JPH09160155A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance reduction characteristics and film strength without increasing applied amounts of silver and gelatin and to obtain an extremely high- contrast image. SOLUTION: This photosensitive material has at least 2 silver haluide emulsion layers on a support, and it contains gelatin in an amount of <=3g/m<2> and a polymer latex made of repeating units derived from an ethylenically unsaturated monomer having an active methylene group on the side of the emulsion layers and the content of the above polymer latex in the emulsion layer nearer to the support is controlled to <=1/2 of the total contents of the above polymer latex in the emulsion layers farther apart from the support.

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 super-hard-contrast silver halide photographic light-sensitive material excellent in reducing power and film strength.

[0002]

2. Description of the Related Art Generally, gelatin is often used as a binder in a hydrophilic colloid layer constituting a silver halide photographic light-sensitive material. Such a hydrophilic colloid layer has drawbacks such as easy expansion and contraction in response to changes in humidity and temperature, and brittleness in a low humidity atmosphere. For the purpose of improving these drawbacks, a polymer latex is contained in a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, a protective layer, and a back layer.

For example, US Pat. No. 2,763,625,
2,852,382, JP-A-62-115,152.
JP-A-5-66,512 and JP-A-5-80,449
No., JP-B-60-15935, JP-B4-64058
No. 5,450,014 and the like disclose that a hydrophilic colloid layer contains a polymer latex composed of various monomers including alkyl acrylate and alkyl methacrylate. Also, Japanese Patent Publication No. 45-581
No. 9, No. 46-22507, JP-A-50-73625
Discloses that a polymer latex obtained by copolymerizing a monomer having an active methylene group with a monomer such as an alkyl acrylate is contained in a gelatin film to improve the strength of the latex-containing gelatin film when wet. . This method is particularly effective when the coating amount of gelatin in the light-sensitive material is reduced.

On the other hand, in obtaining a final halftone dot image or line image, the photosensitive material for plate making is subjected to a process called a reduction process in order to obtain a subtle tone reproduction, and the image is partially finely corrected. There are many. For this reason, it is an important issue for the photosensitive material for plate-making to have a reducing property. However, it has been found that when the above-mentioned conventional polymer latex is used, this reducing property is deteriorated, particularly when the coating amount of gelatin per unit area in the light-sensitive material is reduced.

In order to reduce the strength of a plate-making photosensitive material on which a halftone dot image or a line image has been formed through exposure and development, a method of bleaching the metallic silver forming the halftone dot or line image with an oxidizing agent, etc. It has been known. For example, Mies: The Theory of the Photographic Process 3rd Edition "The Theo
ry of the Photographic Process 3rd.Ed. "738-7
On page 39 (1954 published by Macmillan), there is a reducing fluid using reducing components such as permanganate, ferric salt, cerium salt, red blood salt, dichromate, and persulfate. Have been described.

When a halftone dot image is subjected to a reduction process, it is general that the blackening density per halftone dot decreases in parallel with the decrease in the halftone dot area. The smaller the decrease in blackening density per area, the wider the correctable range of reduction.

Therefore, in the reduction processing, the larger the amount of silver per unit area that oxidizes and dissolves the silver image, the wider the range in which the image can be corrected by the reduction processing. Therefore, in the present invention, when the halftone dot blackening density is reduced to the minimum density value required in the plate making process by the reduction processing, how much the halftone dot area is reduced as compared with that before the treatment The term "" is used.

As described above, it is known that this reduction width can be increased by increasing the amount of silver forming an image, that is, by increasing the coated silver amount and the coated gelatin amount. . However, this direction is not preferable from the viewpoint of resource saving, and causes various problems in the processing steps such as deterioration of development progress, poor fixing and poor drying. Further, in the recent demand for a low replenishment amount of the processing solution, the processing fatigue of the developing solution and the fixing solution becomes large, so that the above-mentioned problem becomes more serious. Therefore, without increasing the coating silver amount and coating gelatin amount,
It is desired to develop a photosensitive material for plate making which has excellent reducing power characteristics and film strength.

Further, in recent years, in the field of printing plate making, a method has been known in which a hydrazine compound is contained in a silver halide photographic light-sensitive material to obtain a high contrast image called nucleation development. For example, in the specification of US Pat. No. 2,419,975, a hydrazine compound was added to a silver chlorobromide emulsion, and 1
It is described that when developed with a developer having a high pH such as 2.8, extremely hard photographic characteristics in which gamma (γ) exceeds 10 are obtained. Also, Japanese Patent Laid-Open No. 1-1799
No. 39, JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorbing group for silver halide emulsion grains and a hydrazine compound also having an adsorbing group is used. A processing method of developing with a developer is described.

The hard halftone image obtained in this way has a smaller reduction width than the soft halftone image. Therefore, there is a demand for the development of a photosensitive material for plate making that can obtain a high contrast image without deteriorating the reduction property.

[0011]

A silver halide photographic light-sensitive material which has excellent reducing properties and film strength without increasing the amount of coated silver and the amount of coated gelatin, and can obtain an extremely high contrast image. To provide.

[0012]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least two silver halide emulsion layers on a support, wherein the amount of gelatin on the emulsion layer side is 3 g / m 2. ² or less, containing a polymer latex containing an active methylene group, the amount of the polymer latex in the emulsion layer close to the support side is one half or less of the total amount of the polymer latex in the emulsion layer above it. Was achieved by a silver halide photographic light-sensitive material.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer latex of the present invention comprises
It is a polymer represented by the following general formula (1). General formula (1)

[0014]

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In the formula, D represents a repeating unit derived from an ethylenically unsaturated monomer containing an active methylene group, A is other than D, and its homopolymer has a glass transition temperature of 35 ° C. or lower. A repeating unit derived from such an ethylenically unsaturated monomer is represented, and B represents a repeating unit derived from an ethylenically unsaturated monomer other than D and A.

X, y and z represent the weight percentage ratio of each component, x is 0.5 to 40, y is 60 to 99.5,
z has a value of 0 to 50. Where x + y + z = 1
Represents 00.

More specifically, the ethylenically unsaturated monomer containing an active methylene group represented by D is
It is represented by the following general formula.

[0018]

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In the formula, R ^{1 represents a} hydrogen atom, a carbon number of 1 to 4 (eg methyl, ethyl, n-propyl, n-butyl) or a halogen atom (eg chlorine atom, bromine atom), preferably a hydrogen atom. Represents a methyl group and a chlorine atom.
L represents a single bond or a divalent linking group, and is specifically represented by the following formula.

[0020]

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L ¹ is -CON (R ² )-(R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms), -COO-, -NHCO-. , -OC
O-,

[0022]

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(R ³ and R ⁴ each independently represent hydrogen, hydroxyl, halogen atom or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), and L ² is a link connecting L ¹ and X. Represents a group, m represents 0 or 1, n represents 0 or 1
Represents The linking group represented by L ² is specifically represented by the following general formula.

[0024]

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J ¹ , J ² and J ³ may be the same or different, and --CO--, --SO _2- , --CON (R ⁵ )-(R
⁵ represents a hydrogen atom, an alkyl group (1-6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon _{atoms), - SO 2 N (R} 5) - (R 5 is as defined above), - N (R ⁵⁾ -R ^6- (R ⁵ is as defined above, R ⁶ is an alkylene group having 1 to about 4 carbon atoms), -N (R
^{5) -R 6 -N (R 7} ) - (R 5, R 6 are as defined above, R ⁷
Represents a hydrogen atom, an alkyl group (1 to 6 carbon atoms), or a substituted alkyl group (1 to 6 carbon atoms). ), -O-, -S-,
^{-N (R 5) -CO-N} (R 7) - (R 5, R 7 are as defined ^{above), - N (R 5)} -SO 2 -N (R 7) - (R 5, R 7 is as defined above), - COO -, - OCO -, - N (R 5) C
O ₂ - (R ⁵ is as defined ^{above), - N (R 5)} CO- (R 5
Is synonymous with the above) and the like.

P, q, r and s represent 0 or 1.
X ¹ , X ² and X ³ may be the same or different from each other, and represent an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group, or a phenylene group;
The alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene group such as benzylidene, and phenylene group such as p-phenylene and m-phenylene. ,
For example, methylphenylene.

X represents a monovalent group containing an active methylene group, and a preferred specific example thereof is R ⁸ --CO--CH ₂ --C.
OO- (R ⁸ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, n-propyl,
n-butyl, t-butyl, n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl, etc.), a substituted or unsubstituted aryl group (eg, phenyl, p-methylphenyl, p-methoxyphenyl, o-chlorophenyl, etc.), an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, n
-Butoxy, etc.),

Cycloalkyloxy groups (eg cyclohexyloxy), allyloxy (eg phenoxy, p
-Methylphenoxy, o-chlorophenoxy, p-cyanophenoxy, etc.), amino group, substituted amino group (for example,
Methylamino, ethylamino, dimethylamino, butylamino, etc.)), NC—CH ₂ —COO—, R ⁸ —CO—
CH ₂ -CO- (R ⁸ is the same), R ⁸ -CO-C
^{_{H 2 -CONR 5 - (R 5}} , R 8 have the same meanings as defined above), and the like.

Examples of the polymer represented by the general formula (1) of the present invention are ethylenically unsaturated monomers having an active methylene group represented by D, but the present invention is not limited thereto. is not.

M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetamidoethyl methacrylate M- 6 2-acetoacetamidoethyl acrylate

M-7 2-cyanoacetoxyethyl methacrylate M-8 2-cyanoacetoxyethyl acrylate M-9 N- (2-cyanoacetoxyethyl) acrylamide M-10 2-propionylacetoxyethyl acrylate M-11 N- (2 -Propionylacetoxyethyl) methacrylamide M-12 N-4- (acetoacetoxybenzyl) phenylacrylamide

M-13 ethyl acryloyl acetate M-14 acryloyl methyl acetate M-15 N-methacryloyloxymethyl acetoacetamide M-16 ethyl methacryloyl acetoacetate M-17 N-allyl cyanoacetamide M-18 methyl acryloyl acetoacetate

M-19 N- (2-methacryloyloxymethyl) cyanoacetamide M-20 p- (2-acetoacetyl) ethylstyrene M-21 4-acetoacetyl-1-methacryloylpiperazine M-22 ethyl-α-acetate Acetoxymethacrylate M-23 N-butyl-N-acryloyloxyethylacetoacetamide M-24 p- (2-acetoacetoxy) ethylstyrene

The ethylenically unsaturated monomer giving the repeating unit represented by A is a monomer whose homopolymer has a glass transition temperature of 35 ° C. or lower, and specifically, an alkyl acrylate (for example, methyl acrylate). ,
Ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, etc.), alkyl methacrylate (for example, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-). Dodecylmethacrylate etc.), dienes (eg butadiene, isoprene etc.), vinyl esters (eg vinyl acetate, vinyl propionate etc.) and the like.

Further preferred monomers are those having a homopolymer glass transition temperature of 10 ° C. or lower,
Examples of such a monomer include an alkyl acrylate having an alkyl side chain having 2 or more carbon atoms (for example, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc.), an alkyl methacrylate having an alkyl side chain having 6 or more carbon atoms (for example, , N-hexyl methacrylate, 2-ethylhexyl methacrylate, etc.),
Dienes (eg, butadiene and isoprene) can be mentioned as particularly preferable examples.

Regarding the value of the glass transition temperature of the above-mentioned polymer, see “Polymer Hand” edited by J. Brandrup and EHImmergut.
book "3rd edition (John Wiley & Sons. 1989) VI / 209 ~
It is described on page VI / 277.

The repeating unit represented by B represents a repeating unit other than A, that is, a repeating unit derived from a monomer whose homopolymer has a glass transition temperature of higher than 35 ° C.

Specifically, acrylic acid esters (eg, t-butyl acrylate, phenyl acrylate,
2-naphthyl acrylate, etc.), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, phenyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate, etc.),

Vinyl esters (eg, vinyl benzoate, viparoyloxyethylene, etc.), acrylamides (eg, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide) , Hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide,
Diacetone acrylamide),

Methacrylamides (eg, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide). Amide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide,
Diethyl methacrylamide, β-cyanoethyl methacrylamide, etc.),

Styrenes (for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester). Such),

Examples thereof include acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, N-vinyloxazolidone, vinylidene chloride and phenyl vinyl ketone.

Further, in the polymer represented by the general formula (1) of the present invention, Japanese Patent Publication Nos. 60-15935 and 45,
-3832, 53-28086, U.S. Pat.
A monomer having an anionic functional group (for example, a carboxyl group or a sulfonic acid group) as described in No. 700,456 may be copolymerized for the purpose of improving the stability of latex.

Examples of such a monomer include the following compounds. Acrylic acid; methacrylic acid;
Itaconic acid; Maleic acid; Monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, etc .; Monoalkyl maleate, such as monomethyl maleate, monoethyl maleate, etc .; Citraconic acid; Styrene sulfonic acid; Vinyl sulfonic acid; acryloyloxyalkyl sulfonic acid,
For example, acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc .; methacryloyloxyalkyl sulfonic acid, such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid, acrylamidoalkyl Sulfonic acid, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-
2-methylpropanesulfonic acid, 2-acrylamide-
2-methylbutanesulfonic acid and the like; methacrylamide alkylsulfonic acid, for example, 2-methacrylamide-2
-Methylethanesulfonic acid, 2-methacrylamide-2
-Methylpropanesulfonic acid, 2-methacrylamide-
2-Methylbutanesulfonic acid and the like; these acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions.

X, y and z represent weight percentage ratios of the respective monomer components in the polymer, x is 0.5 to 40, preferably 0.5 to 30, particularly preferably 1 to 20, and y is 60 to 99.5, preferably 70 to 9
9.5, particularly preferably 75 to 99, and z is 0
To 50, preferably 0 to 35, particularly preferably 0 to 25.

The above-mentioned monomer having an anionic functional group can be used as required for imparting stability to the latex, regardless of the glass transition temperature of the homopolymer thereof. The preferred amount, when used, is 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the total weight of the polymer.

Preferred compounds of the polymer latex of the general formula (1) of the present invention are exemplified below. The values in parentheses indicate the weight percentage of each component in the copolymer.

L-1 ethyl acrylate / M-1 / acrylic acid copolymer (85/10/5) L-2 n-butyl acrylate / M-1 / 2-acrylamido-2-methylpropanesulfonic acid sodium tere copolymer Combined (85/10/5) L-3 n-butyl acrylate / M-1 / methacrylic acid copolymer (85/5/10) L-4 2-ethylhexyl acrylate / M-2 / 2
-Acrylamido-2-methylpropanesulfonic acid sodium copolymer (75/20/5) L-5-9 n-butyl acrylate / M-1 / acrylic acid copolymer (x / y / z) L-5x / Y / z = 95/2/3 L-6 x / y / z = 92/5/3 L-7 x / y / z = 89/8/3 L-8 x / y / z = 81/16 / 3 L-9 x / y / z = 72/25/3

L-10 n-butyl acrylate / styrene / M-1 / methacrylic acid copolymer (65/20/5/10) L-11 methyl acrylate / M-4 / methacrylic acid copolymer (80/15) / 5) L-12 n-butyl acrylate / M-5 / acrylic acid copolymer (85/10/5) L-13 n-butyl acrylate / M-7 / methacrylic acid copolymer (85/10/5) ) L-14 2-ethylhexyl acrylate / M-9 copolymer (75/25) L-15 n-butyl acrylate / M-13 / sodium styrene sulfonate copolymer (85/10/5)

L-16 n-butyl acrylate / styrene / potassium styrene sulfinate copolymer (75/20 /
5) L-17 n-hexyl acrylate / methoxyethyl acrylate / M-2 copolymer (70/20/10) L-18 2-ethylhexyl acrylate / M-15 / methacrylic acid copolymer (90/5/5 ) L-19 n-butyl acrylate / M-1 / M-17 / acrylic acid copolymer (75/5/15/5) L-20 octyl methacrylate / M-20 / sodium styrene sulfonate copolymer (80 / 15/5)

The polymer latex of the present invention is prepared by a generally well-known emulsion polymerization method, and its particle size is preferably in the range of 0.01 to 1.0 μm.
Emulsion polymerization preferably uses at least one emulsifier to emulsify a monomer in water or a mixed solvent of water and an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.) and use a radical polymerization initiator. Generally 3
0 ° C to about 100 ° C, preferably 40 ° C to about 90 ° C
C. at a temperature of .degree. The amount of the water-miscible organic solvent is 0 to 100% by volume with respect to water, preferably 0 to 50.
%.

The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and, if necessary, 0.1 to 10% by weight of an emulsifier based on the monomers to be polymerized. As the polymerization initiator, adibis compound, peroxide,
Hydroperoxide, redox catalyst, etc., such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, Dicumyl peroxide,
Examples include 2,2'-azobisisobutyrate and 2,2'-azobis (2-amidinopropane) hydrochloride.

As the emulsifier, anionic, cationic,
In addition to amphoteric and nonionic surfactants, there are water-soluble polymers and the like. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrimethyl. Ammonium chloride, N-2-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, JP-B-53-61
There are emulsifiers described in No. 90, water-soluble polymers and the like.

In emulsion polymerization, depending on the purpose,
Wide range of polymerization initiator, concentration, polymerization temperature, reaction time, etc.
Needless to say, it can be easily changed. Also,
The emulsion polymerization reaction may be carried out by previously putting all of the monomers, the surfactant and the medium in a container and then adding an initiator,
If necessary, the polymerization may be carried out while dropping a part or the whole of each component.

Regarding the type of the monomer having an active methylene group represented by D or the polymer latex represented by D in the polymer represented by the general formula (1) of the present invention and the method for synthesizing the same, other than the above-mentioned US Pat. No. 3,459. , 790 and 3,
619, 195, 3,929, 482, 3,7
00,456, West German Patent No. 2,442,165, European Patent No. 13,147, Japanese Patent Laid-Open No. 50-73625,
It can be carried out with reference to the description in No. 50-146331 and the like.

Next, the polymer latex having a core / shell structure of the present invention will be described. The core constituting the latex of the present invention is specifically a polymer composed of one or more repeating units of various polymerizable ethylenically unsaturated monomers.

As such a monomer, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, dienes, acrylamides, methacrylamides, vinyl ethers, and various other ethylenically unsaturated monomers are used. In addition, a monomer having two or more ethylenically unsaturated groups can also be preferably used.

More specific examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate. , Amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-
Chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate,
Phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl. Acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (addition mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1 , 1-dichloro-2-ethoxyethyl acrylate and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n.
-Butyl methacrylate, isobutyl methacrylate,
sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, N-ethyl-
N-phenylaminoethyl methacrylate, 2- (3-
Phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate,
2- (2-methoxyethoxy) ethyl methacrylate,
2- (2-butoxyethoxy) ethyl methacrylate,
Allyl methacrylate and the like can be mentioned.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,
3-butadiene, 2-methyl-1,3-pentadiene,
1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1, 3-butadiene, 1-chlorobutadiene, 2-
Fluoro-1,3-butadiene, 2,3-dichloro-
1,3-butadiene, 1,1,2-trichloro-1,3
-Butadiene and 2-cyano-1,3-butadiene.

In addition to the above monomers, acrylamides such as acrylamide, ethyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide and diacetone acrylamide; Amides: For example, methacrylamide, ethyl methacrylamide, tert-butyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, etc .;

Olefins: for example, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, etc .; Styrenes: for example, styrene, methylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, Chlorostyrene,
Dichlorostyrene, bromstyrene, vinyl benzoic acid methyl ester, etc .; Vinyl ethers: For example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, etc .;

In addition, butyl crotonic acid, hexyl crotonic acid, dimethyl itaconic acid, dimethyl maleic acid, dibutyl maleate, diethyl fumarate, dimethyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl. Pyrrolidone, acrylonitrile, methacrylonitrile, methylenemalonnitrile, vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride,
Examples thereof include vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and styrene sulfonic acid.

It is also possible to use at least two monomers having a copolymerizable ethylenically unsaturated group in the core of the latex of the present invention. Examples of such monomers include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Examples include trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol methacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

The monomers listed above may be used alone or in combination of two or more. From the viewpoint of easiness of polymerization and easiness of forming a core / shell structure, among the above-mentioned monomer groups, acrylates, methacrylates, vinyl esters, conjugated dienes, Styrenes, 2
It is a monomer having one or more ethylenically unsaturated groups.
Among the core polymers described above, a particularly preferred embodiment is that the core polymer is produced by emulsion polymerization and exists in the form of a fine particle dispersion (latex) in an aqueous medium.

In such a dispersion, the core polymer is present in the form of fine particles. The particle size of the polymer affects the physical properties of the film mixed with gelatin, the stability of dispersion in water itself, and the ability to form a film. From the above points, the number average particle diameter of the core polymer is 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less. And the lower limit is preferably 0.00001 μm or more.

The shell portion of the core / shell latex of the present invention will be described below. The shell portion of the present invention is a polymer having a repeating unit derived from at least one ethylenically unsaturated monomer having an active methylene group represented by the following general formula (A). General formula (A)

[0068]

[Chemical 6]

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X is R ² COCH ₂ COO—, NC
_{^{-CH 2 COO-, R 2 COCH 2}} CO-, NC-CH
₂ CO- (R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, It represents the 12 substituent amino group), R ⁹ -CO-C
H ₂ CON (R ⁶ ) — (R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁹ represents 1 carbon atom.
X represents an active methylene group selected from substituted or unsubstituted primary or secondary alkyl groups, alkoxy groups having 1 to 12 carbon atoms, amino groups, and substituted amino groups having 1 to 12 carbon atoms; L is linked to alkylene aralkylene or arylene.

More specifically, R ¹ represents a hydrogen atom, a carbon number of 1 to 4 (eg, methyl, ethyl, n-propyl, n-butyl) or a halogen atom (eg, chlorine atom, bromine atom), It is preferably a hydrogen atom, a methyl group or a chlorine atom. L represents a single bond or a divalent linking group, and is specifically represented by the following formula.

[0071]

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L ¹ is -CON (R ³ )-(R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms), -COO-, -NHCO.
-, -OCO-,

[0073]

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(R ⁴ and R ⁵ each independently represent hydrogen, hydroxyl, a halogen atom or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), and L ² represents L ¹ and X. It represents a linking group, and m represents 0 or 1, and n represents 0 or 1. When n = 0, m = 0. L
^The linking group represented by ² is specifically represented by the following general formula.

[0075]

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J ¹ , J ² and J ³ may be the same or different, and --CO--, --SO _2- , --CON (R ⁶ )-
(R ⁶ is a hydrogen atom, an alkyl group (1-6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon _{atoms)), - SO 2 N (} R 6) -
(R ⁶ is as defined above), —N (R ⁶ ) —R ⁷ — (R ⁶ is as defined above, R ⁷ is an alkylene group having 1 to about 4 carbon atoms),
—N (R ⁶ ) —R ⁷ —N (R ⁸ ) — (R ⁶ and R ⁷ are as defined above, R ⁸ is a hydrogen atom, an alkyl group (having 1 to 1 carbon atoms)
6), a substituted alkyl group (1-6 carbon atoms; examples of the substituent include a halogen atom and an alkoxy group (methoxy, ethoxy, etc.)). ), -O-, -S-, -N (R
^{6) -CO-N (R 8} ) - (R 6, R 8 are as defined ^{above), - N (R 6)} -SO 2 -N (R 8) - (R 6, R
⁸ is as defined above), -COO-, -OCO-, -N (R
⁶ ) CO _2- (R ⁶ is as defined above), -N (R ⁶ ) CO
— (R ⁶ is as defined above) and the like.

P, q and r represent 0 or 1. X ¹ ,
X ² , X ³ and X ⁴ may be the same or different from each other, and may be an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or phenylene having 6 to 20 carbon atoms. Represents an alkylene group which may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, methoxymethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decylmethylene. Examples of the aralkylene group include benzylidene. Examples include phenylene, methylphenylene, chlorphenylene, and methoxyphenylene.

X is a monovalent group containing an active methylene group, and more specifically, R ² COCH ₂ COO- and NCCH ₂ C.
_{^{OO-, R 2 COCH 2 CO-,}} NC-CH 2 CO-,
R ⁹ -CO-CH ₂ CON (R ⁶ )-can be mentioned. Here, R ⁶ has the same meaning as described above, and R ² has 1 carbon atom.
~ 12 substituted or unsubstituted alkyl groups (e.g. methyl, ethyl, n-propyl, n-butyl, t-butyl,
n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl etc.),
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl, p-methylphenyl, p-methoxyphenyl, o-chlorophenyl, etc.), an alkoxy group having 1 to 12 carbon atoms (eg, methoxy, ethoxy, methoxyethoxy). , N-butoxy, etc.),

Cycloalkyloxy groups (eg cyclohexyloxy), allyloxy (eg phenoxy, p
-Methylphenoxy, o-chlorophenoxy, p-cyanophenoxy, etc.), an amino group, and a substituted amino group having 1 to 12 carbon atoms (eg, methylamino, ethylamino, dimethylamino, butylamino, etc.). Of the above-mentioned, particularly preferred are substituted or unsubstituted primary or secondary alkyl groups having 1 to 12 carbon atoms.

R ⁹ represents a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group or a substituted amino group having 1 to 12 carbon atoms, Specific examples thereof are the same as those described above for R ² . Particularly preferred as R ⁹ is a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms.

Of the active methylene groups represented by X described above, R is the one which exhibits particularly preferable effects in the present invention.
² COCH ₂ COO-, NCCH ₂ COO-, R ² CO
CH ₂ CO-, a NC-CH ₂ CO-.

Specific examples of the monomer having an active methylene group which gives the repeating unit constituting the shell in the latex of the present invention are shown below, but the present invention is not limited thereto.

M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetamide ethyl methacrylate M- 6 2-acetoacetamidoethyl acrylate

M-7 2-cyanoacetoxyethyl methacrylate M-8 2-cyanoacetoxyethyl acrylate M-9 N- (2-cyanoacetoxyethyl) acrylamide M-10 2-propionylacetoxyethyl acrylate M-11 N- (2 -Propionylacetoxyethyl) methacrylamide M-12 N-4- (acetoacetoxybenzyl) phenylacrylamide

M-13 Ethyl Acryloyl Acetate M-14 Acryloyl Methyl Acetate M-15 N-Methacryloyloxymethylacetoacetamide M-16 Ethyl Methacryloyl Acetoacetate M-17 N-Allyl Cyanoacetamide M-18 2-Cyanoacetylethyl Acrylate

M-19 N- (2-methacryloyloxymethyl) cyanoacetamide M-20 p- (2-acetoacetyl) ethylstyrene M-21 4-acetoacetyl-1-methacryloylpiperazine M-22 ethyl-α-acetate Acetoxymethacrylate M-23 N-butyl-N-acryloyloxyethylacetoacetamide M-24 p- (2-acetoacetoxy) ethylstyrene

In the polymer constituting the shell portion of the present invention, an ethylenically unsaturated monomer other than the above ethylenically unsaturated monomer containing an active methylene group may be copolymerized. Examples of such monomers include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers, and other monomers constituting the core particles. Can be listed,
Of these, acrylic esters, methacrylic esters, vinyl esters, and styrenes are particularly preferred.

In the core / shell polymer latex of the present invention, the proportion of the monomer unit having an active methylene group in the shell polymer can be arbitrarily changed according to the need for performance, and is used in the range of 0.1 to 100% by weight. I can do things. However, when the copolymerization amount of the monomer unit having an active methylene group is increased, the above-mentioned various effects are increased. However, when the amount exceeds a certain amount, the effect may be saturated. %
Particularly preferred is 1 to 40% by weight.

The amount ratio of the core polymer and the shell polymer in the core / shell polymer latex of the present invention can be arbitrarily changed, but the core / shell weight ratio is 10 /.
90-95 / 5, preferably 20 / 80-95
/ 5, particularly preferably 30/70 to 90/10. This means that if the core is too small, the effect of concentrating the active methylene monomer on the shell decreases, and if the shell is too small, it becomes difficult to form a clear core / shell structure. The particle diameter of the core / shell polymer latex is 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less, similarly to the core polymer particles. And the lower limit is preferably 0.00001 μm or more.

As is well known in the field of core / shell latex forming technology in emulsion polymerization, the combination of the core polymer and the shell polymer having polarities close to each other and compatibilizing each other results in the desired core / shell structure. May not be formed sufficiently. In order to form a more effective core / shell structure, it is preferable to select a polymer in which the polymer forming the shell and the polymer forming the core are hardly compatible.

One of the extremely useful embodiments in this respect is to use a polymer having a conjugated diene monomer component as the core. When the conjugated diene monomer is used in a certain amount or more, the core particles have extremely low polarity, so that it is possible to form an effective core / shell structure with most of the monomers used for the shell portion. The standard for forming a core having such performance is that the conjugated diene monomer is contained in an amount of 25% or more by weight. As a preferred example, a styrene-butadiene copolymer (generally called SBR and solution-polymerized SBR) is used.
And emulsion polymerization SBR. As the solution-polymerized SBR, in addition to the random polymer, the above-mentioned block copolymer (for example,
Butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer)), butadiene homopolymer (for example, cis-1,4-butadiene,
Trans-1,2-butadiene, or a rubber in which these are mixed with a trans-1,4-butadiene structure), an isoprene homopolymer (an example of a three-dimensional structure is the same as a butadiene polymer), a styrene-isoprene copolymer (Random copolymer, block copolymer), ethylene-propylene-diene copolymer (diene monomers include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, etc.), acrylonitrile-
Butadiene copolymer, chloroprene copolymer, isobutylene-isoprene copolymer, butadiene-acrylate copolymer (acrylates such as ethyl acrylate and butyl acrylate) and butadiene-acrylate-acrylonitrile copolymer A polymer (the same as the acrylic ester described above) can be used.

Further, it is possible to form an effective core / shell structure by selecting a polymer having a large polarity difference between the polymer forming the core and the shell. For example, poly (n-dodecyl methacrylate) core / poly (methyl acrylate) -Co-2-acetoacetoxyethylmethacrylate) shell or poly (ethylacrylate) core / poly (styrene-co-2-acetoacetoxyethylacrylate)
And the like. However, these are the core /
This shows that the effect of the shell polymer latex can be selected depending on the magnitude of the effect. Even in the case of a combination of polymers having similar polarities, the core / shell polymer latex of the present invention can be used for a non-core / shell type polymer latex. Shell latex exhibits better film strength properties.

Even when a monomer having a similar polarity is used for the core and the shell, the core is the above-mentioned crosslinking monomer (a monomer having two or more ethylenically unsaturated groups in the molecule).
By performing three-dimensional cross-linking using a polymer, an extremely effective core / shell polymer latex can be obtained. As described above, in the present invention, it is possible to form a useful core / shell polymer latex structure irrespective of the type of monomer used.

The core / shell latex of the present invention has a glass transition temperature of the core portion or the shell portion, or both of the core portion and the shell portion, in view of the brittleness improving effect when added to the gelatin film in addition to the film strength characteristics. Tg) is 50 ° C
It is appropriate that the Tg of the core part is lower than the Tg of the shell part, more preferably the Tg of the core part is lower than 0 ° C. (the lower limit is −110 ° C.).
C), and the Tg of the shell part is preferably 0C or more (the upper limit is 150C).

The Tg of the polymer is, for example, “J. Brandrup,
E. FIG. H. Co-authored by Immergut. PolymerHondbook, 2nd Edition,
III-139 to III-192 (1975) ", and in the case of a copolymer, it can be determined by the following formula.

[0096]

[Equation 1]

In the core / shell polymer latex of the present invention, the core polymer, the shell polymer, or both may be crosslinked. In this case, the molecular weight of the obtained polymer is infinite. The molecular weight of the polymer of the present invention in the case of non-crosslinking depends on the kind of the monomer and the synthesis conditions, but is in the range of 5,000 to 2,000,000, and the molecular weight may be adjusted by a chain transfer agent or the like depending on the purpose. Is also possible.

Preferred examples of the compound of the core / shell latex of the present invention are shown below, but the present invention is not limited thereto. The structure of each of the following latex compounds is described in the order of the core polymer structure, the structure of the shell polymer and the ratio of the core / shell, and the copolymer composition ratio and the core / shell ratio in each polymer are all expressed by weight percentage. .

P-1 to 12 core: styrene / butadiene copolymer (37/63) P-1 shell = styrene / M-1 (98/2) core / shell = 50/50 P-2 shell = styrene / M-1 (96/4) Core / Shell = 50/50 P-3 Shell = Styrene / M-1 (92/8) Core / Shell = 50/50 P-4 Shell = Styrene / M-1 (84 / 16) Core / Shell = 50/50 P-5 Shell = Styrene / M-1 (68/32) Core / Shell = 50/50 P-6 Shell = Styrene / M-1 (84/16) Core / Shell = 67/33 P-7 shell = styrene / M-1 (84/16) core / shell = 85/15 P-8 shell = n-butyl acrylate / M-1 (96/4) core / shell = 50/50 P-9 shell = n-butyl acrylate / M-1 (92/8) core / shell = 50/50 P-10 shell = n-butyl acrylate Core / shell = 50/50 P-11 shell = methyl acrylate / M-7 (84/16) core / shell = 50/50 P-12 shell = styrene / methyl acrylate / M-3 (21/63/16) core / shell = 50/50

P-13,14 Core: Styrene / Butadiene Copolymer (22/78) P-13 Shell = Styrene / M-2 (84/16) Core / Shell = 50/50 P-14 Shell = n- Butyl acrylate / M-8 (84/16) core / shell = 50/50

P-15 to 20 Core: polybutadiene homopolymer (100) P-15 shell = styrene / M-1 (84/16) core / shell = 50/50 P-16 shell = ethyl acrylate / M-7 / Methacrylic acid (65/15/20) core / shell = 75/25 P-17 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-18 shell = n-butyl Acrylate / M-2 (84/16) core / shell = 50/50 P-19 shell = 2-ethylhexyl acrylate / M-24 (84/16) core / shell = 50/50 P-20 shell = n-butyl Acrylate / M-18 (84/16) core / shell = 50/50

P-21 to 23 Core: polyisoprene homopolymer (100) P-21 shell = styrene / acrylonitrile / M-1 (63/21/16) core / shell = 90/10 P-22 shell = methyl Methacrylate / Ethyl acrylate / M-2 / 2- Sodium acrylamido-2-methylpropanesulfonate (15/65/15/5) Core / Shell = 75/25 P-23 Shell = Styrene / M-1 (84/16) ) Core / shell = 20/80

P-24 to 26 core: styrene / butadiene copolymer (49/51) P-24 shell = styrene / butyl acrylate / M-1 (26/60/15) core / shell = 50/50 P- 25 Shell = M-1 (100) Core / Shell = 90/10 P-26 Shell = Lauryl Methacrylate / Butyl Acrylate / M-7 (30/55/15) Core / Shell = 40/60 P-27 Core: Acrylonitrile / Styrene / Butadiene Copolymer (25/25/50) Shell: Butyl Acrylate / M-1 (92/8) Core / Shell = 50/50 P-28 Core: Ethyl Acrylate / Butadiene Copolymer (50 / 50) Shell: Styrene / divinylbenzene / M-1 (79/5/16) core / shell = 50/50

P-29 to 33 Core: poly (n-dodecyl methacrylate) homopolymer P-29 shell = styrene / M-1 (92/8) core / shell = 50/50 P-30 shell = styrene / M -1 (84/16) Core / Shell = 50/50 P-31 Shell = Ethyl Acrylate / M-1 (96/4) Core / Shell = 50/50 P-32 Shell = Ethyl Acrylate / M-1 (92 / 8) Core / shell = 50/50 P-33 Shell = styrene / methyl acrylate / M-3 (21/63/16) Core / shell = 50/50

P-34 core: poly (n-butyl acrylate) homopolymer shell: styrene / M-2 (84/16) core / shell = 50/50 P-35,36 core: poly (ethylene glycol dimethacrylate) / n-butyl acrylate) copolymer (10/90) P-35 shell = styrene / M-1 (84/16) core / shell = 50/50 P-36 shell = methyl acrylate / M-7 / methacrylic acid (65/15/20) Core / Shell = 75/25

P-37 to 40 core: poly (ethylene glycol dimethacrylate / n-butyl acrylate) copolymer (20/80) P-37 shell = styrene / M-1 (84/16) core / shell = 50 / 50 P-38 shell = styrene / M-1 (84/16) core / shell = 75/25 P-39 shell = methyl acrylate / M-8 / 2-acrylamido-2-methylsodium sulfonic acid sodium (80 / 15/5) Core / shell = 75/25 P-40 Shell = n-butyl acrylate / M-1 (84/16) Core / shell = 50/50

P-41 to 43 Core: Polyvinyl acetate homopolymer (100) P-41 Shell = styrene / M-1 (84/16) Core / shell = 50/50 P-42 Shell = styrene / divinylbenzene / M-24 (79/5/16) core / shell = 50/50 P-43 shell = n-dodecyl methacrylate / butyl acrylate / M-7 (30/55/15) core / shell = 40/60

P-44 to 46 core: poly (divinylbenzene / 2-ethylhexyl acrylate) copolymer (10/90) P-44 shell = methyl acrylate / M-1 (84/16) core / shell = 50 / 50 P-45 shell = methyl acrylate / styrene / M-1 (74/10/16) core / shell = 50/50 P-46 shell = M-1 (100) core / shell = 90/10 P-47- 49 core: poly (divinylbenzene / styrene / 2-ethylhexyl acrylate) copolymer (10/23/67) P-47 shell = methyl acrylate / M-1 (84/16) core / shell = 50/50 P- 48 shell = methyl acrylate / styrene / M-1 (74/10/16) core / shell = 50/50 P-49 shell = ethyl acrylate / 2-hydroxyethyl methacrylate / M-5 (65/15/20) core / Shi Well = 85/15

P-50 Core: Poly (ethylene glycol dimethacrylate / vinyl palmitate / n-butyl acrylate) copolymer (20/20/60) Shell: Ethylene glycol dimethacrylate / styrene / n-butyl methacrylate / M- 1 (5/40/40/15) core / shell = 50/50 P-51 core: poly (trivinylcyclohexane / n-butyl acrylate / styrene) copolymer (10/55/35) shell: methyl acrylate / M-1 / 2-acrylamido-2-methylpropane sodium sulfonate (88/7/5) core / shell = 70/30 P-52,53 core: poly (divinylbenzene / styrene / methylmethacrylate) copolymer ( 10/45/45) P-52 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-53 shell = n-dodecyl ac Relate / Ethyl Acrylate / M-21 (60/30/10) Core / Shell = 50/50

P-54,55 Core: Poly (p-vinyltoluene / n-dodecylmethacrylate) Copolymer (70/30) P-54 Shell = Methyl Acrylate / n-Butyl Methacrylate / M-2 / Acrylic Acid ( 30/55/10/5) core / shell = 50/50 P-55 shell = n-butyl acrylate / M-19 (84/16) core / shell = 70/30

The core / shell polymer latex of the present invention can be easily prepared by emulsion-polymerizing an aqueous dispersion obtained by emulsion-polymerizing a core latex polymer while adding or dropping a monomer forming a shell all at once. You can get it. The emulsion polymerization method is preferably carried out by emulsifying a monomer in water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) using at least one emulsifier, and using a radical polymerization initiator. Generally from 30 ° C. to about 100 ° C., preferably 40 ° C.
C. to a temperature of about 90.degree. The amount of the organic solvent miscible with water is from 0 to 100%, preferably from 0 to 50%, by volume relative to water.

The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and, if necessary, 0.1 to 10% by weight of an emulsifier based on the monomers to be polymerized. As the polymerization initiator, azobis compounds, peroxides,
Hydroperoxides, redox solvents and the like, for example, potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl-carbonate, 2,4-dichlorobenzyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicane Mil peroxide,
Examples include 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) hydrochloride, and a combination of potassium persulfate and sodium bisulfite.

As the emulsifier, anionic, cationic,
In addition to amphoteric and nonionic surfactants, there are water-soluble polymers and the like. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrisodium Methylene ammonium chloride, N-2-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, sodium dodecyl-diphenylether disulfonate, sodium 2-tetradecene-1-sulfonate, 3-hydroxytetradecane-1- Sodium sulfonate, gelatin, PVA, etc.
No. 6190, emulsifiers, water-soluble polymers and the like, and of these, anionic or nonionic surfactants and water-soluble polymers are particularly preferable.

The addition of the monomer in the emulsion polymerization is preferably carried out while the monomer is added dropwise from the viewpoint of avoiding heat generation due to the polymerization and forming a more definite core / shell structure. Also, by the above initiator, emulsion polymerization in the presence of an emulsifier,
After the core latex particles are formed, when the shell monomer is polymerized, an emulsifier may be further added, or the polymerization may be performed without the emulsifier. In many cases, the addition of an emulsifier is necessary from the viewpoint of the stability of the produced polymer latex. However, if an excess emulsifier is present, particles other than the intended shell polymer alone may be by-produced. Therefore, it is preferable that the amount of the emulsifier added after the formation of the core polymer is suppressed to about 0.001 to 2% by weight based on the core particles, or not added at all.

In order to form a latex having an effective core / shell structure, it is preferable that the polymerization of the core particles at the time of adding the shell-forming monomer be as complete as possible, and the polymerization rate is 90% or more, preferably 95%. Above all, it is particularly preferably substantially 100%.

The active methylene unit functions as a reactive group by improving the film strength of the polymer latex / gelatin composite film and improving various properties of the coating composition and the adhesive latex. Therefore, the amount of active methylene units present on the latex surface is an important factor in performance. The core / shell latex of the present invention is useful in that basically active methylene units can be concentrated on the required latex surface. Further, by controlling other required functions in the core, for example, Tg of the whole latex, the ability to form a film and the physical properties (eg, brittleness) of the resulting film or a composite film with gelatin or the like can be controlled by the shell. Is also very useful in that it can be included independently.

The core / shell latex particles of the present invention are
Although it can be obtained in the form of an aqueous dispersion by the above-mentioned emulsion polymerization method, it is also possible to obtain a fine particle powder while maintaining the core / shell structure. As a method of such powdering,
Lyophilization, aggregation using strong acids or salts, filtration, or aggregation by repeated freeze-thaw of latex solution,
A known method such as a filtration method can be used.

The addition amount of the polymer latex having a repeating unit composed of an ethylenically unsaturated monomer having an active methylene group of the present invention is optional, but preferably,
5 to 400 per weight of gelatin in the hydrophilic colloid layer
%, Preferably 10 to 200%.

The polymer latex of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto. Further, the silver halide photographic light-sensitive material of the present invention has at least two silver halide emulsion layers, but the amount of the polymer latex in the emulsion layer near the support is higher than that of the polymer in the emulsion layer above the support. It is preferably not more than ½ of the total amount of latex, preferably not more than ¼, and it is preferable not to add the polymer latex to the emulsion layer close to the support.

The hydrazine derivative used in the present invention is
It is represented by the following general formula (2). General formula (2)

[0121]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
A —SO ₂ — group, a —SO— group,

[0123]

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Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (2), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (2),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group,
Sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having hydrazide structure, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group , Carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoramide group, diacylamino group, imide group, group having acylurea structure, selenium atom or Examples thereof include a group containing a tellurium atom, a group having a tertiary sulfonium structure or a group having a quaternary sulfonium structure, and a preferable substituent is a linear, branched or cyclic alkyl group (preferably having a carbon number of 1).
~ 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably Amino group substituted with alkyl group having 1 to 20 carbon atoms, acylamino group (preferably having 2 carbon atoms)
To 30), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Stuff).

In formula (2), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (for example, methyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.),
Aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc. ) Etc. Also, G ₁ is -SO
_In the case of a ₂ -group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group).
Or a substituted amino group (eg, dimethylamino group, etc.)
Are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferred. As G _{1 in the} general formula (2), a —CO— group and a —COCO— group are preferable, and a —CO— group is the most preferable. Also, R ₂ is G ₁
Portions of -R ₂ disrupts the residual molecules may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms, examples of which include, for example, Examples thereof include those described in JP-A No. 63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (2) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (2) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (2) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of a silver halide grain, a group having a quaternary ammonium structure or an alkylthio group. A phenyl group having a group, G
_A hydrazine derivative in which ₁ is a -CO- group and R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). It should be noted that any combination of the above-mentioned options of R ₁ and R ₂ is possible and preferable.

In the present invention, a hydrazine derivative characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group is particularly preferably used.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means an atom selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom between a nitrogen atom and an anionic group near the anionic group of hydrazine.
It means that a binding chain formed by the individual is interposed. More preferably, a bond chain formed by 2 to 5 atoms selected from at least one of a carbon atom and a nitrogen atom is present as the vicinity, and a bond chain formed by 2 to 3 carbon atoms is more preferable. It is the case of intervening. The nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and has at least an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (3) to (5). General formula (3)

[0134]

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(In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine, and Represents a nonionic group that forms an intramolecular hydrogen bond.) General formula (4)

[0136]

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(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (5)

[0138]

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(In the formula, X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (3) to (5) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

[0143] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Linear, branched or cyclic alkoxy group such as methoxy, isopropoxy and benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom.
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. n ³ =
In the case of 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group of R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
As described above, for example, a halogen atom (fluorine, chlorine, bromine), a cyano group, a sulfonyl group (methanesulfonyl, benzenesulfonyl), a sulfinyl group (methanesulfinyl), an acyl group (acetyl, benzoyl), an oxycarbonyl group (methoxycarbonyl) ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

Examples of the electron-withdrawing group possessed by L ¹ include R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents of R ^{1 in the} general formula (3). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler or may have an adsorption promoting group to silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (eg, thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,2
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
It is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (3) to (5), radicals from which hydrogen atoms of two compounds are removed may combine with each other to form a bis type. In the general formulas (3) to (5), the general formulas (3) and (4) are preferable, and the general formula (3) is more preferable. Furthermore, in the general formulas (3) to (5), the following general formulas (6) to (8) are more preferable, and the general formula (6) is the most preferable. General formula (6)

[0151]

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(In the formula, R ⁴ , X ⁴ and m ⁴ are respectively synonymous with R ³ , X ³ and m ^{3 in the} general formula (5), and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ^{1 in} the general formula (3). ) General formula (7)

[0153]

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(In the formula, R ⁵ , X ⁵ and m ⁵ are respectively synonymous with R ³ , X ³ and m ^{3 in the} general formula (5), and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (4). ) General formula (8)

[0155]

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(Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ , n ³ or Y in the general formula (5).
Synonymous with ³ . )

Specific examples of the hydrazine derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 356, 898, JP-A-60-1797.
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 2-2541
No. 2, No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442
Nos. 2-220042, 2-221953, 2-221954, 2-285342, and 2-2
No. 85343, No. 2-289843, No. 2-3027
No. 50, No. 2-304550, No. 3-37642,
3-54549, 3-125134, 3-1
No. 84039, No. 3-240036, No. 3-2400
No. 37, No. 3-259240, No. 3-280038.
Nos. 3-282536, 4-51143, and 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
5-45761, 5-45762, 5-45
No. 763, No. 5-45764, No. 5-45765,
Those described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and particularly 1 × 1 mol per mol of silver halide.
The range of 0 ^-5 mol to 2 × 10 ^-2 mol is a preferable addition amount.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. Further, as described in JP-A-2-948, it can be used by being contained in polymer fine particles.

Gelatin is used as the binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids can be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. In the present invention, the coated amount of gelatin as a binder is such that the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less and the total hydrophilic colloid layer on the side having the silver halide emulsion layer is not more than 3 g / m ^2. total gelatin sex colloid layer and all hydrophilic colloid layers on the opposite surface is at 6 g / m ² or less, preferably 2.0 to 6.0 g / m ^2.

The support of the light-sensitive material of the present invention includes cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate described in JP-A-7-28188, and syndine described in JP-A-3-131843. Otatic polystyrene, polyethylene-coated paper, etc. are used.

The developer used in the development processing of the light-sensitive material in the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used. There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable that the developing agent contains dihydroxybenzenes or an ascorbic acid derivative. Further, in view of developing ability, dihydroxybenzenes and 1-phenyl-3- Combination of pyrazolidones, combination of dihydroxybenzenes and p-aminophenols, combination of ascorbic acid derivative and 1-phenyl-3-pyrazolidones, or ascorbic acid derivative and p-
A combination of aminophenols is preferred.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. Ascorbic acid derivative developing agents used in the present invention include ascorbic acid, its stereoisomer erythorbic acid, and its alkali metal salts (sodium and potassium salts). 1 used in the present invention
As a developing agent for phenyl-3-pyrazolidone or a derivative thereof, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3- There is pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , But especially N-methyl-p
-Aminophenol is preferred. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably,
It is in the range of 0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 to 0.6 mol to liter, more preferably 0.2 to 0. 5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less. The ascorbic acid derivative developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, 0.
It is in the range of 2 to 0.6 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 to 0.6 mol / liter, more preferably 0.2 to 0. 5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite.
The sulfite is used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably 0.3
5 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

As the alkaline agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. As additives used in addition to the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as isodazole or its derivatives; mercapto compounds, indazole compounds, benzotriazole compounds, benzimidazole compounds as antifoggants or black spots.
pper) May be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobunzoylaminoindazole, 1-methyl-5-nitroindazole, 6
-Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4
-Thiadiazol-2-yl) thio] butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. it can. The amount of these antifoggants is usually 0.01 to 10 mmol per liter of developer.
And more preferably 0.1 to 2 mmol.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, and itaconic acid , Malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
Nos. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a silver stain preventing agent in the developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, a compound described in JP-A-62-212651 can be used as a development unevenness inhibitor, and a compound described in JP-A-61-267759 can be used as a dissolution aid. , If necessary, toning agent,
A surfactant, a defoaming agent, a hardener, etc. may be included.

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, saccharides (for example, saccharose) described in JP-A-60-93433, and oximes. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The pH of the developer is 9.0 to 13.0, preferably 9.5 to 12.
0. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7 seconds to 1 minute 30 seconds. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 300 ml or less, preferably 250 to 150 ml. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixer used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / l. The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid),
Modifiers (eg, ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, and fixing accelerators can be included. As the surfactant, for example, anionic surfactants such as sulfates and sulfonates, polyethylene surfactants,
Examples include the amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added.
Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator,
For example, JP-B-45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid; and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and 0.01 to
1.0 mol / liter, more preferably 0.02 to 0.1.
Use about 6 mol / l. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. Gluconic acid, iminodiacetic acid, glucoheptanoic acid, 5-sulfosalicylic acid, derivatives thereof, or salts thereof are preferable as the stabilizer for the hardener. Here, gluconic acid may be an anhydride having a lactone ring. Among these compounds, gluconic acid, iminodiacetic acid and their alkali metal salts or ammonium salts are particularly preferable,
These compounds are used at a temperature of 0.01 to 0.45 mol / liter, preferably 0.03 to 0.3 mol / liter in a one-pack type fixing concentrate containing substantially no boron compound. The term "substantially free of boron compound" means that the concentration in the fixing use liquid is 0.04 mol / liter or less. These stabilizers may be used alone or in combination of two or more. Furthermore, malic acid, tartaric acid, citric acid, succinic acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, Tyrone,
Organic acids such as ascorbic acid, glutaric acid and adipic acid, amino acids such as aspartic acid, glycine and cysteine, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid and nitrilotriacetic acid It is also preferable as an aspect of the present invention to use in combination with saccharides and sugars. PH of fixer
Is 3.8 or more, preferably 4.0 to 6.0. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C.
The fixing time at 5 ° C. is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is 300 ml / m ² or less, and particularly preferably 250 ml / m ² or less, with respect to the processing amount of the light-sensitive material.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-287252. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 23
As described in JP-A No. 5133, it can be used for a processing solution having a fixing ability which is a preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, metal compounds such as ammonium compounds, Bi, and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines, and surfactants may be used in this stabilizing bath. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be a powder or may be immobilized.

The solid agent for treatment liquid (powder, granule, granule, lump, paste) and tablet in the present invention are composed of a plurality of layers so that adjacent layers do not have components that react with each other when they contact each other. Alternatively, a single component and / or a blend of plural components which do not react with each other may be coated with a water-soluble coating agent and / or a water-soluble film and packaged.

Any known method can be used for the method for producing the solid agent for treatment liquid and the tablet in the present invention.
For example, as a packaging method, there is JP-A-61-259921.
The methods described in JP-A-4-16841 and JP-A-4-78848 can be used. Further, as a method of solidification and tableting, there are disclosed in JP-A-4-85533 and JP-A-4-85533.
No. 85534, No. 4-85535, No. 5-13436.
No. 2, No. 5-197090, No. 5-204098,
No. 5-224361, No. 6-138604, No. 6-
The method described in 138605 or the like can be used.

As a method for dissolving and replenishing the treating agent of the present invention, a certain amount is dissolved with a dissolving device having a stirring function,
Method of replenishing, dissolving with a dissolving device having a dissolving portion and a portion for stocking the completed liquid, replenishing from the stock portion, adding a treating agent to the circulating system of the automatic developing machine according to the treatment to dissolve and replenish There are methods such as a method and a method of dissolving and replenishing with an automatic developing machine having a dissolving tank built therein, and any other known method can be used.

When the replenishing amount is reduced, it is preferable to prevent the liquid from evaporating and oxidizing by reducing the contact area of the treatment tank with the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. Roller transport type processor is for developing, fixing,
Although it comprises four steps of washing and drying, the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Four steps of a stabilization step may be used instead of the washing step.

There are no particular restrictions on various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Silver halide emulsion and JP-A-2-97937, page 20, lower right column, line 12 The production method (from chemical increase to page 21, lower left column, line 14 and JP-A-2-97937). (1) Sensitive) No. 2236, page 7, upper right column, line 19 to page 8, lower left column, line 12, JP-A-4-330430, JP-A-5-11389, Japanese Patent Application No. 6-250136, Japanese Patent Application No. 6-250159 and Japanese Patent Application No. 6-250146. 2) Spectral sensitizing dyes JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; JP-A-2-39042, page 7, lower right column, line 8, Page 13, lower right column, 5th line. JP-A-2-12236, page 8, lower left column, line 13 to lower right column, JP-A-2-103536, page 16 lower right column, line 3 to page 17, lower left column, line 20 And JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, JP-A-5-11389, and JP-A-4-330434. 3) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) and compound examples II- 1 to II-22, compounds described in JP-A-1-179939.

4) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 5) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 and JP-A-2-55349, page 8, lower right column, line 13 From the same page, page 11, left upper column, line 8. 6) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and JP-A-1-237538. Thiosulfinic acid compounds described in the official bulletin. 7) Polyhydroxyl JP-A-2-55349, page 11, upper left column, page 9 or benzenes, right lower column, line 17; 8) Slip agent, plasticizer From page 6, upper right column, line 6 to page 19, upper right column, line 15 of JP-A-2-103536. 9) Hardener JP-A-2-103536, page 18, line 5 to line 17, upper right column.

10) Dyes JP-A-2-103536, page 17, lower right column, line 1 to line 18, JP-A 2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 The solid dyes described in JP-A-2-2963838 and JP-A-5-11382. 11) Tetrazolium compound JP-A-2-39143, page 4, lower left column, line 8 to page 6, lower left column, line 6, JP-A-3-123346, page 3, upper right column, line 19 to page 5 Line 20 in the upper left column. 12) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 13) Redox compound The compound represented by formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50), and the compound represented by the general formula (3) of JP-A-3-174143, pp. 3 to 20: (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 14) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 15) Colloidal silica A compound described in paragraph [0005] of JP-A-4-214551. 16) Matting agent JP-A-2-103536, page 19, upper left column, line 15 to upper right column, line 6. JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4. JP-A-4-127142, page 3, upper right column, line 7 to page 5, lower right column, line 4. JP-A-6-118542, paragraph numbers "0005" to "0026". 17) Antistatic A conductive compound described in U.S. Pat. No. 4,999,276 and a fluorinated surfactant.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0198]

【Example】

Example 1 <Emulsion preparation> Emulsion A: 3 x 10 ^-5 mol of sodium benzenethiosulfonate per mol of silver and sodium chloride kept at 38 ° C, 3 x 10 ^-3 mol of 4-hydroxy-6-methyl-
PH containing 1,3,3a, 7-tetrazaindene = 2.
An aqueous sodium chloride solution containing 4 × 10 ^-5 mol of K ₂ Ru (NO) Cl ₅ per 1 mol of silver nitrate in a 1.5% gelatin aqueous solution of 0 was finally prepared by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds. Half of the silver amount of the particles was added at the same time to prepare core particles of 0.12 μm. Then, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 4 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per 1 mol of silver were added in the same manner as above for 7 minutes to give a silver chloride cube having an average particle size of 0.13 μm. Particles were prepared. (Coefficient of variation: 12%) After that, washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added,
Compound-A and phenoxyethanol as preservatives in silver 1
After adding 60 mg per mole, pH 5.5, pAg =
After adjusting to 7.5 and adding 4 × 10 ⁻⁵ mol of chloroauric acid to 1 mol of silver, 1 × 10 ⁻⁵ mol of sodium thiosulfate and 1 × 10 ⁻⁵ mol of selenium compound SE were added. In addition, after heating at 60 ° C. for 60 minutes for chemical sensitization, 4-hydroxy-6-methyl-1,3,3 as a stabilizer was added.
1 × 10 ⁻³ mol of a, 7-tetrazaindene was added per mol of silver (as final particles, pH = 5.5, pAg =
7.5, Ru = 4 × 10 ⁻⁵ mol / Ag mol).

Emulsion B: K ₂ doped in grain formation
It was prepared exactly like Emulsion A except that the amount of Ru (NO) Cl ₅ was 7 × 10 ⁻⁵ mol / Ag mol.

<Preparation of Emulsion Layer Coating Solution A and Coating> The following compounds were added to Emulsion A and halogenated so that the gelatin coating amount and coating silver amount were as shown in Table 1 on the following support including the undercoat layer. Silver emulsion layer A was coated. Sodium 3- (5-mercaptotetrazole) benzenesulfonate 5.5 mg / m ² N-oleyl-N-methyltaurine sodium 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² Hydrazine compound I-23 7.5 mg / m ² Compound-B 6.6 mg / m ² compound-C 7.5 mg / m ² compound-D 10 mg / m ² polymer latex Type and amount described in Table 1 Sodium ascorbate 0.5 mg / m ² compound-E (dural membrane) Agent) Amount that makes the swelling rate of distilled water at 25 ° C for 1 minute on the emulsion side after coating be 80%

<Preparation of Emulsion Layer Coating Solution B and its Coating> The following compounds were added to Emulsion B, and the amount of gelatin coating and the amount of coating silver were added to the upper layer of Emulsion A so that the silver halide emulsion layer was as shown in Table 1. B was applied. Sodium 3- (5-mercaptotetrazole) benzenesulfonate 5.5 mg / m ² N-oleyl-N-methyltaurine sodium 10 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² Hydrazine compound I-23 7.5 mg / m ² Compound-B 6.6 mg / m ² compound-C 7.5 mg / m ² compound-D 10 mg / m ² polymer latex Type and amount described in Table 1 Sodium ascorbate 0.5 mg / m ² compound-E (dural membrane) Agent) Amount that makes the swelling rate of distilled water at 25 ° C for 1 minute on the emulsion side after coating be 80%

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer. <Preparation of Emulsion Protection Lower Layer Coating Solution and Its Coating> The following compound was added to an aqueous gelatin solution, and the gelatin coating amount was 0.8 g / g.
It was applied as a m ^2. Gelatin (Ca ⁺⁺ content 2700 ppm) 0.8 g / m ² sodium p-dodecylbenzenesulfonate 10 mg / m ² sodium polystyrene sulfonate 6 mg / m ² compound-A 1 mg / m ² compound-F 14 mg / m ² C ₂ H ₅ SO ₂ SNa 3 mg / m ² compound-H 20 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Liquid and Its Coating>
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.45g / m ² Amorphous silica matting agent 40mg / m ² (average particle size 3.5μ, pore diameter 25Å, surface area 700m ² / g) Amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² p-sodium dodecylbenzenesulfonate 30 mg / m ² compound- A 1 mg / m ² liquid paraffin 40 mg / m ² solid disperse dye-G ₁ 5 mg / m ² solid disperse dye-G ₂ 70 mg / m ² sodium polystyrene sulfonate 4 mg / m ²

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated with the first and second undercoat layers having the following compositions on both sides. <Undercoat first layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g colloidal Silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. 2 The dry film thickness is 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-N 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-A 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm, to prepare a support including an undercoat layer.

Then, a conductive layer and a back layer shown below were simultaneously coated on the side of the support opposite to the side coated with the emulsion layer. <Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² p-sodium dodecylbenzenesulfonate 13 mg / m ² dihexyl-α-sulfo Succinate sodium 12 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound-A 1 mg / m ²

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 3.4μ) 15mg / m ² Compound -H 140 mg / m ² Compound -I 140 mg / m ² Compound -J 30 mg / m ² compound-K 40 mg / m ² p-sodium dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-L 5 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine Potassium 5 mg / m ² Sodium sulfate 150 mg / m ² Sodium acetate 40 mg / m ² Ethyl acrylate / acrylic acid (99/1 wt%) Copolymer (polymer latex) 195 mg / m ² Compound-E (hardener) Coating Samples 1 to 22 were prepared in the manner described above in which the swelling rate of distilled water at 100 ° C. for 1 minute at 25 ° C. on the hack surface side was 100%.

[0208]

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[0209]

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[0210]

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[0211]

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<Evaluation Method> (Evaluation of Membrane Strength) After immersing the sample in distilled water at 25 ° C. for 5 minutes, the sample surface was pressed with a sapphire needle having a radius of 0.4 mm and moved at a speed of 10 mm / sec. While doing so, the load of the needle was continuously changed, and the load (g) when the film was broken was measured.

(Evaluation of Reducing Power) Original having the structure shown in FIG. 1 of Japanese Examined Patent Publication No. 2-28865 "Transparent embedding base / film having line image positive image (line original) / transparent attaching" A film (halftone dot original) on which a dent base / halftone image is formed are stacked in this order ", and the original and the emulsion surface of each sample are brought into close contact with each other, and the FPA-manufactured by Dainippon Screen Co., Ltd. It is exposed with an 800FX (using a Fresnel lens) printer, and is 38 with the following developing solution 1 using Fuji Photo Film Co., Ltd. automatic developing machine FG-680AG.
The treatment was performed at 20 ° C. for 20 seconds, and then fixing, washing with water and drying were performed. The following fixer 1 was used as the fixer. Further, at this time, the replenishing amount of the developing solution was 161 ml per 1 m ² of the sample, and the replenishing amount of the fixing solution was 258 ml per 1 m ² of the sample, and the above treatment was performed. The exposure time of each sample is halftone dot area ratio 5
A 0% halftone original area was determined to be imaged on each sample as halftone dots with a halftone dot area ratio of 50%.

The 50% halftone dot portion thus obtained was immersed in a reducing solution having the following composition at 20 ° C. for 20 to 120 seconds and washed with water. After that, the change in halftone dot area and the change in concentration per halftone dot were measured with a microdensitometer.
After 50% of the halftone dots have been reduced, the density of each halftone dot is 3.0.
The reduction width was measured by the reduction width of the halftone dot area when The larger the value, the better the suitability for reduction.

<Developer 1> Potassium hydroxide 40.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Hydroquinone 40.0 g 5 -Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.50 g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.10 g 2-Mercaptobenzimidazole-5-sulfone Sodium acid 0.30 g Sodium erythorbate 6.0 g Diethylene glycol 5.0 g Potassium hydroxide is added and water is added to 1 liter to adjust the pH to 10.65. 1 liter

<Fixer 1> Ammonium thiosulfate 360.0 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Water added 3 liters

(Reducing Solution) Ceric Sulfate 21.7 g Concentrated Sulfuric Acid 33.3 g Water is added to make 1 liter.

(Evaluation of Image Quality of Blank Characters) Each sample was exposed and processed in exactly the same manner as in the evaluation of the reduction force, and the halftone dot original area having a halftone dot area ratio of 50% was replaced with the halftone dot area ratio of 50%. As a result, the image quality of the extracted characters in the line drawing part when the image was formed on each sample was evaluated. Here, the blank character image quality 5 is an appropriate value so that a halftone dot area of 50% is 50% on the reversal light-sensitive material using a document as shown in FIG. 1 of Japanese Patent Publication No. 28856/1990. It is the image quality with which a character with a width of 30 μm is reproduced when exposed, and it is a very good extracted character image quality.
On the other hand, the same image quality as the blank character image quality 1
The quality of the extracted characters is such that the image quality is such that only characters with a width of 0 μm or more can be reproduced, and a rank of 4 to 2 is provided between 5 and 1 by sensory evaluation. Three or more is a practical level.

The results obtained are shown in Table 1.

[0220]

[Table 1]

[0221]

[Table 2]

As is clear from Table 1, the samples (7, 8, 11, 14 to 18, 22) of the present invention are excellent in film strength, reduction width, and image quality of blank characters.

Example 2 Using Samples 1 to 22 of Example 1, developer 1 and fixer 1
Instead of the above, the same evaluation as in Example 1 was carried out except that the following storage forms were solid and the developer 2 and the fixer 2 were dissolved in water and used. The replenishment amount of each liquid at this time was exactly the same as in Example 1.

(Developer 2) The following storage form was a solid developer, and water was added thereto to make 10 liters to prepare a working solution. The manufacturing method of the solid developer is high-density polyethylene (average thickness = 500 μm, partially 2
The developing component corresponding to 10 liters as a working solution was packed in a container in a solid form. At this time, the components were mixed and then filled in a container. Developer solution used 10
The composition of liter and the form of raw material are shown in Table 2.

[0225]

[Table 3]

Regarding the raw material form, the bulk powder is used as it is as a general industrial product, and alkali metal salt beads,
Commercially available products were used for both pellets. When the raw material was in the form of briquettes, it was pressurized and compressed using a briquetting machine to form an irregular shaped rugby ball type having a length of about 4 to 6 mm, which was then crushed and used. For minor components, each component was blended before briquetting.

(Fixing Solution 2) The following solid agent and liquid agent were added to water to make 10 liters to prepare a working solution. The fixing solution is made of high-density polyethylene in the following formulation for both the solid agent portion and the liquid agent portion (average wall thickness = 500 μm, width 200-
What was filled in a container of 1000 μm) was used. The liquid volume after dissolution was 10 liters, and the pH was 4.85.

<Solid Agent Part> Ammonium thiosulfate 1200 g Sodium thiosulfate 150 g Sodium acetate 400 g Sodium metabisulfite 200 g <Liquid agent part> Aluminum sulfate (27%) 300 g Sulfuric acid (75%) 30 g Sodium gluconate 20 g EDTA 0.3 g Citric acid 40 g solids part is mixed and filled.

The obtained results are similar to those of Example 1, and the effectiveness of the present invention was shown even by such treatment.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 5/31 G03C 5/31 5/395 5/395

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least two silver halide emulsion layers on a support,
The amount of gelatin on the side having an emulsion layer is 3 g / m ² or less, and the polymer latex having a repeating unit composed of an ethylenically unsaturated monomer containing an active methylene group is contained,
When the amount of the polymer latex in the emulsion layer near the support side is
A silver halide photographic light-sensitive material, characterized in that it is one-half or less of the total amount of the polymer latex in the emulsion layer above it. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material contains a hydrazine compound. 3. The polymer latex according to claim 1, wherein the polymer latex has a core / shell structure, and the shell portion is a polymer having a repeating unit composed of an ethylenically unsaturated monomer containing an active methylene group. 2. The silver halide photographic light-sensitive material described in 2. 4. A developer having a pH of 9.0 or more and 12.0 or less, a developer replenishing amount of 300 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material, and a fixer replenishing amount of the silver halide. 4. The silver halide photographic light-sensitive material according to claim 1, which is processed in an amount of 300 ml or less per 1 m ^{2 of the} photographic light-sensitive material.