JPH0566512A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent production of silver sludge and reduction of density even for rapid treatment and to improve drying property by incorporating a polymer latex stabilized with gelatin in an insensitive hydrophilic colloid layer. CONSTITUTION:On the supporting body, there are provided a photosensitive silver halide emulsion layer and an insensitive hydrophilic colloid layer. The insensitive hydrophilic colloid layer contains a polymer latex stabilized with gelatin, and at least part of polymn. of the polymers which constitute the polymer latex is effected in a solvent containing gelatin. More preferably, the latex has <=0.3/mum average particle size and the amt. of hydrophilic binder in the side including the photosensitive silver halide emulsion layer on the supporting body is <=2.7g/m<2> in total. Further, it is preferable to incorporate a polymer latex stabilized with gelatin into the photosensitive silver halide emulsion layer.

Description

Detailed Description of the Invention

[0001]

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 excellent in drying property.

[0002]

BACKGROUND OF THE INVENTION Recently, in silver halide photographic light-sensitive materials, the demand for rapid processing has become extremely strong.
However, various problems arise due to the rapid processing. For example, the drying may be poor and the conveyance may be poor. Therefore, if you raise the drying temperature in the automatic processor,
The dimensional stability of the film is impaired. Further, reducing the amount of gelatin, which is a binder generally used for light-sensitive materials, is effective for drying, but the silver produced by the processing tends to become sludge. Alternatively, if the hardness of gelatin is increased in order to control the water absorption of gelatin, problems such as a decrease in image silver concentration occur.

It is well known to incorporate a polymer latex into a silver halide emulsion layer and a backing layer to improve the physical properties of a light-sensitive material. For example, Research Disclosure 19951, Japanese Patent Publication No. 39-4272, 39-17702,
43-13482, U.S. Pat.Nos. 2376005, 2763625, 2772.
No. 166, No. 2852386, No. 2853457, No. 3397988, etc.

However, simply adding a latex dispersion-stabilized with a conventional surfactant cannot suppress the above-mentioned formation of silver sludge and cannot improve the drying property.

[0005]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having an improved drying property without generating silver sludge and reducing the concentration even when subjected to rapid processing. Is to provide.

[0006]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, the non-light-sensitive hydrophilic At least one of the colloid layers contains a gelatin-stabilized polymer latex, and at least a part of a polymerization reaction of a polymer constituting the polymer latex is carried out in a solvent containing at least gelatin. And a silver halide photographic light-sensitive material.

The average particle size of the latex of the present invention is 0.3.
μm or less, and the total amount of hydrophilic binder on the side including the photosensitive silver halide emulsion layer on the support is 2.7 g.
It is a preferred embodiment of the present invention that it is not more than / m ² and that at least one light-sensitive silver halide emulsion layer contains a gelatin-stabilized polymer latex.

The present invention will be described in more detail below.

In the present invention, the object of the present invention can be achieved by using a latex stabilized with gelatin.

That is, the ordinary latex is dispersed in water by a surfactant, but the latex which can be used in the present invention is characterized in that the surface and / or the inside of the polymer latex is dispersed and stabilized by gelatin. And The polymer constituting the latex and gelatin may have some kind of bond. in this case,
The polymer and gelatin may be directly bound or may be bound via a crosslinking agent. Therefore, the monomers constituting the latex include carboxyl group, amino group,
It is desirable to include those having a reactive group such as an amide group, an epoxy group, a hydroxyl group, an aldehyde group, an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group and an unsaturated carbon bond. When a cross-linking agent is used, those used as a cross-linking agent for ordinary gelatin can be used. For example, aldehyde system,
A cross-linking agent such as glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, methacrylic-based, and acrylic-based crosslinking agents can be used.

The gelatin-stabilized latex of the present invention is characterized in that at least a part of the polymerization reaction of the polymer is carried out in a solvent containing at least gelatin. USP 5026632 has a prepolymerized Tg of 25
A technique for improving pressure resistance by adding particles having a hard shell of gelatin hardened with a cross-linking agent in a layer to polymer particles having a temperature of not higher than 0 ° C. is disclosed. See also USP4920004
No. 4,855,219 also discloses a technique of improving adhesiveness by using a prepolymerized polymer particle covalently bound to gelatin as a matting agent. However, in such particles, the effect of preventing silver sludge, which is the object of the present invention, could not be recognized.

Although USP2852382 describes that a polymer is synthesized in the presence of gelatin, it is intended to be contained in a silver halide emulsion layer of a color photographic light-sensitive material, and the effect of preventing silver sludge as in the present invention can be obtained. I can't.

US Pat. No. 2,787,545 discloses a method of desalting a silver halide emulsion using a graft polymer of gelatin and acrylic acid. Even if such an emulsion is used, the effect of preventing silver sludge as in the present invention can be obtained. I can't. Further, JP-A-59-121327, JP-A-62-115152 and the like describe examples of adding latex to a non-photosensitive upper layer (protective layer), but the effect of the latex of the present invention cannot be obtained. ..

The present inventor has found that in the course of continuing to study the above problems, there is a preferable range for the ratio of the amount of gelatin and latex added during synthesis. The weight ratio of gelatin and polymer at the time of synthesis (finally obtained as latex) is preferably Gel / Poly = 1/100 to 2/1, and particularly preferably 1/50 to 1/2. The effect of the present invention is that the addition amount of the polymer component of the latex,
Particularly preferable results are obtained when the amount is 20% or more based on the gelatin in the layer to which the latex is added.

The addition amount of the polymer is 0.05-5 g / m ^2, particularly preferably 0.1~2.5g / m ^2.

The polymer latex used in the present invention can change the MFT (minimum film forming temperature) depending on the composition of the monomer, but it is particularly effective when the MFT is 60 ° C. or lower, and more preferably the MFT is 50. It is below ℃.

Further, the present invention has a latex particle size of 0.3 μm.
The following is preferable. It is presumed that the reason why the effect of preventing silver sludge is decreased when the particle size is large is that the packing density is decreased when the particle size is large. A particularly preferred particle size is 0.01 to 0.27 μm.

The composition of the monomer of the polymer latex contained in the photographic light-sensitive material of the present invention includes, for example, US Pat. Nos. 2,772,166, 3,325,286 and 3,411,911.
, 3,311,912, 3,525,620, Research Disclosure No.195 1955
1 (July 1980) and the like, acrylates, methacrylates, hydrates of vinyl polymers such as styrene, and the like.

Examples of gelatin used for stabilizing the latex of the present invention include gelatin and gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used in combination.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, and Bulletin of Society of Japan (Bull.Soc.Sci.Phot.Japan) No. 16, page 30 (196
You may use the acid-processed gelatin as described in 6),
Also, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used. Examples of gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds in gelatin. What is obtained by reacting is used. Specific examples thereof are U.S. Patents 2,614,928 and 3,132,9.
45, 3,186,846, 3,312,553, British Patent 861,41
No. 4, No. 1,033,189, No. 1,005,784, Japanese Patent Publication No. 42-26845
No. etc.

The proteins include albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

Examples of the graft polymer of gelatin and other polymers include gelatin, acrylic acid, methacrylic acid,
Those obtained by grafting a derivative such as an ester or amide thereof, or a homopolymer or copolymer of a vinyl-based monomer such as acrylonitrile or styrene can be used. Particularly, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are described in US Pat. Nos. 2,763,625, 2,831,767, and 2,956,884.

The latex used in the present invention must be added to at least one non-photosensitive hydrophilic colloid layer. It may be added in other optional layers (a plurality of non-photosensitive hydrophilic colloid layers and / or photosensitive hydrophilic colloid layers). It may be contained on only one side of the support, or may be contained on both sides. A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When included on both sides of the support, the type and / or amount of polymer latex included on each side may be the same or different.

The polymer component of the latex contained in the photographic light-sensitive material of the present invention is, for example, US Pat.
No. 166, No. 3325286, No. 3411911, No. 3311912, No. 352562
No. 0, Research Disclosur
e) There are hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters and styrene as described in No. 19519551 (July 1980). Specifically, acrylic acid, methacrylic acid or salt, maleic acid or salt, fumaric acid or salt,
Alkyl acrylic acid esters such as methyl acrylate and ethyl acrylate, metaalkyl acrylic acid esters such as methyl methacrylate and ethyl methacrylate, styrene, styrene sulfonic acid or salt, N-substituted or unsubstituted acrylamide, vinyl alcohols, hydroxyalkyl methacrylate Any compound having a double bond such as a group or butadiene may be selected as a homopolymer or a copolymerization component.

Specific examples of preferable monomers are given below. The latex of the present invention can take any combination (type, composition ratio) of these monomers. Needless to say, the present invention is not limited to these monomers.

[0026]

[Chemical 1]

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

In the present invention, the total amount of the hydrophilic binder on the side having the photosensitive silver halide emulsion layer with respect to the support is
It is particularly effective in cases where it is 2.7 g / m ² or less. Even when the total amount of the hydrophilic binder is 2 g / m ² or more, the latex of the present invention is effective, but the effect of the present invention is to use a hydrophilic colloid such as gelatin in order to improve the drying property of the light-sensitive material. This is because it prevents silver sludge when it is reduced. Particularly preferred is a case where the total amount of hydrophilic binders on the side having the photosensitive silver halide emulsion layer with respect to the support is 2.5 g / m ² or less.

There are no particular restrictions on the general additives of the present invention, the known contrast enhancer, the method for producing silver halide grains, the sensitizing method, and the like. For example, JP-A 1-230035,
You can refer to Japanese Patent Application No. 1-266640.

In the present invention, one or more antistatic layers may be provided on the backing side and / or emulsion layer side of the support for the purpose of antistatic property which is another physical property of the light-sensitive material.

In this case, the surface specific resistance on the side provided with the antistatic layer is preferably 1.0 × 10 ¹² Ω or less at 25 ° C. and 50%, and particularly preferably 8 × 10 ¹¹ Ω or less.

The antistatic layer is preferably an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of a curing agent, or an antistatic layer containing a metal oxide.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group polyethylene oxide group. .. Among these groups, a sulfonic acid group, a sulfuric acid ester group and a quaternary ammonium salt group are preferred. The conductive group needs to be 5% by weight or more per molecule of the water-soluble conductive polymer.

Further, the water-soluble conductive polymer contains a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinyl sulfone group and the like. Of these, a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, and an aldehyde group are preferably contained. 5% by weight of these groups per polymer molecule
The above must be included. The number average molecular weight of the water-soluble conductive polymer is 3,000 to 100,000, preferably 3500 to 50,000.

As the above-mentioned metal oxide, tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or a substance obtained by doping these metal oxides with metal phosphorus, metal silver, or metal indium is preferable. Used. The average particle size of these metal oxides is 1
μ to 0.01 μ is preferable.

As the undercoat layer which can be used in the present invention, an undercoat layer in an organic solvent system containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-49-11118.
No. 52, No. 104913, No. 59-19941, No. 59-19940, No. 5
9-18945, 51-112326, 51-117617, 51-5846
No. 9, No. 51-114120, No. 51-121323, No. 51-123139,
51-114121, 52-139320, 52-65422, 52-1
09923, 52-119919, 55-65949, 57-128332
No. 59-19941 and the like aqueous latex undercoating layer, but also U.S. Pat. No. 2698235, No. 2779684.
No. 425421, No. 4645731, vinylidene chloride-based undercoating and the like.

The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, surface activation treatment such as ozone oxidation treatment. ..

The undercoat layer is distinguished from the coating layer according to the present invention, and there is no restriction on the coating timing or conditions.

In the present invention, in addition to the usual water-soluble dye, a solid-dispersed dye may be contained in any of the hydrophilic colloid layers. The layer may be the outermost layer on the emulsion surface side, or may be added below the emulsion layer and / or on the backing surface side for the purpose of preventing halation. Further, an appropriate amount may be added to the emulsion layer for adjusting the irradiation. Of course, plural kinds of solid disperse dyes may be contained in plural layers.

The addition amount of the solid disperse dye is preferably 5 mg / m ^{2 to 1} g / m ² , and particularly preferably 10 mg / m ^{2 to 1} g / m ^2.
a ^{mg / m 2 ~800mg / m 2} .

The fine particles of the solid dispersion to be used are obtained by pulverizing the dye with a dispersing machine such as a ball mill or a sand mill, and then water or a hydrophilic colloid such as gelatin, sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate. , Saponin, nonylphenoxy polyethylene glycol and the like can be dispersed and obtained.

General formulas for solid disperse dyes are described in US Pat.
Examples thereof include those described in No. 4,857,446, and for example, those represented by the general formulas [I] to [V] are preferably used.

The present invention can be applied to various photosensitive materials for printing, X-ray, general negative, general reversal, general positive, direct positive, etc., but requires extremely high dimensional stability. When it is applied to the photosensitive material for printing, a particularly remarkable effect is obtained.

The development temperature of the silver halide photographic light-sensitive material according to the present invention is preferably 50 ° C. or less, more preferably around 25 ° C. to 40 ° C., and the development processing time is generally completed within 2 minutes. However, it is particularly preferable to perform rapid processing for 5 to 60 seconds.

[0049]

EXAMPLES Examples of the present invention will be specifically shown below, but it goes without saying that the present invention is not limited to these examples.

Example 1 (Latex Synthesis Method Lx-1) 0.12 gelatin was added to 40 l of water.
Liquid temperature 8 in a solution containing 5 kg and 0.05 kg ammonium persulfate
While stirring at 0 ° C, under a nitrogen atmosphere, use a mixed solution of the following components (a) to (c) (or (a)) to prepare 1
Add over time, then stir for 1.5 hours, then gelatin 1.25K
g and 0.005 Kg ammonium persulfate were added and stirred for 1.5 hours,
After completion of the reaction, the residual monomer was removed by steam distillation for 1 hour, and then the mixture was cooled to room temperature and adjusted to pH 6.0 with ammonia. The latex solution obtained is 50.
Finished to 5Kg.

(Comparative Latex Synthesis Method LX-2) Lx
In -1, Meito Sangyo KMDS (dextran sulfate sodium salt) was used in place of gelatin in the system before polymerization.
Latex Lx- was prepared in the same manner as Lx-1 except that 25 kg was added and gelatin was not added after the monomer was added.
2 was synthesized.

(Emulsion preparation) A silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × of a rhodium hexachloride complex.
The solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate, and after desalting, the particle size was 0.13
A cubic crystal, monodisperse, silver chlorobromide emulsion containing μ, 1 mol% of silver bromide was obtained.

This emulsion was subjected to sulfur sensitization by a conventional method, 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene was added as a stabilizer, and then the following additives were added to apply the emulsion. Liquid E
-1 to 14 were prepared, and then emulsion protective layer coating solution P-0, backing layer coating solution B-0, backing protective layer coating solution BP-0.
Was prepared with the following composition.

(Preparation of Emulsion Coating Solution) Compound (a) 1 mg / m ² NaOH (0.5N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² Saponin (20%) 0.5 cc / m ² sodium dodecylbenzene sulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg compound (f) 6 mg / m ² latex Lx-1 type Table 1 Styrene-maleic acid copolymer polymer (thickener) 90 mg / m ²

[0055]

[Chemical 7]

[0056]

[Chemical 8]

(Emulsion protective layer coating liquid P-0) Gelatin 0.5 g / m ² compound (g) (1%) 25 cc / m ² compound (h) 120 mg / m ² Spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3μm) 10mg / m ² compound (i) adjusted to 100 mg / m ² citric acid pH 6.0 (backing layer coating solution B-0) gelatin 1.0 g / m ² compound (j) 100mg / ^{m 2} compound (k ) 18 mg / m ² compound (l) 100 mg / m ² savonin (20%) 0.6 cc / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene-maleic acid copolymer polymer (thickening Agent) 45 mg / m ² glyoxal 4 mg / m ² compound (o) 100 mg / m ² (backing protective layer coating solution BP-0) gelatin 0.5 g / m ² compound (g) (1%) ² cc / m ² spherical polymethyl Methacrylate (4μ) 25mg / m ² Sodium chloride 70mg / m ² Glyoxal 22mg / m ² Compound (n) 10mg / m ²

[0058]

[Chemical 9]

[0059]

[Chemical 10]

[0060]

[Chemical 11]

On the emulsion surface side, a corona discharge was applied at 10 W / (m ² · min) on a polyethylene terephthalate base having a thickness of 100 μm and subjected to undercoating shown in JP-A-59-19941. Roll fit coating pan,
And applied using an air knife. Drying is 90
Under parallel flow drying conditions of ℃ and overall heat transfer coefficient of 25 Kcal (m ² · hr · ℃)
It was carried out for 30 minutes, and subsequently at 140 ° C. for 90 seconds. The thickness of this layer after drying is 1 μm, and the surface resistivity of this layer is 1 at 23 ° C 55%.
It was × 10 ⁸ Ω.

[0062]

[Chemical formula 12]

Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 60 6 g / l Curing agent 12 g / l

[0064]

[Chemical 13]

On this base, a formalin solution was used as a hardening agent solution by a slide hopper system while maintaining the emulsion layer and emulsion protective layer in this order from the side closer to the support as the emulsion side, and 30 mg of formalin solution was added per 1 g of gelatin. Simultaneous multi-layer coating while adding so that cold air set zone (5
C.), the backing layer and the backing protective layer were coated with a slide hopper while adding a hardening agent, and set with cold air (5.degree. C.). The coating liquid showed sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, it was conveyed without winding to the roller and to other parts until winding. At this time, the coating speed was 100 m / min.

(Drying conditions) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin reached 800%, and then 800 to 20.
0% was dried with 35 ° C (30%) dry air, and the air was blown as it was, and after 30 seconds from the time when the surface temperature reached 34 ° C (which is considered as the end of drying), it was dried with 48% 2% air for 1 minute. .. At this time,
Drying time is 50 seconds from the start of drying to 800% of H ₂ O / Gel, 800
% To 200% is 35 seconds, and 200% to completion of drying is 5 seconds.

This light-sensitive material was wound up at 40 ° C. at 23 ° C., then cut in the same environment, and placed in a barrier bag which had been conditioned for 3 hours in the same environment. Sealed with cardboard (40% conditioned for 2 hours).

In the light-sensitive material produced as described above, the coated silver amount was 4.0 g / m ² , and the gelatin amount was 2.
It was 0 g / m ² .

Further, 1.0 g / m ^{2 of the following} latex (6) prepared by the synthesis method Lx- ^{2 was} added to the emulsion layer as a conventional latex, and the latex (1) to
(6) was added as shown in Table 1 to prepare sample Nos. 1-27. Latex (1) to (5) was then synthesized by method LX-1.
And latex (6) is according to Synthetic Method LX-2. A sample in which latex was not added to the protective layer was designated as No. 28, and a sample in which the amount of the hardener was tripled compared to the sample of No. 28 was designated as No. 29.

The latex in Table 1 is as follows. (Unit: Kg) (1) (a) n-Butyl acrylate 4.51 (b) Styrene 5.49 (c) Acrylic acid 0.1 (2) (a) Ethyl acrylate 3.52 (b) Methyl methacrylate (two-component system) 5.1 (3) ) (A) Ethyl acrylate 3.52 (B) Methyl methacrylate 4.9 (C) Ethylene glycol 0.2 (4) (A) Ethyl acrylate 3.52 (B) Methyl methacrylate 4.9 (C) 1-N, N-dimethyltoluene 0.1 (5) ( A) Methyl methacrylate (b) Acrylic acid (two-component system) 5.16 2.26 (6) The monomer composition was the same as in (1). The evaluation was performed as follows.

(Silver Sludge) Konica Automatic Developing Machine GR-27
(Developer tank 40 liters) large size (610 x 508 m
The silver concentration in the developing solution was analyzed when 500 samples of m) were continuously processed at 5 second intervals. One of the five samples was completely blackened, and the other four were unexposed.

The total amount of replenishment was 20 cc for each of the developing solution and the fixing solution.

(Drying property) The above continuous treatment was carried out at 30 ° C. and 80 RH%.
And the drying temperature was 33 ° C.

The dry state immediately after being discharged from the automatic processor was evaluated by touch.

The evaluation rank was 5: good dry condition was observed until the end 4: poor drying was not more than 5 out of 500 sheets. 3: poor drying was not caused by 10 sheets, but not less than 6 out of 500 sheets. 2) Defects occur in the 4th to 10th sheets 1: Defects occur in the 3rd or less sheet (maximum density Dmax) Density when the exposure amount is changed to give the maximum density ..

(Standard processing conditions) Development 28 ° C. 30 seconds Fixing 28 ° C. 20 seconds Washing with water 15 seconds at room temperature Drying 40 ° C. 35 seconds [Developer formulation] (Composition A) Pure water (ion exchange water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 50g Potassium sulfite (55% W / V aqueous solution) 100ml Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to make the pH of the solution 10.9 Potassium bromide 4.5 g (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 mg Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg Water 500 ml when using the developer In the above composition A and composition B
Were melted in this order and finished to 1 liter before use.

[Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid ( 90% W / V aqueous solution) 8.1 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 5.8 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) When 26.5 g of the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter and used. The pH of this fixer is approximately
It was 4.3.

The results are shown in Table 1.

[0079]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention has improved dryness without causing deterioration of silver sludge and reduction of concentration.

Example 2 Table 2 shows the results when the Lx-1 type latex of the present invention was also added and used in the emulsion layer.

[0082] The addition amount of Lx-1 type latex protective layer 1 g / m ^2, the emulsion layer 1 g / m ^2, the amount of gelatin is the protective layer 0.7 g /
m ² and emulsion layer 0.8 g / m ² . However, the amount of gelatin contained in the Lx-1 type latex is included.

[0083]

[Table 2]

Good results were obtained from the results shown in Table 2.

Example 3 (Latex Synthesis Method Lx-3) As another preparation example of the latex of the present invention, 7.5 g of sodium dodecylbenzene sulfonate was added to a solution prepared by adding 1.25 kg of gelatin and 0.05 kg of ammonium persulfate to 40 l of water. While stirring at a liquid temperature of 50 ° C, add a mixture of the monomers (a) to (c) or (d) shown below under a nitrogen atmosphere at a rate such that the average particle size of the finished product is 0.10μ. After that, after stirring for 3 hours, 0.05 kg of ammonium persulfate was added and stirred for 1.5 hours, and after the reaction was completed, steam distillation was performed for 1 hour to remove residual monomers, and after cooling to room temperature, pH was adjusted to 6.0 using ammonia, Finished to 80.5 kg with water.

(Comparative Latex Synthesis Method Lx-4) Lx
As a comparison of -3, Lx- except that 0.75 kg of sodium dodecylbenzene sulfonate was added instead of 1.25 kg of gelatin.
A latex was obtained in the same manner as in 3.

Regarding the above synthetic methods Lx-3 and Lx-4, Lx (7) to (12) were prepared using monomers having the following compositions.
((7) to (11) is synthetic method Lx-3, 12 is synthetic method Lx-4) MFT (7) (a) n-butyl acrylate 4.51 kg (b) styrene 5.49 kg 25 ° C (c) acrylic acid 0.1 kg (8) (A) Ethyl acrylate 3.9 kg (B) Methyl methacrylate 3.9 kg 65 ℃ (C) Styrene 4.8 kg (9) (A) Ethyl acrylate 5.0 kg (B) Methyl methacrylate 1.4 kg 35 ℃ (C) Styrene 3 kg (D) Sodium acrylamide 2-methylpropone sulfonate 0.6g (10) (a) Ethyl methacrylate 6.0kg (b) Styrene 2.9kg 25 ° C (c) Acrylic acid 0.1kg (d) Hydroxyethyl methacrylate 1kg (11) ( A) Ethyl acrylate 4.3 kg (b) Styrene sulfonic acid 3.0 kg (c) Acrylic acid 0.5 kg 47 ° C (d) Trimethylamine methyl acrylimide 1.5 kg (12) Monomer composition is the same as (7) (Synthesis method Lx-4) Example 13 of USP 5026632 The gelatin-grafted polymer particles made according to 15 was (13). Using the above Lx, the amount of gelatin was 1.2 g / m ^{2 for the} emulsion layer, 1.1 g / m ² for the emulsion protective layer, the same emulsion layer and the same emulsion protective layer were used for the latex, and the addition amount was 0.5 g / m ^2. I created what I did. (No.36
-42) As the fixer, in addition to the above fixer formulation, the fixer formulation ~
Was used for the treatment.

The following compound Fa was added to the emulsion protective layer in an amount of 1.5 mg / m ²
Was added.

[0089]

[Chemical 14]

[Fixing Solution Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml 168.2 g Sodium sulfite 5.6 g Sodium acetate trihydrate 27.8 g Boric acid 9.8 g Sodium citrate dihydrate 2 g Acetic acid ( 90% W / V aqueous solution) 6.4 g (Composition B) Pure water (ion exchanged water) 2.8 ml Sulfuric acid (50% W / V aqueous solution) 6.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / V) 25.31 g of the fixing solution was dissolved in 500 ml of water in this order in the order of composition A and composition B, and the solution was made up to 1 liter. The pH of this fixer is about 4.
Was 4.

1-Phenyl-3-pyrazolidone When the developer was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter.

[Fixing liquid formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml 168.2 g Sodium sulfite 5.6 g Sodium acetate trihydrate 27.8 g Boric acid 9.8 g Sodium citrate dihydrate 2 g Acetic acid ( 90% W / V aqueous solution) 6.4 g (Composition B) Pure water (ion-exchanged water) 2.3 ml Sulfuric acid (50% W / V aqueous solution) 6.6 g When using the fixer, the above composition A and composition B in 500 ml of water in this order It was melted and finished to 1 l for use. The pH of this fixer is about 4.
Was 3.

1-Phenyl-3-pyrazolidone When the developer was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter.

[Fixing Solution Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml 176cc Sodium sulfite 23 g Sodium acetate trihydrate 44.16 g Boric acid 9.8 g Acetic acid (90% W / V aqueous solution) 10.5 ml Tartaric acid 1.0g Sulfuric acid (50% W / V aqueous solution) 9.12g Aluminum sulphate EDTA 0.1g Glutaraldehyde 8g (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 20g Finished to 1 liter when used as a fixing solution .. This fixer
The pH was about 4.7.

The results are shown in Table 3.

[0096]

[Table 3]

From the results shown in Table 3, it can be seen that the latex of the present invention is excellent regardless of the composition of the fixing solution.

Example 4 Samples 36 to 42 of Example 3 in which the grain size of silver halide grains was 0.3 μm to 0.35 μm, 43 to 49 and 50 to 56, respectively.
And The same evaluation as in Example 3 was performed with the fixing solution No. 2. The results are shown in Table 4.

[0099]

[Table 4]

From the results of Table 4, Lx with a particle size exceeding 0.3 μm
, The silver sludge prevention effect was significantly deteriorated, and Dmax
It can be seen that the decrease of

Example 5 For sample No. 38 of Example 3, the amount of gelatin was the same as that of the emulsion layer and the protective layer, and the total amount was 3.3 g / m ² and 2.7 g / m ² .
m ^2, what was 1.9 g / m ² and Nanba64,65,66, also No.6
For each of 4, 65, 38, 66, Lx was not added at all and was set to 67 to 70.

The results of the same experiment as in Example 4 are shown in Table 5.
Shown in.

[0103]

[Table 5]

As is clear from Table 5, in the latex of the present invention, the generation of silver sludge was extremely small as compared with the case where Lx was replaced with the same amount of gelatin.

[0105]

Industrial Applicability According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is free from silver sludge and a decrease in density even when subjected to rapid processing and has good drying property.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, in at least one of the non-photosensitive hydrophilic colloid layers. A silver halide photographic light-sensitive material, characterized in that a polymer latex stabilized with gelatin is contained in the solution, and at least a part of a polymerization reaction of a polymer constituting the polymer latex is carried out in a solvent containing at least gelatin. .. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the average particle size of the latex is 0.3 μm or less. 3. The total amount of the hydrophilic binder on the side containing the photosensitive silver halide emulsion layer with respect to the support is 2.7 g / m 2.
^{3. The} silver halide photographic light-sensitive material according to claim ^2, which is ² or less. 4. A silver halide photographic light-sensitive material according to claim 3, wherein at least one light-sensitive silver halide emulsion layer contains a gelatin-stabilized polymer latex.