JPH05289243A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material and the image forming method superior in antistatic characteristic and not causing uneven development during processing with an automatic developing machine by making it contain a specified water-soluble polymer and a specified surfactant. CONSTITUTION:The silver halide photographic sensitive material is characterized by that a hydrophilic colloidal layer on the silver halide emulsion layer side of a support contains at least one kind of the water-soluble polymer represented by formula I or having repeating units represented by formula II, and at least one kind of nonionic surfactant represented by formula III or the like. In formula I, A is a group of formula IV; each of B and C is a group having a vinyl monomer unit copolymerizable with A; each of R1 and R2 is H, an alkyl, or the like; (a) is -CONH-; (b) is an alkylene; j is 0 or 1; k is 1-10; and M is H or the like. In formula II, each of R1-R6 is H, an alkyl, or the like, and in formula III, R1 is an alkyl or the like; and A is -O-or the like.

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 an image forming method.
In addition, the present invention relates to a silver halide photographic light-sensitive material that does not cause uneven development during processing by an automatic processor and a rapid image forming method.

[0002]

BACKGROUND OF THE INVENTION It is effective to incorporate a nonionic surfactant in a hydrophilic colloid layer of a silver halide photographic light-sensitive material in order to improve static marks generated by frictional charging, peeling charging and the like. Are known.

However, when a nonionic surfactant is contained in the hydrophilic colloid layer on the side having the silver halide emulsion layer in order to improve the antistatic property, uneven development often occurs during the processing by the automatic processor. The problem came out.

Therefore, it has been desired to provide a silver halide photographic light-sensitive material which is excellent in antistatic performance and which does not cause uneven development when processed by an automatic processor, and a rapid image forming method.

[0005]

It is an object of the present invention to have excellent antistatic performance,
Another object of the present invention is to provide a silver halide photographic light-sensitive material and a rapid image forming method in which development unevenness does not occur in processing by an automatic processor.

[0006]

The objects of the present invention have been achieved by the following structures.

That is ,. In a silver halide photographic light-sensitive material processed by an automatic processor, in the hydrophilic colloid layer on the side having the silver halide emulsion layer, the following general formula [I]
Or at least one water-soluble polymer comprising at least one compound having a repeating structural unit represented by the following general formula [II] and containing the following general formulas [III] and [III ' ] Or [III ″] at least one nonionic surfactant is contained in the silver halide photographic light-sensitive material.

[0008] The silver halide photographic light-sensitive material as described above, wherein the surface matting degree on the side having the silver halide emulsion layer is 50 mmHg or less.

[0009]. The object of the present invention has been achieved by the image forming method using the light-sensitive material described above, which is characterized in that the total processing time is 50 seconds or less.

That is, as a means for improving uneven development in a system containing a nonionic surfactant. The hydrophilic polymer of the general formula [I] or the general formula [II] in the hydrophilic colloid layer on the side having the silver halide emulsion layer.
The present inventors have discovered a new fact that uneven development can be greatly improved by containing at least one hydrophilic polymer consisting of at least one compound having a repeating structural unit represented by

[0011]. It was discovered that the lower the surface matte degree on the side having the silver halide emulsion layer (50 mmHg or less), the greater the merit of including the above compound.

[0012]. Fast total processing time (less than 50 seconds)
The object of the present invention was achieved by discovering that the merit of including the above compound is great.

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[0016]

[Chemical 9]

[0017]

[Chemical 10]

The present invention is described in detail below.

The water-soluble polymer of the general formula [I] used in the present invention will be described below.

[0020]

[Chemical 11]

In the formula, A represents the following general formula [A], and B and C represent compounds having a vinyl monomer copolymerizable with A. The general formula [I] contains the repeating unit of the general formula [A] in an amount of 10 to 100 mol% in one molecule of the polymer (that is, n = 10 to 100).
Mol% m + 1 = 0 to 90 mol%).

[0022]

[Chemical 12]

In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent. For example, a methyl group. , Ethyl group, propyl group, butyl group, etc.), halogen atom (eg chlorine atom) or --CH ₂ COOM
Represents a, -CONH-, -NHCO-, -COO-, -OCO-,
_{-CO -, - SO 2 -,} > NHSO 2 -, - SO 2 NH- or an -O-, b is an alkylene group, preferably having 1 to 10 carbon atoms
And alkylene groups (including those having a substituent. For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.), arylene groups (including those having a substituent, such as phenylene group, etc. ), An aralkylene group (including those having a substituent), M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group, and j represents an integer of 0 or 1. , K is 1-10
Represents an integer of, Y is a hydrogen atom or

[0024]

[Chemical 13]

Represents

Specific examples of the compound (water-soluble polymer) represented by the general formula [I] preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

[0033]

[Chemical 20]

The water-soluble polymer which is used in the present invention and comprises at least one compound having a repeating structural unit represented by the general formula [II] will be described below.

[0035]

[Chemical 21]

In the formula, R _{1 to} R ₆ are hydrogen atoms and have 1 carbon atom.
To an alkyl group having 8 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or --SO ₃ X, wherein X is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group, and R _At least one of _{1 to} R ₆ is -SO.
₃ X.

The compound having the repeating structural unit represented by the general formula [II] used in the present invention can be obtained by a method in which a diene monomer is sulfonated and then polymerized, or a diene monomer is polymerized and then sulfonated. it can.

In the compound used in the present invention, the repeating structural unit represented by the general formula [II] may be 10 mol% or more, preferably 20 mol% or more.

Examples of the diene monomer used in the present invention include 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene and 1,2- Hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-
Hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1, 6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-
In addition to heptadiene, 3,5-heptadiene, 2-phenylbutadiene and the like, various branched diene monomers can be mentioned.

These diene monomers can be used alone or in combination of two or more.

In the method in which the diene monomer is sulfonated and then polymerized, the sulfonated product can be produced, for example, by the sulfonation method described below while leaving the double bond of the diene monomer.

That is, sulfur trioxide can be used as a sulfonating agent in the diene monomer to effect sulfonation under known conditions as shown in the Chemical Society of Japan, Practical Chemistry Lecture, JP-A 1-26310.

The cation species of the sulfonated product thus obtained are not particularly limited, but hydrogen, alkali metal, alkaline earth metal, ammonium, amine and the like are required to make them water-soluble. preferable.

The alkali metal is sodium,
Potassium and the like, amines include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, and other alkylamines, ethylenediamine, diethylenetriamine, triethylenetetramine, and other polyamines, morpholine, piperidine, and the like. Examples of alkaline earth metals include calcium and magnesium.

Further, these cation species can be exchanged with other cation species by various ion exchange techniques.

The compound having a repeating structural unit represented by the above-mentioned general formula [II], which is related to the present invention, is a diene monomer during the polymerization, and other compounds copolymerizable therewith. It is also possible to copolymerize the monomer (hereinafter referred to as "other monomer") in an amount of 99% by weight or less, preferably 1 to 98% by weight, more preferably 10 to 90% by weight.

As the other copolymerizable monomer,
Aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; methyl acrylate,
Alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacryl;
Acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Mono- or dicarboxylic acids such as fumaric acid and itaconic acid or anhydrides of dicarboxylic acids; butadiene, isoprene,
Aliphatic conjugated dienes such as 2-chloro-1,3-butadiene and 1-chloro-1,3-butadiene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl methyl ether, acetic acid Vinyl, vinyl formate, allyl acetate, methallyl acetate, acrylamide, methacrylamide, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, allyl alcohol and the like are used.

That is, the sulfonated diene monomer and, if necessary, another monomer copolymerizable therewith are added to a radical polymerization initiator and a chain in the presence of a polymerization solvent such as water or an organic solvent. Radical polymerization is performed using a transfer agent.

The sulfonated polymer thus obtained may have a repeating structural unit represented by the general formula [II '] and / or the general formula [II "] in addition to the general formula [II]. ..

General formula [II '] and / or general formula [II "]
The structural unit represented by 0 to 70 mol%, preferably 0 to 50
It is contained in mol%. The content can be controlled by the polymerization conditions.

[0051]

[Chemical formula 22]

(In the general formulas [II '] and [II "], R
_{1 to} R ₆ are the same as those in the general formula [II]. The sodium sulfonate-converted weight average molecular weight of the sulfonated polymer thus obtained cannot be uniquely determined depending on the intended use,
Usually, it is 500 to 5,000,000, preferably 1,000 to 500,000.

The sulfonated polymer obtained by the present invention can be exchanged with the acid type or salts of alkali metal, alkaline earth metal, ammonium, amine and the like by ion exchange method or neutralization reaction.

If a salt is not formed in the monomer sulfonated product prior to polymerization, the sulfonated polymer thus obtained is then treated in an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide or aqueous ammonia. Neutralized, whereupon salts of water-soluble or hydrophilic polymers are obtained in which at least some of the sulfone groups form salts.
Here, the cation species for forming a salt in the sulfone group of the sulfonated polymer, that is, the cation species of the sulfonate is not particularly limited, in order to make water-soluble, the above-mentioned hydrogen atom, Alkali metal, alkaline earth metal, ammonium, amine and the like are preferable.

Further, these cationic species can be exchanged with other cationic species by various ion exchange techniques.

Thus, an aqueous solution of a water-soluble (co) polymer salt is prepared.

The degree of neutralization of the sulfone group is (co)
The polymer salt may be appropriately selected within the range of being water-soluble or water-dispersible, and further salts having different sulfo groups may be formed.

The (co) polymer according to the present invention is obtained from the sulfonated diene monomer as described above, but as another method, it can be obtained by polymerizing the diene monomer and then sulfonated, and produced by any method. It may be a thing. These are manufactured by a known method.

Specific examples of the compound having a repeating structural unit represented by the general formula [II] used in the present invention are shown below, but the present invention is not limited thereto.

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

Some of these compounds are commercially available as JSR water-soluble polymers from Japan Synthetic Rubber Co., Ltd., for example.

Next, the general formula [II used in the present invention
The nonionic surfactant represented by I], [III ′] or [III ″] will be described below.

[0066]

[Chemical 27]

R ₂ , R ₃ , R ₇ , and R ₉ are hydrogen atoms, substituted or unsubstituted alkyl groups, aryl groups, alkoxy groups,
It represents a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. In the formula, R ₆ and R ₈ represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen atom, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group. In the general formula [III ″], the substituents on the phenyl ring may be left-right asymmetric. R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R ₄ and R ₅ , R ₆ and R _7, and R ₈ and R ₉ may be linked to each other to form a substituted or unsubstituted ring. n ₁ ,
n ₂ , n ₃ and n ₄ represent the average degree of polymerization of ethylene oxide,
It is a number from 2 to 50. Further, m represents the average degree of polymerization, and is 2 to 50.
Is the number of.

Specific examples of the compounds represented by formula [III], [III '] or [III "] preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0069]

[Chemical 28]

[0070]

[Chemical 29]

[0071]

[Chemical 30]

[0072]

[Chemical 31]

And Exemplified Compound Nos. I-1 to I-7 described in JP-A-52-55521, page 2, and Exemplified Compounds I-15 to 18 in JP-A-60-76741, pages 5-8. , I-20 to 21, I-24,
I-29, I-34, I-44, I-60 and the like can be mentioned.

The above compounds can be easily synthesized, for example, by adding ethylene oxide to the corresponding fatty acid monoethanolamide and reacting them. For example, commercially available Amizet 5C, Amizet 10C (both manufactured by Nikko Chemical Co., Ltd.) and the like belong to the compound 4, and can be used in the present invention.

The amount of the above surfactant used varies depending on the form, type, coating method, etc. of the photographic light-sensitive material to be used.
Generally, it is preferably used in an amount of 1 to 1,000 mg, and particularly preferably 5 to 200 mg per 1 m ² of the photographic light-sensitive material. The method for applying the above surfactant in the layer of the photographic light-sensitive material is
After dissolving in water or an organic solvent such as methanol, ethanol, acetone or a mixed solvent of water and the organic solvent, a photosensitive emulsion layer on a support, a non-photosensitive auxiliary layer (for example, an antihalation layer, an intermediate layer, It may be contained in a protective layer or the like) or sprayed, coated on the surface of the support or dipped in the solution and dried. At this time, two or more nonionic and anionic surfactants may be mixed and used.

[0076]

EXAMPLES The present invention will be further described below with reference to examples.

Needless to say, the present invention is not limited to this embodiment.

Example-1 [Preparation of Emulsion A] 130 g of KBr, 2.5 g of Kl, 1-phenyl-5
-While stirring 1 l of a solution containing 30 mg of mercaptotetrazole and 15 g of gelatin at 40 ° C, 500 ml of a solution containing 0.5 mol of ammoniacal silver nitrate was added in 1 minute, and acetic acid was added 2 minutes after the addition to give a pH of 6.0. I chose After another minute, silver nitrate is reduced to 0.
After adding 500 ml of a solution containing 5 mol for 1 minute and stirring for 15 minutes, an aqueous solution of formalin condensate of naphthalenesulfonic acid naphthalene and magnesium sulfate was added to agglomerate the emulsion. After removing the supernatant liquid, 2 liters of warm water at 40 ° C. was added, and after stirring for 10 minutes, an aqueous solution of magnesium sulfate was added again to aggregate the emulsion,
After removing the supernatant, add 300 ml of 5% gelatin solution and add 3 at 55 ℃.
An emulsion was prepared by stirring for 0 minutes.

This emulsion has an average grain size of 0.27 μm and 0.1 μm.
90% of the total number of particles was contained from m to 0.70 μm.

[Preparation of Emulsion B] AgBr having an average particle size of 0.1 μm
I (AgI content 6 mol%) seed emulsion was used to add an aqueous solution of ammoniacal AgNO _{3 and an} aqueous solution of potassium bromide by the double jet method to obtain AgBrI (average Ag
A cubic monodisperse emulsion having an I content of 0.4 mol% was grown. The coefficient of variation (σ / r) was 0.17.

These emulsions A and B were dissolved just before chemical ripening, and when the temperature became constant, a dye of the following formula (1) was added, and ammonium thiocyanate, chloroauric acid and hypo were added for chemical sensitization. After application, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added.

[0082]

[Chemical 32]

[Coating of red-sensitive emulsions A and B] Coating of backing layer and protective layer As a backing layer, 400 g of gelatin, 2 g of polymethylmethacrylate having an average particle size of 6 μm, 24 g of KNO ₃ and 6 g of sodium dodecylbenzenesulfonate, halation described below. Equivalent to 2 g / m ^{2 of} dye emulsion dispersion consisting of 20 g of anti-dye,
And a backing layer liquid consisting of glyoxal,
Glycidyl methacrylate 50 wt%, methyl acrylate
A polyethylene terephthalate base coated with an aqueous dispersion of a copolymer obtained by diluting a copolymer composed of three kinds of monomers of 10 wt% and 40 wt% of butyl methacrylate so that the concentration becomes 10 wt% A backed support obtained by coating on one surface with a protective layer liquid containing gelatin, a matting agent, glyoxal, and sodium dodecylbenzenesulfonate was prepared.

The coating amount was 2.0 g / m ² with the backing layer and the protective layer coated with gelatin.

[0085]

[Chemical 33]

Preparation of Red-Sensitive Sample Nos. 1-14, 17-43, 45 Red-sensitive silver halide emulsion layer solution 10 g of trimethylolpropane, nitrophenyl-triphenylphosphine per mol of silver halide of emulsions A and B. Fonium chloride 50mg, 1,3-dihydroxybenzene-4
-Ammonium sulfonate 1 g, 2-mercaptobenzimidazole-5-sodium sulfonate 10 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1,1-dimerol-1-bromo-1- Nitromethane 10 mg

[0087]

[Chemical 34]

And the like were added to prepare a red-sensitive silver halide emulsion layer liquid.

Emulsion side protective layer liquid having the following composition.
The added amount is shown as an amount per 1 l of the coating liquid.

Lime treated inert gelatin 68g Acid treated gelatin 2g

[0091]

[Chemical 35]

Polymethylmethacrylate 4 μm particles were added so as to have a mat degree shown in Table 1.

Silicon dioxide particles Matting agent having an area average particle size of 1.2 μm 0.5 g Ludox AM (manufactured by DuPont) (colloidal silica) 30 g 2-4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution 2 % (Hardener) 10 ml Formalin 35% (Hardener) 2 ml Glyoxal aqueous solution 40% (Hardener) 1.5
ml

[0094]

[Chemical 36]

C ₄ F ₉ SO ₃ K
2mg Topside 300 (manufactured by Permachem Asia Ltd.) 45mg General formulas [III] to [III ""] (nonionic surfactant) (addition other than sample No. 1) Exemplified compound III-15 0.4g Exemplified compound III- 22 2.5g Each layer was coated on the opposite side of the backed base by the slide hopper method from the support in the order of two layers of silver halide emulsion layer solution and protective layer solution simultaneously at a coating speed of 80 m / min to obtain a red-sensitive sample. .. Silver amount is 2.5 g / m ² , gelatin amount is emulsion layer 2.2 g / m ² .
m ² and the protective layer were 1.2 g / m ² .

As shown in Table 1, water-soluble polymers represented by the general formulas [I] and [II] to [II ""] were added to the emulsion layer or the protective layer.

[Preparation of Emulsion C] 1) Preparation of Seed Emulsion 0.05N potassium bromide aqueous solution containing hydrogen peroxide-treated gelatin vigorously stirred at 40 ° C. containing silver nitrate aqueous solution and hydrogen peroxide treated gelatin, etc. Molar aqueous potassium bromide solution was added by the daffle jet method, and after 1.5 minutes, the solution temperature was lowered to 25 ° C over 30 minutes.
80 ml of ammonia water (28%) was added and stirring was continued for 5 minutes. After that, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of demole Na manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added and redispersed. The resulting seed emulsion had an average grain size of 0.23 μm and a coefficient of variation of 0.28.
It was a spherical particle.

2) Growth from Seed Emulsion Grains were grown as follows using the above seed emulsion. 75
An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a daffle jet method to an aqueous solution containing ossein gelatin and propyleneoxy polyethyleneoxydisuccinate disodium salt vigorously stirred at ℃. During this period, pH was kept at 5.8 and pH was kept at 9.0. After the addition is complete, adjust the pH to 6.
At 0, 400 mg / mol AgX of anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt was added. Further, after desalting at 40 ° C. with an aqueous solution of Demol Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, gelatin aqueous solution was added and redispersed.

By this method, a tabular silver iodobromide emulsion (C) having an average silver iodide content of 1.5 mol% and a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 4.0. Was prepared.

[Preparation of Green Sensitive Samples No. 13, 14, 34, 35]
The resulting emulsion (C) was heated at 55 ° C. with 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium anhydride and 5,5'- Di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride 20
500 mg was added per mol of silver halide in a weight ratio of 0: 1.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added 3 × per mol of silver halide. 10 ^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin. The following additives were added to the aged emulsion C. The addition amount is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butylcatechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1, Ammonium 3-dihydroxybenzene-4-sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 1-Phenyl-5-mercaptotetrazole 10 mg Trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂ 1g

[0103]

[Chemical 37]

Further, 1.2 g of the dye emulsion dispersion shown below.
Was added to prepare an emulsion coating solution.

[Preparation Method of Dye Emulsion Dispersion] The following dyes
10 kg of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate
Was dissolved in a solvent consisting of This is called an oil-based solution. On the other hand, 270 l of a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) was prepared. This is called an aqueous solution. Next, the oil-based solution and the aqueous solution were put into a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C. To the resulting dispersion, appropriate amounts of phenol and 1,1'-dimethylol-1-brom-1-nitromethane were added and the weight was adjusted to 240 kg with water.

[0106]

[Chemical 38]

The additives used in the protective layer solution on the emulsion side are as follows. The added amount is shown as an amount per 1 l of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate, a matting agent having an area average particle size of 4 μm was added so as to have a matting degree shown in Table 1. ..

Silicon dioxide particles Matting agent having an area average particle size of 1.2 μm 0.5 g Ludox AM (manufactured by DuPont) (colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ). ₂ O (hardener) 500mg Topside 300 (Permachem Asia Ltd.) 45mg

[0110]

[Chemical Formula 39]

Nonionic surfactant (general formulas [III] to [III ″]) III-15 0.4 g III-22 2.5 g The emulsion layer has a silver conversion value of 2.9 g / m ² , and the protective layer has a gelatin coating amount. Of 1.1 g / m ² with two slide hopper type coaters at a speed of 90 m / min, a copolymer consisting of three monomers of 50 wt% glycidyl methacrylate, 10 wt% methyl acrylate and 40 wt% butyl methacrylate. Of the 175 μm polyethylene terephthalate film base coated with an aqueous dispersion of a copolymer obtained by diluting it to a concentration of 10 wt%, with the emulsion layer on one side and the protective layer on the other side on the backing. The lower layer was coated on both sides simultaneously and dried in 2 minutes and 15 seconds to obtain green-sensitive samples Nos. 15, 16, and 44.

The composition of the backing layer liquid was as follows, and the water-soluble polymer was added as shown in Table 1.

Backing Layer Liquid Composition The backing layer was coated in two layers, the upper layer having a gelatin coating amount of 1.2 g / m ² and the lower layer having a coating amount of 3.0 g / m ² .

For the backing layer, the following liquids were prepared and used.

(Backing layer) (Backing lower layer liquid) Per 1 liter of coating liquid Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A 1.0 g Backing dye B 1.0 g Glyoxal aqueous solution (40%) (hardening agent) 8 g (backing upper layer liquid) Per liter of coating liquid Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A 1.0 g Backing dye B 1.0 g Backing dye C 1.0 g KNO ³ 0.5
g

[0116]

[Chemical 40]

F ₁₉ C ₉ O (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ —SO ₃ Na
0.1g 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 2% aqueous solution 20ml Polymethylmethacrylate particles with area average particle size 6μm 1.1g C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 1.0 g

[0118]

[Chemical 41]

Evaluation of Matte Degree The matte degree refers to an unexposed film (so-called raw film) which has been subjected to humidity control for 3 hours at 23 ° C. and 48% RH.
The suction pressure is measured under the same conditions, and the value is expressed in mmHg. The larger this value is, the higher the matteness is. A smoother (manufactured by Toei Denshi Kogyo Co., Ltd.) was used for measuring the suction pressure in Examples described later.

[0120]

[Table 1]

Evaluation of Antistatic Properties (Static Marks) The static marks were evaluated in order to examine the antistatic properties of the obtained samples. Samples 1 to 45 were conditioned at 23 ° C. and 20% RH for 1 hour, then cut into 6 cm × 30 cm pieces, and a 500 g weight 13 was hung on the tip as shown in FIG. Approximately 30 mmφ at one reciprocating speed in 0.8 seconds
It was brought into contact with the neoprene rubber rod 10 and was rubbed forcibly. Then, leave it unexposed, Konica X-ray automatic processor SRX-50
1 was used for development, and the presence or absence of static marks was visually checked to evaluate antistatic properties according to the following criteria. The results are shown in Table 2.

Evaluation criteria ◎ Very good ○ Good △ No problem in practical use × Inferior evaluation of development unevenness Sample Nos. 1 to 45 were uniformly exposed to a density of 1.1 ± 0.1 with tungsten light, and then After performing the [development treatment and post-treatment] as shown, the level of development unevenness was visually evaluated. The results are shown in Table 2.

Evaluation Criteria ◎ Very good ○ Good △ No practical problems × Inferior × × Very inferior

[0124]

[Table 2]

From the results shown in Table 2, it can be seen that the samples of the present invention are excellent in antistatic property and development unevenness.

[Development processing and post-processing] For development, an automatic developing machine SRX-501 (manufactured by Konica Corporation) was used with a developing solution and a fixing solution having the following compositions, the developing temperature was 35 ° C, the fixing temperature was 33 ° C, and washing was performed with water. Water was supplied at 3.5 ° C./min at a temperature of 18 ° C., and the entire treatment process was performed at 45 ° C. and 45 ° C. for 90 seconds as shown in Table 1.

[Treatment process] Process Treatment temperature (° C) Treatment time (sec) Compensation Insertion-1.2 Development + Crossover 35 14.6 33cc / 4-cut Fixing + Crossover 33 8.2 63cc / 4-cut Wash + Crossover 18 7.2 3.51 / min Squeeze 40 5.7 Dry 45 8.1 Total-45.0 (Developer) H Potassium sulfite 70g Hydroxyethylethylenediaminetriacetate trisodium 8g 1,4-Dihydroxybenzene 28g Boric acid 10g 5-Methylbenzotriazole 0.04g 1-phenyl -5-Mercaptotetrazole 0.01g Sodium metabisulfite 5g Acetic acid (90%) 13g Triethylene glycol 15g 1-Phenyl-3-pyrazolidone 1.2g 5-Nitroindazole 0.2g Glutaraldehyde 4g Potassium bromide 4g 5-Nitrobenzimidazole 1 g of 1 l of an aqueous solution was prepared, and the solution was adjusted to pH 10.5 with sodium hydroxide.

(Fixer) Sodium thiosulfate-5-hydrate 4.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Aluminum sulfate 10-18 hydrate 10 g Sulfuric acid (50 wt%) 5 g Citric acid 1 g An aqueous solution of 7 g of boric acid and 5 g of 1 g of glacial acetic acid was used to prepare glacial acetic acid as a pH 4.2 solution.

(Developer) K Glutaraldehyde was removed from the developer H.

[0130]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material excellent in antistatic performance and free from uneven development during processing by an automatic processor, and a rapid image forming method.

[Brief description of drawings]

FIG. 1 is an apparatus for preparing a sample to be subjected to a static mark test.

[Explanation of symbols]

 10 Neoprene rubber rod 12 Silver halide photosensitive material sample 13 Weight

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material processed by an automatic processor, wherein the hydrophilic colloid layer on the side having the silver halide emulsion layer has a water-soluble polymer represented by the following general formula [I] or It contains at least one water-soluble polymer consisting of at least one compound having a repeating structural unit represented by the general formula [II], and has the following general formula [II
A silver halide photographic light-sensitive material containing at least one nonionic surfactant of I], [III ′] or [III ″]. [In the formula, A represents the following general formula [A], and B and C represent a compound having a vinyl monomer copolymerizable with A. The general formula [I] contains the repeating unit of the general formula [A] in an amount of 10 to 100 mol% in one molecule of the polymer (that is, n = 10 to 100 mol% m).
+ 1 = 0 to 90 mol%). ] [Chemical 2] [In the formula, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom or —CH ₂ COOM.
Represents a, -CONH-, -NHCO-, -COO-, -OCO-,
_{-CO -, - SO 2 -,} > NHSO 2 -, - SO 2 NH- or an -O-, b represents an alkylene group, an arylene group, an aralkylene group, j represents an integer of 0 or 1, k Represents an integer of 1 to 10, M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group, and Y represents a hydrogen atom or Represents. ] [Chemical 4] [Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or -SO ₃ X. Where X is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₅
At least one of ₆ is -SO ₃ X. ] [Chemical 5] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the surface matte degree on the side having the silver halide emulsion layer is 50 mmHg or less. 3. The image forming method using the light-sensitive material according to claim 1, wherein the total processing time is 50 seconds or less.