JPH05100359A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having high antistatic property without deteriorating photographic performance and film strength, preventing the occurrence of a mark of leaching on the surface of the sensitive material after development and causing no trouble to transfer in the drying zone of an automatic processing machine. CONSTITUTION:This silver halide photographic sensitive material has one or more silver halide emulsion layers on the base and contains a dispersed anionic crosslinked polymer represented by the formula, wherein A is a crosslinkable monomer having two or more copolymerizable ethylenic unsatd. groups, B is N,N-dimethylacrylamide or N-acryloyl-morpholine, D is a copolymerizable ethylenic unsatd. monomer, R is H, alkyl or halogen, L is a di-, tri- or tetravalent combining group, M is H or a cation, (k) is 0-1, (m) is 1-3, (x) is 1-70wt.%, (y) is 1-50wt.%, (z) is 25-98wt.%, (w) is 0-50wt.% and x+y+z+w=100 wt.%.

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 having improved antistatic properties, transportability of the photographic light-sensitive material in an automatic processor, and surface properties after processing. ..

[0002]

2. Description of the Related Art Since a photographic light-sensitive material generally comprises a support having an electrically insulating property and a photographic layer, contact friction or peeling with the surface of the same kind or different kinds of materials during the manufacturing process of the photographic light-sensitive material and during use. Electrostatic charges are often accumulated by receiving this. This accumulated electrostatic charge causes many obstacles, but the most serious obstacle is that the photosensitive emulsion layer is exposed by discharging the accumulated electrostatic charge before development processing, and the photographic film is processed. In this case, dot-like spots or dendritic or feather-like line spots are generated.

This is a so-called static mark, which significantly impairs the commercial value of photographic film,
In some cases, the product value is completely lost. This phenomenon becomes apparent only after development, and is one of the very troublesome problems. In addition, these accumulated electrostatic charges also cause secondary failures such as dust adhering to the film surface before and after processing, and uneven 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 of the photographic film. It is caused by peeling of the support surface and the emulsion surface during the rewinding process.
Further, it may occur due to contact peeling between the mechanical portion of the X-ray film in the automatic photographing device or the fluorescent intensifying screen. It also occurs when contacting other packaging materials.

The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become remarkable due to the increase in the sensitivity of the photographic light-sensitive material and the increase in the processing speed. Particularly in recent years, photographic light-sensitive materials have become more susceptible to static marks due to their increased sensitivity and increased opportunities to undergo severe handling such as high-speed coating, high-speed photography, and high-speed automatic development processing. ..

In order to eliminate these problems caused by 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 not only excellent antistatic performance but also adversely affects 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, scratches are not easily scratched by friction or scratching), and the adhesion resistance is not adversely affected (that is, the surfaces 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 liquid 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. Applying antistatic agents to is subject to numerous constraints.

One method of 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 Patent Publication Nos. 57-53587 and 57-5
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 JP-B No. 47-28937 disclose attempts to utilize a (anionic) polymer having a carboxyl group for preventing electrification 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 Polymer) accumulates in the developing solution due to elution into the developing solution and contaminates the silver halide photographic light-sensitive material to be subsequently developed, or minute elution marks on the surface of the silver halide photographic light-sensitive material. However, there was a problem that the silver halide photographic light-sensitive material remained fogged.

Further, these polymers also have a problem that the antistatic performance is remarkably deteriorated by diffusing from the layer of the added silver halide photographic light-sensitive material to other layers.

In order to solve such a problem, several attempts have hitherto been made to crosslink the above polymer with an ethylenically unsaturated monomer having an anionic group to form a crosslinked latex. For example, in U.S. Pat. No. 4,301,240,
It has been disclosed that cross-linking polymerization can be carried out by the following methods (a) and (b), and it has become possible to solve the above-mentioned problems relating to a water-soluble anionic polymer. (A) Acrylic acid or methacrylic acid and a crosslinking monomer are made into a dispersion of a crosslinked polymer by water-in-oil type reverse phase emulsion polymerization in the presence of an alkali and an emulsifier, and then the dispersion is broken, A method of redispersing coalesced particles in water. (B) Polymerization of a short-chain aliphatic ester of acrylic acid or methacrylic acid with a crosslinking monomer is carried out by oil-in-water (normal phase) emulsion polymerization in the presence of an emulsifier, and then an alkali is added to add acrylic acid or methacrylic acid. A method of saponifying a short chain aliphatic ester portion of an acid.

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

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 embodiment of said patent (US Pat. No. 4,301,240), 1
It requires a long time of 45 hours at a high temperature of 25 ° C.

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, naturally the production cost of the photographic light-sensitive material using the crosslinked polymer also increases, and the value as a commercial 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
No. 2 describes a monomer having a carboxyl group (for example,
A means for producing a crosslinked polymer dispersion by directly polymerizing an acrylic acid, methacrylic acid) and a crosslinkable monomer by an oil-in-water type (normal phase) emulsion polymerization and then neutralizing by addition of an alkali is disclosed. ing. 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 such a crosslinked anionic latex dispersion is applied to the back layer as an antistatic agent, curling (front and back) is caused because the film swelling on the back surface side with respect to the silver halide emulsion layer side during the development processing is extremely small. Curvature of the film caused by the difference in elongation of the film. This deteriorates the transportability of the photographic light-sensitive material in the automatic processor. Further, it is necessary that the photographic light-sensitive material does not curl due to various temperature and humidity changes not only after processing but also during storage of the light-sensitive material. Therefore, if curling after the treatment is taken, for example, by increasing the amount of gelatin in the back layer or increasing the hardness of the emulsion layer, curling during storage becomes a problem.

The reduction of the amount of hydrophobic crosslinking monomer is
Although it has some effect on the high swelling and curl prevention of the antistatic agent-containing layer, the amount of the acid component converted into crosslinked particles decreases, and as a result, the proportion of the water-soluble polymer increases. For this reason, there is a drawback in that the above problems due to the water-soluble polymer become apparent.

[0020]

SUMMARY OF THE INVENTION A first object of the present invention is to carry a photographic light-sensitive material in a drying zone of an automatic development processor without the problem of elution marks on the surface of the photographic light-sensitive material after development processing. Another object of the present invention is to provide a silver halide photographic light-sensitive material that is free from problems and is antistatic.

A second object of the present invention is to provide a silver halide photographic light-sensitive material containing an antistatic agent, which has good film strength when applied.

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

[0023]

These objects of the present invention are to provide an anion represented by the following general formula (I) in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. Achieved by a silver halide photographic light-sensitive material characterized by containing a crosslinkable polymer dispersion.

General formula (I)

[0025]

[Chemical 2] In the formula, A represents a repeating unit composed of a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups. B represents a repeating unit composed of N, N-dimethylacrylamide or N-acryloylmorpholine. D represents a repeating unit composed of a copolymerizable ethylenically unsaturated monomer. R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. L
Represents a divalent to tetravalent linking group. M represents a hydrogen atom or a cation. k represents 0 or 1, m represents 1, 2 or 3
Represents. x, y, z, w represent the weight percentage of each component,
The value of x is 1 to 70, the value of y is 1 to 50, the value of z is 25 to 98, and the value of w is 0 to 50. Where x + y + z
+ W = 100.

The polymer represented by the general formula (I) used in the present invention will be described in detail below.

A is a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups (hereinafter referred to as "crosslinkable monomer"), and examples of the crosslinkable monomer include the following. However, the present invention is not limited to this.

Divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate,
Diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trivinyl cyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate,
Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate. Of these, ethylene glycol dimethacrylate, divinylbenzene,
Pentaerythritol tetramethacrylate is preferred.

B is N, N-dimethylacrylamide, N
Represents any monomer unit of acryloylmorpholine.

Next, in the general formula (I)

[0031]

[Chemical 3] The anionic monomer which gives the repeating unit represented by is described below.

Examples of R ¹ include hydrogen or an unsubstituted alkyl group such as methyl, ethyl and n-propyl, and a substituted alkyl group such as a carboxymethyl group. Of these, hydrogen,
A methyl or carboxymethyl group is preferred.

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

[0034]

[Chemical 4] In the case of a tetravalent linking group

[0035]

[Chemical 5] Is preferred.

Q is a divalent linking group, examples of which include alkylene groups (eg, methylene, ethylene, trimethylene), arylene groups (eg, phenylene),
-COO-X- (. However, X represents from 1 to about 6 alkylene group or an arylene group having carbon atoms hereinafter the same) (e.g., -COOCH ₂ CH ₂ -),

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8] Etc. can be mentioned.

K is 0 or 1. m is 1, 2 or 3. M represents hydrogen or a cation. Examples of cations include alkali metal ions (eg sodium ion, potassium ion), ammonium ion (eg,
Examples thereof include trimethylammonium ion, triethylammonium ion, and tributylammonium ion, but alkali metal ions are particularly preferable.

[0041]

[0042]

[Chemical 9] Preferred examples of the anionic monomer providing the repeating unit represented by the following are, but are not necessarily limited to the following.

[0043]

[Chemical 10]

[0044]

[Chemical 11]

[0045]

[Chemical 12] The monomer having these anionic groups should be subjected to polymerization in the form of a salt thereof, for example, an alkali metal salt (for example, Na or K salt) or an ammonium salt (for example, a salt with ammonia, methylamine or dimethylamine). Is also possible.

Two or more of these anionic monomers may be used.

D represents a repeating unit composed of a copolymerizable ethylenically unsaturated monomer. Examples of such copolymerizable ethylenically unsaturated monomers include acrylic acid esters (eg, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate). , Hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, methoxyacrylate, 2-methoxyacrylate, 2-ethoxyacrylate, 2- (2-methoxyethoxy) ethyl acrylate).

Methacrylic acid esters (for example,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t
-Butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate), and crotonic acid esters (eg, butyl crotonic acid, hexyl crotonic acid). Furthermore, vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl butyrate,
Vinyl methoxyacetate, vinyl benzoate), maleic acid diesters (eg, dimethyl maleate, diethyl maleate, dibutyl maleate), fumaric acid diesters (eg, dimethyl fumarate, diethyl fumarate, dibutyl fumarate), itacon Acid diesters (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate) can also be mentioned.

Acrylamides (eg, acrylamide, N-methylacrylamide, N-ethylacrylamide, propylacrylamide, n-butylacrylamide, t-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, diethylacrylamide, phenylacrylamide) Methacrylic amides (for example, methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, t-butyl methacrylamide, 2-methoxyethyl methacrylamide, diethyl methacrylamide) are also included.

In addition, vinyl ethers (eg, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether), styrenes (eg, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, Chloromethyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, brom styrene), unsaturated nitriles (eg, acrylonitrile, methacrylonitrile, α-ethyl acrylonitrile, α-methoxy acrylonitrile). Are not limited to these.

X, y, z, w represent the weight percentage of each monomer component, x is 1 to 70, y is 1 to 50, z
Has a value of 25 to 98 and w has a value of 0 to 50. Further, x is preferably 35 to 60, y is 3 to 20, z is 35 to 70, and w is preferably 0 to 15. Here, x + y + z + w = 100.

The compound represented by the general formula (I) used in the present invention can be synthesized by a generally well-known emulsion polymerization method, but it is particularly preferable to use the monomer and the polymerization in heated water. This is a method of adding an initiator at the same time.

This method is disclosed in JP-A-61-2963.
No. 52 for details.

Next, the polymerization initiator will be described. As the polymerization initiator, there are books on polymer synthesis, for example, Takayuki Otsu and Masayoshi Kimura, “Experimental Method for Polymer Synthesis” (1st edition, 1
Although it is possible to use a polymerization initiator known in Kagaku Dojin, published in 972, it is preferable to use a water-soluble polymerization initiator in the production method of the present invention. As water-soluble polymerization initiators, persulfates and azo compounds are known, but persulfates such as potassium persulfate give particularly preferable results in the production method of the present invention. The amount of the polymerization initiator used is 0.05 to 5% by weight, preferably 0.1 to 1.0% by weight, based on the monomers.

Since the anionic crosslinked polymer produced has an electric charge and is present in a relatively stable dispersed state in water, it is not necessary to add a surfactant in water, but the auxiliary It is also possible to add an activator to stabilize the dispersion state of the crosslinked polymer in water. Examples of the surfactant that can be used in the present invention are shown below, but the surfactant that can be used is not limited to these.

[0056]

[Chemical 13] The anionic crosslinked polymer preferably used in the present invention,
It is obtained by simultaneously adding a monomer and a polymerization initiator to heated water.

Polymerization temperature is one of the most important production conditions in the production of the polymer used in the present invention. The polymerization temperature is usually 50 to 80 ° C. in many cases. In the production of the polymer used in the present invention, it is possible to polymerize at 50 to 80 ° C., but under such conditions, a large amount of non-dispersed and non-dissolved aggregates in water or an organic solvent is produced as a by-product. Therefore, unless these are completely removed, it becomes impossible to form a coated article having a good surface condition. Removal of these agglomerates results in increased cost of the crosslinked polymer due to reduced cost and reduced yield.

In the present invention, the higher the polymerization temperature is, the more preferable. However, it is usually desirable to carry out the polymerization at 90 to 98 ° C. because of the restriction because it is carried out in water, but it is also possible to carry out the polymerization at a higher temperature by devising the polymerization equipment.

After the polymerization reaction, the polymer of the present invention is preferably partially neutralized with an alkali. 50-100 mol% of all the anionic groups in the polymer, especially 70-
It is preferred that 100 mol% is neutralized.

Specific examples of the polymer of the present invention are shown below.
It is not necessarily limited to these.

The copolymerization ratios given in the examples represent weight percentages. M represents a mol ratio.

[0062]

[Chemical 14]

[0063]

[Chemical 15]

[0064]

[Chemical 16]

[0065]

[Chemical 17]

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20] Polymer Synthesis Example (Synthesis of P-4) In a 2 liter glass three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser,
0.44 g of surfactant K-1 shown in 3 and distilled water 7
64 ml was added, and the mixture was heated and stirred at 95 ° C under a nitrogen stream. A solution of 4.41 g of potassium persulfate dissolved in 240 ml of distilled water and 12.12 g of N, N-dimethylacrylamide,
A mixed solution of 60.60 g of acrylic acid and 48.48 g of ethylene glycol dimethacrylate was added dropwise using a constant-speed dropping device over 2 hours. Immediately after completion of the dropping, a solution prepared by dissolving 0.49 g of potassium persulfate in 22.4 ml of distilled water was added, and the mixture was heated and stirred at 95 ° C. for 1 hour and a half.

After cooling to 80 ° C., 26.8 g of sodium hydroxide dissolved in 120 ml of distilled water was added,
Stirring was continued at 80 ° C for 30 minutes.

After cooling to room temperature and pressure filtration, the solid content is 1
1.6 weight percent, pH 6.2, average particle size 710 μm
1299.7 g (yield 92%) of the latex was obtained.

Similarly, P-1 shown in Chemical Formulas 14 to 20 above
~ P-23 latexes were synthesized.

The anionic crosslinked polymer represented by the general formula (I) in the present invention is contained in at least one of the non-photosensitive layers provided on the opposite side of the support from the silver halide emulsion layer. Is desirable.

In the present invention, the gelatin coating amount of the back layer is preferably 0.1 g / m ² or more and 30 g / m ² or less,
Further, it is preferably 3 g / m ² or more and 10 g / m ² or less. The coating amount of the carboxylic acid polymer represented by the general formula (I) in the back layer is preferably 0.1 g / m ² or more and 30 g / m ² or less, more preferably 1 g / m ² or more and 5 g / m ² or less. The amount of the carboxylic acid polymer represented by the general formula (I) in the antistatic layer is preferably 1% by weight or more, and more preferably 20% by weight or more and 70% by weight or less with respect to gelatin. The coating amount of the hardener in the back layer is preferably 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻³ mol or less, and more preferably 3 × 10 ⁻⁵ mol or more and 3 × 10 ⁻⁴ mol or less per 1 g of gelatin.

[0074]

EXAMPLES Examples of the present invention will be described below.

A multi-layer silver halide color light-sensitive material comprising a back layer provided on one side of a cellulose triacetate film support and each layer including a photosensitive layer provided on the opposite side of the support was prepared. (Back layer composition) The number corresponding to each component indicates the coating amount in 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 2. 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

[0076]

[Chemical 21] 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 multilayer coated. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. 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 2.0x10 ^-3 U-1 0.060 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 4th layer (2nd red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 × 0 sensitized ^-5 Sensitizing dye II 1.4 × 10 ^-5 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 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 .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-sensitive 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 9th layer (3rd green 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 10th layer (yellow filter layer) Yellow colloidal silver 0.050 EX-5 0.08 HBS-1 0.030 Gelatin 0.95 11th 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 12th layer (2nd 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 Layer 13 (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 15th layer (second protective layer) H-1 0.40 B-1 ( diameter 1 ^{7μm) 5.0 × 10 -2 B-} 2 ( diameter 1.7μm) 0.10 B-3 0.10 S -1 0.20 Gelatin 1.20 In addition, storage stability in all layers, processability, pressure resistance , W-1, in order to improve antifungal and antibacterial properties, antistatic properties and coating properties,
W-2, W-3, B-4, B-5, F-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.

[0077]

[Table 1]

[0078]

[Chemical formula 22]

[0079]

[Chemical formula 23]

[0080]

[Chemical formula 24]

[0081]

[Chemical 25]

[0082]

[Chemical formula 26]

[0083]

[Chemical 27]

[0084]

[Chemical 28]

[0085]

[Chemical 29]

[0086]

[Chemical 30]

[0087]

[Chemical 31]

[0088]

[Chemical 32]

[0089]

[Chemical 33]

[0090]

[Chemical 34] The following samples 1 to 10 were prepared by weight coating as described above.

Sample 1 was prepared by replacing the antistatic agent in the back surface second layer with an equal weight of gelatin. Samples 2-1
0 was prepared using an antistatic agent as shown in Table 2. Of these, the exemplified compounds P-3, P-15, P-19, P-
22 is a compound included in the general formula (I) of claim 1. Only Sample 10 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.

1) The surface resistivity was such that the test piece of the sample, with the back surface of the film facing upward, had an electrode interval of 0.14 cm and length of 1
It is sandwiched between 0 cm brass electrodes (the part in contact with the test piece is made of stainless steel), and it is 1 with Takeda Riken TR8651 type insulation meter.
Measure the minute value.

2) The static mark generation test was carried out by causing the emulsion surface of the unexposed light-sensitive material to face down on a rubber sheet, pressing it with a rubber roller from above, and peeling it to generate a static mark. .. This was developed and the amount of static marks generated was examined.

The humidity was adjusted at 25 ° C. and 25% RH for both surface resistivity and static mark measurement tests. The humidity of the test piece was controlled under the above conditions for one day. The evaluation of the static mark was performed in three stages: A: no static mark was generated, B: static mark was slightly generated, and C: static mark was generated on the entire surface. (Measuring method of film swelling ratio) Test pieces are shown below at 38 ° C.
After dipping in the developing solution for 2 minutes, the thickness of the swollen film was measured, and the swelling ratio of the film 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 determined by J. Photographic Science.
20, 205 to 210 (1972). (Conveyance test with a roller conveyance type automatic development processor) The test piece was processed into 2B (120 size) and dried using a roller conveyance type automatic development processor (QSS-B9L manufactured by Noritsu) without a pressing roller. A transport test of the film to the zone was conducted (the larger the curl during transport in the drying zone, the more the film is caught and scratched by the roller at the zone exit). The evaluation was carried out in three grades, depending on the degree of scratches on the film: A: no scratches, B: scratches occurred on the edges of the film, and C: the film was severely broken. (Determination Method of Elution Mark of Antistatic Agent) After the test piece was treated by the treatment method (A) described later, a surface condition inspection was performed. Regarding the suitability of elution traces, the following three steps were carried out: A: no elution traces were generated, B: elution traces were slightly observed, C: elution traces were generated all over the surface.

[0096] (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 ml Hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) ( Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol

[0097]

[Chemical 35] Ammonia water (27%) 15.0 ml Water was added to 1.0 liter pH 6.3 (bleach-fixing solution) (unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5 0.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water was added to 1.0 liter pH 7.2 (Washing liquid) Tap water was used as H type strong acidic cation. Exchange resin (Amber Light IR-120B manufactured by Rohm and Haas)
And a OH-type strongly basic anion exchange resin (Amberlite IRA-400) are passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanurate dichloride. Sodium nourate 20 mg / liter and sodium sulfate 150 mg / liter were added. The pH of this liquid is in the range of 6.5 to 7.5. (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 Water was added to the mixture 1. 0 liter pH 5.0-8.0 (Film strength) A scratch strength meter in which a sample piece was immersed in a developing solution at 38 ° C for 5 minutes and then a load of 0-100 g was continuously applied 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 and scratching started. 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, there is a problem that scratches are caused when passing through a roller-conveying type automatic development processor.

[0098]

[Table 2] As shown in Table 2, Samples 2 to 5 using the anionic crosslinked polymer according to the present invention had good antistatic properties, had a good balance with the emulsion surface, and did not cause any problems in the transport test. On the other hand, in Samples 6, 7 and 9 which do not contain the polymer represented by the general formula (I) according to the present invention, the back side dries faster than the emulsion side in the processor drying zone, and the back side shrinks strongly, Curl was generated and caught on the roller at the exit of the drying zone, and a fold was generated. In addition, Sample 10 had a remarkably low film strength and could not be used practically.

Further, when the polymer represented by the general formula (I) was used, the problem of elution marks did not occur at all, but the comparative polymer example C used in Sample 8 had elution marks.

From the above, it is apparent that the use of the polymer represented by the general formula (I) is effective for improving the antistatic property, the transportability in the processor, the film strength and the elimination of elution marks.

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

[0102]

[Chemical 36]

[0103]

As described above, according to the present invention, it has a high antistatic property without deteriorating the photographic performance and the film strength. Therefore, no elution mark is generated on the surface after the development processing, and it is automatic. Provided is a photographic light-sensitive material which does not have a problem of being conveyed in a drying zone of a developing processor. Furthermore, this photographic light-sensitive material can be easily manufactured at low cost.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yuichi Ohashi, No. 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material comprising an anionic crosslinked polymer dispersion represented by the following general formula (I). General formula (I): In the formula, A represents a repeating unit composed of a crosslinkable monomer having at least two copolymerizable ethylenically unsaturated groups. B is N, N-dimethylacrylamide or N
Represents a repeating unit consisting of any of acryloylmorpholine. D represents a repeating unit composed of a copolymerizable ethylenically unsaturated monomer. R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. L represents a divalent to tetravalent linking group. M represents a hydrogen atom or a cation. k represents 0 or 1, and m represents 1, 2 or 3. x, y, z, w represent the weight percentage of each component, x
Is 1 to 70, y is 1 to 50, z is 25 to 9
8, w has a value of 0 to 50. Where x + y + z +
w = 100. 2. An anionic crosslinked polymer dispersion represented by the general formula (I) is provided in at least one of the non-photosensitive layers provided on the opposite side of the support from the silver halide emulsion layer. The silver halide photographic light-sensitive material according to claim 1, characterized in that 3. The anionic crosslinked polymer dispersion represented by the general formula (I) is prepared by adding at least one of the three monomers shown in the following 1) to 3) and a polymerization initiator to water. 3. The silver halide photographic light-sensitive material according to claim 1, which is obtained through a process of copolymerization. 1) a copolymerizable ethylenically unsaturated monomer having an anionic functional group 2) a crosslinking monomer having at least two copolymerizable ethylenically unsaturated groups 3) N, N-dimethylacrylamide or N- Acryloylmorpholine