As is clear from the results in Table 2, the film (1-
1), (1-2) and (1-3) are compared with the comparative film (1-4) in which none of them are coated.
It can be seen that the scratch resistance is improved and the abnormal yellowing area is almost eliminated. Example 2 20 ml of a solution having the following composition was placed on one side of a 120 μ thick cellulose triacetate film.
It was applied at a rate of m ² and dried at 90°C for 3 minutes. Cellulose diacetate 1g Acetone 70ml Methanol 30ml On top of this, a copolymer of vinyl stearate and methyl methacrylate with different composition ratios (molecular weight 10-15
The solution shown in Table 3 below was applied at a rate of 20 ml/m ² and dried at 90° C. for 3 minutes.

【table】

[Table] The above four bases [2-1], [2-2], [2-
The same high-sensitivity photographic color negative emulsion as in Example 1 was coated on the opposite sides of [3] and [2-4], respectively, and photographic color negative film samples (2-1), (2-2), and (2-3) and (2-4)
I got it. The same slip performance, scratch resistance, and abnormal yellow color failure tests as in Example 1 were conducted, and the results shown in Table 4 below were obtained.

[Table] As is clear from the results in Table 4, the sample (2-1) coated with the copolymer of vinyl stearate and methyl methacrylate, which is the polymer compound of the present invention,
It can be seen that both (2-2) and (2-3) have excellent scratch resistance before and after development, and no abnormal yellowing occurs at all. Example 3 The following antistatic agents [A], [B] and [C] were each applied at a rate of 25 ml/m ² as the first back layer on a 120 μ thick cellulose triacetate film, and heated at 90°C. After drying for 3 minutes, bases [3-1], [3-2] and [3-3] shown in Table 5 below were prepared.

[Table] Antistatic agent This base [3-1], [3-2] and [3-
3], apply 20% of the coating liquid for the second back layer shown below.
It was overcoated at a rate of ml/m ² and dried at 90°C for 3 minutes. Acetone 20ml Ethyl acetate 60ml Toluene 20ml Cellulose diacetate 0.4g Compound of the present invention (8) 0.1g Fine-particle silica (particle size 1μ or less) 0.05g On the opposite side of each base obtained, the same high sensitivity as in Example 1 was placed. Sample of photographic color negative film coated with photographic color negative emulsion (3-1),
(3-2) and (3-3) were obtained. The same sliding performance, scratch resistance test, and abnormal yellow color failure test as in Example 1 were conducted, and the results shown in Table 6 below were obtained.

[Table] As is clear from Table 6, all of the samples according to the present invention had excellent scratch resistance before and after development, and no abnormal yellowing occurred at all. Example 4 25 ml/m ² of the coating solution for the first back layer shown below was applied to a 120 μ thick cellulose triacetate film.
It was applied at the same rate and dried at 90°C for 3 minutes. Alumina sol (manufactured by Nissan Chemical Co., Ltd.) 2g Cellulose diacetate 0.5g Acetone 50ml Methanol 50ml Furthermore, overcoat the coating liquid for the second back layer shown in Table 7 below at a rate of 20ml/m ² at 90°C. was dried for 3 minutes to form a second back layer.

【table】

[Table] Comparative compound [A] Above bases [4-1], [4-2] and [4-
The same high-sensitivity photographic color negative emulsion as in Example 1 was coated on the opposite side of the photographic color negative film samples (4-1) and (4-3), respectively.
2) and (4-3) were obtained. The same sliding performance, scratch resistance test, and abnormal yellowing test as in Example 1 were conducted, and the results shown in Table 8 below were obtained.

[Table] As is clear from the results in Table 8, by adding the polymer compound of the present invention, the scratch resistance was significantly improved both before and after the development process, and no abnormal yellowing was observed at all. On the other hand, when the comparative compound is used, some effect is observed before development, but no overall effect is observed after development, and no abnormal yellow coloring is observed at all. Example 5 The coating solution for the first back layer shown in Example 4 was applied to a cellulose triacetate film having a thickness of 120μ for 20 minutes.
It was applied at a rate of ml/m ² and dried at 90°C for 3 minutes.
Further, on this base, a second back layer coating solution shown in Table 9 below was overcoated at a rate of 25 ml/ ^m2 ,
It was dried at 90° C. for 3 minutes to form a second back layer.

【table】

[Blooming test]

(1) Place the sample in a container at 23℃ and 90% RH for (A) 14 days and
(B) After being left for one month, the surface of the back layer was observed with the naked eye under white light. (2) Place each sample in a cartridge and heat at 40℃.
After being left at 80% RH for 14 days, the surface of the back layer was observed with the naked eye under white light.

[Table] However, 〓○〓 shows no change, 〓×〓
〓××〓 has white powder precipitated on the surface.
Each indicates that white powder is significantly deposited on the surface.
As is clear from Table 10, the sample (5-1) to which the polymer compound of the present invention was added had excellent scratch resistance, no abnormal yellowing, and no blooming at all. On the other hand, samples (5-2), (5-3) and (5-
Although 4) shows some effect on scratch resistance, it has a large area of abnormal yellow color, and if left under high humidity, a blooming phenomenon in which compounds precipitate on the surface is observed, which may adversely affect the transparency of the film. Recognize. Example 6 The coating solution for the first back layer shown in Example 4 was applied for 20 minutes on a cellulose triacetate film with a thickness of 120μ.
It was applied at a rate of ml/m ² and dried at 90°C for 3 minutes. Furthermore, overcoat the coating liquid for the second back layer shown in Table 11 below at a rate of 20ml/ ^m2 .
Dry at ℃ for 3 minutes, [6-1] and [6-
2] and [6-3] bases were created.

【table】

[Table] The same high-speed photographic color negative emulsion as in Example 1 was coated on the opposite side of the obtained bases [6-1], [6-2] and [6-3], and each color negative film was coated with the same high-speed photographic color negative emulsion as in Example 1. Sample (6-1), (6-
2) and (6-3) were obtained. The same slipperiness test and scratch resistance test as in Example 1 were conducted on each sample. The results are shown in Table 12 below.

[Table] As is clear from the results shown in Table 12, the comparison sample (6-1) made of polystyrene alone has very poor scratch resistance, but the sample of the present invention (6-1) containing the polymer compound of the present invention (6-1) has very poor scratch resistance. It can be seen that samples 2) and (6-3) have significantly improved scratch resistance.

Claims (1)

[Claims] 1. 20wt of repeating units represented by the following general formula [] on at least one surface of the photographic light-sensitive material.
% or more and a non-photosensitive layer containing a polymer compound insoluble in water or a developer. General formula [] [In the formula, R represents a straight chain alkyl group having 12 to 24 carbon atoms. ]