JP2001033913A - Preparation of coating fluid for lubricative layer, coating fluid for lubricative layer, production of lubricative substrate, lubricative substrate and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material excellent in scuffing and wear resistances, traveling stability, etc., by preparing a coating fluid for a lubricative layer through a step for mixing a specified polyvinyl alcohol solution with a specified lubricant dispersion. SOLUTION: A polyvinyl alcohol having >=96 mol% saponification degree is dissolved in water under heating to >=40 deg.C to form a polyvinyl alcohol solution. A lubricant is dispersed in water to form a lubricant dispersion. The polyvinyl alcohol solution is mixed with the lubricant dispersion to prepare the objective coating fluid for a lubricative layer. Since the polyvinyl alcohol is hardly dissolved in an organic solvent, in order to form a uniform solution, >=35 wt.% water is preferably contained in the solvent. The lubricant may be a known lubricant but preferably has >=50 deg.C melting point. A silicone compound, a higher aliphatic carboxylic acid or its derivative may be used as the lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slippery support, and more particularly, to a silver halide photographic material having a slippery layer. The present invention also relates to a method for preparing a coating solution for a slippery layer.

[0002]

2. Description of the Related Art Hitherto, there has been a problem of deterioration of quality due to scratches and stains on the surface of a silver halide photographic light-sensitive material, and various methods have been tried, but satisfactory methods have not been obtained. It is the current situation. The scratches on the silver halide photographic material
It comes in contact with all kinds of things, such as friction between films, rubbing with rolls, sliding with processing components, rubbing, and friction. The stains are caused by substances that elute or fall off from the silver halide photographic light-sensitive material during the development processing.

In order to cope with these problems, generally, a method of imparting a slip property to the surface of a silver halide photographic material,
Methods such as improving the wettability of the surface and increasing the strength (scratch strength) of the film on the surface are employed.

[0004] As a method for imparting lubricity, there is generally a method of forming a slippery layer by applying a lubricating agent such as wax on the surface (especially the back surface) of a silver halide photographic material. For example, Japanese Patent Laid-Open No. 9-204638 discloses that
There is disclosed a technique for setting a contact angle with water in a specific range as a property value of a slippery layer. If the contact angle to water is 90 ° or more, it is certainly difficult to damage, but on the other hand, the wettability to water deteriorates, water such as a developing solution becomes easy to repell, and the surface of the silver halide photographic material is developed. After the process, the water mark remains and becomes a stain on the screen. Also,
The slippery layer made of wax or the like may easily fall off due to contact with a roll during the coating process, and may contaminate the coating and drying process.
Therefore, in order to stabilize the slippery layer, Japanese Unexamined Patent Publication No.
No. 43251 discloses that a slip agent coating solution is applied and then brought into contact with a roll having a melting point or higher. In order to strengthen the slippery layer, a hydrophobic resin is generally mixed.
It is also known to mix a slipping agent with a hydrophilic resin (water-soluble resin). For example, JP-A-4-219569
Nos. 4,243,251 and 9-325450, and U.S. Pat. No. 4,021,241, describe gelatin and hydroxyalkyl cellulose esters.

A silver halide photographic material is provided with an antistatic layer on the back layer side. When the antistatic layer is on the uppermost layer, it is generally weak against abrasion, and by providing a slippery layer thereon, abrasion resistance can be imparted. Issues.

Therefore, the antistatic layer has been provided with various slippery layers on its protective layer, but has a problem that the combination of the antistatic layer and the slippery layer is very difficult. It is difficult to make the antistatic layer easy to remove electricity and to have abrasion resistance. For example, ion conductive polymers that are ion conductive are not only susceptible to the influence of the external atmosphere, but the antistatic layer changes when they are treated with an aqueous processing solution such as a developing process for silver halide photographic materials. However, in many cases, the adhesiveness of the upper slippery layer was deteriorated, and the slippery layer was detached. In addition, the electron-conductive metal oxide fine particles had to be provided with a slippery layer just enough to cover the susceptibility of the antistatic layer to damage. Therefore, in order to make the slipping agent in the slippery layer more slippery, it is necessary to treat the stain, to attach a water droplet mark, to slip so that the film cannot be positioned during work, and to make the slippery layer hydrophilic. I was

On the other hand, gelatin is conventionally used for the intermediate layer and the protective layer not using a slipping agent. Gelatin hardens the layer using a hardening agent, but it is easily eluted by processing with a developing solution, etc., and easily stains silver halide photographic materials and baths and rolls of processing equipment. Was sought. However, although a water-soluble polymer has a protective colloid property, it has been difficult to find a polymer having applicability and insolubility in water.

[0008]

However, these documents do not positively suggest the enhancement of wettability of a slippery layer containing a slipping agent, but have other objects. The slippery layer has a moderate slip property (running stability of the silver halide photographic material), scratch resistance, blocking resistance,
The present inventor has found that the use of a mixture of a slipping agent and a hydrophilic resin can be used to impart properties such as no bleed-out. However, we have hardly ever seen any examples that have solved this problem, but we believe that this problem is so difficult.

A first object of the present invention is to provide a silver halide photographic light-sensitive material having excellent scratch resistance, running stability, blocking resistance, bleed-out resistance of a slipping agent, coating properties and stain resistance. To provide. A second object is to provide a slippery support which imparts these properties to the silver halide photographic material. A third object is to provide a slippery layer coating solution suitable for these slippery supports and a method for preparing the same. A fourth object is to provide a slippery support having an antistatic effect and the above-mentioned scratch resistance and a silver halide photographic material having the slippery support.

[0010]

The present invention has the following constitution.

(1) A step of heating polyvinyl alcohol having a degree of saponification of 96 mol% or more and dissolving it in water at a temperature of 40 ° C. or higher to form a polyvinyl alcohol solution; a step of dispersing a slipping agent in water to form a slipping agent dispersion; A method for preparing a coating liquid for a slippery layer, which is prepared through a step of mixing a polyvinyl alcohol solution and a dispersion of a slipping agent.

(2) The method for preparing a coating solution for a slippery layer according to (1), wherein the temperature at which the polyvinyl alcohol is dissolved is 60 ° C. or higher.

(3) The polyvinyl alcohol is 98
The method for preparing a coating solution for a slippery layer according to (1) or (2), having a saponification degree of not less than mol%.

(4) The polyvinyl alcohol is 99
(3) The method for preparing a coating solution for a slippery layer according to (3), which has a saponification degree of not less than mol%.

(5) The polyvinyl alcohol is 40
The method for preparing a coating solution for a slippery layer according to any one of (1) to (4), having a degree of polymerization of 0 or more.

(6) The polyvinyl alcohol is 90
(5) The method for preparing a coating solution for a slippery layer according to (5), which has a degree of polymerization of 0 or more.

(7) The lubricity according to any one of (1) to (6), wherein the slipping agent contains an ester of a higher aliphatic carboxylic acid and a higher aliphatic alcohol. Preparation method of layer coating solution.

(8) A coating solution for a slippery layer, prepared by the method according to any one of (1) to (7).

(9) After keeping the slippery layer coating solution described in (8) in a temperature range of 20 to 35 ° C., the slippery layer coating solution is supported on a support at a temperature within the range. A method for producing a slippery support, wherein the method is applied as a layer furthest from a body.

(10) The coating solution for the slippery layer has a saponification degree of 96
(9) The method for producing a slippery support according to (9), comprising polyvinyl alcohol having a mole percentage of less than 400 and a degree of polymerization of 400 or more.

(11) The coating method of (9) or (1), wherein the polyvinyl alcohol contained in the coating solution for the slippery layer is applied in a range of 0.5 to 80 mg / m ^2.
0) The method for producing a slippery support according to 0).

(12) A slippery layer is provided on one or more constituent layers on the support produced by the method described in (9) to (11), on the layer farthest from the support. A slippery support, characterized in that:

(13) The slippery support according to (12), wherein at least one of the constituent layers between the slippery layer and the support is an antistatic layer.

(14) At least one of the constituent layers is composed of particles having an average primary particle diameter of 0.4 μm or less and a Mohs hardness of 6 or more, and an average primary particle diameter of 0.5 μm or more and a Mohs hardness of 5 or less. The slippery support according to (12) or (13), comprising particles of (12) or (13).

(15) The slippery support according to any one of (12) to (14), wherein the support is a polyester film or a cellulose ester film.

(16) The surface of the slippery support according to any one of (12) to (15) opposite to the slippery layer side,
A silver halide photographic light-sensitive material having a silver halide emulsion layer.

(17) On a support, a saponification degree of 96 mol%
A silver halide photographic material comprising a layer containing a polyvinyl alcohol having a degree of polymerization of 400 or more.

(18) The polyvinyl alcohol has a saponification degree of 98 mol% or more (17).
3. The silver halide photographic light-sensitive material described in 1. above.

(19) The polyvinyl alcohol has a degree of saponification of at least 99 mol% (18).
3. The silver halide photographic light-sensitive material described in 1. above.

(20) The silver halide photographic material as described in any one of (17) to (19), wherein the degree of polymerization of the polyvinyl alcohol is 900 or more.

(21) The layer containing polyvinyl alcohol has a saponification degree of less than 96 mol% and a polymerization degree of 400
(17) The silver halide photographic material as described in any one of (17) to (20), comprising the polyvinyl alcohol.

The present invention will be described in detail.

First, the degree of saponification of polyvinyl alcohol will be described.

There are two types of polyvinyl alcohol, a complete saponification type and a partial saponification type. When the acetyl group in the polyvinyl acetate molecule is changed to a hydroxyl group in the saponification step during the production, the saponification reaction proceeds almost completely. The “completely saponified type” is called “completely saponified type”, and the one in which the reaction is stopped halfway after the reaction has progressed and an acetyl group remains at a certain ratio is called “partially saponified type”. In addition, an intermediate saponification degree may be referred to as “intermediate saponification type”.
The degree of progress of the saponification reaction is referred to as "degree of saponification" and is expressed in mol%.

Assuming that the degree of saponification of polyvinyl acetate is n, the acetyl group remaining in polyvinyl alcohol is j, and the hydroxyl group formed by saponification is m, the degree of saponification (mol%) is represented by the following formula.

N = {m / (m + j)} × 100 where m + j = n.

When saponifying polyvinyl acetate to form polyvinyl alcohol, partially saponified polyvinyl alcohol is usually water-soluble even if saponification is not complete. Conversely, fully saponified polyvinyl alcohol swells in water but hardly dissolves at room temperature at room temperature, and completely dissolves in hot water.

In the constitutions (1) to (6) of the present invention, polyvinyl alcohol having a saponification degree of 96 mol% or more is dissolved in water at 40 ° C.
Applying a slippery layer through a step of heating and dissolving to form a polyvinyl alcohol solution, a step of dispersing a slip agent in water to form a slip agent dispersion, and a step of mixing the polyvinyl alcohol solution and the slip agent dispersion This is a method for preparing a liquid.

In the polyvinyl alcohol dissolving step, polyvinyl alcohol having a degree of saponification of 96 mol% or more is not completely dissolved in normal temperature water, and must be dissolved with heated water at 40 ° C. or more to completely dissolve it. When the degree of saponification is increased, it is dissolved in heated water of 60 ° C. or higher, and in the case of completely saponified polyvinyl alcohol, it is dissolved in hot water of 90 ° C. or higher.

Since the polyvinyl alcohol used in the coating solution for the slippery layer of the present invention is hardly dissolved in an organic solvent, it is desirable that the solvent contains 35% by weight or more of water in order to form a uniform solution. . The coating liquid for the slippery layer is 5% by weight of polyvinyl alcohol in warm water or hot water.
It is desirable to add, dilute, and supply other additives, solvents, and the like in the step of preparing the coating solution for the slippery layer after preparing the aqueous solution of from 20 to 20% by weight. The present inventors have found that once dissolved polyvinyl alcohol is stored at 20 to 35 ° C., it is stable without generating gelling or precipitation (configuration (9)). A stable polyvinyl alcohol solution can be obtained as long as the solution is kept at that temperature even if a diluting solvent at room temperature is added to the diluting solvent at room temperature.

In the present invention, the lower the solubility of polyvinyl alcohol after forming the layer in water (normal temperature to 40 ° C.), the more preferable, the more preferable it is 98 mol% or more (configuration (3)). It is preferably at least mol% (configuration (4)). The degree of saponification of 94 mol% or more is called intermediate saponified polyvinyl alcohol, and the degree of saponification of 98 mol% or more is particularly called completely saponified polyvinyl alcohol. Among the intermediate saponified types, those having a mole percentage of 96 mol% or more show properties similar to those of the completely saponified type polyvinyl alcohol, and can be used in the present invention.

The solubility of polyvinyl alcohol in water is mainly governed by the degree of saponification, but also affects the degree of polymerization.

In general, where the degree of saponification is low, the effect of the degree of polymerization hardly appears, but where the degree of saponification is high, the solubility tends to decrease as the degree of polymerization increases. In the present invention, the degree of polymerization is preferably 400 or more (configuration (5)). Preferably, it is 900 or more (configuration (6)).

In the present invention, the preferred combination of the degree of polymerization and the degree of saponification of polyvinyl alcohol is 900
The degree of saponification is at least 98 mol%, more preferably at least 900 and at least 99 mol%. By using polyvinyl alcohol in these combinations, an excellent slippery layer surface can be obtained as described later.

Incidentally, regarding polyvinyl alcohol,
There are some introductions in the catalogs of manufacturers, for example, Kuraray Co., Ltd. “Kuraray Polyvar” or Shin-Etsu Chemical Co., Ltd. “Shin-Etsu Poval, PVA Product General Catalog”.

Further, "Poval" co-authored by Koichi Nagano et al. (Polymer Publishing Association) has a detailed description of polyvinyl alcohol.

Commercially available intermediate-saponified polyvinyl alcohols usable in the present invention include MA-23GP and MA-17GP as products of Shin-Etsu Chemical Co., Ltd., and PVA-624 as products of Kuraray Co., Ltd. And fully saponified polyvinyl alcohol include C-Chem of Shin-Etsu Chemical Co., Ltd.
04GP, C-05GP, C-10GP, A, C-15
GP, C-17GP, C-20GP, C-25GP, and Kuraray's PVA-105, PVA-11
0, PVA-117, PVA-117H, PVA-12
0, PVA-124, PVA-124C, PVA-12
6H, PVA-135H, PVA-CSA, PVA-C
ST, PVA-HC, and the like.

Of these, C-10GP, A, C-1
5GP, C-17GP, C-20GP, C-25GP,
PVA-105, PVA-110, PVA-117, P
VA-117H, PVA-120, PVA-124, P
VA-124C, PVA-126H, PVA-135
H and PVA-HC are particularly preferred.

In the step of preparing the polyvinyl alcohol solution of the present invention, an organic solvent having good compatibility with water may be contained, but an organic solvent which does not cause the polyvinyl alcohol to aggregate in an aqueous solution is preferable. Organic solvents satisfying these are methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol,
Glycerin and the like can be mentioned, and methanol or ethanol is preferable. Glycerin and ethylene glycol slightly remain even after the coating liquid for the slippery layer is applied and dried, and function as a plasticizer. Methanol and ethanol have a degree of saponification of 96 mol% or more, and polyvinyl alcohol having a saponification degree of 40 mol% or less dissolves even when mixed with water, evaporates after coating and drying, and does not coagulate the polyvinyl alcohol during drying.
It is preferable because the drying speed is increased.

Next, the slipping agent used in the slipping agent dispersions and the coating solution for the slippery layer according to the constitutions (1) to (7) of the present invention will be described.

In the present invention, any of known slip agents can be used, but a slip agent having a melting point of 50 ° C. or higher is preferably used. Known slip agents are roughly classified into silicone compounds, higher aliphatic carboxylic acids and derivatives or salts thereof, higher alcohols and derivatives thereof, polyethylene waxes, fluoropolymers,
Examples include fluorine compounds and natural waxes.

The silicone compound is not particularly limited as long as it is a commercially available or synthetically available silicone compound. Polyorganosiloxanes are preferred as the silicone compound. The molecular weight is not particularly limited.
The range of 0 to 2,000,000 is preferred. The synthesis of these compounds is described in German Patent 1,938,959.
No. 2,694,637, U.S. Pat.
042,522, JP-B-51-33600,
Nos. 52-22040, JP-A-59-31543, JP-A-62-203152, JP-A-62-269139, and 6
0-54015, JP-A-2-301750 and JP-A-2-301750.
No. 115836, JP-B-3-2285, JP-A-6-1
There is a detailed description in Japanese Patent Publication No. 02615 and the like. Silicone compounds are available from Dow Corning in the United States, BYK Chemo in Germany,
Shin-Etsu Chemical Co., Ltd., Toshiba Silicone Co., Ltd., Toray Silicone Co., Ltd., Nippon Unicar Co., Ltd., and Chisso Co., Ltd. can easily obtain products having various structures as commercially available chemical products. In addition, derivatization can be easily performed by ordinary chemical reaction using these commercially available silicones as raw materials. For the derivatization reaction, for example, E.I. G. FIG. Rochow, "An Introduction to the Si"
You can find descriptions of many books and dissertations such as "licons" (translated by Shin-Etsu Chemical Central Research Institute, Maruzen).

As the polyethylene, a low polymer can be used, and a polyethylene having a degree of polymerization of 30 or more is preferable, and a wax is preferable.

[0054] Paraffin wax can also be used. As the paraffin, C _n H _{2n + 2} (n ≧ 24) is preferable.

As higher aliphatic carboxylic acids and derivatives or salts thereof, for example, US Pat. No. 4,275,146
Aliphatic carboxylic acid amides disclosed in Japanese Patent Publication No. 58-33541, British Patent No. 9
27,446, or JP-A-55-1262.
No. 38 and No. 58-90633, higher aliphatic carboxylic acid esters as disclosed in U.S. Pat. No. 3,933,516, and higher aliphatic carboxylic acid metal salts as disclosed in U.S. Pat. No. 3,933,516. Also, Japanese Patent Application Laid-Open No. 58-50
No. 534, linear higher aliphatic carboxylic acids-esters of linear higher aliphatic alcohols, higher aliphatic carboxylic acids containing branched alkyl groups as disclosed in WO 90108115.8- Higher aliphatic alcohol esters, higher aliphatic ethers, higher aliphatic amines and the like can be used. In addition, fluorinated fatty acids, fluorinated alcohols, esters of fluorinated fatty acids (lower to higher aliphatic alcohols), esters of fluorinated alcohols (lower to higher fatty acids), fluorinated alcohol esters of fluorinated fatty acids, and the like can also be used. The number of carbon atoms in the higher aliphatic carboxylic acid moiety is preferably from 8 to 100, and more preferably from 10 to 80. When the alcohol portion of the higher aliphatic carboxylic acid ester is a higher aliphatic alcohol, the number of carbon atoms in the higher aliphatic carboxylic acid portion may be slightly smaller. The alcohol portion preferably has 1 to 80 carbon atoms, more preferably 4 to 60 carbon atoms. When the alcohol moiety is a polyol such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, or a polyhydroxy aromatic compound, the fatty acid moiety esterified thereto is a carboxylic acid having the same number of carbon atoms. Or each may be different. In the case of pentaerythritol, one OH group may remain without being esterified. Also useful are esters of higher aliphatic alcohols of polyfunctional aromatic carboxylic acids. Further, in the case of such a polyfunctional alcohol, not only higher aliphatic carboxylic acids but also at least one fatty acid having at least 2 carbon atoms may be used. Ethers of higher aliphatic alcohols have terminal alcohol groups such as polyethylene glycol and polyoxyalkylene as described in JP-A-7-5616, even if the partner alcohol component is a higher aliphatic alcohol. may have, also, higher aliphatic alcohols -SO ₃ N
_{a, -SO 3 N (CH 3} ) 3, -PO 3 esters of K ₂ or -SO ₃ Na ethylene oxide adducts of higher aliphatic alcohols, esters of _{-SO 3 N (CH 3) 3} ,, higher fatty Aromatic sulfonic acid sodium salt and the like are also useful in the present invention.

In the present invention, one of the above-mentioned slip agents may be used, or two or more thereof may be used in combination. In particular, it is particularly preferable to mix in such a combination that the slip agents are stabilized by the interaction between the slip agents.

Representative examples of the above-mentioned slipping agents are shown below.
Shown in

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[0059]

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[0060]

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[0063]

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[0064]

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[0065]

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[0066]

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In the present invention, higher aliphatic carboxylic acids and derivatives thereof, higher aliphatic alcohols and derivatives thereof are preferred, and esters of higher aliphatic carboxylic acids and higher aliphatic alcohols are particularly preferred (configuration (7)). In addition, fat waxes and oils, which are natural waxes, can also be used.For example, montanic acid esters, carnauba wax, beeswax, etc. contain a large amount of esters of higher aliphatic carboxylic acids and higher aliphatic alcohols. Useful. In particular, carnauba wax is particularly useful.

The dispersion of the slip agent of the present invention is prepared by dispersing the slip agent in water. For example, a method in which a slip agent is melted and dispersed in hot water, in which case the above-described surfactant or a compound having a surfactant (such as a water-soluble polymer) is contained in water, The method of dispersing in water is preferable. Another way is
A method of dispersing a slip agent having a high affinity for a slip agent, for example, using an ester of a higher aliphatic carboxylic acid and a higher aliphatic alcohol with a polyethylene glycol ether of a higher aliphatic alcohol, This is the preferred method. As still another method, a method in which a slip agent is dissolved in an organic solvent, dispersed in water, and then heated or decompressed and the solvent is discharged out of the system and dispersed,
Dispersibility is improved by adding a surfactant or a compound having surface activity. Further, a method of dispersing in water in an organic solvent compatible with water is also good. Other known various methods can be used.

As a method for preparing the dispersion, for example, the method described in “Techniques of emulsification and solubilization” by Tsuji recommendation (Kogaku Tosho Co., Ltd.) can be used. When used as a dispersion, the slip agent is preferably in the form of particles having a size of about 1 to 1000 nm.

Examples of the solvent for the slipping agent include alcohols such as methanol, ethanol, propanol, butanol, i-propyl alcohol, i-butyl alcohol and t-butyl alcohol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, dioxane, and the like. , 3-
Dioxolan, ethers such as ethylene glycol dimethyl ether, etc., glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc., methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene chlorohydrin, etc. Halogenated hydrocarbons, aromatic hydrocarbons such as benzene and toluene, alicyclic hydrocarbons such as cyclopentane and cyclohexane, N, N-dimethylformamide, N, N
Examples thereof include dimethylacetamide and dimethylsulfoxide.

Surfactants useful in preparing the slip agent dispersion of the present invention include commonly used anionic, cationic, nonionic and betaine activators. Preferred are aliphatic carboxylic acid soaps, aliphatic alcohol ethylene oxide adducts, aliphatic alcohols, and fluorine-containing surfactants having about 8 to 20 carbon atoms interacting with.

As the compound having a surfactant, a water-soluble polymer is usually preferable, and gelatin, derivative gelatin, pectin, carboxymethylcellulose soda,
-Hydroxyethyl cellulose, 2-hydroxypropyl cellulose, acrylamide homopolymer or copolymer, 2-hydroxyethyl acrylate (or methacrylate) homopolymer or copolymer, vinylpyrrolidone homopolymer or copolymer, dextrin, casein, Water-soluble polymers such as sodium polyacrylate, sodium alginate, and polyvinyl alcohol can be exemplified, and dextrin, casein, sodium polyacrylate, sodium alginate, and polyvinyl alcohol are preferable, and the polyvinyl alcohol having the constitution (10) of the present invention is particularly preferable. Is preferred.

Polyvinyl alcohol having a degree of saponification of less than 96 mol% and a degree of polymerization of 400 or more of the constitution (10) of the present invention is used as a dispersant as a compound having surface activity in the preparation of a slip agent dispersion. When used with the polyvinyl alcohols described in 1) to (7), the dispersion stability of the slip agent can be further increased, and the applicability can be further improved. The degree of saponification is preferably less than 95 mol%, more preferably 90 mol% or less. However, the use of the above dispersant should be kept within a range that does not impair the effects of the present invention.

Polyvinyl alcohol useful in the slip agent dispersion of the present invention includes, for example, Shin-Etsu Chemical Co., Ltd.
PA-24GP, PA-20GP, PA-18GP, P
A-15GP, PA-10GP, PA-05GP, E-
Type, MA-05GP, LA-05GP and the like. Kuraray Co., Ltd., PVA-61
7, PVA-624 (of which saponification degree is low), P
VA-613, PVA-706, PVA-205, PV
A-205C, PVA-210, PVA-217, PV
A-217C, PVA-220, PVA-220C, P
VA-224, PVA-224C, PVA-228, P
VA-235, PVA-217E, PVA-217E
E, PVA-220E, PVA-224E, PVA-4
05, PVA-420, PVA-420H, PVA-4
24H, L-8, L-9, L-9-78, L-10, P
VA-505 and the like. As an example in which polyvinyl alcohol is used for dispersing the slip agent layer, see
Kurarepovar MP-203 is described in Example 1-9 of JP-A-152678, and polyvinyl alcohol is simply mentioned in Japanese Patent Application No. 10-184101. In addition, the saponification degree of Kuraray Povar MP-203 is 86.5-89.5,
The degree of polymerization is 300.

In the constitution (10) of the present invention, the degree of saponification of 9
In addition to using less than 6 mol% of polyvinyl alcohol as a dispersant for a slipping agent as described above, the coating properties can be improved by adding the polyvinyl alcohol to a slippery layer coating solution.
Even if the degree of saponification is 96 mol% or more, there is an ability to lower the surface tension of the coating solution, but a lower saponification degree is significantly more preferable. The saponification degree is preferably 90 mol% or less,
Molar% or less is particularly preferred.

Further, a crosslinking agent and a plasticizer may be used in combination with the slippery layer coating solution in order to control the surface hardness and wettability of the polyvinyl alcohol in the slippery layer after coating.

As a stirring (dispersing) means for preparing the slip agent dispersion of the present invention, a usual means can be used. For example, an ultrasonic wave, a homogenizer, a dissolver, a high-pressure jet mixer, a vibration mill, a polytron and the like can be mentioned.

The configuration (8) according to the present invention includes the configurations (1) to (4) described above.
The present invention relates to a coating solution for a slippery layer prepared by the method (7).

According to the constitution (9) of the present invention, by keeping the coating solution for the slippery layer at 20 to 35 ° C., the polyvinyl alcohol solution is not clouded (without aggregation or sedimentation), and The coating liquid can be uniformly applied to the layer to which the slipping layer coating liquid is applied without causing coating defects or the like. By applying a slippery coating solution containing polyvinyl alcohol and a slipping agent in a temperature range of 20 to 35 ° C, a slippery support having high transparency, high film strength and free from uneven coating and streaks is produced. Therefore, it is important in the present invention to hold and handle in a temperature range of 23 to 35 ° C.

The object can be achieved by applying the coating amount of all polyvinyl alcohol contained in the slippery layer of the present invention at 0.5 to 80 mg / m ² (configuration (11)). , 1-100 mg / m ² , more preferably 10-50 mg / m ² .

In the constitution (12) of the present invention, the coating solution for the slippery layer of the constitution (8) is applied onto one or more constituent layers on the support at a position farthest from the support. Configurations (9) to (1)
By manufacturing as in 1), a slippery layer support having excellent quality is formed. A slippery support coated on the outermost layer of the constituent layers (that is, so that the slippery layer is located on the outermost layer). The constituent layers according to the present invention are constituent layers in a silver halide photographic material, and include an undercoat layer, an antistatic layer, an ultraviolet absorbing layer, an antioxidant layer,
Examples include an antihalation layer, a back layer, and a protective layer. Before coating the slippery layer, the one or more constituent layers farthest from the support include a protective layer for the back layer, an antistatic layer, and the like. It is provided as an outermost layer on the back layer side (the side without the silver halide emulsion layer) and protects external force such as abrasion, and has excellent abrasion resistance.

The method of providing various coating materials including the slippery layer of the present invention on a support includes extrusion coating, air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, and reverse coating. Roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat and the like can be used.

In the constitution (13) of the present invention, at least one of the constituent layers between the slippery layer as the outermost layer and the support,
This is to form an antistatic layer.

In the combination of the slippery layer and the antistatic layer according to the present invention, the slippery layer has an appropriate slip property and strong abrasion resistance and is insoluble and firm even by an aqueous treatment such as a development treatment. It retains the surface film, and has appropriate wettability, so that it does not generate watermarks or processing stains.
In addition, the performance of the lower antistatic layer can be maximized. After providing the antistatic layer, the layer may be calendered to improve the smoothness, and the filling property of the conductive agent may be improved, and then the coating liquid for the slippery layer may be applied. In this case, it is preferable to apply the silver halide photosensitive layer after applying the slippery layer.

As the antistatic agent useful for the antistatic layer of the present invention, most of the antistatic agents and antistatic compositions useful for general silver halide photographic materials can be used. As the antistatic agent useful in the present invention, for example, ZnO described in JP-A-57-104931,
SnO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , M
metal oxides such as gO, BaO, MoO ₃ , ZiO ₂ and / or
Or a crystalline metal oxide fine particle antistatic agent mainly composed of these metal composite oxides; a metal oxide antistatic agent such as V ₂ O ₅ described in JP-B-56-5982;
Alumina sol composition described in JP-A-12979, styrene-sodium maleate copolymer described in JP-B-47-28937 and JP-B-49-23828,
Anionic antistatic agents such as sodium vinyl benzyl sulfonate copolymer described in JP-A-3-82876, sodium styrene sulfonate polymer or copolymer described in JP-B-48-23451, and JP-A-51-42535.
Nos. 54-159222 and 55-7763 (for example, a polymer of triethylenediamine and xylidenedichloride), for example, those described in U.S. Pat. No. 2,882,157. Polymethacryloylethyldiethylammonium methylsulfonate, JP-B-60-51693, JP-A-61-22
No. 3736 and Japanese Patent Application Laid-Open No. 62-9346.
Crosslinked copolymer particles having a quaternary ammonium group in the side chain (for example, copolymer (N, N, N-trimethyl-N-vinylbenzylammonium chloride-co-divinylbenzene)) described in Japanese Patent Application No. 5-174572. A cationic antistatic agent of a copolymer particle having an ionene polymer crosslinked type or an ionene polymer side chain, for example, a polyvinyl benzyl chloride and a terminal N- (a cross-linked reaction product of a polymer of triethylenediamine and xyliden chloride); Those comprising an alumina sol described in JP-B-57-12979 as a main component, higher fatty alcohol phosphate ester antistatic agents described in JP-B-52-32572,
Poly (isothianaphthene) systems described in JP-A-2-252726, JP-A-2-255770 and 2-3.
And a conjugated double bond conductive polymer such as poly (thiophene) described in JP 08246-A. In particular, among the above antistatic agents, polymers or copolymers of sodium styrenesulfonate, alkali metal sulfonic acid type anionic polymer antistatic agents such as sodium vinylbenzylsulfonate copolymer, triethylenediamine and xylidenedichloride and the like Ionene polymers represented by polymers made of dihalides, condensates made of dihalides such as diethylene dichloride and diamines such as triethylenediamine, or ionene polymers in which an ionene polymer serves as a crosslinking agent for vinyl copolymers Constituents of copolymer particles, condensates of diamines such as triethylenediamine and dihalides such as xylidene chloride or quaternary triethylenediamines of ionicene side chain pendant crosslinked copolymer particles bonded to the side chains of the polymer Cation as element Ionene polymer antistatic agents, quaternary benzylamine cationic polymer antistatic agents such as crosslinked copolymer particles having a benzyltrialkylammonium chloride group in the side chain, poly- (5-dodecylbenzothiazothiophene), Polythiophene-based conductive polymer antistatic agents having a conjugated double bond represented by poly- (3-dodecylthiophene), poly-methacryloylethyloxymethyl-3-polythiophene and the like are preferable, and polyfuran and polypyrrole are also useful. .

In the present invention, the metal oxide fine particle antistatic agent as described above is particularly preferred. A specific example is Nb
Oxygen-excess oxides such as ₂ O _{5 + X} , RhO _2-X , Ir ₂ O
Oxygen-deficient oxides such as _3-X or non _- stoichiometric hydrides such as Ni (OH) X, HfO ₂ , ThO ₂ , ZrO ₂ , C
eO ₂ , ZO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
O, BaO, MoO ₂ , V ₂ O _{5 and the} like, or a composite oxide thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable.
Is preferred. In the case of a composite oxide, a small amount of hetero atoms can be contained in addition to the main metal atoms. Examples of containing hetero atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sn and Sn to TiO ₂ .
Addition of Sb, Nb, a halogen element or the like is effective for O ₂ . The addition amount of these hetero atoms is 0.01 to 25.
The range of mol% is preferred, but the range of 0.1 to 15 mol% is particularly preferred.

In the present invention, the effect can be further exhibited by combining two or more kinds of antistatic agents.

The antistatic layer using an antistatic agent such as a metal oxide as described above is vulnerable to scratches and other scratches, and therefore requires a protective layer or outermost layer having scratch resistance. By using a slipping support, the function of the antistatic layer can be sufficiently exhibited.

The antistatic layer may be a layer in which a slip agent and an antistatic agent coexist, but the antistatic layer may be present in a layer (close to a photographic support) below the layer containing the slip agent. Is preferred.

It is preferred that the same binder as described above coexists in the antistatic layer according to the present invention. Particularly, as the binder, cellulose esters and gelatin are preferable. It is preferable that a surfactant is also present. For example, nonionic surfactants such as alkylene oxides, glycerin and glycidol, higher alkylamines, quaternary ammonium salts, salts of pyridine and other heterocyclic compounds, cationic surfactants such as phosphonium or sulfoniums And anionic surfactants containing an acidic group such as a carboxyl group, a phosphate group, a sulfate group, or a phosphate group, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphate esters of amino alcohol. be able to.

The polyvinyl alcohol of the present invention may be used as a binder or a dispersant for these antistatic agents. Further, an antistatic agent may be contained in the slippery layer. An intermediate layer may be provided between the slippery layer and the antistatic layer of the present invention. The intermediate layer helps stabilize the antistatic layer,
It is preferable to use the same binder as the antistatic layer.

According to the constitution (14) of the present invention, at least one of the constituent layers is composed of particles having an average primary particle diameter of 0.4 μm or less, Mohs hardness of 6 or more, an average particle diameter of 0.5 μm or more, and By incorporating particles having a hardness of 5 or less in combination, the effect of increasing the hardness of the layer and withstanding the wear of the layer is increased. In the present invention, the constituent layer refers to a layer from the undercoat layer to the uppermost slippery layer, and the constitution (14) may contain the particles in any of these layers. Preferably, it is contained in the antistatic layer or the slippery layer.

When the coating solution for the silver halide emulsion layer is applied after the application of the slippery layer, the slipping agent often falls off due to contact with the rolls of the drying device, etc. (Hereinafter sometimes referred to as “hard particles”) is preferably contained in the slippery layer. Particles having this hardness are known as abrasives in magnetic materials.

The term “average primary particle size” as used herein refers to a particle (primary particle) that can maintain a uniform shape having a chemical bond and a crystal grain boundary after physically adsorbing or aggregating particles are dispersed. ) Means the average particle size. It is calculated by arbitrarily measuring 1000 particles from the projected image of the particles with an electron microscope.

These hard particles include aluminum oxide (α-alumina, γ-alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), and iron oxide (α-Fe
₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond. Their average particle size is from 0.01 to
2.0 μm is preferable, and it can be used in an amount of 0.25 to 400 mg / m ² , added in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of polyvinyl alcohol, and applied per unit area.

The antistatic layer of the present invention preferably also contains the hard particles. As the hardness particles, it is preferable to use particles having an average primary particle diameter of 0.2 μ or more among the aforementioned particles. Further, a polymer matting agent such as polymethyl methacrylate may be mixed with the resin particles. Particle size is 0.
It is also preferable to use particles of 2 to 1.5 μm or less.

When added to the slippery layer, it is desirable that the thickness of the slippery layer be at least ４ of the primary particle size of the matting agent.

The preferable particle size of the matting agent is 0.2 to 1.0.
μ. The addition amount of the matting agent is 0.5 to 50 mg /
m ² is preferred.

[0099] Conventionally known dispersers and kneaders such as an antistatic agent and a matting agent which are difficult to uniformly suspend and disperse by impeller agitation such as a normal dissolver can be appropriately used. For example, it can be selected from a Henschel mixer, an open kneader, a pressure kneader, a ball mill, a sand mill, a twin screw kneader, a pin mill, a high-speed attritor, a roll mill, an ultrasonic disperser, and the like.

The constitution (15) of the present invention relates to a support. Examples of the support useful in the present invention include a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polycarbonate film and a polyethylene terephthalate film. And a polyethylene ester film such as a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, or a polyethylene terephthalate film. And a polyester film such as a polyethylene-2,6-naphthalate film.

The degree of substitution of all acyl groups such as acetyl group, propyl group or butyl group of cellulose ester with hydroxyl group of glucose unit of cellulose is 2.6 to 3.0.
Is preferred.

A cellulose ester film support such as a cellulose triacetate film can be formed by a usual solution casting method. That is, a cellulose ester raw material is dissolved in an organic solvent to form a dope, cast from a pressure die onto an endless stainless steel belt or a rotating metal drum that is transported infinitely, and the organic solvent is evaporated on the belt or drum. Before making one round, the web is peeled off, and the web is conveyed to a staggered roll, or both ends of the web are clipped and conveyed by a tenter, dried and wound up as a film to produce a cellulose ester support. Film. After winding, or until the web is peeled off and wound, or at any time after winding,
A backing layer constituting layer such as an undercoat layer, an antistatic layer, and the slippery layer of the present invention can be applied. Film thickness of the cellulose ester support 50 to 300 μm, preferably 70 to 200 μm
m, more preferably 80 to 150 μm.

The polyester support such as polyethylene terephthalate can be formed into a film by a usual melt film forming biaxial stretching method. That is, the polyester chip is dried, melted in an extruder at a temperature of about 300 ° C., extruded from a pressure die to a cooling drum, and made into a raw material. First, it is uniaxially stretched about three times in the machine direction, and then, in the width direction. The film is stretched about 3 times, heat-set, cooled, and wound up to form a film as a polyester support. The undercoat layer or the slippery layer can be applied at any arbitrary place before uniaxial stretching, after uniaxial stretching, or after biaxial stretching. The thickness of the polyester support is 10
２００200 μm, preferably 30-120 μm, particularly preferably 40-100 μm.

In order to reduce the curl of the polyester support, it is preferable to perform a heat treatment after film formation. The heat treatment temperature ranges from the glass transition point Tg of the polyester to (Tg-50).
° C), more preferably Tg to (Tg-30 ° C), and still more preferably Tg to (Tg-20 ° C). When the heat treatment temperature exceeds Tg, the support is likely to have curl. The heat treatment temperature is 0.1 to 1500 hours, more preferably 0.5 to
500 hours, more preferably 1 to 200 hours.

The support may be provided with a matting agent, an antistatic agent, a slipping agent, a surfactant, a stabilizer, a dispersant, a plasticizer, an ultraviolet absorber, a conductive substance, a tackifier, a softener, and a fluidizer. Agents, thickeners, antioxidants and the like can be added.

The support is neutralized in the tint of the minimum density portion, prevention of the light piping phenomenon (edge fogging) which occurs when light is incident on the film coated with the silver halide emulsion layer from the cross section of the support, and halation. A dye can be contained for the purpose of prevention or the like. The type of the dye is not particularly limited, but when using cellulose triacetate as a support, it is preferable that the film has excellent heat resistance, solvent solubility, and dispersibility in the film forming process, and examples thereof include an anthraquinone-based chemical dye. . When the purpose is to prevent light piping, the color is preferably colored gray as seen in color or black-and-white silver halide photographic materials. In the case of a silver halide photographic light-sensitive material for medical use, blue is preferably used. The dyes may be used alone or in combination of two or more. The target can be achieved by using a dye such as Diaresin (manufactured by Mitsubishi Kasei Co., Ltd.) or MACROLEX (manufactured by Bayer) as a commercially available product, alone or in an appropriate mixture.

Substrates for cellulose triacetate film, cellulose acetate propionate film, or cellulose acetate butyrate film support useful in the present invention include gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, and vinyl acetate-anhydrous. Examples include hydrophilic resins such as maleic acid copolymers and hydrophobic resins such as cellulose diacetate and cellulose nitrate. The undercoat layer coating liquid is preferably an organic solvent. As the organic solvent, acetone, methyl ethyl ketone, methanol, isopropanol, methylene chloride, ethylene chloride, 1,3-dioxolan, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, Methyl acetate, ethyl acetate, ethyl formate, formamide, dimethylformamide and the like can be used, and these may be mixed and used as necessary.

As a subbing material for a polyethylene terephthalate or polyethylene-2,6-naphthalate support (polyester support), those described in Japanese Patent Application No. 10-305312 can be used. For example, butyl acrylate-styrene-glycidyl methacrylate copolymer,
Styrene-2-hydroxyethyl methacrylate-butyl acrylate-, styrene-butadiene copolymer, alkyl acrylate-vinylidene chloride copolymer, polymer having an active methylene group, glycidyl methacrylate-diolefins-butyl acrylate copolymer, Glass transition point difference of 10 with two kinds of acrylic polymer latex
A modified polyester containing a vinyl-based polymer polymerized in a water-soluble polyester liquid, and a mixture of copolymers having a temperature of from 80 to 80 ° C can be exemplified. Further, an upper layer of a hydrophilic polymer such as gelatin or a water-soluble polyester may be provided thereon.

Since the surfaces of the cellulose ester support and the polyester-based support are hydrophobic, their wettability and adhesiveness can be compensated for by performing various surface treatments in advance. Such surface treatments include, for example, surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, discharge plasma treatment in gas, active plasma treatment, and laser treatment.
Examples thereof include resorcinol, phenols, alkali, and amine treatment. In order to firmly adhere one or more constituent layers to the support, an undercoat layer may be provided on the treated support, or the above-mentioned treatment may be applied to the surface of the undercoat layer. The undercoat layer may be a hydrophilic polymer aqueous coating or a water-insoluble solvent coating.

The structure (16) of the present invention comprises the structures (12) to (12).
(15) The silver halide photographic material wherein a silver halide emulsion layer is provided on the side of the support having no slippery layer.

The silver halide photographic light-sensitive material having a slippery layer according to the present invention includes a silver halide photographic light-sensitive material for black and white, a silver halide photographic light-sensitive material for color negative, a light-sensitive material for color reversal, and a silver halide photographic light-sensitive material. Silver halide photographic materials such as photosensitive materials, medical silver halide photographic materials, silver halide photographic materials for printing, silver halide photographic materials for microphotography, silver halide photographic materials for aerial photography Useful.

The silver halide emulsion and other materials of the silver halide photographic light-sensitive material according to the present invention will be described with reference to RD.

RD 3081 for the silver halide emulsion
19 can be used. The places to be described are shown below.

[Items] [Page RD308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal wall Normal crystal 993 IA Twin crystal 999 IA Section Epitaxial 993 I -A halogen composition uniform 993 IB non-uniform 993 IB halogen conversion 994 IC halogen substitution 994 IC metal-containing 994 ID monodispersion 975 IF solvent added Item 995 I-F Latent image forming position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I Section-J Desalting 995 II-A The silver halide emulsion according to the present invention is preferably subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD17643, RD
18716 and RD308119. The places described in these RDs are shown below.

Item [308119] [17643] [18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-A to D 23 to 24 948 to 649 H to J Superchromic sensitization Agent 996 IV-A to E section 23 to 24 648 to 649 Section J Antifoggant 998 IV 24 to 25 649 Stabilizer 998 IV 24 to 25 649 The known silver halide emulsion layer according to the present invention is added to the silver halide emulsion layer. As the agent, those described in the above RD can be used. The relevant sections are described below.

Item [308119] [17643] [18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII-C 25- 26 XIII-C Section Light Absorbing Agent 1003 VIII 25-26 Light Scattering Agent 1003 VIII Filter Dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic Agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Slipper 1006 XII 27 650 Coating aid 1005 XI 27 650 Matting agent 1007 XVI Developer 1011 XX-B Various couplers can be used in the silver halide color emulsion layer according to the present invention. Is the above R
D. The relevant sections are described below.

Item [308119] [17643 and 18716] Yellow coupler 1001 Sections VII-D VII-C to G Magenta coupler 1001 VII-D Sections VII-C to G Cyan coupler 1001 Sections VII-D to VII-C Section G Colored coupler 1002 VII-G Section VII-G Section DIR coupler 1001 VII-F Section VII-F BAR coupler 1002 VII-F Other useful residues Emission coupler 1001 VII-F Section Alkali-soluble coupler 1001 VII- Section E The additives used in the silver halide emulsion layer according to the present invention can be added by the dispersion method described in RD308119, XIV.

As the silver halide photographic constituent layer, the above-mentioned R
An auxiliary layer such as a filter layer or an intermediate layer described in D308119, section VII-K can be provided.

The photographic constituent layers used in the present invention are the same as those described above for R.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section VII-K of D308119 can be employed.

For developing processing of the photographic constituent layer used in the present invention, for example, T.I. H. James, Theory of the Photographic Process, 4th Edition (Th
eTheory of The Photograph
ic Process Fourth Edition
n) pages 291-334, and Journal of the American Chemical Society (Journal o)
f the American Chemical S
ociety), vol. 73, p. 3100 (1951), known developers can be used. The color photographic constituent layer is the same as that of the aforementioned RD17643.
Pages 28-29 of RD18716, page 615 and RD3
Development processing can be performed by a usual method described in 08119XIX.

The silver halide photographic light-sensitive material can be prepared by a manufacturing process such as coating, drying, cutting and packaging, an exposure process such as automatic exposure, photographing or baking, a pre-processing process such as splicing or cutting, a developing process, In various processes such as post-development processing processes such as splicing and cutting, contact with various substances, cutting to a predetermined size, slitting, separation with a knife such as punching, immersion of aqueous liquid, drying, etc. are performed. Will be

The silver halide photographic light-sensitive material having a slippery layer of the present invention exhibits excellent performance in these steps, and the slippery layer obtained by mixing the polyvinyl alcohol and the slipping agent plays a role. I can fulfill it enough. Its features are superior slipping properties, strong abrasion resistance, moderate wettability, insolubility of the slippery layer, and other unprecedented properties that overcome various problems. Can be done.

The basic point of this property is 98 mol%
As described above, polyvinyl alcohol having a polymerization degree of preferably 99 mol% or more and 400 or more, preferably 900 or more is used for the slippery layer, and the above properties can be exhibited together with the slipping agent.

In the constitutions (17) to (20) of the present invention, at least one layer containing polyvinyl alcohol having a saponification degree of 96 mol% or more and a polymerization degree of 400 or more is provided on the support.
It is a silver halide photographic material having a layer. Further, the degree of saponification is particularly preferably at least 99 mol% and the degree of polymerization is preferably 9%.
00 or more is preferable. By including such polyvinyl alcohol in any one of the constituent layers of the silver halide photographic light-sensitive material, the polyvinyl alcohol-containing layer has good coatability, good wettability, and is insoluble. Hardly eluted in the liquid or the coating liquid applied on it,
Moreover, it is characterized by having an appropriate surface strength. Conventional water-soluble polymers other than gelatin do not have these properties, and can be solved by using this polyvinyl alcohol. From such characteristics, it is suitable for the protective layer and the intermediate layer.

The polyvinyl alcohol used in the constitutions (17) to (20) was added to water at the stage of preparing the coating solution.
It is preferable to use those dissolved at a temperature of at least 60 ° C, preferably at least 60 ° C. Further, when using polyvinyl alcohol having a saponification degree of 99 mol% or more, it is preferable to dissolve it with hot water of 90 ° C. or more.

It is preferable that the polyvinyl alcohol solution after dissolution is maintained at a temperature in the range of 20 to 35 ° C., and that the coating is performed at the same temperature.

The coating amount of polyvinyl alcohol is 0.5
It is preferably contained so that about 80 mg / m ^{2 is} applied.

The structure (21) according to the present invention comprises the structures (17) to (17).
Along with the polyvinyl alcohol used in (20), a polyvinyl alcohol having a degree of saponification of less than 96 mol% and a degree of polymerization of 400 or more may be contained to such an extent that the effects exhibited by the constitutions (16) to (18) are not impaired. Good. 96
Since polyvinyl alcohol having a degree of saponification of less than mol% has protective colloidal properties and appropriate surface activity, it easily contains various additives, dispersibility is improved, and coatability is also improved.

[0129]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

[Evaluation Method] << Scratch Resistance >><ScratchTest> After the silver halide photographic light-sensitive material before and after development was conditioned for 24 hours in an atmosphere of 23 ° C. and 55% RH,
Using a HEIDON-18 scratch-strength tester, the tip with a diameter of 25 μm was formed on the surface without the silver halide emulsion layer.
Sapphire needle is applied vertically and a continuous load of 0 to 50 g is applied, and the sapphire needle is scratched at a speed of 10 mm / sec. The sample after being scratched was placed on a Schaukasten, and the load-bearing strength at which a flaw began to be seen by transmitted light was read on a scale to determine the load of the abrasion. The larger the value, the better the scratch resistance.

<Durability test> A silver halide photographic light-sensitive material was fixed on a carrier that reciprocated horizontally for a distance of 15 cm with the side without the silver halide emulsion layer facing upward. 5 mmφ) and a load of 150 g was applied. Slide the carrier at a speed of 10 cm / sec.
Zero reciprocation was repeated. The degree of damage after the end of the test was measured according to the rank shown below. Measurement environment: 25 ° C, 55%
Performed at RH.

A: scar is not visible B: scar is slightly visible C: scar is visible but not very deep D: deep scar is seen E: deep scar is present and reaches the film (support) surface .

<< Waterfastness >> A sample was fixed on a flat plate reciprocating horizontally for a distance of 5 cm with the side of the sample not having the silver halide emulsion layer facing upward, and water / ethanol = 4/1 from above.
Was pressed with a load of 100 g against a 5 mm square felt that had been sufficiently impregnated. 20cm / sec for the flat plate on which the sample is placed
The sample was reciprocated 30 times at a speed of 負荷, the load resistance was measured during running on the felt, and the change in the measured surface was observed.

A: The running load does not change and the sample surface does not change at all. B: The running load increases very slightly, but the sample surface hardly changes. C: The running load increases by 5 to 10%. D: The running load increased by 10 to 25% within 5 passes, and the sample surface was shaved. E: The running load increased rapidly in 2 to 5 passes, and the sliding noise was observed. Is large and the sample surface is shaved.

<< Transferability >><Slip Agent Transfer Test> As a drive roll, a chrome plating roll having a smooth surface (width: 50 cm, diameter: 10 cm)
) And one of the same size and the same size that is free to rotate
Prepare a free roll and one tension roll with the same surface and the same size that is free to rotate, fix the horizontal distance between the drive roll and the free roll to 40 cm, and place the tension roll under the chin, Each was parallel.
Outside these three rolls, width 30 cm x length 120
cm. The silver halide photographic light-sensitive material or the support was connected endlessly so that the back surface of the support was in contact with the roll. The tension roll was lowered to apply a load of 55 to the sample at a tension of 3 kg / 30 cm and a line speed of 100 m. / Min for 10 minutes. The silver halide photographic material or the support was conditioned for 24 hours in an atmosphere of 30 ° C. and 65% RH. This test was also performed in the same condition atmosphere. After completion, the sample was removed. Without cleaning each roll, continue to set another undercoat-coated support on these rolls so that the undercoat layer surface is in contact with these rolls, and rotate them to perform the transfer test. went. The tested sample with an undercoat layer was immersed in a 1% by weight solution of methyl violet at 40 ° C. for 5 minutes, and then suspended and dried. 20c from this tested support
Three samples having a size of mx 20 cm were cut out, the number of unstained points of those samples was counted, and the average number of the three samples was evaluated as a transfer degree as follows. In each transfer test, each roll was washed with methylene chloride so that no waxy substance remained on each roll, further washed with acetone, and subjected to the next test.

A: No unstained portion B: One unstained portion C: Less than 5 unstained portions D: 5 to less than 20 unstained portions E: 20 or more unstained portions.

<< Running Stability >><TransportabilityTest> Photographed and developed using Notcher (KPN-1200DX (manufactured by Konica Corporation)).
A silver halide photographic light-sensitive material roll film of 5 cm × 120 cm was transported one frame at a time. The amount of deviation of the frame from the frame alignment guide in the frame of the notch position was measured by a frame detection unit using transmitted light, and evaluated as follows.

A: No displacement B: Less than 1 mm piece displacement C: Less than 1 to 2 mm piece displacement D: Less than 2 to 3 mm piece displacement E: 3 mm or more piece displacement

<< Evaluation of Blocking Property >> The silver halide photographic light-sensitive material coated with everything was wound up, and was taken at 40 ° C. and 55% RH.
For 3 weeks to evaluate the blocking property when unwound.

A: Can be extended without any resistance or peeling sound B: There was some resistance, but it can be extended without peeling sound C: There is some resistance and the peeling sound is slightly reduced D: Extending E: The peeling sound is quite audible. E: Some parts cannot be peeled off, and some parts are crunchy.

<< Evaluation of bleed-out property of slip agent >> 150
After leaving the 0 m slippery support in the environment of 40 ° C. and 65% RH for 3 months while keeping the roll, the surface of the slippery layer side was observed while unwinding, and the degree of bleed out of the slip agent was evaluated.

A: The glossy surface is maintained as it is. B: The gloss is maintained to the extent that it is thought that there is only a slight haze. C: There is slight haze but no precipitate is observed (microscopic observation. D: The surface is slightly cloudy, and a very fine white crystal is observed with the naked eye. E: A fairly large white crystal is observed all over.

<< Evaluation of Coating Property >> After coating only the back surface,
A sample cut out to a length of 50 cm with a full width was set at 45 ° from a lamp provided with a Schaukasten and three fluorescent lamps in parallel.
The coating property was observed by reflecting light from an angle of, and evaluated according to the following ranking.

A: There is no coating unevenness or streak at all, and it is in a good coating state. B: It seems that coating unevenness or streak-like streaks can be seen. C: Application unevenness or streak is slightly seen. D: Application unevenness or streak. E: coating unevenness and streaks are clearly visible but not so much F: coating unevenness and streaks are clear and numerous.

<< Stain Resistance >><Evaluation of Watermark (Watermark)> Twenty pieces of silver halide photographic light-sensitive material were taken and prepared into a 35 mm film.
This was exposed, only 50 pieces of the same type of sample were connected, passed through an automatic processor for color photography under normal conditions, and the number of watermarks attached to the back surface of the film after washing and drying was counted and evaluated. .

<Drug Adhesion Test> The fixing solution and the stabilizing solution were each concentrated 30-fold (the dilution of water was reduced to 1/30), and a mixture was prepared by mixing these concentrated solutions. Each exposed 20-shot 35 mm film of each sample was subjected to normal development processing, and then immersed in this mixed solution for 10 minutes, suspended under an environment of 23 ° C. and 50% RH, and air-dried. Was. The adherence of stains of the sample to the chemicals in the fixer and stabilizer was evaluated according to the following criteria.

A: No adhesion was observed on the film surface, and there was no abnormality even when observed under a microscope. B: No adhesion was observed on the film surface, but observed under a microscope. Then, something like dirt is partially seen. C: Very little attached matter is seen on the film surface, and something like stain is seen under the microscope. D: Dirt on the film surface. Slight adhesion is observed, and in particular, many scale-like stains are seen around the perforations. E: Soil adheres to the entire film, solids are solidified, and the transparency is obviously deteriorated.

<< Staining of Processing Liquid >> 36 samples of each sample were taken.
Prepare 1000 or more mm films. Separately, a commercially available film is prepared as a reference sample. A minilab developing machine (manufactured by Konica Corporation, Konica Nice Print System 878JW Type II Trendy W) was used as a developing machine. The developing solution was renewed for each sample and reference sample film, and the same sample film was continuously used.
After passing through the number of 100, the film continuous 1 of the same type
After passing through 2,000 lines, a part of the developing solution and the fixing solution was sampled to observe the state of dirt.
From the color tone of the 0th film, uneven development, stain on the film surface, etc., the stain on the processing solution was comprehensively judged by comparing it with the processing level of the reference sample.

A: The condition of the liquid stain is equal to or more than that of the reference sample even after 1000 lines. B: The condition of the liquid stain is equivalent to the reference sample after 1000 lines. C: The liquid stain is after 500 lines. D is slightly inferior to the reference sample after 1000 lines. D: After 500 lines, the situation of liquid stain is slightly inferior to the reference sample, and after 1,000 lines, it is considerably inferior to the reference sample.
Stain is very bad E: After 500 lines, the condition of liquid stain is very inferior to the reference sample, and after 1,000 lines, the stain is severe.

<< Coefficient of Dynamic Friction >> A sample was heated at 23 ° C. and 55% RH.
After the humidity was adjusted in the environment described above, the measurement was performed using a HEIDON-14 dynamic friction coefficient measuring device. A stainless steel hard sphere having a diameter of 5 mm is placed on the measurement surface of the sample, a load of 100 g is applied, and the speed is 60 c.
The kinetic friction coefficient was measured by moving at a constant speed of m / min.

<< Adhesiveness >> A cut having a width of 30 to 40 mm was made at an angle of 45 ° with a razor on the surface on the back layer side of the sample, and a commercially available cellophane tape having a width of 25 mm was sandwiched between the cuts to obtain a fixed area. After applying a constant load with a rubber roller and applying uniform contact, hold the end of the cellophane tape and peel it off about 180 ° (horizontally) to the opposite side at an angle of 45 ° to remove the outermost layer. Examined. It was calculated from the area ratio to the portion where the tape was first applied.

A: The outermost layer is not peeled at all. B: The peeled area is less than 5%. C: The peeled area is 6 to 10%. D: The peeled area is 11 to 50%. E: The peeled area is 51% or more.

[Preparation of Cellulose Triacetate Support] A cellulose triacetate support was produced as follows. That is, cellulose triacetate flake (60.3 to 61.6% of acetylation degree) 1 manufactured by Courtles Co., Ltd.
5.7 parts by weight and triphenyl phosphate (TP
P) 1.6 parts by weight was dissolved in 82.7 parts by weight of a mixed solvent of methylene chloride: ethanol (84:16 weight ratio) to obtain a dope. The dope was cast on an endless stainless steel belt running infinitely so that the thickness after drying became 100 μm, and was dried on the belt until the residual solvent became 100% by weight. The obtained dope film (hereinafter referred to as web) was peeled off from the belt, and heated and dried while being conveyed on a plurality of conveying rolls. The residual solvent amount was 0.5% by weight.

[Preparation of polyethylene-2,6-naphthalate support] 0.05 parts by weight of magnesium acetate hydrate as a transesterification catalyst was added to 126 parts by weight of 2,6-dimethylnaphthalate and 65 parts by weight of ethylene glycol. A transesterification reaction was performed according to a conventional method. 0.05 parts by weight of antimony trioxide and 0.03 parts by weight of trimethyl phosphate were added to the obtained product. Then
The temperature was gradually increased and the pressure was reduced, polymerization was performed at 300 ° C. and 0.5 mmHg, and polyethylene-2,6- having an intrinsic viscosity of 0.65.
Naphthalate was obtained.

Further, the polyethylene terephthalate was vacuum-dried at 150 ° C. for 8 hours, and then dried using an extruder.
It was melt-extruded at 0 ° C., adhered to a cooling drum at 30 ° C. while applying static electricity, cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the machine direction at 85 ° C. using a roll-type longitudinal stretching machine. The temperature difference between the front and back surfaces was within 5 ° C.

The obtained uniaxially stretched film was stretched in a first stretching zone at 90 ° C. by 50% of the total transverse stretching ratio using a tenter-type transverse stretching machine, and further, at a second stretching zone at 100 ° C. at a total transverse stretching ratio of 3. The film was stretched three times. Then 70
C. for 2 seconds, heat set at 150 ° C. in the first heat setting zone for 5 seconds, and heat set at 220 ° C. in the second heat setting zone for 15 seconds. Next, after being relaxed in the horizontal (width) direction at 160 ° C. and leaving the tenter, utilizing the difference in peripheral speed of the drive roll, the film is relaxed in the vertical (longitudinal) direction at 140 ° C. and wound up. A biaxially stretched polyethylene-2,6-naphthalate film having a thickness of 80 μm was obtained.

[Preparation of polyvinyl alcohol solution] << Preparation of polyvinyl alcohol solution (p-1) >> Polyvinyl alcohol A (manufactured by Shin-Etsu Chemical Co., Ltd., saponification degree 99.8)
(Mol%, polymerization degree: 1500) was dispersed and suspended in 100 parts by weight of water and heated. It was kept at 95 ° C. or higher for 3 hours while stirring slowly so as not to form bubbles, and it was confirmed that the polyvinyl alcohol was completely dissolved and turned into a transparent solution. The solution was slowly cooled and kept at 25 ° C. to obtain a polyvinyl alcohol solution (p-1). Store this p-1 at 25-30 ° C until use.

<< Preparation of Polyvinyl Alcohol Solution (p-2) >> 10 parts by weight of polyvinyl alcohol C-05GP (manufactured by Shin-Etsu Chemical Co., Ltd., saponification degree 98.5, polymerization degree 500) was dispersed in 100 parts by weight of water. As in the case of p-1, a transparent polyvinyl alcohol solution (p-2) was obtained. Store this p-2 at 25-30 ° C until use.

<< Preparation of Polyvinyl Alcohol Solution (p-3) >> 10 parts by weight of polyvinyl alcohol PVA-110 (Kuraray Co., Ltd., degree of saponification 98.5 mol%, degree of polymerization 1100) was dispersed in 100 parts by weight of water. A transparent polyvinyl alcohol solution (p-3) was obtained in the same manner as in p-1. This p-
Store 3 at 25-30 ° C until use.

<< Preparation of Polyvinyl Alcohol Solution (p-4) >> Polyvinyl alcohol PVA-135H (manufactured by Co., Ltd.)
Kuraray, degree of saponification 99.3 mol%, degree of polymerization 1350) 10
Parts by weight were dispersed in 100 parts by weight of water to obtain a transparent polyvinyl alcohol solution (p-4) in the same manner as in p-1. Store this p-4 at 25-30 ° C until use.

<< Preparation of Polyvinyl Alcohol Solution (p-5) >> Polyvinyl alcohol C-20 (Shin-Etsu Chemical Co., Ltd., saponification degree 99.5 mol%, polymerization degree 2000) 10
Parts by weight were dispersed in 100 parts by weight of water to obtain a transparent polyvinyl alcohol solution (p-5) in the same manner as in p-1. Store this p-5 at 25-30 ° C until use.

<< Preparation of Polyvinyl Alcohol Solution (p-6) >> 10 parts by weight of polyvinyl alcohol PVA-217 (Kuraray Co., Ltd., degree of saponification: 87.8 mol%, degree of polymerization: 1700) was added to 100 parts by weight of water at 20 ° C. Add it slowly and slowly to dissolve it so that mamako is not formed while stirring well, then gradually increase the temperature while continuing to stir, heat to 95 ° C, and completely dissolve the transparent polyvinyl alcohol solution in 3 hours ( p-6) was obtained.

<< Preparation of Polyvinyl Alcohol Solution (p-7) >> 10 parts by weight of polyvinyl alcohol PA-05GP (manufactured by Shin-Etsu Chemical Co., Ltd., saponification degree: 88.0, polymerization degree: 500) were added to 100 parts by weight of water at 20 ° C. After stirring, a transparent polyvinyl alcohol (p-7) was obtained in the same manner as in p-6.

<< Preparation of Polyvinyl Alcohol Solution (p-8) >> Polyvinyl alcohol PVA-420H (trade name)
A transparent polyvinyl alcohol solution (p-8) was obtained by treating 10 parts by weight of Kuraray, having a saponification degree of 79.0 and a polymerization degree of 2400) in 100 parts by weight of water at 20 ° C. in the same manner as in p-6.

<< Preparation of Polyvinyl Alcohol Solution (p-9) >> 10 parts by weight of polyvinyl alcohol PA-15GP (manufactured by Shin-Etsu Chemical Co., Ltd., degree of saponification: 87.2, degree of polymerization: 1500) was added to 100 parts by weight of water at 20 ° C. A transparent polyvinyl alcohol solution (p-9) was obtained in the same manner as in p-6.

<< Polyvinyl alcohol solution (p-10)
Preparation of 10 parts by weight of polyvinyl alcohol PA-05GP (manufactured by Shin-Etsu Chemical Co., Ltd., saponification degree 87.2, degree of polymerization 1500) in 100 parts by weight of water at 20 ° C. in the same manner as in p-6, transparent polyvinyl alcohol solution (P-10) was obtained.

[Preparation of slip agent dispersion] <Preparation of slip agent dispersion (sd-1)>
After heating to 0 ° C. to melt the wax, the mixture was sufficiently stirred using a high-speed stirring homogenizer, and then cooled to prepare a yellow translucent slightly sticky slipping agent dispersion (sd-1).

Carnauba wax 20 parts by weight WX41 4 parts by weight Water 72 parts by weight << Preparation of slip agent dispersion liquid (sd-2) >> Carnauba wax 20 parts by weight Gelatin 2 parts by weight C ₁₈ H ₃₇ O (CH ₂ CH ₂₎ O) ₁₅ H (surfactant) 2 parts by weight Pure water 72 parts by weight Gelatin is dissolved in pure water at 60 ° C., a surfactant is added, the temperature is raised to 100 ° C., and carnauba wax is added and melted. Then, the mixture was sufficiently stirred and dispersed using a high-speed stirring homogenizer to prepare a slip agent dispersion (sd-2).

<< Preparation of Slip Agent Dispersion (sd-3) >> Carnauba Wax 20 parts by weight C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₂₀ H (surfactant) 4 parts by weight Pure water 72 parts by weight 95 The surfactant was added to pure water heated to ° C. Separately 9
After adding carnauba wax melted at 0 ° C. to the aqueous surfactant solution heated to 95 ° C., the mixture was sufficiently stirred using a high-speed stirring type homogenizer to obtain a slip agent dispersion liquid (s
d-3) was prepared.

<< Preparation of Sliding Agent Dispersion (sd-4) >> Polyvinyl alcohol (p-6) (10% by weight solution) 44 parts by weight Carnauba wax 20 parts by weight Pure water 28 parts by weight In addition, the temperature was raised to 100 ° C., carnauba wax was added and melted, and the mixture was sufficiently stirred using a high-speed stirring homogenizer to prepare a slip agent dispersion liquid (sd-4).

<< Preparation of Slip Agent Dispersion (sd-5) >> Polyvinyl alcohol (p-10) 44 parts by weight Carnauba wax 20 parts by weight WX41 2 parts by weight Pure water 28 parts by weight Add p-10 to pure water, This was heated to 100 ° C., melted by adding carnauba wax, and sufficiently stirred using a high-speed stirrer homogenizer to prepare a slip agent dispersion (sd-5).
Was prepared.

<< Preparation of Slip Agent Dispersion (sd-6) >> Polyvinyl alcohol (p-8) 44 parts by weight WX29 20 parts by weight WX41 2 parts by weight Pure water 28 parts by weight Add p-8 to pure water, and add Increase to 100 ° C and n-C ₅₀
H ₁₀₁ COOC ₄₀ H ₈₁ and melted with the addition of WX41, sufficiently stirred using a high speed stirring type homogenizer to prepare lubricant dispersion (sd-6).

[0173] The slip agent of the above-mentioned slip agent dispersion liquid forms particles, which are formed by COULTER model N
4 to 50 to 2 by measuring with Coulter
It was confirmed that the particles had an average particle size of 00 nm (the particle sizes are described in Table 1).

[Preparation of Smooth Layer Coating Solution] << Preparation of Smooth Layer Coating Solution (w-1) >> Pure Water 250 parts by weight Methanol 180 parts by weight Propylene glycol monomethyl ether (PGME) 20 parts by weight Polyvinyl alcohol solution (P-1) 5 parts by weight Sliding agent dispersion liquid (sd-1) 2 parts by weight Mix pure water, methanol and PGME, adjust to 30 ° C., add p-1, stir well, and filter. Filtered. To this solution, sd-1 was added, and the mixture was sufficiently stirred using a high-speed stirring homogenizer. After filtration with a filter, the liquid temperature was maintained at 30 ° C. to prepare a coating liquid w-1 for a slippery layer.
The coating solution is kept at 30 ° C. until coating.

<< Preparation of Smooth Layer Coating Solution (w-2) >> The polyvinyl alcohol solution was p-2, and the slip agent dispersion was sd-
In the same manner as in w-1, except that it was 2, the slippery layer coating solution w
-2 was obtained.

<< Preparation of Smooth Layer Coating Solution (w-3) >> The polyvinyl alcohol solution was p-3, and the slip agent dispersion was sd-
Except having changed to 3, it carried out similarly to w-1, and obtained the slippery layer coating solution (w-3).

<< Preparation of Smooth Layer Coating Solution (w-4) >> The polyvinyl alcohol solution was p-4, and the slip agent dispersion was sd-
Except having changed to 4, it carried out similarly to w-1, and obtained the slippery layer coating solution (w-4).

<< Preparation of Smooth Layer Coating Solution (w-5) >> The polyvinyl alcohol solution was p-5, and the slip agent dispersion was sd-
Except having changed to 5, it carried out similarly to w-1, and obtained the slippery layer coating solution (w-5).

<< Preparation of Smooth Layer Coating Solution (w-6) >> The polyvinyl alcohol solution was p-7, and the slip agent dispersion was sd-
Except having changed to 6, it carried out similarly to w-1, and obtained the slippery layer layer coating liquid (w-6).

<< Preparation of Coating Liquid for Easy Layer (w-7) >> The polyvinyl alcohol solution was p-9, and the slip agent dispersion was sd-
Except having changed to 4, it carried out similarly to w-1, and obtained the slippery layer coating solution (w-7).

[Preparation of Antistatic Layer Coating Solution] << Preparation of Antistatic Layer Coating Solution (as-1) >> Cellulose diacetate 10 parts by weight Ionene-type cationic polymer (described below) 35 parts by weight Acicular vanadium pentoxide 5 parts by weight SnO ₂ / Sb ₂ O ₃ (9/1, weight ratio) 70 parts by weight Ethylene glycol 30 parts by weight Acetone 315 parts by weight Methanol 475 parts by weight

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<< Coating Solution for Antistatic Layer (as-2) Cellulose Diacetate 10 parts Cationic Polymer 35 parts Acicular Vanadium Pentoxide 5 parts SnO ₂ / Sb ₂ O ₃ (9/1 (weight ratio)) 70 parts Hardness Particle dispersion stock solution (MX100 / α-alumina, solid content 40% by weight) * 20 parts Ethylene glycol 30 parts Acetone 315 parts Methanol 475 parts * The above hardness particle dispersion stock solution has the following particles, Mohs hardness 4 particles MX100 and Mohs After mixing the MX100 slurry solution and the HIT slurry solution having the following composition so that the weight ratio of the particles HIT60 having a hardness of 7 becomes 1:20, the particles were mixed with an acetone / methanol (1: 1, weight ratio) mixed solvent. A hard particle dispersion stock solution was prepared by diluting the solid content so as to have a solid content of 40%. With such adjustment, it is possible to easily supply both particles having different particle diameters and ratios.

A MX100 slurry liquid: The following was prepared by dispersing in a sand mill.

MX100 (polymethyl methacrylate particles having an average primary particle size of 1.0 μm) 5 parts by weight Ethylene glycol 10 parts by weight HIT slurry solution: The following was prepared by dispersing in a sand mill.

HIT60 (α-alumina having an average primary particle of 0.2 μm) 10 parts by weight Cellulose diacetate 1 part by weight Methyl ethyl ketone 11 parts by weight << Coating solution for antistatic layer (as-3) >> Cellulose diacetate 10 parts Alumina sol AS100 ( Solid content 10%, Nissan Chemical Co., Ltd. 80 parts SiO ₂ fine particles (average particle diameter 0.1 μm) 7 parts Acetone 450 parts Methanol 400 parts << Coating solution for antistatic layer (as-4) >> Cellulose diacetate 10 parts Alumina sol AS100 (solid) 10 parts by weight, manufactured by Nissan Chemical Industries, Ltd.) 80 parts Hard particle dispersion stock solution (MX100 / α-alumina, solid content 40% by weight, same as above) 20 parts Acetone 450 parts Methanol 400 parts [Preparation of coating solution for intermediate layer] << Preparation of Intermediate Layer Coating Solution (md-1) >> Cellulose diacetate 60 parts by weight S O ₂ particles (average particle size 0.1 [mu] m) 7 parts by weight _{C 18 H 37 O (CH 2} CH 2 O) 15 H 1 part by weight of methanol 120 parts by weight of acetone 680 parts by weight [Preparation of undercoat layer coating liquid] "below Preparation of Undercoat Layer Coating Solution (u-1) >> Gelatin 1 part by weight Formalin 0.1 part by weight Pure Water 49 parts by weight << Preparation of Undercoat Layer Coating Solution (u-2) >> (Preparation of Undercoat Layer Liquid Stock Solution) 5 parts by weight of vinyl acetate / maleic anhydride copolymer (1/1 molar ratio) 4.5 parts by weight of pure water 36 parts by weight of acetone are stirred and mixed. A layer stock solution was mixed with the following composition to obtain a subbing layer coating solution (u-2).

Acetone 60 parts by weight Ethyl acetate 13.5 parts by weight 4 parts by weight isopropyl alcohol 4 parts by weight Undercoat layer stock solution 4.3 parts by weight SiO ₂ (manufactured by Aerosil, ultrafine silica 200) / acetone (2% by weight) 0.8 parts "undercoat coating solution (u-3) preparation of" cellulose diacetate 60 parts by weight _{C 18 H 37 O (CH 2} CH 2 O) 15 H 1 part by weight of methanol 120 parts by weight of acetone 680 parts by weight of "subbing Preparation of Layer Coating Solution (u-4) >> Cellulose diacetate 60 parts SiO ₂ fine particles (average particle diameter 0.1 μm) 7 parts C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ H 1 part Methanol 120 parts Acetone 680 Part << Preparation of Undercoat Layer Coating Solution (u-5) >> Butyl acrylate / (t) butyl acrylate / styrene / 2-hydroxyethyl acrylate (3 by weight ratio) / 20/25/25) Copolymer latex liquid (solid content 30%) 270 parts by weight (C-1) 0.6 parts by weight Hexamethylene-1,6-bis (ethylene urea) 0.8 parts by weight Pure 720 parts by weight of water << Preparation of Undercoat Layer Coating Solution (u-6) >> 270 parts by weight of a copolymer latex solution of butyl acrylate / styrene / glycidyl acrylate (40/20/40 in weight ratio) (solid content 30%) (UL-1) 0.6 parts by weight Hexamethylene-1,6-bis (ethylene urea) 0.8 parts by weight Pure water 720 parts by weight << Preparation of Undercoat Layer Upper Layer Coating Solution (u-7) >> Gelatin 0.0 Weight to become 4 g / m ² (UL-1) 0.2 part by weight (UL-2) 0.2 part by weight (UL-3) 0.1 part by weight Silica particles (average particle diameter 3 μm) 0.1 part by weight 990 parts by weight of pure water << Coating solution for undercoat layer upper layer u-8 (UL-4) 60 parts by weight Latex liquid containing (UL-5) as a component (solid content: 20%) 80 parts by weight Ammonium sulfate 0.5 part by weight (UL-6) 12 parts by weight Polyethylene glycol (weight average molecular weight 600) 6 parts by weight 840 parts by weight of pure water.

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[Preparation of Coating Solution for Protective Layer] A coating solution for the protective layer is prepared and stored at 30 ° C. until coating.

<< Preparation of protective layer coating liquid (pr-1) >> Pure water 250 parts by weight Methanol 180 parts by weight Propylene glycol monomethyl ether 15 parts by weight Polyvinyl alcohol solution (p-1) 10 parts by weight << Protective layer coating liquid (pr-1) Preparation of -2) Pure water 250 parts by weight Methanol 180 parts by weight Propylene glycol monomethyl ether 15 parts by weight Polyvinyl alcohol solution (p-2) 10 parts by weight << Preparation of protective layer coating solution (pr-3) >> Pure water 250 parts by weight Parts methanol 180 parts by weight propylene glycol monomethyl ether 15 parts by weight Polyvinyl alcohol solution (p-3) 10 parts by weight << Preparation of protective layer coating solution (pr-4) >> pure water 250 parts by weight methanol 180 parts by weight propylene glycol monomethyl ether 15 Parts by weight polyvinyl alcohol Solution (p-5) 10 parts by weight Polyvinyl alcohol solution (p-8) 1 part by weight << Preparation of protective layer coating solution (pr-5) >> pure water 250 parts by weight methanol 180 parts by weight propylene glycol monomethyl ether 15 parts by weight polyvinyl Alcohol solution (p-5) 10 parts by weight Polyvinyl alcohol solution (p-9) 0.5 parts by weight << Preparation of protective layer coating solution (pr-6) >> pure water 250 parts by weight methanol 180 parts by weight propylene glycol monomethyl ether 15 Parts by weight Polyvinyl alcohol solution (p-6) 10 parts by weight << Preparation of protective layer coating solution (pr-7) >> pure water 250 parts by weight methanol 180 parts by weight propylene glycol monomethyl ether 15 parts by weight polyvinyl alcohol solution (p-10) 10 parts by weight Example 1 Cellulose triacetate filler One surface antistatic layer coating liquid arm support body (as-1) was coated so as to 15ml / m ^2, 3 minutes at 120 ° C., and dried to form an antistatic layer (AS-1) . An intermediate layer coating solution (md-1) was applied on AS-1 to a concentration of 25 ml / m ² ,
Drying was performed at 00 ° C. for 3 minutes to form an intermediate layer (MD-1). Further, a coating liquid for the slippery layer (w-
1) was kept at 30 ° C., and polyvinyl alcohol in the solution was applied so as to have a concentration of 30 mg / m ^2.
After drying for minutes, a slippery layer (W-1) was formed.

On the cellulose triacetate film support on the side opposite to the slippery layer side, a corona discharge treatment and an ultraviolet irradiation treatment were performed, and the undercoat layer coating solution (u-1) was coated with gelatin at 100 mg / m ² . The coating was performed so as to obtain a subbing layer (U-1) of a silver halide emulsion layer.

A silver halide emulsion photosensitive layer shown below was provided on the undercoat layer (U-1) to prepare a silver halide multilayer color photographic material.

[Composition and Formation of Silver Halide Emulsion Photosensitive Layer] A layer such as a silver halide emulsion layer having the following composition was coated on the undercoat layer to prepare a silver halide photographic light-sensitive material.

The coating amount is expressed in terms of g / m ² in terms of metallic silver for silver halide and colloidal silver, and g / m ^{2 for} couplers and other additives.
/ M ² , and the sensitizing dye was represented by the number of moles per mole of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound ( SC-1) 0.14 High boiling solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A (average Ag content: 4.0 mol%, average grain size) 0.15 silver iodobromide emulsion B (average Ag content: 8.0 mol%, average grain size: 0.42 μm, normal crystal, diameter / thickness = 1) 0.30 μm in diameter, normal crystal, diameter / thickness = 1 0.35 sensitizing dye (SD-1) 2.0 × 10 ^-4 sensitizing dye (SD-2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing Dye (SD-4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0 .04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C (average Ag content 6.0 mol%, average particle size 0.55 μm, normal crystal, diameter / thickness = 1) 0.34 sensitizing dye (SD-1) 1.7 × 10 ^-4 sensitizing dye ( SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-1) 33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide Emulsion D (average Ag content 6.0 mol%, average particle size 0.85 μm, twin plane, diameter / thickness = 4) 0.95 sensitization Dye (SD-1) 1.0 × 10 ^-4 sensitizing dye (SD-2) 1.0 × 10 ^-4 sensitizing dye (SD-3) 1.2 × 10 ^-5 cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling solvent (OIL-) 2) 0.11 gelatin 0.80 seventh layer: low-sensitivity green-sensitive layer silver iodobromide emulsion A 0.12 silver iodobromide emulsion B 0.38 sensitizing dye (SD-4) 4.6 × 10 ^{− 5} Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 gelatin 0.70 eighth layer: intermediate layer gelatin 0.41 ninth layer: medium Domidori sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 -4 Sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.2 × 10 _-4 magenta coupler (M-1) 0.04 magenta coupler (M-2) 0.04 colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: Highly sensitive green-sensitive layer Silver iodobromide emulsion D 0. 95 sensitizing dye (SD-6) 7.1 × 10 ^-5 sensitizing dye (SD-7) 7.1 × 10 ^-5 sensitizing dye (SD-8) 7.1 × 10 ^-5 magenta coupler (M -1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling solvent (OIL-4) 0.11 Zera 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 gelatin 1.40 13th layer: high-sensitivity blue-sensitive layer silver iodobromide emulsion C 0.15 silver iodobromide emulsion E (average Ag content: 6.0 mol%, average particle size) 0.95 μm, twin flat plate, diameter / thickness = 4) 0.80 sensitizing dye (SD-9) 8 0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 -5 Yellow coupler (Y-1) 0.12 High boiling solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: second 1 Protective layer Silver iodobromide emulsion (average particle size 0.08 μm, silver iodide content 1.0 mol%) 0.40 Ultraviolet absorber (UV-1) 0.065 High boiling solvent (OIL-1) 0 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Polymethyl methacrylate (average particle size: 3 μm, monodispersity: 3.5) 0.018 Slip agent (WAX-1) 0.04 gelatin 0.55 In addition to the above composition, a coating aid (Su-1), a dispersion aid (Su-2), a viscosity modifier, a hardener (H-1),
(H-2), stabilizer (ST-1), antifoggant (AF
-1), average molecular weights 10,000 and 1,100,00
0 antifoggants (AF-2) and preservatives (D
I-1) was added.

The average grain size of the silver halide emulsion used in the above sample was shown as a cubic grain size. Each silver halide emulsion was optimally subjected to gold and sulfur sensitization.

The samples were simultaneously coated with a multi-slide hopper type coater.

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The silver coating amount of each silver halide emulsion layer was 6.
25 mg / m ² , dry film thickness was 18 μm, and specific photographic sensitivity was ISO420.

Comparative Example 1 A slippery layer was prepared using (W-7 (coating solution for slippery layer: (w-7)))
A silver halide photographic light-sensitive material was produced in the same manner as in Example 1 except that the composition was changed to.

Examples 2 to 10 and Comparative Example 2 In Examples 2, 4, 5, 8, 10 and Comparative Example 2, an undercoat layer (U-3 (undercoat layer) was formed on one surface of the cellulose triacetate film support. The coating liquid is provided with (u-3))),
In Examples 3, 6, 7 and 9, the undercoat layer (U-
4 (undercoat layer coating liquid is (u-4)),
In 5, 7, and 9, an undercoat layer (U-1 (undercoat coating solution (u-1))) was provided on the other surface of the cellulose triacetate film support. 8, 10
And in Comparative Example 2, an undercoat layer (U-2 (undercoat layer coating liquid (u-2))) was similarly provided, and (U-3) or (U-
4) As shown in Table 1 above, each of the antistatic layers (AS
-1) and (AS-2 (Antistatic layer coating solution is (as-
2))) and (AS-3 (Antistatic layer coating solution is (as-
3))) and (AS-4 (the antistatic layer is (as-
4))) and the antistatic layers (AS-1) and (AS-
2) On (AS-3) or (AS-4), as shown in Table 1, the slippery layer (W-1) and (W-2 (coating solution for slippery layer (w-2)) )) And (W-3 (the coating liquid for the slippery layer is (w
-3))) and (W-4 (the coating solution for the slippery layer is (w-
4))) and (W-5 (the coating solution for the slippery layer is (w-
5))) and (W-6 (the coating solution for the slippery layer is (w-
6))) or (W-7 (the coating solution for the slippery layer is (w-
7) A silver halide photographic light-sensitive material was produced in the same manner as in Example 1 except that each was changed by providing (1) and (2).

Example 11 One surface of a polyethylene-2,6-naphthalate film support was subjected to a corona discharge of 8 w / m ² · min. 1 μm and dried at 140 ° C. to form an undercoat layer U-6.
Corona discharge 8w / m ² · min over, and applied so that the undercoat layer upper coating solution (u-8) in a dry thickness of 0.8 [mu] m, dried at 130 ° C., the other support 8w / m ^{2 on} the surface of
・ The undercoat layer coating liquid (u-5) was applied so as to have a thickness of 0.1 μm and dried at 140 ° C. to form an undercoat layer upper layer (U-5). 8w / on U-5
m ² · m of corona discharge, and further, an undercoat layer upper layer coating solution (u-7) is applied so as to have a thickness of 0.1 μm;
It dried at 0 degreeC, and the undercoat layer upper layer U-7 was formed. An antistatic layer coating solution (as-1) was applied onto U-8 at a concentration of 15 ml / m ² and dried at 120 ° C. for 3 minutes to form an antistatic layer (AS-1). 30 mg of polyvinyl alcohol in the slippery layer coating solution (w-1) on AS-1
/ M ² and dried at 100 ° C. for 5 minutes to form a slippery layer (W-1). Further, a silver halide emulsion layer and the like were coated on U-7 in the same manner as in Example 1, and dried to prepare a silver halide color photographic light-sensitive material.

Example 12 and Comparative Example 3 In Example 12, the undercoat layer (U-8) on the back layer side was not applied.
2), and in Example 12 and Comparative Example 3, (AS-
Halogenation was performed in the same manner as in Example 11 except that coating liquids (W-5) and (W-7) for the slippery layer were provided as shown in Table 1 on 2) and (AS-1), respectively. A silver photographic light-sensitive material was prepared.

[0215]

[Table 1]

[Evaluation of slippery support and silver halide color photographic light-sensitive material] For each sample of the silver halide color photographic light-sensitive material prepared as described above, scratch resistance, water resistance, transferability and running stability were evaluated. The properties, blocking properties, bleed-out, coating properties, stain resistance, kinetic friction coefficient, conductivity, adhesiveness, etc. were tested and evaluated. The results are shown in Table 2.

The development was carried out as follows.

[Development processing] The produced silver halide photographic light-sensitive material was developed according to the following processing steps.

Processing step Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fix 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 05 seconds Processing solutions used in each step The composition was as follows.

<Color Developer> Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethyl) amino-2-methylaniline sulfate 4.5 g Water is added to 1 liter, and the pH is adjusted to 10.0.

<Bleaching solution> Ferric ammonium ethylenediaminetetraacetate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to 1 liter to adjust the pH to 6.0. .

<Fixing Solution> Disodium ethylenediaminetetraacetate 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 g Sodium bisulfite 4.6 g Water is added to 1 liter to adjust the pH to 6.6.

<Stable Liquid> Formalin (40%) 2.0 mg Polyoxyethylene-p-nonylphenyl ether (average degree of polymerization: 10) 0.3 g Water was added to make 1 liter.

[0224]

[Table 2]

(Results) As can be seen from Table 2, the polyvinyl alcohol having a saponification degree of 96 mol% or more of the present invention was used in an amount of 40%.
The slippery layer support and the silver halide photographic material coated with the slippery layer coating solution using a coating solution dissolved at 20 ° C. or more and kept at 20 to 35 ° C. have the following characteristics. Had. That is, it was found that the film had excellent abrasion resistance, a film having strong water resistance, was hardly stained, had a suitable sliding property and strong adhesiveness, and did not deteriorate even after development. On the other hand, it was revealed that the comparative sample prepared with polyvinyl alcohol having a degree of saponification of less than 96 mol% was inferior in the above items except for the applicability.

Example 13 An antistatic layer coating solution (as-1) was applied to one surface of a cellulose triacetate film support at a concentration of 15 ml / m ² , dried at 120 ° C. for 3 minutes, and dried. (AS-1) was formed. An intermediate layer coating solution (md-1) was applied on AS-1 to a concentration of 25 ml / m ² ,
Drying was performed at 00 ° C. for 3 minutes to form an intermediate layer (MD-1). Further, a protective layer coating solution (pr
-1) was set to 30 ° C., and the polyvinyl alcohol in the coating was applied at 30 mg / m ² and dried at 100 ° C. for 5 minutes to form a protective layer (PR-1).

On the cellulose triacetate film support on the side opposite to the slippery layer side, a corona discharge treatment and an ultraviolet irradiation treatment were carried out, and the undercoat layer coating solution (u-2) was applied for 15 m.
It was coated so as to have a concentration of 1 mg / m ² to give a subbing layer (U-2) of a silver halide emulsion layer.

A silver halide color emulsion photosensitive layer and the like were provided on the undercoat layer (U-2) in the same manner as in Example 1 to produce a silver halide multilayer color photographic photosensitive material.

Comparative Example 4 A protective layer was prepared using (PR-6 (protective layer coating solution: (pr-6)))
A silver halide photographic light-sensitive material was produced in the same manner as in Example 13 except that the above was changed.

Examples 14 to 17 and Comparative Example 5 In Examples 14, 16 and 17, the undercoat layer (U-layer) was formed on one surface of the cellulose triacetate film support.
3), and in Example 16 and Comparative Example 5, an undercoat layer (U-4) was provided, and as shown in Table 3, an antistatic layer (U-4) or (U-4) AS-1),
(AS-2), (AS-3) or (AS-4) is provided, and a protective layer (PR-2),
(PR-3), (PR-4), (PR-5) or (P
Example 1 except that R-7) was provided and changed as shown in Table 3.
In the same manner as in Example 3, a silver halide photographic light-sensitive material was prepared.

[0231]

[Table 3]

The evaluations shown in Table 4 were performed on Examples 13 to 17 and Comparative Examples 4 and 5, and the results are shown in Table 4.

[0233]

[Table 4]

(Results) As can be seen from Table 4, the polyvinyl alcohol having a saponification degree of 96 mol% or more of the present invention was used in an amount of 40%.
A silver halide photographic light-sensitive material having a protective layer coated with a protective layer coating solution using a coating solution dissolved at a temperature of 20 ° C. or higher and maintained at 20 to 35 ° C. had the following characteristics. That is, it was found that the protective film had scratch resistance and water resistance, was hardly stained, and had excellent adhesion.

[0235]

As described above, the present invention provides a silver halide photographic light-sensitive material having a slippery layer having excellent scratch resistance, running stability, blocking resistance, bleed-out resistance of a slipping agent, coating property, and stain resistance. I can do it.

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Claims (21)

[Claims] 1. A step of heating polyvinyl alcohol having a degree of saponification of 96 mol% or more and dissolving it in water at a temperature of 40 ° C. or higher to form a polyvinyl alcohol solution; dispersing a slip agent in water to form a slip agent dispersion; A method for preparing a slippery layer coating solution, which is prepared through a step of mixing an alcohol solution and a slip agent dispersion. 2. The method according to claim 1, wherein the temperature at which the polyvinyl alcohol is dissolved is 60 ° C. or higher. 3. The poly (vinyl alcohol) is 98 mol%.
3. The method for preparing a coating solution for a slippery layer according to claim 1, wherein the coating liquid has the above-mentioned degree of saponification. 4. The method according to claim 1, wherein the polyvinyl alcohol is 99 mol%.
4. The method for preparing a coating liquid for a slippery layer according to claim 3, wherein the coating liquid has the above-mentioned degree of saponification. 5. The method according to claim 1, wherein the polyvinyl alcohol has a degree of polymerization of 400 or more. 6. The method according to claim 5, wherein the polyvinyl alcohol has a polymerization degree of 900 or more. 7. The coating liquid for a slippery layer according to claim 1, wherein the slipping agent contains an ester of a higher aliphatic carboxylic acid and a higher aliphatic alcohol. Preparation method. 8. A coating liquid for a slippery layer, prepared by the method according to claim 1. Description: 9. The coating liquid for a slippery layer according to claim 8,
After maintaining the temperature in the range of ~ 35 ° C, applying the coating solution for the slippery layer on the support as a layer furthest from the support at a temperature in the range. How to make the body. 10. The coating solution for a slippery layer has a degree of saponification of 96 mol%.
The method for producing a slippery support according to claim 9, comprising polyvinyl alcohol having a degree of polymerization of less than 400 and a degree of polymerization of 400 or more. 11. The slipperiness according to claim 9, wherein the polyvinyl alcohol contained in the slippery layer coating solution is applied in a range of 0.5 to 80 mg / m ² . A method for producing a support. 12. A slippery layer is provided on one or more constituent layers of the support produced by the method according to claim 9 or 11 on the layer farthest from the support. And a slippery support. 13. The slippery support according to claim 12, wherein at least one of the constituent layers between the slippery layer and the support is an antistatic layer. 14. At least one of the constituent layers has a particle having an average primary particle diameter of 0.4 μm or less and a Mohs hardness of 6 or more, and an average primary particle diameter of 0.5 μm or more and a Mohs hardness of 5 or more.
The slippery support according to claim 12 or 13, comprising the following particles. 15. The slippery support according to any one of claims 12 to 14, wherein the support is a polyester film or a cellulose ester film. 16. A silver halide emulsion comprising a silver halide emulsion layer on the surface of the slippery support according to claim 12 opposite to the side of the slippery layer. Photosensitive material. 17. On a support, a degree of saponification of 96 mol% or more,
A silver halide photographic material comprising a layer containing polyvinyl alcohol having a degree of polymerization of 400 or more. 18. The silver halide photographic material according to claim 17, wherein the degree of saponification of the polyvinyl alcohol is 98 mol% or more. 19. The silver halide photographic material according to claim 18, wherein the degree of saponification of the polyvinyl alcohol is 99 mol% or more. 20. The method according to claim 17, wherein the degree of polymerization of the polyvinyl alcohol is 900 or more.
6. The silver halide photographic light-sensitive material according to any one of the above. 21. The layer according to claim 17, wherein the layer containing polyvinyl alcohol contains polyvinyl alcohol having a degree of saponification of less than 96 mol% and a degree of polymerization of 400 or more. Silver halide photographic material.