JPH05197081A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve coatability and to obtain a sufficient antistatic property even at a low temp. by incorporating a fluorine-contained polymer derived from a polymerizable hydrophobic fluorine-contained polymer and a polymerizable hydrophilic monomer into the above material. CONSTITUTION:This photographic sensitive material contains the fluorine- contained polymer derived from the polymerizable hydrophobic fluorine-contained monomer having a metal oxide sol and at least one piece of fluorine atoms and the polymerizable hydrophilic monomer in at least one layer of its constituting layers. The examples of the preferable metals of the metal oxide in such a case are Al, Zn, Ti, Sn, In, W and Y. The above-mentioned metal oxide sol is formed by a process for production consisting in hydrolyzing the alkoxide of the metal. The polymerizable hydrophobic fluorine-contained polymer having at least one piece of the fluorine atoms as the fluorine-contained polymer is selected by polymn. types and is preferably an addition polymerized monomer having an ethylenic unsatd. group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material having excellent coating properties and improved antistatic properties.

[0002]

2. Description of the Related Art A photographic light-sensitive material generally comprises a support having an electric insulation property and a photographic constituent layer such as a photographic emulsion layer, an intermediate layer, a filter layer, a protective layer, a subbing layer and a back surface layer, and the production thereof. During or during use, the photographic light-sensitive materials are charged with each other by friction or peeling between the photographic light-sensitive materials or other substances, and when this is discharged, the photographic light-sensitive layer is exposed to light to generate static marks after development, dust, etc. Foreign matter is attracted and adheres, causing various charging problems. Conventionally, various methods are known as techniques for preventing such troubles. As one of well-known and utilized methods, there is known a method of applying a layer containing an inorganic metal oxide sol dispersion to a support constituting a photographic light-sensitive material.

However, in the case of applying a liquid in which a metal oxide sol is dispersed, agglomeration / precipitation easily occurs during coating and drying, and coating defects such as cissing and unevenness occur, and the coating of the antistatic layer is weak, and scratch resistance, There are problems such as poor adhesion resistance.

In order to prevent such coating failure and improve the coating property, a method of adding a solvent having a relatively high boiling point to the coating system has been attempted, but it is not possible to completely prevent coagulation / precipitation and is sufficient. Not a solution.

Further, a method of preventing a coating failure by using a surfactant is common, but US Pat. Nos. 2,240,476 and 3,0
26,202, 3,068,101, 3,220,847, 3,415,64
The low-molecular-weight activator disclosed in No. 9 or the like is used in a large amount in order to obtain the effect, and is deposited on the surface of the coating layer or sticks between the emulsion surface of the photographic light-sensitive material and the back layer. Further, there have been raised the problems that the photographic characteristics are adversely affected such as deterioration of sensitivity and occurrence of fog.

On the other hand, in JP-A-54-158222 and JP-A-60-210613, a fluorine-containing polymer is used as an antistatic agent, but the antistatic effect is insufficient, and it is particularly satisfactory under low humidity conditions. However, if used in a large amount in order to enhance the antistatic effect, the sensitivity is lowered and fog is generated, which adversely affects the photographic characteristics, and it is difficult to use these polymers in photographic light-sensitive materials.

The present inventors have earnestly studied in order to obtain a photographic light-sensitive material excellent in coating property, improved in antistatic effect, and overcome adverse effects on photographic characteristics. As a result, a fluorine-containing polymer was used as a metal oxide sol. It has been found that, when applied to a coating system containing, a small amount is effective for coating properties and the antistatic performance of the metal oxide sol can be sufficiently exhibited. This result is
It was completely unexpected from the conventional knowledge that the metal oxide sol and the fluorine-containing polymer were used alone.

[0008]

Therefore, the object of the present invention is to have excellent coating properties and sufficient antistatic properties even at low humidity.
An object is to provide a photographic light-sensitive material that does not adversely affect photographic characteristics.

[0009]

The above object of the present invention is to polymerize a metal oxide sol and a polymerizable hydrophobic fluorine-containing monomer having at least one fluorine atom in at least one of the constituent layers of a photographic light-sensitive material. It is achieved by a photographic light-sensitive material containing a fluorine-containing polymer derived from a hydrophilic monomer.

The present invention will be described in detail below.

Examples of preferable metals of the metal oxide sol used in the present invention are Al, Zn, Ti, Sn, In,
W and Y are preferred, and Al, Ti, Sn, In and Y are particularly preferred.

The method for producing the metal oxide sol used in the present invention is a chemical synthesis method such as a method of hydrolyzing a metal alkoxide, a method of hydrolyzing a metal chloride in an alkaline aqueous solution, and the like. Although there is a method of melting a metal oxide and quenching it in water, a method of hydrolyzing a metal chloride is preferable.

The average particle size of the metal oxide sol used in the present invention is preferably 100 nm or less, particularly preferably 50 nm or less.

The coating amount is preferably 5 to 500 mg, and more preferably 10 to ²⁰⁰ mg per 1 m ² .

The metal oxide sol used in the present invention may contain a different metal element. The different metal elements include Al, Ga, In, Sn, Sb, Tl, V, Nb, Ta and A.
g, Bi and the like are preferable, but In, Sn and S are particularly preferable.
b, Nb, Ag, etc.

The content of the different metal element is preferably 1 to 25% by weight, and more preferably 3 to 20% by weight.

The metal oxide of the present invention may contain an electrolyte, and examples of the electrolyte include an inorganic acid (eg hydrochloric acid, nitric acid etc.), a carboxylic acid (eg formic acid, acetic acid, propionic acid etc.) and an aromatic carboxylic acid. Examples thereof include organic acids (eg, cinnamic acid), alkali metal hydroxides, and salts (eg, sodium chloride, sodium acetate, etc.), and among these, inorganic acids and carboxylic acids are preferable.

A layer containing the metal oxide sol of the present invention may be applied together with a binder.

Any polymer can be used as the binder as long as it is a polymer used for ordinary coating. For example, gelatin, modified gelatin, polyvinyl alcohol, vinyl alcohol copolymer, carboxymethyl cellulose, polyacrylic acid, acrylic acid copolymer. Coalescing,
Water-soluble polymers such as polyvinylpyrrolidone, vinylpyrrolidone copolymer, hydroxyethyl acrylate copolymer, diacetylcellulose, triacetylcellulose, nitrocellulose, acetylbutylcellulose, acetylpropylcellulose, phthaloxyacetylcellulose and other cellulose derivatives, styrene , Α-methylstyrene, hydroxystyrene, vinyl acetate, alkyl (alkyl group having 1 to 4 carbon atoms) acrylate, alkyl (alkyl group having 1 to 4 carbon atoms) methacrylate, vinyl chloride, homopolymer such as vinylidene chloride And these monomer-containing copolymers, maleic anhydride-containing copolymers, soluble nylon, soluble polyester, polyvinyl formal, polyvinyl acetal,
Examples thereof include acetals such as polyvinyl penzal, polyurethane, and the like.

When coating the metal oxide sol, additives such as a matting agent, a slipping agent and a cross-linking agent and a surfactant other than the present invention may be contained in addition to the binder, if necessary.

As the active agents other than the present invention, natural surface active agents such as saponin, nonionic surface active agents such as alkylene oxide type, glycerin type and glycidol type, carboxylic acid, sulfonic acid, phosphoric acid, sulfuric ester, phosphoric acid. Examples include anionic surfactants containing an acidic group such as ester.

As the cross-linking agent, a so-called hardener for photographic gelatin, for example, aldehyde compounds such as formaldehyde and glyoxal, mucochloric acid, tetramethylene, etc.
-1,4-bis (ethylene urea), hexamethylene-1,6-bis
Compounds having an ethyleneimine group such as (ethyleneurea), methanesulfonic acid esters such as trimethylene-1,3-bismethanesulfonic acid ester, bisacryloylurea, active vinyl compounds such as methaxylenevinylsulfonic acid, 2-methoxy- 4,6-dichlorotriazine, 2-hydroxy-4,6-dichlorotriazine sodium salt and other compounds having active halogen, bisphenol glycidyl ether and other epoxy group-containing compounds, isocyanate carboxyl group active type compounds and epoxy compounds, etc. Can be used. Among these, a compound having an ethyleneimine group, a methanesulfonic acid ester, an epoxy compound and a compound having an active halogen are particularly preferable.

Water or an organic solvent is used as a solvent for dissolving or dispersing the metal oxide sol of the present invention, but water and an organic solvent may be mixed if necessary. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, methyl cellosolve, ethyl cellosolve, benzene and the like.

Next, the fluorine-containing polymer will be described.

The polymerizable hydrophobic fluorine-containing monomer having at least one fluorine atom is selected according to the polymerization mode, but an addition polymerization monomer having an ethylenically unsaturated group is preferable.

The addition-polymerizable fluorine-containing monomer having an ethylenically unsaturated group is preferably a monomer represented by the following general formula [I].

[0027]

[Chemical 1]

In the formula, R ¹ represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms.

Rf represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group or an alkylaryl group in which at least one hydrogen atom is replaced by a fluorine atom.

X is of the general formula-(R) m-L- or -L- (R) m.
Represents a divalent linking group represented by-. Where R is 1 carbon
~ 10 represents an alkylene group, an arylene group or an aralkylene group, -L- is -O- group, -S- group, -NR ² -group, -C.
O- group, -OCO- group, -SCO- group, -CONR ² - group, -SO ₂ -
Represents a group, —NR ² SO ₂ — group, —SO ₂ NR ² — group, and —SO— group.
(Here, R ² represents an alkyl group having 1 to 4 carbon atoms.) M is 0 or 1.

L is an integer of 0 to 4, preferably 0 or 1.

In the general formula [I], R ¹ is more preferably a hydrogen atom or a methyl group.

Rf represents an alkyl group, an aralkyl group, an aryl group or an alkylaryl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in which at least one hydrogen atom is substituted with a fluorine atom, and among them, a perfluoromethyl group , Perfluoroethyl group, perfluoropropyl group, perfluorohexyl group, perfluorooctyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,4,4,5,5- Octafluoroamyl group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroputyl group, 2,2,2-trifluoroethyl group, 2,2,3 , 3,4,4,4-
Heptafluorobutyl group, 1,1,1,3,3,3-hexafluoro
-2-propyl group, 1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl group, 1,1,2,2-tetrafluoro-2-hydroxyethyl group, p-fluoro Phenyl group, p-trifluoromethylphenyl group, 2,3,4,5,6-pentatrifluoromethylphenyl group and the like are preferable.

Examples of the monomer represented by the general formula [I] are shown below, but the present invention is not limited thereto.

[0035]

[Chemical 2]

[0036]

[Chemical 3]

Like the hydrophobic fluorine-containing monomer, the polymerizable hydrophilic monomer is selected according to the polymerization method, but an addition polymerization monomer having an ethylenically unsaturated group is preferable.

The hydrophilic monomer having an ethylenically unsaturated group and capable of addition polymerization is, for example, acrolein, acrylimide, methacrylimide, N-methylolacrylamide,
N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminopropyl acrylamide, hydroxyethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, poly
(Ethyloxy) acrylate, poly (ethyloxy) methacrylate, 2-vinylpyridine, 4-vinylpyridine, 1-
Nonionic monomers typified by vinyl-2-pyrrolidone, 1-vinylimidazole, 1-vinyl-2-methylimidazole, vinylbenzyltrimethylammonium salt,
Cationic monomers such as vinylbenzyltriethylammonium salt, vinylbenzyltripropylammonium salt, vinylbenzyldimethylamine hydrochloride, methacryloxyethyldimethylethylammonium salt, N, N-dimethylaminoethylmethacrylate hydrochloride, acrylic Examples thereof include anionic monomers represented by acids, methacrylic acid, maleic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like, or salts thereof, but are not limited thereto. ..

The fluorine-containing polymer used in the present invention is exemplified, but the present invention is not limited thereto.

[0040]

[Chemical 4]

[0041]

[Chemical 5]

The added layer of the metal oxide sol and the fluorine-containing polymer is preferably a layer other than the silver halide emulsion layer, for example, a surface protective layer, an intermediate layer, an undercoat layer or a back layer.

When the back layer is composed of two or more layers, any of the layers may be used, but the outermost surface layer of the back layer is more preferable.

[0044] The amount of fluorine-containing polymer according to the present invention is preferably photosensitive material 1 m ² per 0.01～3.0Mg, particularly 0.0
5-2.0 mg is preferred.

The method for adding the fluorine-containing polymer of the present invention to a layer of a photographic light-sensitive material is water, an organic solvent (for example, methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dioxane, dimethylformamide, formamide, dimethyl sulfoxide). , Methyl cellosolve, ethyl cellosolve, etc.), or a mixed solvent thereof, and the mixture is dissolved and then contained in the photographic constituent layer.

The support of the photographic light-sensitive material to which the metal oxide sol and the fluorine-containing polymer of the present invention can be applied is, for example, a polyolefin such as polyethylene; a cellulose derivative such as polystyrene and cellulose triacetate; a film such as polyester such as polyethylene terephthalate. Alternatively, a substrate made of a sheet in which both surfaces of a baryta paper, a synthetic paper or a paper is coated with these polymer films, and the like, and the like are used.

As the coating method for each of the layer containing the metal oxide sol and the fluorine-containing polymer of the present invention and the layer adjacent to this layer, various known methods such as curtain coating, reverse roll coating and fountain air can be used. Doctor coating, slide hopper coating, extrusion coating,
Dip coating or the like is used.

As the photographic light-sensitive material according to the present invention, a normal black-and-white silver halide light-sensitive material (for example, a black-and-white light-sensitive material for photographing, a black-and-white light-sensitive material for X-ray, a black-and-white light-sensitive material for printing, etc.) is used. Various silver halide light-sensitive materials such as materials (for example, color reversal film, color negative film, color positive film, etc.) can be mentioned.

[0049]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Preparation of metal oxide sol] Stannous chloride aqueous solution (Sn: 1)
6.5%) 1000 parts, antimony trichloride 45 parts and hydrochloric acid (HCl,
100 parts of 34.0%) were mixed and dissolved to prepare a uniform aqueous solution.

This aqueous solution was gradually added to 5,420 parts of an ammonium bicarbonate aqueous solution (NH ₄ HCO ₃ 2.5%) with stirring to obtain a tin antimony oxide gel.

After the produced gel was filtered off, washing and filtration were repeated until chlorine was not found in the gel to obtain a tin antimony oxide gel. To 100 parts of this gel, 42 parts of ammonia water (NH ₃ , 1.0%) and 298 parts of water were added and stirred, and the pH was adjusted to 10.4.
The gel slurry of was prepared and stirred to obtain a tin antimony oxide sol. The pH was 10.0, and the average particle size measured by transmission electron microscopy was 6 nm.

On one side of the cellulose triacetate film support, the following first layer composition was applied in an amount of 20 ml / m ² and dried at 90 ° C. for 3 minutes.

(Composition for the first layer) Antimony tin oxide sol 1.2 g Diacetylcellulose 6 g Acetone 400 ml Water 600 ml Compound of the present invention (shown in Table 1) 20 ml of the following composition for the second layer on the first layer The coating solution was applied at a rate of / m ² and dried at 80 ° C. for 3 minutes.

(Composition for the second layer) Diacetyl cellulose 5 g Acetone 500 ml Ethyl acetate 500 ml Further, a coating solution having the following composition was coated on the above layer so as to be 20 ml / m ² and dried at 95 ° C. for 5 minutes. Sample Nos. 1 to 6 were obtained.

Carnauba wax 8 g Toluene 700 ml Methyl ethyl ketone 300 ml The coating properties of each of the obtained samples were visually evaluated. The results are shown in Table 1.

The sample was conditioned under conditions of 23 ° C. and 20% RH for 24 hours, and under the same conditions, Kawaguchi Denki's teraohm meter VE-30.
Was used to measure the surface resistivity at an applied voltage of 100V. The results are shown in Table 1.

[0058]

[Table 1]

As is clear from Table 1, when the coating was carried out without using the compound of the present invention (Sample No. 6), there was an increase in haze which was thought to be due to aggregation of tin oxide antimony oxide sol. While the coatability is poor and the surface resistivity is poor,
When the compound of the present invention is used (Sample Nos. 2 to 5), the coatability is good, but when a large amount is used (No. 4, 5)
Was found to affect the surface resistivity.

Example 2 The following composition for the first layer was applied to the back surface of a known cellulose triacetate film support coated with a subbing layer at 20 ml / m ² and dried at 90 ° C. for 3 minutes.

(Composition for the first layer) Alumina sol As-100 (manufactured by Nissan Chemical Industries, Ltd.) 7.5 g Diacetyl cellulose 7.5 g Acetone 400 ml Methanol 500 ml Dimethylformamide 100 ml Compound of the present invention (shown in Table 2) The first layer The following composition for the second layer was applied onto the above so as to be 20 ml / m ² and dried at 80 ° C. for 3 minutes.

(Composition for the second layer) Diacetyl cellulose 5g SiO ₂ fine particles (average particle size 3.0 μm) 0.2g Acetone 500ml Ethyl acetate 500ml Next, on the surface opposite to the back surface, a silver halide emulsion is prepared as follows. Layers and protective layers were applied.

Α-pivaloyl-containing yellow coupler containing 300 g of gelatin per mol of silver halide, and
α- (1-benzyl-2,4-dioxyimidazolin-3-yl) -2-
Chloro-5 [γ- (2,4-tert-amylphenoxy) butyramide] acetanilide 2.5 × 10 ^-2 mol and 1,2-bis (vinylsulfonyl) ethane as a hardening agent 1 g of gelatin
A blue-sensitive silver iodobromide (silver iodide content: 7 mol%) emulsion for color containing 0.02 g per gram was prepared. Along with this emulsion, an alkali-soluble matting agent (100 mg / m ² ) having a composition of MMA / MAA = 6/4 and a particle size of 2 to 4 μm was used as a protective layer.
-2-Hexylhexyl sodium sulfosuccinate (coating aid) (0.01 g / m ² ) and a hardener (0.02 g / 1 g gelatin) containing a gelatin solution on the surface having the above-mentioned subbing layer from the support side to halogen. Sample Nos. 6 to 12 were obtained by coating the silver halide emulsion layer and the protective layer in this order.

Evaluation of Samples The backside coatability of each of the obtained samples was visually evaluated.
Further, the sample was conditioned at 23 ° C. and 20% RH for 24 hours, and the surface specific resistance was measured under the same conditions with a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd. at an applied voltage of 100V.

Also, ^two samples each having a size of 5 cm ² are used.
Prepare 23 sheets, 23 ℃ 80% RH so that they do not touch each other.
After storing for 24 hours in the atmosphere of, the non-photosensitive protective layer of the same sample and the outermost surface layer of the back layer are brought into contact with each other, a load of 800 g is applied, and further stored in the atmosphere of 55 ° C 80% RH for 24 hours. After that, the area of the bonded portion when the sample was peeled off was measured, and the adhesion resistance was evaluated.

The evaluation criteria of the adhesion resistance are as follows.

[0067] Next, these unexposed samples were stored at 55 ° C. for 3 days, then subjected to normal wedge exposure, and subjected to the following development processing,
The sensitivity and fog were measured.

The sensitivity value is the deviation from the reference sensitivity value (fog +0.3) expressed in absolute value of logE with reference to the sensitivity of the control sample (Sample No. 12) immediately after coating, Those with no deviation indicate that the photographic performance is not affected.

Development process (38 ° C.) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry each The composition of the processing liquid used in the processing step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter.

[Bleach] Ethylenediaminetetraacetic acid ammonium ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water was added to make 1 liter, and the pH was adjusted with ammonia water.
Adjust to 6.0.

[Fixing Solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 m
l Conidax (Konica) 7.5m
l Add water to make 1 liter.

Table 2 shows the backside coating properties, surface resistivity, adhesion resistance, fog of stored samples, sensitivity and the like.

[0075]

[Table 2]

As is clear from Table 2, when the coating was carried out without using the compound of the present invention (Sample No. 12), there was an increase in haze, which is thought to be due to agglomeration of the alumina sol, and the coating properties were poor. The surface resistivity at low humidity is inferior, whereas when the compound of the present invention is used in an appropriate amount (Sample Nos. 7 to 9), the coatability is good, the surface resistivity at low humidity is excellent, and the compound does not form an emulsion protective layer. It was found that the adhesion resistance was also good and did not adversely affect the photographic characteristics. On the other hand, it was found that when a large amount of the compound of the present invention was used (Sample Nos. 10 and 11), the adhesion resistance was deteriorated and the photographic characteristics were adversely affected.

[0077]

According to the present invention, it is possible to provide a photographic light-sensitive material which is excellent in coating property, has sufficient antistatic property even at low humidity, and has no adverse effect on photographic characteristics.

[Procedure amendment]

[Submission date] January 29, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

The average particle size of the metal oxide sol used in the present invention is preferably 100 nm or less, particularly preferably 50 nm or less. Regarding particle size
For particle size distribution measurement by sedimentation method, laser diffraction method, etc.
It is preferable to adopt the average particle diameter obtained by
However, the particle size may be determined by an electron micrograph. Shi
If a scanning electron microscope is used, the
Adopt the shortest diameter of the child.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

The hydrophilic monomer of the present invention means water at 20 ° C.
It is a monomer having a solubility of 1 wt% or more. Similar to the hydrophobic fluorine-containing monomer, the polymerizable hydrophilic monomer is selected according to the polymerization mode, but an addition polymerization monomer having an ethylenically unsaturated group is preferable.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

The hydrophilic monomer having an ethylenically unsaturated group and capable of addition polymerization is, for example, acrolein, acrylimide, methacrylimide, N-methylolacrylamide,
N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminopropyl acrylamide, hydroxyethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, poly
(Ethylene alkyleneoxy) acrylate, poly (ethylene alkyleneoxy)
Methacrylate, (Polyethyleneoxypropylene Oki
Si) acrylate, (polyethyleneoxypropylene
Xy) methacrylate, 2-vinylpyridine, 4-vinylpyridine, 1-vinyl-2-pyrrolidone, 1-vinylimidazole, 1-vinyl-2-methylimidazole, and other nonionic monomers, vinylbenzyltrimethylammonium Salt, vinylbenzyltriethylammonium salt,
Cationic monomers represented by vinylbenzyltripropylammonium salt, vinylbenzyldimethylamine hydrochloride, methacryloxyethyldimethylethylammonium salt, N, N-dimethylaminoethylmethacrylate hydrochloride, acrylic acid, methacrylic acid, maleic acid. acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc., or is anionic monomer represented by these salts, and the like, but is not limited thereto.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

The fluorine-containing polymer used in the present invention is exemplified, but the present invention is not limited thereto. Na
Fluorine-containing copolymer monomer in fluorine-containing polymer
The polymerization ratio is 5 to 70% (mol%), preferably 10 to
50%. Further, the weight average content of the fluorine-containing polymer of the present invention
The amount of child should be 3,000 or more, but preferably 5,000 or more 5
It is less than 0,000.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

When the back layer is composed of two or more layers, any of them may be used.

Claims (1)

[Claims] 1. A fluorine-containing derivative derived from a polymerizable hydrophobic fluorine-containing monomer having a metal oxide sol and at least one fluorine atom in at least one of the constituent layers of a photographic light-sensitive material and a polymerizable hydrophilic monomer. A photographic light-sensitive material containing a polymer.