JPH0519412A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material which is hardly curled in preservation and development and having a sufficient antistatic effect by incorporating a specified anionic cross-linked polymer dispersion. CONSTITUTION:At least one photosensitive silver halide emulsion layer is provided on a substrate, and an anionic cross-linked polymer dispersion shown by formula I is incorporated. In the formula, A is a repeating unit obtained by copolymerizing at least two cross-linkable monomers having a copolymerizable ethylenically unsaturated group, B is a repeating unit obtained by copolymerizing the homopolymer and a monomer shown by formula II having a clouding point in an aq. soln., D is a repeating unit obtained by copolymerizing the copolymerizable ethylenically unsaturated monomers other than the above- mentioned monomers, R<1> is hydrogen atom, lower alkyls, etc., L is a 2 to 4-valence connecting group, M is hydrogen atom or cation, m is 0 or 1, n is 1, 2 or 3, w to z are the weight percentage of the respective monomer components, R<2> is hydrogen atom or lower alkyls, and R<3> and R<4> are hydrogen atom and 1-8C alkyls.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which an antistatic agent has improved antistatic ability, curl before and after processing and surface properties after processing. .

[0002]

BACKGROUND OF THE INVENTION Since a photographic light-sensitive material generally comprises a support having an electrically insulating property and a photographic layer, contact friction or peeling between the surface of the same kind or different kinds of materials is caused during the manufacturing process of the photographic light-sensitive material and during use. Electrostatic charges are often accumulated by receiving them. This accumulated electrostatic charge causes many obstacles, but the most serious obstacle is when the photosensitive emulsion layer is exposed by developing the photographic film by discharging the accumulated electrostatic charge before the development processing. It is the formation of spotted spots or dendritic or feather-like line spots.

This is a so-called static mark, which significantly impairs the commercial value of the photographic film and, in some cases, completely loses the commercial value. This phenomenon becomes apparent only after development, and is one of the very troublesome problems. Further, these accumulated electrostatic charges may cause a secondary failure such as dust adhering to the film surface before or after the treatment, or non-uniform coating.

As described above, such electrostatic charges are often accumulated during the manufacture and use of the photographic light-sensitive material. For example, in the manufacturing process, contact friction between the photographic film and the roller or winding or winding of the photographic film. It is caused by peeling of the support surface and the emulsion surface during the returning process. Or, it may be caused by contact peeling between the mechanical part of the X-ray film in the automatic photographing device or the fluorescent intensifying screen. It is also generated by contact with other packaging materials.

The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases. In particular, in recent years, the occurrence of static marks has become more likely due to the increased sensitivity of photographic light-sensitive materials and the increased opportunities for severe handling such as high-speed coating, high-speed photography, and high-speed automatic development processing. .

In order to eliminate these troubles due to static electricity, it is preferable to add an antistatic agent to the photographic light-sensitive material. However, as the antistatic agent that can be used in the photographic light-sensitive material, the antistatic agent generally used in other fields cannot be used as it is, and is subject to various restrictions peculiar to the photographic light-sensitive material.

That is, an antistatic agent that can be used in a photographic light-sensitive material has excellent antistatic properties and does not adversely affect photographic characteristics such as sensitivity, fog, graininess and sharpness of the photographic light-sensitive material. That the film strength of the photographic light-sensitive material is not adversely affected (that is, it is not easily scratched by friction or scratching) and that the adhesion resistance is not adversely affected (that is, the surface of the photographic light-sensitive material or other It does not easily stick to the surface of the substance), does not accelerate the fatigue of the processing solution of the photographic light-sensitive material, does not reduce the adhesive strength between the constituent layers of the photographic light-sensitive material, and so on. The application of antistatic agents is subject to numerous restrictions.

One method for eliminating the damage caused by static electricity is to increase the electric conductivity of the surface of the photosensitive material so that the electrostatic charges can be dissipated in a short time before the accumulated charges are discharged. Therefore, conventionally, a method of improving the conductivity of the support of the photographic light-sensitive material and various coated surface layers has been considered, and the use of an ionic polymer has been tried as one of them.

For example, Japanese Examined Patent Publication Nos. 57-53587 and 5;
7-15375, West German Patent No. 1,745,061
No. 49-23827 and 55-14415.
No. 55-15267, JP-A-48-89979.
U.S. Pat. Nos. 2,279,410 and 3,79.
No. 1,831 and Japanese Patent Publication No. 47-28937 disclose an attempt to utilize a (anionic) polymer having a carboxyl group for antistatic of a photographic light-sensitive material.

However, these polymers are water-soluble, and when a silver halide photographic light-sensitive material to which these polymers are added in an amount sufficient to obtain the necessary antistatic property is subjected to development processing, the )) Elution into the development processing solution causes accumulation in the development processing solution and contaminates the silver halide photographic light-sensitive material to be subsequently developed, or leaves minute elution marks on the surface of the silver halide photographic light-sensitive material. There were problems such as fog on the silver halide photographic light-sensitive material.

Further, there is a problem that these polymers diffuse from the layer of the silver halide photographic light-sensitive material to which these polymers are added to other layers and the antistatic performance is remarkably lowered. .

In order to solve such a problem, several attempts have been made in the past to form an ethylenically unsaturated monomer having an anionic group into a crosslinked latex. For example, U.S. Pat. No. 4,301,240 has the following (a) and (b):
It is disclosed that cross-linking polymerization can be carried out by the above method, and it has become possible to solve the above-mentioned problems relating to a water-soluble anionic polymer.

(A) Acrylic acid or methacrylic acid together with a crosslinking monomer are subjected to water-in-oil type reverse phase emulsion polymerization in the presence of an alkali and an emulsifier to give a dispersion of a crosslinked polymer, and then the dispersion is destroyed. And a method of redispersing the polymer particles in water.

(B) A short-chain aliphatic ester of acrylic acid or methacrylic acid is subjected to an oil-in-water (normal phase) emulsion polymerization in the presence of an emulsifier together with a crosslinking monomer, and then an alkali is added to the acrylic acid or methacrylic acid. A method of saponifying a short-chain aliphatic ester portion of an acid.

However, any of the above methods has the drawback that the manufacturing is troublesome and the manufacturing cost is extremely high. That is, the method (a) requires a large amount of an organic solvent in the reverse phase emulsion polymerization, and further requires an operation of destroying the dispersion and redispersing the polymer particles in water. is there.

On the other hand, in the method (b), it is necessary to continue heating and stirring at high temperature for a long time in order to saponify the short-chain aliphatic ester of acrylic acid or methacrylic acid. According to the examples of said patent (US Pat. No. 4,301,240), 125 ° C.
It requires a long time of 45 hours at a high temperature.

As described above, any of the above methods is difficult to operate, and the manufacturing cost is extremely high. If the production cost of the crosslinked polymer increases, the production cost of the photographic light-sensitive material using the crosslinked polymer also naturally increases, and the value as a product is impaired accordingly. Therefore, there is a strong demand for inexpensive production of the crosslinked polymer.

To solve this problem, Japanese Patent Laid-Open No. 61-29635
In No. 2, a monomer having a carboxyl group (eg acrylic acid, methacrylic acid) together with a crosslinkable monomer,
There is disclosed a means of directly carrying out oil-in-water type (normal phase) emulsion polymerization and neutralizing by addition of an alkali to obtain a crosslinked polymer dispersion. According to this method, the production cost is low, and a polymer having excellent antistatic performance without problems such as film peeling during processing can be obtained.

However, when the above materials are used as an antistatic agent (especially in the layer opposite to the silver halide emulsion layer), the curl of the film after the development processing becomes large,
It has been found that the roller-conveying type automatic developing machine may cause a problem in that the film is broken. To make acrylic acid and methacrylic acid, which are water-soluble monomers, into a crosslinked latex by (normal phase) emulsion polymerization, a large amount of hydrophobic crosslinked monomers is required. Therefore, the latex particles produced are highly crosslinked.

When such a crosslinked anion latex dispersion is applied to the back layer as an antistatic agent, the curl is caused by the development treatment, since the film swelling on the back surface side is significantly smaller than that on the silver halide emulsion layer side. It is considered that (curvature of the film caused by the difference in elongation between the front and back) occurs. The photographic light-sensitive material is required not to curl due to various temperature and humidity changes not only after processing but also during storage of the light-sensitive material. If you take measures such as increasing the amount of gelatin or increasing the hardness of the emulsion layer,
Curls during storage become a problem.

Further, the reduction of the amount of the hydrophobic crosslinking monomer is
Although it has some effect on high swelling and curl prevention of the antistatic agent-containing layer, the amount of the acid component converted into crosslinked particles is reduced, and as a result, the proportion of the water-soluble polymer is increased. It had a drawback that the problems based on the polymer became apparent.

[0022]

SUMMARY OF THE INVENTION The first object of the present invention is to:
Another object of the present invention is to provide a silver halide photographic light-sensitive material which has good curl properties during storage and after development and is sufficiently antistatic. Secondly, an object of the present invention is to provide an antistatic agent which has no problem of scum generation during development processing and elution marks on the surface of the photosensitive material and has good film strength when applied, and a halogen containing the antistatic agent. It is to provide a silver halide photographic light-sensitive material.

A third object of the present invention is to provide an antistatic agent which is easy to manufacture and is inexpensive to manufacture, and a silver halide photographic light-sensitive material containing the antistatic agent.

[0024]

The above object of the present invention is to provide an anion having at least one photosensitive silver halide emulsion layer on a support and having an anion represented by the following general formula [I]. It was achieved by a silver halide photographic light-sensitive material characterized by containing a functional cross-linked polymer dispersion. General formula [I]

[0025]

[Chemical 3]

In the formula, A represents a repeating unit obtained by copolymerizing a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups. B represents a repeating unit obtained by copolymerizing a monomer represented by the following general formula [II] whose homopolymer has a cloud point in an aqueous solution. D represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above.

R ¹ represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a halogen atom. L represents a divalent to tetravalent linking group, and M represents a hydrogen atom or a cation. m represents 0 or 1, and n represents 1, 2 or 3. w,
x, y, and z represent the weight percentage ratio of each monomer component, and w
Is 0, 1 to 60, x is 10 to 70, y is 0 to 30, and z is 25 to 85. Where w + x
+ Y + z = 100. General formula (II)

[0028]

[Chemical 4]

In the formula, R ² represents a hydrogen atom or a lower alkyl group. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted alkyl group. R ² and R ³ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine with each other to form a nitrogen-containing heterocycle with the nitrogen atom.

The compound represented by formula (I) of the present invention will be described in detail below. Examples of the copolymerizable ethylenically unsaturated monomer that gives the repeating unit represented by A include methylenebisacrylamide, ethylenebisacrylamide, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Examples thereof include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, and tetramethylene dimethacrylate. Of these, methylenebisacrylamide, divinylbenzene, and ethylene glycol dimethacrylate are particularly preferable.

B represents a repeating unit derived from a monomer represented by the general formula [II] whose homopolymer has a cloud point in water. Here, the cloud point means that the homopolymer is 1 in distilled water.
This is a phenomenon in which when an aqueous solution formed by being dissolved in wt% is heated, it precipitates from a transparent state at a certain temperature or higher (0 ° C to 100 ° C) and becomes cloudy.

The monomer represented by the general formula [II] will be described in more detail. R ² is a hydrogen atom or a carbon number of 1 to 4.
Represents a lower alkyl group (preferably a methyl group).
R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4), a cycloalkyl group or a substituted alkyl group. Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, a cyclopropyl group, an isopropyl group, an n-butyl group, and a sec-butyl group are preferable.

R ³ and R ⁴ may be bonded to each other to form a nitrogen-containing heterocycle together with a nitrogen atom, and preferable heterocycles include a pyrrolidine ring and a piperidine ring. R ³ and R ⁴ cannot be hydrogen atoms at the same time.

Preferred examples of the monomer represented by the general formula [II] include N-ethylacrylamide, N-methyl-N-ethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide and N-isopropyl. Acrylamide, N-cyclopropylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N
-Acryloyl pyrrolidine, N-acryloyl piperidine, Nn-propyl methacrylamide, N-isopropyl methacrylamide, N-cyclopropyl methacrylamide, etc. can be mentioned. For the cloud point of homopolymers of these monomers, see JSME Proc.
Vol. 104, p.

Next, in the general formula [I]

[0036]

[Chemical 5]

The anionic monomer which gives the repeating unit represented by the following is described below. Examples of R ¹ include a hydrogen atom, an unsubstituted alkyl group such as a methyl group, an ethyl group and an n-propyl group, and a substituted alkyl group such as a carboxymethyl group. Of these, a hydrogen atom, a methyl group or a carboxymethyl group is preferable.

L is a divalent, trivalent or tetravalent linking group,
In the case of a divalent linking group, -Q-

[0039]

[Chemical 6]

Is preferred. Here, Q is a divalent linking group, examples of which include an alkylene group (for example, a methylene group, an ethylene group, and a trimethylene group), an arylene group (for example, a phenylene group), -COO-X- (where X is the number of carbon atoms. 1 to
Represents about 6 alkylene or arylene groups. Hereinafter the same) (e.g. -COOCH ₂ CH ₂ -),

--COO--X--OCO-- (for example, --CO
OCH ₂ CH ₂ OCO-), -OCO-X- (eg-
_{OCOCH 2 CH 2 -), -} OCO-X-COO- ( e.g. _{-OCOCH 2 CH 2 CH 2 CH 2} COO -), -
CONH-X- (e.g. _{-CONH-C 6 H 4 (p} )
-), -CONH-X-NHCO- (for example, -CONH
_{CH 2 CH 2 NHCO -),} - CONH-X-OCO-
(E.g. -CONHCH ₂ CH ₂ OCO-), and the like.

M is 0 or 1. n is 1, 2 or 3. M represents a hydrogen atom or a cation. Examples of the cation include an alkali metal ion (sodium ion, potassium ion), ammonium ion (for example, trimethylammonium ion, triethylammonium ion, tributylammonium ion), and the like, but an alkali metal ion is particularly preferable.

Specific examples of such anionic monomer include acrylic acid, methacrylic acid, itaconic acid, p-vinylbenzoic acid, maleic anhydride,

[0044]

[Chemical 7]

[0045]

[Chemical 8]

And the like. Of these, those soluble in distilled water at room temperature are particularly preferable. Such anionic monomers include acrylic acid, methacrylic acid, itaconic acid,

[0047]

[Chemical 9]

And the like.

Monomers having these anionic groups can be used as salts thereof, for example, alkali metal salts (for example, N
a, K salt) and an ammonium salt (for example, a salt with ammonia, methylamine, dimethylamine, etc.) can be used for the polymerization.

As the ethylenically unsaturated monomer represented by D, a monomer soluble in distilled water at room temperature is preferable. Such monomers include acrylamide,
Acrylamides such as methacrylamide, N-methylacrylamide, N-acryloylmorpholine, N-methacryloylmorpholine and N, N-dimethylacrylamide, N-vinyl cyclic compounds such as N-vinylpyrrolidone and N-vinylcaprolactam,

2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-methoxyethyl acrylate,

[0052]

[Chemical 10]

Esters of acrylic acid or methacrylic acid such as 2-methanesulfonamide ethyl acrylate,
Examples thereof include 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, styrene sulfonate, styrene sulfinate, and other monomers having an anionic functional group other than the -COOH group. Of these, -COO
It is particularly preferable to use one or more monomers having an anionic group other than the H group.

Further, as the ethylenically unsaturated monomer represented by D, a monomer other than the above may be used, and as such a monomer, ethylene, propylene, 1
-Butene, isobutene, styrene, α-methylstyrene, vinyl ketone, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate, allyl acetate), esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids

(For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-
Examples include hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (eg acrylonitrile), dienes (eg butadiene, isoprene) and the like.

W, x, y and z represent weight percentage ratios of the respective monomer components, w is 0, 1 to 60, preferably 0.
5 to 40, particularly preferably 1 to 20, x
Is 10 to 70, preferably 20 to 60, particularly preferably 25 to 55, and y is 0 to 30, preferably 0.5 to 25, particularly preferably 1 to 2
0 and z is 25 to 85, preferably 30 to 75, particularly preferably 35 to 70.

In the polymer represented by the general formula [I] of the present invention, it is preferable that 80% by weight or more of all the constituent components are repeating units derived from a water-soluble monomer.

The method for producing the polymer dispersion represented by the general formula [I] of the present invention will be described below.

The compound represented by the general formula [I] of the present invention is a copolymerizable monomer generally containing at least two ethylenically unsaturated groups represented by the above A, and a monomer represented by the general formula [II]. , D, and the ethylenically unsaturated monomer having at least one anionic functional group can be synthesized by using a well-known emulsion polymerization method.

When the anionic functional group in the polymer is used in the form of a salt, the monomer may be polymerized in the form of a salt or a basic compound may be added after the polymerization. It is particularly preferred to add the compound. In the finally obtained polymer dispersion represented by the general formula [I], the proportion of M having a salt structure such as an alkali metal or ammonium ion is preferably 70 to 100 mols based on all -COOM. %.

Since the anionic crosslinked polymer produced has a charge and is present in a relatively stable dispersed state in water, it is often unnecessary to add a surfactant in water, but an auxiliary An activator may be added to stabilize the dispersion state of the anionic crosslinked polymer in water.

As the surfactant to be used, for example, an anionic surfactant (for example, sodium dodecyl sulfate, Triton 770 (commercially available from Rohm & House), a nonionic surfactant (for example, Emarex NP-20).
(Commercially available from Nippon Emulsion)). Also,
Water-soluble polymers such as polyvinyl alcohol and gelatin may be used.

The polymerization reaction is generally a radical polymerization initiator (for example, a combination of potassium persulfate and sodium hydrogen sulfite, commercially available from Wako Pure Chemical Industries under the name V-50).
In the presence of, generally at temperatures of from 30 ° C to about 100 ° C.

The polymerization may be carried out by adding the whole amount of the monomers to be used to a medium (water or a mixed solvent of water and an organic solvent miscible with water-for example, methanol and acetone), or dropping the monomer mixture. It may be carried out, but it is particularly preferred to carry out by dropping.

The surfactants, polymerization initiators, and polymerization methods described above can be carried out with reference to the descriptions in "Experimental Method of Polymer Synthesis" by Takayuki Otsu and Masaetsu Kinoshita (Kagaku Dojin).

Specific examples of the anionic crosslinked polymer dispersion synthesized by the production method of the present invention are shown below, but the present invention is not limited thereto. The copolymerization ratio of each monomer component of the polymer dispersion represents weight percent and M represents mole percent.

[0067]

[Chemical 11]

[0068]

[Chemical 12]

[0069]

[Chemical 13]

[0070]

[Chemical 14]

[0071]

[Chemical 15]

A synthesis example of the crosslinked polymer dispersion of the present invention is shown below. Synthesis Example 1 Synthesis of Exemplified Compound P-1 In a 1 liter three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 6 g (of 3 of Nissan Tracks H-45).
0% aqueous solution),

[0073]

[Chemical 16]

340 ml of distilled water was added and the mixture was heated and stirred at 80 ° C. under a nitrogen stream.

A solution prepared by dissolving 0.7 g of potassium persulfate in 25 ml of distilled water was added, and further 25 g of acrylic acid, 17.5 g of acryloylpiperidine, 2-acrylamido-
5.0 g of 2-methylpropanesulfonic acid soda, 2.5 g of ethylene glycol dimethacrylate, 10 g of distilled water
The solution consisting of was added dropwise over 1 hour. After the dropping, add an aqueous solution of potassium persulfate having the same composition as above,
Further, heating and stirring were continued at 80 ° C. for 3 hours.

After the obtained polymer dispersion was cooled, a solution prepared by dissolving 10.2 g of sodium hydroxide in 50 ml of distilled water was added, and the mixture was stirred at room temperature for 30 minutes and filtered under pressure to give Exemplified compound P-1. 491 g of dispersion were obtained. The polymer obtained had a solid content of 11.7% by weight and a pH =
The solution viscosity at 6.58 and 25 ° C. was 85 cp. Further, the polymer before neutralization was a white dispersion, but it became a transparent liquid by the neutralization.

Synthesis Example 2 Exemplified Compound P-3 6 g of the above Nissan Tracks H-45 was added to a 1 liter three-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
300 ml of distilled water was added, and the mixture was heated and stirred at 90 ° C. under a nitrogen stream.

0.72 g of potassium persulfate was added to 25 ml of distilled water.
Add the melted mixture, and add acrylic acid 22.5
g, N-isopropylacrylamide 20.0 g, 2-
A solution of 5.0 g of sodium acrylamido-2-methylpropanesulfonate, 2.5 g of methylenebisacrylamide and 50 g of distilled water was added dropwise over 1 hour. After the dropping was completed, an aqueous potassium persulfate solution having the same composition as described above was added, and the mixture was further heated and stirred at 90 ° C. for 3 hours.

After the obtained polymer dispersion was cooled, a solution prepared by dissolving 9.1 g of sodium hydroxide in 50 ml of distilled water was added, and the mixture was stirred at room temperature for 30 minutes and filtered under pressure to give Exemplified compound P-3. 465 g of a dispersion are obtained. The polymer obtained had a solid content of 11.4% by weight and a pH =
The solution viscosity at 5.9 and 25 ° C. was 52 cp.
In this case as well, the polymer was a white dispersion before neutralization and changed to a clear liquid after neutralization. Other polymers were also synthesized using the same method.

The anionic crosslinked polymer dispersion represented by the general formula [I] of the present invention may be used alone as an antistatic agent, but the antistatic property, swelling property and the like of the coated film may be adjusted. For the purpose of optimization, for example, Japanese Examined Patent Publication Nos. 57-53587 and 57-15375, West German Patent 1,745,061.
No. 49-23827 and 55-14415.
No. 55-15267, JP-A-48-89979.
U.S. Pat. Nos. 2,279,410 and 3,791,8
31, water-soluble polymers containing a carboxyl group described in JP-B No. 47-28937, US Pat.
40, and anionic latex polymers described in JP-A No. 61-296352 and the like can be used in combination.

When used in combination, the amount added is preferably 0 to 40% in the case of a water-soluble acid polymer, and preferably 0 in the case of a crosslinked anionic latex polymer, based on the compound represented by the general formula [I] of the present invention. Is in the range of up to 95%. It goes without saying that the combined ratio of these changes depending on the structure of each polymer.

The amount of the compound represented by the general formula [I] used in the present invention (the total amount of the antistatic agent when used in combination with a carboxyl group-containing water-soluble polymer or anionic latex polymer) is generally 0.1-2 per 1 m ²
0 g is preferable, and 1-5 g is particularly preferable. The amount of the antistatic agent containing the compound represented by the general formula [I] of the present invention in the antistatic layer is preferably 10 to 90% by weight, and particularly preferably 30 to 90% by weight.
60 wt% is preferable. The amount of gelatin in the antistatic layer is preferably 10 to 90% by weight, and particularly preferably 40 to 70%. The amount of hardener added is 1.0 x 1 per 1 g of gelatin.
0 ^{−5 to} 1.0 × 10 ⁻³ mol is preferable, and particularly 5.0 × 1
0 ^{−5 to} 3.0 × 10 ⁻⁴ mol is preferable.

[0083]

EXAMPLES Examples of the present invention will be described below.

Example 1 A multilayer silver halide color light-sensitive material having a back layer on one side of a cellulose triacetate film support and a layer containing a photosensitive layer on the opposite side was prepared. (Back layer composition) The numbers corresponding to the respective components indicate the coating amount in units of g / m ² . 1st layer Binder: Gelatin 0.45 Coating agent: p-dodecylbenzene sulfonic acid sodium salt 1.6 × 10 ^-3 2nd layer Binder: Gelatin 3.72 Coating agent: p-dodecyl benzene sulfonic acid sodium salt 0.011 Antistatic Agent: described in Table 1. 2.96 Thickener: Sodium polystyrene sulfonate 0.028 Third layer Binder: Gelatin 0.96 Matting agent: Polymethylmethacrylate (average particle size 2.5μ) 0.094 Coating agent: Dioctyl Sodium sulfosuccinate 0.075 Fluorine-containing surfactant 6.4 × 10 ^-3

[0085]

[Chemical 17]

[0086]           Hardener: Bis (vinylsulfonylmethyl)                         Ether 0.20

On the opposite side of the sample coated with the back surface as described above, each layer having the composition shown below was coated in multiple layers.

(Photosensitive layer composition) The numbers corresponding to the respective components are as follows:
The coating amount is shown in units of g / m ^{2 and} , for silver halide, the coating amount in terms of silver is shown. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer)   Black colloidal silver 0.18   Gelatin 1.40

Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.18 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-10 .060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 gelatin 1.04

Third Layer (First Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing Dye I 6.9 × 10 ⁻⁵ Sensitizing Dye II 1.8 × 10 ⁻⁵ Sensitizing Dye III 3.1 × 10 ⁻⁴ EX-2 0.17 EX-10 0.020 EX-14 0.17 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0. 060 gelatin 0.87

Fourth layer (second red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ^-4 EX-2 0.20 EX-3 0.050 EX-10 0.015 EX-14 0.20 EX-15 0.050 U-1 0.070 U-2 0.050 U-3 0. 070 gelatin 1.30

Fifth layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-2 0.097 EX-3 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63

Sixth layer (intermediate layer)   EX-5 0.040   HBS-1 0.020   Gelatin 0.80

Seventh Layer (First Green Sensitive Emulsion Layer) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Sensitizing Dye IV 3.0 × 10 ^-5 Sensitizing Dye V 1.0 × 10 ^-4 Sensitizing Dye VI 3.8 × 10 ⁻⁴ EX-1 0.021 EX-6 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth layer (second green emulsion layer) Emulsion C Silver 0.45 Sensitizing dye IV 2.1 × 10 ⁻⁵ Sensitizing dye V 7.0 × 10 ⁻⁵ Sensitizing dye VI 2.6 × 10 ⁻⁴ EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ⁻³ Gelatin 0.50

Ninth layer (third green-sensitive emulsion layer) Emulsion E Silver 1.20 Sensitizing dye IV 3.5 × 10 ^-5 Sensitizing dye V 8.0 × 10 ^-5 Sensitizing dye VI 3.0 × 10 ^-4 EX-1 0.013 EX-11 0.065 EX-13 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54

Tenth layer (yellow filter layer)   Yellow colloidal silver 0.050   EX-5 0.080   HBS-1 0.030   Gelatin 0.95

Eleventh Layer (First Blue Sensitive Emulsion Layer) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F Silver 0.070 Sensitizing Dye VII 3.5 × 10 ⁻⁴ EX-8 0.042 EX -9 0.72 HBS-1 0.28 Gelatin 1.10

Twelfth layer (second blue-sensitive emulsion layer) Emulsion G Silver 0.45 Sensitizing dye VII 2.1 × 10 ⁻⁴ EX-9 0.15 EX-10 7.0 × 10 ⁻³ HBS-1 0.050 Gelatin 0.78

Thirteenth Layer (Third Blue Sensitive Emulsion Layer) Emulsion H Silver 0.77 Sensitizing Dye VII 2.2 × 10 ⁻⁴ EX-9 0.20 HBS-1 0.070 Gelatin 0.69

14th layer (first protective layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-30 .10 S-1 0.20 Gelatin 1.20

Furthermore, all layers have preservability, processability, pressure resistance,
W-1, W-2, W-3, B-4, B-5, F- for improving antifungal / antibacterial properties, antistatic properties and coating properties.
1, F-2, F-3, F-4, F-5, F-6, F-
7, F-8, F-9, F-10, F-11, F-12,
F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are contained.

[0105]

[Table 1]

[0106]

[Chemical 18]

[0107]

[Chemical 19]

[0108]

[Chemical 20]

[0109]

[Chemical 21]

[0110]

[Chemical formula 22]

[0111]

[Chemical formula 23]

[0112]

[Chemical formula 24]

[0113]

[Chemical 25]

[0114]

[Chemical formula 26]

[0115]

[Chemical 27]

[0116]

[Chemical 28]

[0117]

[Chemical 29]

[0118]

[Chemical 30]

Samples 1 to 3 were prepared by applying multiple layers as described above.
Created 7.

Sample 1 was prepared by replacing the antistatic agent in the back surface second layer with an equal weight of gelatin. Samples 2-7
Was prepared using an antistatic agent as shown in Table-2. Of these, Polymer Examples 1 and 2 are compounds included in the general formula [I] of claim 1. Only Sample 7 was coated with the hardener coating amount reduced to 1/2.

(Determination Method of Antistatic Property) The antistatic property was determined by measuring the surface resistivity and the generation of static marks. The surface resistivity was measured by sandwiching the test piece of the sample with the back side of the film facing up between the electrodes made of brass with an electrode spacing of 0.14 cm and a length of 10 cm (the part in contact with the test piece is made of stainless steel) and made by Takeda Riken. Measure 1-minute value with a total TR8651 type. The static mark generation test was carried out by a method in which the emulsion surface of the unexposed light-sensitive material was faced downward on a rubber sheet, and after pressing with a rubber roller from above, peeling was performed to generate static marks. This was developed and the amount of static marks generated was examined. The humidity control conditions were 25 ° C. and 25% RH for both surface resistivity and static mark measurement tests. The humidity of the test piece was adjusted under the above conditions all day and night. The evaluation of the static mark was performed in three stages: A: no static mark was generated, B: static mark was slightly generated, C: static mark was generated on the entire surface.

(Method for measuring the swelling ratio of the film) After immersing the test piece in a developing solution (developing solution of Example 1) at 38 ° C for 2 minutes, the thickness of the swollen film was measured to determine the swelling ratio of the film. It was calculated by the following formula. Swelling rate = thickness of swollen film / thickness of film before swelling The thickness of the swollen film here is J. Photographic Sciience
20, 205 to 210 (1972).

(Conveyance test using a roller conveying type automatic processor)
The test piece was processed into 2B (120 size), and a transport test was performed using a roller transport type automatic developing machine (QSS-B9L manufactured by Noritsu) which holds the film in the drying zone and has no roller. The evaluation was A, depending on the degree of scratches on the film, B without scratches, scratches C on the edges of the film, and severe folds on the film. It went in three steps.

(Determination of Elution Mark of Antistatic Agent) After the test piece was processed by the processing method (A) described later, a surface condition inspection was performed. Regarding the suitability of elution traces, the following three steps were performed: A: No elution traces were generated B: Elution traces were slightly observed C: Elution traces were all over the surface.

[0125]

[0126] (Color developer) (Unit: g)   Diethylenetriamine pentaacetic acid 1.0   1-hydroxyethylidene-1,1-diphospho     Acid 3.0   Sodium sulfite 4.0   Potassium carbonate 30.0   Potassium bromide 1.4   1.5 ml of potassium iodide   Hydroxylamine sulfate 2.4   4- (N-ethyl-N-β-hydroxyethyl     Amino) -2-methylaniline sulfate 4.5   1.0 liter with water   pH 10.05

[0127] (Bleaching solution) (Unit: g)   Ethylenediaminetetraacetic acid ferric ammonium chloride     Water salt 120.0   Ethylenediaminetetraacetic acid disodium salt 10.0   Ammonium bromide 100.0   Ammonium nitrate 10.0   Bleaching accelerator 0.005 mol

[0128]

[Chemical 31]

[0129]   Ammonia water (27%) 15.0 ml   1.0 liter with water   pH 6.3

[0130] (Bleaching fixer) (Unit: g)   Ethylenediaminetetraacetic acid ferric ammonium chloride     Water salt 50.0   Ethylenediaminetetraacetic acid disodium salt 5.0   Sodium sulfite 12.0   Ammonium thiosulfate aqueous solution (70%) 240.0 ml   Ammonia water (27%) 6.0 ml   1.0 liter with water   pH 7.2

(Washing Solution) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / liter, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 15
0 mg / l was added. The pH of this solution is 6.5
It is in the range of 7.5.

[0132] (Stabilizer) (Unit: g)   Formalin (37%) 2.0 ml   Polyoxyethylene-p-monononylphenyl     Ether (average degree of polymerization 10) 0.3   Ethylenediaminetetraacetic acid disodium salt 0.05   1.0 liter with water   pH 5.0 to 8.0

(Film Strength) The sample piece was immersed in a developing solution at 38 ° C. for 5 minutes, and then 0 to 10 with a sapphire needle having a diameter of 0.5 mm.
The film strength was evaluated based on the magnitude of the load at which scratching was started with a scratch strength meter to which a load of 0 g was continuously applied and scratches began. When measured by this method, if the load at the time when scratches start to be 40 g or more, there is a track record in the market and there is no problem.
If the amount is 20 g or less, it is a problem because it is scratched when passing through a roller-conveying automatic developing machine.

[0134]

[Table 2]

As shown in Table 2, Samples 2 and 3 of the present invention
Has good antistatic properties. Further, since Polymer Examples 1 and 2 have a latex structure, unlike Samples 4 and 5 where Comparative Polymer Examples A and B are desired to be used, the problem of elution marks does not occur at all.
Further, since Samples 2 and 3 have a higher swelling ratio than Sample 6 using Comparative Polymer C, the curl in the drying zone of the processor is small, and no scratches occur in the transport test. On the other hand, since the sample 6 having a small swelling rate strongly curls to the back side in the drying zone, it was caught by the roller at the exit of the drying zone and was broken. Further, although the samples 2 and 3 have a high swelling rate, they have relatively strong film strength. On the other hand, since a material having a small swelling ratio such as Sample 7 is used well, when the swelling ratio is increased by lowering the hardness, the film strength is significantly lowered. From the above, it is clear that the use of the polymer of the present invention is effective in all of antistatic properties, elimination of elution marks, and film strength.

The chemical structural formulas of the compounds used in Table 2 are shown below.

[0137]

[Chemical 32]

(Example 2) Using the back surface coating sample prepared in Example 1, each layer having the composition shown below was multilayer coated on the surface opposite to the back surface coated. Numbers indicate the amount added per m ² .

First layer: antihalation layer   Black colloidal silver 0.25g   Gelatin 1.9g   Ultraviolet absorber U-1 0.04g   UV absorber U-2 0.1g   UV absorber U-3 0.1g   UV absorber U-4 0.1g   UV absorber U-6 0.1g   High boiling organic solvent Oil-1 0.1 g

Second layer: intermediate layer   Gelatin 0.40g   Compound Cpd-D 10 mg   High boiling organic solvent Oil-3 0.1 g   Dye D-4 0.4mg

Third layer: intermediate layer   Surface and internal fogged fine grain silver iodobromide emulsion (average grain size 0.06 μm, fluctuation     Coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g   Gelatin 0.4g

Fourth layer: low-sensitivity red-sensitive emulsion layer   Emulsion A Silver amount 0.2g   Emulsion B Silver amount 0.3g   Gelatin 0.8g   Coupler C-1 0.15g   Coupler C-2 0.05g   Coupler C-9 0.05g   Compound Cpd-D 10 mg   High boiling organic solvent Oil-2 0.1 g

Fifth layer: Medium sensitivity red-sensitive emulsion layer   Emulsion B Silver amount 0.2g   Emulsion C Silver amount 0.3g   Gelatin 0.8g   Coupler C-1 0.2g   Coupler C-2 0.05g   Coupler C-3 0.2g   High boiling organic solvent Oil-2 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer   Emulsion D Silver amount 0.4g   Gelatin 1.1g   Coupler C-1 0.3g   Coupler C-3 0.7g   Additive P-1 0.1 g

Seventh layer: intermediate layer   Gelatin 0.6g   Additive M-1 0.3g   Color mixing inhibitor Cpd-K 2.6 mg   UV absorber U-1 0.1g   UV absorber U-6 0.1g   Dye D-1 0.02g

Eighth layer: intermediate layer   Surface and internal fogged silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 1     6%, AgI content 0.3 mol%) Silver amount 0.02 g   Gelatin 1.0g   Additive P-1 0.2g   Color mixing inhibitor Cpd-J 0.1 g   Color mixing inhibitor Cpd-A 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer   Emulsion E Silver amount 0.3g   Emulsion F Silver amount 0.1g   Emulsion G Silver amount 0.1g   Gelatin 0.5g   Coupler C-7 0.05g   Coupler C-8 0.20g   Compound Cpd-B 0.03 g   Compound Cpd-D 10 mg   Compound Cpd-E 0.02 g   Compound Cpd-F 0.02 g   Compound Cpd-G 0.02 g   Compound Cpd-H 0.02 g   High boiling organic solvent Oil-1 0.1 g   High boiling organic solvent Oil-2 0.1 g

Tenth layer: Medium-speed green-sensitive emulsion layer   Emulsion G Silver amount 0.3g   Emulsion H Silver amount 0.1g   Gelatin 0.6g   Coupler C-7 0.2g   Coupler C-8 0.1g   Compound Cpd-B 0.03 g   Compound Cpd-E 0.02 g   Compound Cpd-F 0.02 g   Compound Cpd-G 0.05 g   Compound Cpd-H 0.05 g   High boiling point organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer   Emulsion I Silver amount 0.5g   Gelatin 1.0g   Coupler C-4 0.3g   Coupler C-8 0.1g   Compound Cpd-B 0.08 g   Compound Cpd-E 0.02 g   Compound Cpd-F 0.02 g   Compound Cpd-G 0.02 g   Compound Cpd-H 0.02 g   High boiling organic solvent Oil-1 0.02 g   High boiling organic solvent Oil-2 0.02 g

Twelfth layer: intermediate layer   Gelatin 0.6g   Dye D-1 0.1g   Dye D-2 0.05g   Dye D-3 0.07g

Thirteenth layer: Yellow filter layer   Yellow colloidal silver Silver amount 0.1g   Gelatin 1.1g   Color mixing inhibitor Cpd-A 0.01 g   High boiling organic solvent Oil-1 0.01 g

14th layer: intermediate layer   Gelatin 0.6g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer   Emulsion J Silver amount 0.4g   Emulsion K Silver amount 0.1g   Emulsion L Silver amount 0.1g   Gelatin 0.8g   Coupler C-5 0.6g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer   Emulsion L Silver amount 0.1g   Emulsion M Silver amount 0.4g   Gelatin 0.9g   Coupler C-5 0.3g   Coupler C-6 0.3g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer   Emulsion N Silver amount 0.4g   Gelatin 1.2g   Coupler C-6 0.7g

Eighteenth layer: First protective layer   Gelatin 0.7g   Ultraviolet absorber U-1 0.04g   UV absorber U-2 0.01g   Ultraviolet absorber U-3 0.03g   UV absorber U-4 0.03g   UV absorber U-5 0.05g   UV absorber U-6 0.05g   High boiling organic solvent Oil-1 0.02 g   Formalin scavenger     Cpd-C 0.2g     Cpd-I 0.4g   Dye D-3 0.05g

19th layer: second protective layer   Colloidal silver Silver amount 0.1 mg   Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%)                                                         Silver amount 0.1g   Gelatin 0.4g

20th layer: third protective layer   Gelatin 0.4g   Polymethylmethacrylate (average particle size 1.5μ) 0.1g   4: 6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ)                                                                 0.1 g   Silicone oil 0.03g   Surfactant W-1 3.0mg   Surfactant W-2 0.03g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. Furthermore, in each layer,
In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3 and W-4 were added. More antiseptic,
Phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added as antifungal agents.

[0160]

[Table 3]

[0161]

[Table 4]

[0162]

[Chemical 33]

[0163]

[Chemical 34]

[0164]

[Chemical 35]

[0165]

[Chemical 36]

[0166]

[Chemical 37]

[0167]

[Chemical 38]

[0168]

[Chemical Formula 39]

[0169]

[Chemical 40]

[0170]

[Chemical 41]

[0171]

[Chemical 42]

[0172]

[Chemical 43]

[0173]

[Chemical 44]

[0174]

[Chemical formula 45]

Sample 12 was prepared by applying multiple layers as described above.
~ 17 were created.

Sample 12 was prepared by replacing the antistatic agent in the second layer of the back surface with an equal weight of gelatin. Sample 13-
No. 18 was prepared using an antistatic agent as shown in Table 5.
For these samples, as in Example 1, the antistatic property,
The swelling rate, the film strength were measured and the processing and transportation test was performed.

The elution traces were treated and evaluated by the treatment methods (B) and (C) described later.

Treatment recipe (B) Treatment process time Temperature Tank capacity Replenishment amount (liter) (ml / m ² ) First development 6 minutes 38 ° C. 12 2200 First washing 2 minutes 38 ° C. 4 7500 Inversion 2 minutes 38 ° C. 4 1100 Color development 6 minutes 38 ° C 12 2200 Adjustment 2 minutes 38 ° C 4 1100 Bleach 6 minutes 38 ° C 12 220 Settlement 4 minutes 38 ° C 8 1100 Second water wash 4 minutes 38 ° C 8 7500 Stability 1 minute 25 ° C 2 1100

The composition of each treatment liquid was as follows. (First developer)                                                   Mother liquor replenisher   Nitrilo-N, N, N-trimethylenephos     Fonic acid / 5 sodium salt 2.0g 2.0g   Sodium sulfite 30g 30g   Hydroquinone / potassium monosulfonate 20g 20g   33 g of potassium carbonate 33 g   1-phenyl-4-methyl-4-hydroxy     Cimethyl-3-pyrazolidone 2.0 g 2.0 g   Potassium bromide 2.5g 1.4g   Potassium thiocyanate 1.2g 1.2g   Potassium iodide 2.0 mg-   Add water 1000ml 1000ml     pH 9.6 9.6 The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Reversal liquid)                                                   Mother liquor replenisher   Nitrilo-N, N, N-Trimethylenephos Same as mother liquor     Phonic acid-5 sodium salt 3.0 g   Stannous chloride / dihydrate 1.0 g   p-aminophenol 0.1 g   Sodium hydroxide 8g   Glacial acetic acid 15 ml   Add water 1000ml     pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Color developer)                                                   Mother liquor replenisher   Nitrilo-N, N, N-trimethylenephos     Fonic acid / 5 sodium salt 2.0g 2.0g   Sodium sulfite 70g 70g   Trisodium phosphate dodecahydrate 36g 36g   Potassium bromide 1.0 g-   Potassium iodide 90mg-   Sodium hydroxide 3.0g 3.0g   Citrazine acid 1.5g 1.5g   N-ethyl- (β-methanesulfonamide     Ethyl) -3-methyl-4-aminoani     Phosphate sulfate 11g 11g   3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g   Add water 1000ml 1000ml     pH 11.80 12.00 The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Preparation liquid)                                                   Mother liquor replenisher   Ethylenediaminetetraacetic acid, disodium salt Same as mother liquor     ・ Dihydrate salt 8.0g   Sodium sulfite 12g   1-thioglycerin 0.4 ml   Add water 1000ml     pH 6.20 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleaching solution)                                                   Mother liquor replenisher   Ethylenediamine tetraacetic acid ・ 2 sodium salt     ・ Dihydrate 2.0 g 4.0 g   Ethylenediaminetetraacetic acid / ferric ammonium     Um ・ dihydrate 120g 240g   Potassium bromide 100g 200g   Ammonium nitrate 10g 20g   Add water 1000ml 1000ml     pH 5.70 5.50 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Fixer)                                                   Mother liquor replenisher   Ammonium thiosulfate 80g Same as mother liquor   Sodium sulfite 5.0g   Sodium bisulfite 5.0g   Add water 1000ml     pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

(Stabilizer)                                                   Mother liquor replenisher   Formalin (37%) 5.0 ml Same as mother liquor   Polyoxyethylene-p-monononylfe     Nyl ether (average degree of polymerization 10) 0.5 ml   Add water 1000ml     without adjusting pH

Treatment recipe (C) Treatment process time Temperature Tank capacity Replenishment amount (liter) (ml / m ² ) First development 6 minutes 38 ° C. 12 2200 First washing 2 minutes 18 ° C. 4 7500 Inversion 2 minutes 38 ° C. 4 1100 Color development 6 minutes 38 ° C 12 2200 Adjustment 2 minutes 38 ° C 4 1100 Bleach 6 minutes 38 ° C 12 220 Settlement 4 minutes 38 ° C 8 1100 Second water wash 4 minutes 18 ° C 8 7500 Stability 1 minute 25 ° C 2 1100

The composition of each processing solution is the same as that of the processing recipe (B).
The results are shown in Table 5.

[0188]

[Table 5]

It was found that Samples 9 and 10 had good antistatic property, swelling ratio, and film strength as in Example 1.
No major curling occurs during processing, and the transport test is also good. Further, in the measurement of the elution trace, a remarkable difference was observed between the comparative compounds A and B under the condition such as the treatment condition (C). This indicates that the present invention has good performance regardless of the magnitude of fluctuations in processing conditions.

[Procedure amendment]

[Submission date] May 15, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] In the formula, A represents a repeating unit obtained by copolymerizing a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups. B represents a repeating unit obtained by copolymerizing a monomer represented by the following general formula [II], whose homopolymer has a cloud point in an aqueous solution. D represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above. R
¹ represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a halogen atom. L represents a divalent to tetravalent linking group, and M represents a hydrogen atom or a cation. m represents 0 or 1, and n represents 1, 2 or 3. w, x, y, z represent the weight percentage ratio of each monomer component, and w is 0.1 to 6
0, x is 10 to 70, y is 0 to 30, z is 25
It takes a value of 85 to 85. Where w + x + y + z = 100
Is. General formula [II]

[Chemical 2] In the formula, R ² represents a hydrogen atom or a lower alkyl group.
R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or a substituted alkyl group. R ³ and R ⁴ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine with each other to form a nitrogen-containing heterocycle with the nitrogen atom.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

[Chemical 3]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

R ¹ represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a halogen atom. L represents a divalent to tetravalent linking group, and M represents a hydrogen atom or a cation. m represents 0 or 1, and n represents 1, 2 or 3. w,
x, y, and z represent the weight percentage ratio of each monomer component, and w
Has a value of 0.1 to 60, x has a value of 10 to 70, y has a value of 0 to 30, and z has a value of 25 to 85. Where w + x
+ Y + z = 100. General formula [II]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

[0036]

[Chemical 5]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

W, x, y and z represent weight percentage ratios of the respective monomer components, w is 0.1 to 60, preferably 0.
5 to 40, particularly preferably 1 to 20, x
Is 10 to 70, preferably 20 to 60, particularly preferably 25 to 55, and y is 0 to 30, preferably 0.5 to 25, particularly preferably 1 to 2
0 and z is 25 to 85, preferably 30 to 75, particularly preferably 35 to 70.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Chemical 15]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0072

[Correction method] Change

[Correction content]

A synthesis example of the crosslinked polymer dispersion of the present invention is shown below. Synthesis Example 1 Synthesis of Exemplified Compound P-1 A 1 liter three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 6 g of Nissan Tracks H-45 (30% aqueous solution of the following compound),

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0137

[Correction method] Change

[Correction content]

[0137]

[Chemical 32]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0160

[Correction method] Change

[Correction content]

[0160]

[Table 3]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0162

[Correction method] Change

[Correction content]

[0162]

[Chemical 33]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0175

[Correction method] Change

[Correction content]

Multilayer coating was performed as described above, and the following Samples 8 to
Twelve created.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0176

[Correction method] Change

[Correction content]

Sample 8 was prepared by replacing the antistatic agent in the second layer on the back surface with an equal weight of gelatin. Samples 9-12
Was prepared using an antistatic agent as shown in Table 5. For these samples, the measurement of the antistatic property, the swelling ratio, the film strength and the processing and transporting test were carried out in the same manner as in Example 1.

Continued front page    (72) Inventor Yuichi Ohashi             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd.

Claims (3)

[Claims] 1. A support comprising at least one photosensitive silver halide emulsion layer on a support, and containing an anionic crosslinked polymer dispersion represented by the following general formula [I]. A silver halide photographic light-sensitive material. General formula [I] In the formula, A represents a repeating unit obtained by copolymerizing a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups. B represents a repeating unit obtained by copolymerizing a monomer represented by the following general formula [II] whose homopolymer has a cloud point in an aqueous solution. D represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer other than the above. R ¹
Represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a halogen atom. L represents a divalent to tetravalent linking group, and M represents a hydrogen atom or a cation. m represents 0 or 1, and n represents 1, 2 or 3. w, x, y, z represent the weight percentage ratio of each monomer component, and w is 0, 1 to 6
0, x is 10 to 70, y is 0 to 30, z is 25
It takes a value of 85 to 85. Where w + x + y + z = 100
Is. General formula [II] In the formula, R ² represents a hydrogen atom or a lower alkyl group.
R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or a substituted alkyl group. R ³ and R ⁴ do not become hydrogen atoms at the same time, and R ³ and R ⁴ may combine with each other to form a nitrogen-containing heterocycle with the nitrogen atom. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the polymer dispersion of the general formula [I] is provided on the support on the side opposite to the silver halide emulsion layer. . 3. The halogen according to claim 1, wherein 80% by weight or more of all the constituents in the polymer of the general formula [I] consist of repeating units derived from a water-soluble monomer. Silver halide photographic light-sensitive material.