JP3513282B2 - Silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved adhesion resistance, surface properties such as matte pinholes and film physical properties. More specifically, it relates to a silver halide photographic light-sensitive material excellent in the above-mentioned characteristics even at a low gelatin coating amount.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials generally prevent adhesion under high-temperature and high-humidity conditions, prevent Newton's rings, improve front / back distinction, impart wear resistance, improve vacuum adhesion during contact exposure, For the purpose of improving antistatic property, transporting property (adjusting friction coefficient), etc., fine particles of organic or inorganic substances (so-called matting agent) are contained in the surface protective layer of the emulsion layer of the photosensitive material Matting (roughening) is widely performed. As the matting agent, those having various sizes are used depending on the purpose, but those having a size in the range of 1 μm to 10 μm are preferably used.

Matting agents often used in silver halide photographic light-sensitive materials include inorganic substances such as silicon dioxide, titanium dioxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate and strontium sulfate, polymethyl acrylate, polymethyl methacrylate, Examples thereof include fine particle powders of organic substances such as polyacrylonitrile, polystyrene, cellulose acetate, and cellulose acetate propionate. Examples of such matting agents are Research Disclosure 17643 and US Pat. No. 3,411,907 and British Patent 837,52.
No. 9 and the like. However, many conventional matting agents have a broad particle size distribution. For example, when trying to impart adhesion resistance to a silver halide photographic light-sensitive material,
A large amount of matting agent including a matting agent having a size other than the required size had to be present in the surface protective layer or the back layer. Polymer particles having a particle size of 1 μm or less are not sufficient for imparting adhesion resistance, and are unfavorable because they cause haze deterioration in a light-sensitive material requiring transparency. Also,
Polymer particles having a particle diameter of 10 μm or more are not preferable because they deteriorate the graininess of an image, and further have the drawbacks that they settle in a coating liquid or produce aggregates to make coating difficult. Particles should be removed as much as possible.

Further, when a large amount of the matting agent is used, the depression of the matting agent often causes the formation of minute holes (pinholes) on the image. This phenomenon is more likely to occur as the size of the matting agent particles is larger. Therefore, the phenomenon is remarkable in a matting agent having a large particle size distribution and containing many coarse particles.

To solve such a problem, Japanese Patent Laid-Open No. 59-14
No. 9537, No. 60-156056, No. 63-873
6, 63-235314, JP-A-1-28144.
No. 3, No. 2-54249, No. 4-78845, No. 5
-289225, European Patent 341,200, European Patents 118,793, 610,522, 618,
490, US Patent 4,940,653, US Patent 4,614,708, US Patent 4,885,530.
Issue, Research Disclosure 21617 (198
2) describes the use of a monodispersed polymer matting agent, and further improves adhesion resistance, granularity, transportability, antistatic property, transparency and mat pinholes. It is possible to do However, the improvement of the matte pinhole is not sufficient only by imparting the monodispersity to the matting agent.

In the recent photographic light-sensitive materials, there is a strong demand for reduction of the amount of gelatin used as a binder for the purpose of speeding up processing, improving dimensional stability of printing light-sensitive materials, and improving image quality. There is. However, the reduction of gelatin causes the problem that the above matte pinholes are more likely to occur, and therefore a means for further improving the matte pinholes has been strongly demanded.

Gelatin used as a binder for the hydrophilic colloid layer of a photographic light-sensitive material is not necessarily universal in terms of physical properties of the film, such as plasticization of the film under high humidity and embrittlement of the film under low humidity. However, it has been attempted to improve the above-mentioned physical properties of the film by incorporating a polymer latex in the hydrophilic colloid layer. Among these, for example,
JP-B-45-5819, JP-B-46-22507, and JP-A-50-73625 disclose that in photographic light-sensitive materials, 2-
By allowing a polymer latex obtained by copolymerizing a monomer having an active methylene group such as acetoacetoxyethyl methacrylate or 2-cyanoacetoxyethyl methacrylate with a monomer such as an alkyl acrylate to coexist in the gelatin film, the latex-containing gelatin film (especially in a wet state) It has been disclosed that the wear resistance and hardness (in the above) are significantly improved.

However, the use of this type of latex in the hydrophilic colloid layer has shown little significant effect on the above-mentioned problem of matte pinholes. As a result of intensive studies, the present inventors have found that the above-mentioned monodisperse matting agent is provided in the protective layer, and the polymer latex having an active methylene group is used in at least one layer of the hydrophilic colloid layer. The inventors have found that the holes are specifically improved and have reached the present invention.

[0009]

The object of the present invention is to improve the strength, brittleness and adhesion resistance of a gelatin film without significantly improving mat pinholes and adversely affecting photographic properties.
An object is to provide a silver halide photographic light-sensitive material excellent in transportability.

[0010]

The above objects of the present invention have been achieved by the following means. (1) A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one hydrophilic colloid layer contains a latex-like polymer having an active methylene group. A silver halide photographic light-sensitive material, wherein the protective layer contains a monodisperse particulate alkali-insoluble polymer having an average particle diameter of 1 μm or more.

Preferred embodiments of the silver halide photographic light-sensitive material of the present invention are the following (2) to (6). (2) A halogenated polymer according to (1) above, wherein the latex polymer having an active methylene group has a repeating unit derived from an ethylenically unsaturated monomer represented by the following general formula (I). Silver photographic light-sensitive material. General formula (I)

[0012]

[Chemical 2]

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, or 1 carbon atom 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.
To 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). In contrast, L is bound in the form of alkylene, aralkylene or arylene.

(3) The silver halide photographic light-sensitive material described in (1) or (2) above, wherein the latex polymer is a core / shell polymer latex having a shell having an active methylene group. (4) In the above (1) to (3), the glass transition temperature of the latex polymer latex is 50 ° C. or lower, and the glass transition temperature of the alkali-insoluble monodisperse polymer particles is 60 ° C. or higher. The described silver halide photographic light-sensitive material.

(5) The silver halide according to the above (1) to (4), wherein the particle size distribution of the monodisperse particulate alkali insoluble polymer has a coefficient of variation of 0.2 or less. Photographic material. (6) The silver halide according to the above (1) to (5), wherein the total hydrophilic colloid layer on the side having the silver halide emulsion layer has a total gelatin amount of 3.0 g / m ² or less. Photographic material.

The present invention will be described in detail below. Examples of the latex-like polymer (hereinafter referred to as polymer latex) in the present invention include polymers represented by the following general formula (2). General formula (2)

[0017]

[Chemical 3]

In the formula, D represents a repeating unit derived from an ethylenically unsaturated monomer having an active methylene group, and A
Represents a repeating unit derived from another ethylenically unsaturated monomer. x and y represent the weight percentage ratio of each component, x represents 0.1 to 100, and y represents 0 to 99.9.

More specifically, a preferable ethylenically unsaturated monomer having an active methylene group represented by D is represented by the following general formula (1). General formula (1)

[0020]

[Chemical 4]

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, or 1 carbon atom 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.
To 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). On the other hand, L is bound in the form of alkylenearalkylene or arylene.

Explaining in more detail, 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.

[0023]

[Chemical 5]

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-,

[0025]

[Chemical 6]

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

[0027]

[Chemical 7]

J¹, J², J³Are the same but different
Well, -CO-, -SO₂-, -CON (R⁶) −
(R⁶Is a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), a substitution
Alkyl group (C1-6)), -SO₂N (R⁶) −
(R⁶Is as defined above), -N (R ⁶) -R⁷-(R⁶Is
Synonymous with the above, R⁷Is an alkylene group having 1 to about 4 carbon atoms),
-N (R⁶) -R⁷-N (R⁸)-(R⁶, R⁷Is above
Synonymous with R⁸Is a hydrogen atom, an alkyl group (having 1 to
6) represents a substituted alkyl group (having 1 to 6 carbon atoms). ),
-O-, -S-, -N (R⁶) -CO-N (R⁸) −
(R⁶, R⁸Is as defined above), -N (R⁶) -SO₂−
N (R⁸)-(R⁶, R⁸Is synonymous with the above), -COO
-, -OCO-, -N (R⁶) CO₂-(R⁶And above
Synonyms), -N (R⁶) CO- (R⁶Is synonymous with the above)
Can be mentioned.

P, q and r represent 0 or 1. X ¹ ,
X ^2, X ^3, X ⁴ may be the same as or different from each other, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 20 carbon atoms or phenylene having 6-20 carbon atoms, Represents a group, and the alkylene group may be linear or branched. Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, methoxymethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as phenylenemethylene, phenyleneethylene, and phenylene groups such as p-. Examples include phenylene, m-phenylene, methylphenylene, chlorphenylene and the like.

X is a monovalent group containing an active methylene group, and 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 exemplified. Here, R ⁶ has the same meaning as described above, and R ² has 1 carbon atom.
~ 12 substituted or unsubstituted alkyl groups (eg 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.), amino group, and 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 . Further, R ⁹ is particularly preferably a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms.

Of the above-mentioned active methylene group represented by X,
Of these, R is particularly preferable in the present invention.
²COCH₂COO-, NCCH₂COO-, R²CO
CH ₂CO-, NC-CH₂CO-.

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

[0035] 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 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-aceto Acetoxymethacrylate M-23 N-butyl-N-acryloyloxyethylacetoacetamide M-24 p- (2-acetoacetoxy) ethylstyrene

Examples of the ethylenically unsaturated monomer represented by A include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, dienes, acrylamides, methacrylamides, vinyl ethers and other various ethylenes. A non-saturated monomer can be used, and 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 etc. 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. As the conjugated diene monomer, 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 may be mentioned.

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, styrene sulfonic acid, and the like.

The latex of the present invention contains at least 2
It is also possible to use a monomer having a single copolymerizable ethylenically unsaturated group. Examples of such monomers include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trivinylcyclohexane, trimethylolpropane triacrylate. Examples thereof include acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol methacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

Of these, use of acrylic esters, methacrylic esters and vinyl esters is preferred,
Further, two or more kinds of monomers may be copolymerized.

X and y represent the weight percentage ratio of each monomer component in the polymer, x is 0.1 to 100, preferably 0.5 to 60, particularly preferably 1 to 40, and y is 0 to 0. 99.9, preferably 40 to 9
9.5, particularly preferably 60 to 99. Here, x + y = 100 is represented.

The glass transition temperature (Tg) of the polymer represented by the general formula (2) of the present invention is preferably 50 ° C. or lower, and particularly preferably 30 ° C. or lower from the viewpoint of improving the physical properties of the latex-containing gelatin film.

Among the polymers having an active methylene group of the present invention, particularly preferred is a core / shell polymer latex having a shell having an active methylene group.
More specifically, the core constituting the core / shell latex is specifically a polymer composed of one or more repeating units of various polymerizable ethylenically unsaturated monomers, and specifically, the above-mentioned polymer. It is a polymer composed of monomers selected from the same group as the ethylenically unsaturated monomers described in A.

From the viewpoint of ease of polymerization and ease of core / shell structure formation, acrylic acid esters, methacrylic acid esters, vinyl esters, conjugated dienes are preferably used among the above monomer groups. , Styrenes, and monomers having two 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 is present in the aqueous medium in the form of a fine particle dispersion (latex).

In such a dispersion, the core polymer is present in the form of fine particles. The particle size of this polymer affects the physical properties of the film mixed with gelatin, the water dispersion stability of itself, and the film-forming property, and is not preferable if it is too large. 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, and particularly preferably 0.5 μm or less. The lower limit is preferably 0.00001 μm or more.

The shell portion of the core / shell latex is a polymer having an active methylene group-containing monomer as a repeating unit, preferably a polymer having an ethylenically unsaturated monomer repeating unit represented by the above general formula (1). is there.

An ethylenically unsaturated monomer other than the above-mentioned ethylenically unsaturated monomer containing an active methylene group may be copolymerized in the polymer constituting the shell portion of the present invention. Specific examples of such a monomer include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers, and other monomers constituting the core particles. I can give you
Of these, acrylic acid esters, methacrylic acid esters, vinyl esters, and styrenes are particularly preferable.

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 depending on the performance requirements, and is used in the range of 0.1 to 100% by weight. I can do things. However, if the copolymerization amount of the monomer unit having an active methylene group is increased, the above-mentioned various effects are increased, but if the amount is more than a certain amount, the effects may be saturated. %
It is particularly preferably 1 to 40% by weight.

The amount ratio of the core polymer to 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 to 95/5, preferably 20/80 to 95
/ 5, particularly preferably 30/70 to 90/10. This means that if the number of cores is too small, the concentration effect of the active methylene monomer on the shell part is reduced, and if the number of shells is too small, it becomes difficult to form a clear core / shell structure. The particle size 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, like the core polymer particles. The lower limit is preferably 0.00001 μm or more.

As is well known in the field of core / shell latex formation 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 a 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 less likely to be compatible with each other.

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

It is also possible to form an effective core / shell structure by selecting a polymer having a large polarity difference between the polymer constituting 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)
Shell etc. are mentioned. However, these are the core of the present invention /
It shows that the effect can be selected in terms of the magnitude of the effect in the shell polymer latex, and even in the combination of polymers having similar polarities, the core / shell of the present invention can be used for the 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).
It is possible to obtain a very effective core / shell polymer latex by three-dimensionally crosslinking with. As described above, in the present invention, it is possible to form a useful core / shell polymer latex structure regardless of the kind of the monomer used.

The core / shell latex of the present invention has a glass transition temperature of the core part or the shell part, or both of the core part and the shell part, in view of the brittleness improving effect when added to the gelatin film in addition to the film strength characteristics. Tg) is 50 ° C
The temperature is suitably below, preferably below 30 ° C, particularly preferably below 20 ° C. And the lower limit is -110
C. or higher is preferable.

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

[0063]

[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 uncrosslinked is within the range of 5,000 to 2,000,000 although it varies depending on the kind of the monomer and the synthesis conditions, and the molecular weight may be adjusted by a chain transfer agent or the like depending on the purpose. Is also possible.

The preferred compounds of the polymer latex containing an active methylene group in the present invention are listed below in the order of core / shell latex and non-core / shell latex, but the present invention is not limited thereto. The ratio of each component represents a weight ratio, and in the case of the core / shell polymer, the core polymer structure, the shell polymer structure, and the core / shell ratio are described in this order.

[0066] 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 / M-1 (84/16)                                               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

[0067] 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

[0068] P-15-20   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

[0069] P-21-23   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-methylpropane sulfonate (15/65/15/5)                                               Core / shell = 75/25   P-23 Shell = Styrene / M-1 (84/16) Core / Shell = 20/80

[0070] P-24 to 26   Core: styrene / butadiene copolymer (49/51)   P-24 Shell = Styrene / Butyl acrylate / M-1 (25/60/15)                                               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

[0071] P-29 ~ 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

[0072] 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

[0073] P-37-40   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-me           Sodium chill propane sulfonate (80/15/5)                                               Core / shell = 75/25   P-40 shell = n-butyl acrylate / M-1 (84/16)                                               Core / shell = 50/50

[0074] 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

[0075] 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 to 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 / Shell = 85/15

[0076] P-50   Core: Poly (ethylene glycol dimethacrylate / vinyl palmitate / n         -Butyl acrylate) copolymer (20/20/60)   Shell: ethylene glycol dimethacrylate / styrene / n-butylmethac         Relate / 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 acrylate / ethyl acrylate / M-21           (60/30/10) Core / Shell = 50/50

[0077] P-54, 55   Core: poly (p-vinyltoluene / n-dodecyl methacrylate) 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

[0078]   P-56 ethyl acrylate / M-1 / acrylic acid copolymer (85/10/5)   P-57 n-butyl acrylate / M-1 / 2-acrylamido-2-methyl               Sodium propane sulfonate copolymer (85/10/5)   P-58 n-butyl acrylate / M-1 / methacrylic acid copolymer                                                           (85/5/10)   P-59 2-ethylhexyl acrylate / M-2 / 2-acrylamide-2             − Sodium methyl propane sulfonate copolymer (75/20/5)   P-60 ~ 64       n-Butyl acrylate / M-1 / acrylic acid copolymer (x / y / z)           P-60 x / y / z = 95/2/3           P-61 x / y / z = 92/5/3           P-62 x / y / z = 89/8/3           P-63 x / y / z = 81/16/3           P-64 x / y / z = 72/25/3

[0079]   P-65 n-butyl acrylate / styrene / M-1 / methacrylic acid copolymer             (65/20/5/10)   P-66 methyl acrylate / M-4 / methacrylic acid copolymer (80/15/5)   P-67 n-butyl acrylate / M-5 / acrylic acid copolymer                                                           (85/10/5)   P-68 n-butyl acrylate / M-7 / methacrylic acid copolymer                                                           (85/10/5)   P-69 2-ethylhexyl acrylate / M-9 copolymer (75/25)   P-70 n-butyl acrylate / M-13 / sodium styrene sulfonate copolymer             Combined (85/10/5)

[0080]   P-71 n-butyl acrylate / styrene / potassium styrene sulfinate             Copolymer (75/20/5)   P-72 n-hexyl acrylate / methoxyethyl acrylate / M-2             Polymer (70/20/10)   P-73 2-ethylhexyl acrylate / M-15 / methacrylic acid copolymer             (90/5/5)   P-74 n-butyl acrylate / M-1 / M-17 / acrylic acid copolymer             (75/5/15/5)   P-75 Octyl Methacrylate / M-20 / Styrene Sulfonate Sodium Copolymer             Combined (80/15/5)

The polymer latex of the present invention can be prepared by a generally well-known emulsion polymerization method. The emulsion polymerization method preferably uses a radical polymerization initiator by emulsifying the 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. Generally 30 ° C to about 100 ° C, preferably 40 ° C to about 9
It is carried out at a temperature of 0 ° C. The amount of the organic solvent miscible with water is 0 to 100% by volume, preferably 0 to 5 with respect to water.
It is 0%.

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,
Hydroperoxide, redox catalyst, etc., such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, Dicumyl peroxide, 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) hydrochloride,
There is 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. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrisulfate. Methylene ammonium chloride, N-2-ethylhexyl pyridinium chloride, polyoxyethylene nonyl phenyl ether, polyoxyethylene sorbitan lauryl ester, sodium dodecyl-diphenyl ether 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 core / shell polymer latex can be easily obtained by emulsion-polymerizing an aqueous dispersion obtained by emulsion-polymerizing a core latex polymer while adding or dropping a shell-forming monomer all at once. it can. The addition of the monomer in the emulsion polymerization is preferably carried out while dropping, from the viewpoint of avoiding heat generation due to the polymerization and forming a more definite core / shell structure. Further, the above-mentioned initiator, by emulsion polymerization in the presence of an emulsifier, after forming the core latex particles, when the shell monomer is polymerized, an emulsifier may be further added, or the polymerization may be carried out without addition. Good. Addition of an emulsifier is often necessary from the viewpoint of stability of the produced polymer latex, but conversely, if an excessive amount of emulsifier is present, particles other than the intended shell polymer may be by-produced. Therefore, the amount of the emulsifier added after the core polymer is formed is
It is preferable to suppress the amount to about 0.001 to 5% by weight or not add it 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 is completed as much as possible, and the polymerization rate is 90% or more, preferably 95%. Above all, it is particularly preferably substantially 100%.

In improving the film strength of the polymer latex / gelatin composite film, the active methylene unit is
Functions as a reactive group. Therefore, the amount of active methylene units present on the latex surface is an important factor for performance. The core / shell latex of the present invention is useful in that the active methylene unit can be basically concentrated on the surface of the latex, which is a necessary site. In addition, by controlling other required functions in the core part, such as controlling the Tg of the whole latex, the film forming ability and the physical properties (eg, brittleness) of the resulting composite film with the film or gelatin can be changed to the shell part. Is also extremely 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 can be made into a fine particle powder while maintaining the core / shell structure. As such a method of powdering,
Freeze-drying method, aggregation using strong acid or salt, filtration method, or aggregation by repeated freeze-thawing of latex solution,
A known method such as a filtration method can be used.

Regarding the type of the monomer having an active methylene group and the polymer latex in the polymer represented by the general formula (2) of the present invention and the method for synthesizing the same, other than the above-mentioned US Pat. Nos. 3,459,790 and 3 , 619, 195
Issue 3, Issue 3,929,482, Issue 3,700,456
, West German patent 2,442,165, European patent 13,1
47, JP-A-50-73625, and JP-A-50-1463.
The description of No. 31, etc. can be used for reference. Regarding the core / shell latex, the description in Japanese Patent Application No. 7-3296 can be referred to.

Next, the monodisperse particulate alkali-insoluble polymer (hereinafter referred to as alkali-insoluble monodisperse polymer particles) of the present invention will be described. The matting agent of the present invention may be either inorganic particles or organic polymer particles. As a representative example of the inorganic particles, polymethylsiloxane particles (may be spherical or amorphous, for example, commercially available from Toshiba Silicone Co. under the name Tospearl) I can name it. However, organic polymer particles are preferable from the viewpoint of improving the mat pinhole of the present invention.

As the organic polymer matting agent, homopolymers or copolymers of ethylenically unsaturated monomers are preferable, and examples of such a monomer include acrylic acid such as methyl acrylate, cyclohexyl acrylate, benzyl acrylate and phenyl acrylate. Esters, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, styrene, o-methyl Styrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, pt
Examples thereof include styrenes such as er-butyl styrene and p-chlorostyrene, acrylonitrile, methacrylonitrile, and vinyl halides such as vinylidene chloride. Further, water-soluble monomers such as acrylic acid, methacrylic acid, acrylamide, and methacrylamide can also be used as long as they do not impair the water insolubility of the matting agent.

The average particle size of the matting agent of the present invention is 1 μm or more, preferably in the range of 2 to 15 μm.
The preferred glass transition temperature of the matting agent polymer is 50.
C. or higher, particularly preferably 80.degree. C. or higher.

In the present invention, the polymer matting agent having a monodispersed particle size distribution means that 200 or more particle sizes are measured in a scanning electron micrograph magnified 1500 times and the number average particle size and standard deviation are calculated. Obtained coefficient of variation (= standard deviation /
It means polymer particles having a number average particle diameter of 0.2 or less, and particularly preferably 0.15 or less. Also,
Alkali-insoluble means that the solubility in an aqueous solution of pH = 10 at room temperature is 10 g / liter or less.

The monodisperse polymer matting agent used in the present invention is a method of monodispersion by controlling the polymerization method or the like during the production of the particle polymer, the polymer is dissolved in a suitable solvent, and this is dispersed in water with a suitable dispersant. It can be obtained by any method such as a method of dispersing and a method of separating polymer particles into monodisperse particles.

Examples of monodispersion by the polymerization method include soap-free emulsion polymerization (for example, Makromol. Chem. Rapid Commu
n. 6 315 (1985)), dispersion polymerization method (eg K.
EJBarrett, Dispersion Polymerization in Organic
media, JOHN WILEY & SONS, JP-A-61-19602
No. 7, Japanese Patent Application No. 7-50735), nozzle vibration method (for example, Chemical Engineering 47 540 (1983)), swelling seed method (for example, US Pat. No. 4,247,437), molecular dispersion method (for example, J. Polym. Sci., Polym.Letlers.Edition, 2
1 937 (1983)), two-stage swelling method (for example, JP-B-57-24369, JP-A-61-215602, 61-215603, 61-215604, 6).
No. 1-215605) and suspension polymerization method (for example, Japanese Patent Publication No.
9-30224, 58-41464, 58-175.
26). Further, the monodisperse particles can be produced by a synthesis method according to these methods or a synthesis method combining the above methods.

Examples of the method of dissolving the polymer in a solvent and monodispersing it in water include a method according to the above-mentioned nozzle vibration method and a batch method. Solvents that can be used have a solubility in water of 0 to 50 (g / 100 g), and examples thereof include chloromethylene, dichloroethylene, chloroform, dichloroethane, chloroethane, ethyl acetate, butyl acetate and methyl ethyl ketone. As the dispersant, a water-soluble polymer (for example, polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, etc.), a surfactant (for example, C ₁₆ H ₃₃ O— (C ₂ H ₄ O) _n —H, etc.) is used. Can be done by In the case of a batch system, monodispersion can be performed by optimizing the stirring speed of the solvent, the dispersant, and the system (in this case, a dispersion stabilizer such as gelatin may be used in combination).

A particularly preferred embodiment of the dispersion polymerization method which is the synthesis method of the present invention will be described in detail below. The dispersion polymerization method is a free radical polymerization carried out in a polymerization medium in which vinyl monomers are soluble but polymers are insoluble. To do. The polymerization system is uniform at the start of the polymerization, but when the growing oligomer radicals grow to a chain length of a certain level or more,
It becomes insoluble in the medium and precipitates, and at the same time as the coagulation, the dispersant is adsorbed and stabilized in the form of particles [nucleation]. After that, the particles grow in a heterogeneous system mainly by polymerization of the vinyl-based monomer absorbed inside the particles [particle growth].

The dispersion polymerization method comprises the constituent factors of the hydrophilic organic medium, the dispersant, the vinyl monomer, and the initiator. Precise control of these polymerization conditions is necessary as it has a large effect on distribution.

First, each constituent factor of the dispersion polymerization will be described in order. The hydrophilic organic medium is an alcohol having 1 to 6 carbon atoms, and examples thereof include methanol, ethanol, propanol, isopropanol, 2-methoxy-1-propanol, butanol, t-butanol, pentanol, neopentanol and cyclo. Hexanol etc. are mentioned as a preferable example. These media may be used alone, may be used in combination with each other, and may be used in admixture with water or another organic solvent in some cases. When producing polymer particles containing 70% by weight or more of methyl methacrylate, methanol, ethanol and isopropanol are preferable polymerization media.

The dispersant has a role of adsorbing the precipitated oligomer radicals and stabilizing it in the form of particles.
When used in the hydrophilic organic medium, N-vinylpyrrolidone, acrylic acid, methacrylic acid, maleic acid, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, vinyl alcohol, methyl vinyl ether, vinyl acetate, acrylamide. , Methacrylamide,
Homopolymers or copolymers having an ethylenically unsaturated monomer such as diacetone acrylamide or vinylimidazole as a constituent element, or polyoxyethylene, polyoxypropylene, poly-2-methyloxazoline, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc. Can be used. Among these, polyvinylpyrrolidone homopolymer, polyvinyl alcohol, polyacrylic acid and polymethacrylic acid are preferable. The preferred dispersant molecular weight range is 1
The concentration of the dispersant is preferably from 1 g / liter to 5 g / liter.

The one used as the polymerization initiator is, for example,
2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) (dimethyl 2,2'- Azo-based initiators such as azobisisobutyrate) and peroxide-based initiators such as lauryl peroxide, benzoyl peroxide and ter-butyl peroctoate are used.

The particle size of the obtained polymer tends to increase as the molecular weight of the polymer decreases.
As a rough guideline for obtaining particles of μm, the number average molecular weight is about 5,000 to 70,000. The polymerization temperature can be changed appropriately, but the preferred temperature is 45 ° C to 8 ° C.
It is in the range of 5 ° C.

Examples of the monodisperse matting agent used in the present invention and the matting agent having a wide particle size distribution as a comparative example are shown in Table 1 below, and production examples thereof are shown below, but the present invention is not limited thereto. Not something.

[0103]

[Table 1]

Particle Synthesis Example 1 (Synthesis of Exemplified Matting Agent Q-1) Polyvinylpyrrolidone 10.0 g, methanol 900 g
In a 2000 ml three-necked flask and stirred (150 rp
m), nitrogen was introduced. Then, the solution was heated to 50 ° C. and 100 g of degassed methyl methacrylate, 2,2′-
2.0 g of azobis (isobutyronitrile) was added. Four
After 8 hours, the reaction solution was cooled and filtered to obtain 949 g of a milky white polymethylmethacrylate particle dispersion (solid content concentration 10.8% by weight). The number average molecular weight was 29,100, the molecular weight distribution (Mw / Mn) was 1.4, the particle size was 5.1 μm, the variation coefficient was 0.038, and the solid content yield was 92%.

The particle size and particle size distribution were evaluated as follows. The particle dispersion was cast and dried on a copper thin film, and a sample coated with Au was scanned with a scanning electron microscope (JSM-
5400, JEOL) and magnified 1500 times and photographed. The magnification correction was performed by simultaneously photographing the diffraction grating (500 lines / mm). Using the obtained photographs, the particle cross-sectional diameter of 200 or more particles per sample
measured using alyzer TGZ-3 (Carl Zeiss),
The number average particle diameter (particle diameter) was calculated, and the standard deviation was calculated, and then the coefficient of variation was calculated by the following formula.

[0106]

[Equation 2]

Particle Synthesis Example 2 (Synthesis of Exemplified Matting Agent Q-2) The same operation as in Synthesis Example 1 was carried out except that the polymerization temperature was changed to 55 ° C., and 958 g of polymethylmethacrylate particle dispersion was obtained.
Was obtained (solid content concentration 11.1% by weight). The number average molecular weight is 23,000, the molecular weight distribution (Mw / Mn) is 2.1, the particle size is 5.5 μm, the variation coefficient is 0.032, and the solid content yield is 9
It was 2%.

Particle Synthesis Example 3 (Synthesis of Exemplified Matting Agent Q-3) Polyvinylpyrrolidone 10.0 g, methanol 1800
g into a 3000 ml three-necked flask and stirred (150 r
pm) and nitrogen substitution was performed sufficiently. After this, add 55
100 g of degassed methyl methacrylate heated to ℃,
3.0 g of 2,2'-azobis (isobutyronitrile) was added. After 48 hours, the reaction solution was cooled and filtered to obtain 1847 g of a milky white polymethylmethacrylate particle dispersion (solid content concentration 5.3% by weight). Number average molecular weight is 19,2
00, the molecular weight distribution (Mw / Mn) is 3.1, and the particle size is 7.
The coefficient of variation was 8 μm, the coefficient of variation was 0.056, and the solid content yield was 91%.

Particle Synthesis Example 4 (Synthesis of Exemplified Matting Agent Q-7) Polyvinylpyrrolidone 10.0 g, methanol 420
g, Surfynol ^™ 104 (manufactured by Air Products) 2.65
g into a 1000 ml three-necked flask and stirred (60 rp
m), melted at 45-50 ° C. After that, 67 g of methyl methacrylate was added, and the temperature was raised to the boiling point of methanol to obtain 2,2'-azobis (isobutyronitrile) 0.0
5g was added. 18 hours after the start of polymerization, again 2,2'-
Add 0.05 g of azobis (isobutyronitrile),
The reaction was continued for another 6 hours. After this, the reaction liquid is cooled,
It was filtered with a 225 mesh filter cloth to obtain a milky white polymethylmethacrylate particle dispersion. The dispersion was allowed to settle for 24 hours, the clear supernatant was removed and the precipitate was washed with distilled water. Number average molecular weight is 36,200, molecular weight distribution (M
w / Mn) was 3.7, the particle size was 4.1 μm, the coefficient of variation was 0.09, and the solid content yield was 91%.

Comparative Synthesis Example 1 (Synthesis of Comparative Example Matting Agent QH-1) 44 g of methyl methacrylate, 600 ml of 0.5% aqueous solution of polyvinyl alcohol and 2,2'-azobis-2,4.
-Dimethylvaleronitrile (1 g) was stirred for 20 minutes with a dissolver (7500 rpm) under ice cooling. After polymerizing this at 80 ° C. for 8 hours under a nitrogen stream, decantation was repeated twice with water, three times with acetone, three times with methanol and twice with water to obtain 117 g of a polymethylmethacrylate particle dispersion. (Solid content concentration 12.0% by weight). Number average molecular weight is 87,000, molecular weight distribution (Mw
/ Mn) is 6.4, the particle size is 5.5 μm, and the coefficient of variation is 0.
38, the solid content yield was 32%.

Comparative Synthesis Example 2 (Synthesis of Comparative Example Matting Agent QH-2) Polyvinylpyrrolidone 5 g, methanol 420 g, Surf
2.25 g of ynol ^TM 104 (manufactured by Air Products)
Put in a 00 ml three-necked flask and stir (60 rpm), 4
Melted at 5-50 ° C. After this, methyl methacrylate 6
After adding 7 g, the temperature was raised to the boiling point of methanol,
0.075 g of 2'-azobis (isobutyronitrile) was added. 18 hours after the initiation of the polymerization, 0.075 g of 2,2'-azobis (isobutyronitrile) was added again, and the reaction was continued for another 6 hours. After this, the reaction liquid is cooled and
The mixture was filtered through a 5-mesh filter cloth to obtain 471 g of a milky-white polymethylmethacrylate particle dispersion (solid content concentration: 14.
4% by weight). The dispersion was allowed to settle for 24 hours, the clear supernatant was removed and the precipitate was washed with distilled water. The number average molecular weight is 30,500, and the molecular weight distribution (Mw / Mn) is 4.
5, the particle size was 8.7 μm, the coefficient of variation was 0.24, and the solid content yield was 88%.

The layer containing the alkali-insoluble monodisperse polymer particles of the present invention is preferably the uppermost protective layer, but when the protective layer comprises two or more layers, either layer may be used.
Addition amount of alkali-insoluble monodisperse particles is 3-400 mg /
m ^2, preferably from 5 to 200 mg / m ^2.

Gelatin is preferably used as a binder for the silver halide emulsion layer, the protective layer and the 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A hydrophilic polymer substance can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The silver halide photographic light-sensitive material containing the latex of the present invention and the monodisperse matting agent is specifically X.
Examples thereof include a line photosensitive material, a printing photosensitive material, a black and white photographic photosensitive material, a color negative photosensitive material, a color reversal photosensitive material, and a color printing paper.

In the preferred embodiment of the light-sensitive material for printing and the X-ray light-sensitive material, the coating amount of gelatin as a binder has sufficient effect at any coating amount, but the silver halide emulsion layer The total amount of gelatin in the hydrophilic colloid layer on the side having the
g / m ² or less, particularly preferably 1.0 to 2.5 g / m ^2.

In the present invention, the polymer latex is contained in at least one of the silver halide emulsion layer, the back layer and the other hydrophilic colloid layer, and the addition amount is 0.1 to 200 relative to the gelatin of the hydrophilic colloid layer. %, Preferably 5 to 150% by weight.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as a silver halide, a usual halogenated silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide or the like. Any of those used for silver emulsions can be used. The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method. The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside and the surface layer of the grain, and the latent image is mainly on the surface. The particles may be particles that are formed inside the particles, or particles that are mainly formed inside the particles. The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. US Pat. No. 4,183,75
6, No. 4,225,666, JP-A-55-2658.
No. 9, Japanese Patent Publication No. 55-42737, and the Journal of Photographic Science (J. Photog
r.Sci.), 21-39 (1973), and the like, particles having a shape such as an octahedron, a tetrahedron, and a dodecahedron can be prepared and used. Further, grains having twin planes may be used. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes. In the present invention, a monodisperse emulsion is preferred. The monodisperse silver halide grains in the monodisperse emulsion have an average grain size γ
It is preferable that the weight of silver halide contained in the grain size range of ± 10% with respect to is 60% or more of the total weight of silver halide grains.

The silver halide grains used in the emulsion of the present invention are cadmium salt, zinc lead, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt in the course of grain formation and / or growth. , An iron salt or a complex salt may be used to add a metal ion, and the metal ion may be included inside the particle and / or on the surface of the particle. The photographic emulsion used in the present invention may be used in combination with sulfur sensitization, gold / sulfur sensitization, and reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound. As the photosensitive emulsion, the above emulsions may be used alone, or two or more kinds of emulsions may be mixed. In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene, 5-mercapto-1
Various stabilizers can be used including phenyltetrazole and 2-mercaptobenzothiazole. Further, if necessary, a silver halide solvent such as thioether, or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized with blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. The silver halide photographic light-sensitive material according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation and prevention of halation.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are West German Patent 616,0.
07, British Patents 584,609 and 1,117,4
No. 29, Japanese Patent Publication No. 26-7777, No. 39-22069
No. 54-38129, JP-A-48-85130.
No. 49-99620, No. 49-114420,
49-129537, PB Report 74175,
Photographic Abstract (Photo.Abstr.)
128 ('21) and the like. In particular, it is preferable to use these dyes in a bright room reversal light-sensitive material. Also, Japanese Patent Application No. 5-244717, No. 23-
The solid fine particle dispersion of the dye described on page 30 may be used. In the silver halide photographic light-sensitive material according to the present invention,
When the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

The latex and the monodisperse matting agent of the present invention can also be used in a color silver halide photographic light-sensitive material. The color photographic light-sensitive material may have at least one silver halide emulsion layer of a blue color sensitive layer, a green color sensitive layer and a red color sensitive layer provided on a support. Also, there is no particular limitation on the number and order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light,
In the multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. But,
Depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. In installation, each layer may be applied sequentially,
It may be carried out in a single coating in a multilayer (so-called simultaneous multilayer coating), which is a manufacturing method which is quite common in the industry,
There is no particular mention.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers and DIR compounds as described in 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-112751.
No. 62-200350, No. 62-206541.
No. 62-206543, No. 56-25738,
62-63936, 59-202464, JP-B-55-34932, and 49-15495.

Various color couplers can be used in the color light-sensitive material, and specific examples thereof are described in the patents and the like described in Research Disclosure (RD) No. 17643, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961
No. 5, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
5,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649, 5,298,383, European Patent No. 249,473A, JP-A-5-165171
And the like are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, W.
Those described in O (PCT) 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,753,871, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
199, JP-A-61-42658, JP-A-5-34
Those described in No. 1467 and the like are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,163,67
0, 5,266,456, Japanese Examined Patent Publication No. 57-3941
3, U.S. Pat. Nos. 4,004,929 and 4,13.
Those described in No. 8,258 and British Patent No. 1,146,368 are preferable. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat. No. 4,366,237, British Patent 2,125,570, and European Patent 96,57.
Those described in No. 0 and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, and US Pat. No. 4,576,910,
It is described in British Patent No. 2,102,137 and the like. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are RD17643, VI described above.
Patents described in paragraphs I-F, Japanese Patent Laid-Open No. 151944/1982
No. 57-154234, No. 60-184248.
No. 63-37346, U.S. Pat. No. 4,248,96.
No. 2, JP-A-5-113635 and the like are preferable.

As couplers which release a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252 and the like, and after separation as described in EP 173,302A Couplers that release dyes that recolor, R.I. D. No. 11449, 24
241, a bleaching accelerator releasing coupler described in JP-A-61-201247 and the like, a ligand releasing coupler described in U.S. Pat. No. 4,553,477 and the like, JP-A-63-75.
Examples thereof include couplers releasing the leuco dye described in No. 747.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. The process of latex dispersion method, effects and specific examples of latex for impregnation are described in US Pat.
199,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

[0128] The color light-sensitive material is a total film thickness of all hydrophilic colloid layers on the side having emulsion layers is 28μm or less and the film swelling speed T _^1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured at 25 ° C. 55% relative humidity (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example,
Photographic Science and Engineering (Photogr.Sci.En) by A. Green et al.
g.), 19 Certificates, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _^1/2 is 30 ° C. in a color developing solution, 3 minutes 15 seconds 90% of the maximum swollen film thickness reached when treated with a saturated film thickness, which time defined to reach the thickness of the T _^1/2. Film swelling rate T _^1/2 can be adjusted to gelatin as a binder by adding a hardening agent, or by changing the aging conditions after coating. The swelling rate is 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness.

In the present invention, an antistatic agent is preferably used. The antistatic agent is not particularly limited, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt, and a sulfonic acid salt.
159, JP-A-51-30725 and JP-A-51-1.
29216 and Japanese Patent Application Laid-Open No. 55-95942. Examples of the cationic polymer include JP-A-49-121523 and JP-A-48-911.
65 and Japanese Patent Publication No. 49-24582. In addition, ionic surfactants are also anionic and cationic. For example, JP-A-49-85826.
No. 49-33630, U.S. Pat. No. 2,99.
No. 2,108, U.S. Pat.
Examples thereof include compounds described in JP-A No. 8-87826, JP-B-49-11567, JP-B-49-11568, and JP-A-55-70837.

The most preferable antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
At least one crystalline metal oxide selected from SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ or a composite oxide thereof (Sb, P, B, In, S, Si,
C) and further, sol-like metal oxides or fine particles of composite oxides thereof. The fine particles or acicular filler of the conductive crystalline oxide or its composite oxide used in the present invention has a volume resistivity of 10 ⁷ Ω-cm or less, more preferably 10 ⁵ Ω-cm or less. The particle size is 0.001 to 1.0 μm, especially 0.001
It is desirable to set the thickness to 0.3 μm. In order to give conductivity more efficiently, the primary fine particles are partially aggregated to 0.0
It is preferable to use fine particles or filler of a conductive crystalline oxide or a composite oxide thereof having a particle size of 1 to 0.2 μm.
Furthermore, the conductivity reached when producing an antistatic layer using these is preferably 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω, both in the raw state and after the treatment.
Hereafter, it is particularly preferable that the electric resistance is 10 ^9.5 Ω or less. In that case, the content in the photosensitive material is generally 5 to 5.
00 mg / m ² is preferable and particularly preferably 10 to 350 mg /
m ² . The amount of the binder is preferably from 1-500 mg / m ^2, in particular 5 to 300 mg / m ² is preferred. The ratio of the amount of fine particles of the conductive crystalline oxide or its composite oxide or the acicular filler to the binder is 1/300 to 100/1.
Is preferable, and more preferably 1/100 to 100/5.

The light-sensitive material of the present invention preferably has slipperiness. The slipperiness is good on both the photosensitive layer surface and the back surface, but the back surface is more effective. A preferable sliding property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents a value when the stainless steel ball having a diameter of 5 mm is moved at 60 cm / m ² . In this evaluation, even if the surface of the photosensitive layer is replaced as the mating material, the values are almost the same. Examples of the slip that can be used in the present invention include polyorganosiloxanes as disclosed in Japanese Patent Publication No. 53-292 and higher fatty acids as disclosed in U.S. Pat. No. 4,275,146. Amide, Japanese Patent Publication No. 58-33541, British Patent No. 927,446, or Japanese Patent Laid-Open No.
Higher fatty acid esters (having 10 to 10 carbon atoms) as disclosed in JP-A Nos. 5-126238 and 58-90633.
(Ester of 24 fatty acids and alcohols having 10 to 24 carbon atoms), and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, and disclosed in JP-A-58-50534. As described above, esters of linear higher fatty acids and higher alcohols, published in the world 90
Higher fatty acid-higher alcohol ester containing a branched alkyl group as disclosed in 108115.8 is known.

The higher fatty acids and their derivatives and the higher alcohols and their derivatives include higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides,
Polyhydric alcohol esters of higher fatty acids, etc., higher aliphatic alcohols, monoalkyl phosphites of higher aliphatic alcohols, dialkyl phosphites, trialkyl phosphites, monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, higher alkyls Aliphatic alkyl sulfonic acid, its amide compound, its salt, etc. can be used. In addition, Japanese Patent Application Nos. 5-153909, 5-153910, and 5-
The higher fatty acid-higher alcohol ester described in No. 345871 or the like is preferably used. Further, the slipping agent used in the present invention may be dispersed in an organic solvent by various methods. As a method for dispersing in an organic solvent, a lubricant is dispersed in an organic solvent by a ball mill, a sand grinder or the like, a solid dispersion method is used, a lubricant is dissolved in an organic solvent by heating, and cooling precipitation is performed while stirring. Dispersion method, or a method in which a lubricant is dissolved in an organic solvent by heating, and this is added to an organic solvent at room temperature or in a cooled state to disperse by cooling and precipitation, and mutually compatible. Not emulsifying with organic solvents. As the disperser used, an ordinary stirrer can be used, but an ultrasonic disperser and a homogenizer are particularly preferable.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, syndiotactic polystyrene, baryta paper,
Polyethylene coated paper or the like may be used. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating processing by a known method, if necessary.

The present invention can be applied to a silver halide photographic light-sensitive material having a transparent magnetic recording layer. Conventionally, in silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials),
Although only image information was provided at the time of shooting or printing, as disclosed in JP-A-4-68336 and JP-A-4-73737, by providing a transparent magnetic recording layer on the entire surface of a light-sensitive material, , Other than images, date and time of shooting, weather,
It is possible to input shooting conditions such as reduction / enlargement ratio, the number of reprints, the portion to be zoomed, a message, development, print conditions, etc. as sensitive materials, and also input to video equipment such as TV / video. In that case, it is desired to remove the influence of dust due to electrification, improve the slipperiness of the film, and eliminate the influence of curl containing the support.

These will be described in detail below. Magnetic particles which can be used in the present invention, gamma-Fe ferromagnetic iron oxide such as _{2 O 3 (FeOx, 4/} 3 <x ≦ 3/2), Co deposition strength such as Co-coated γ-Fe ₂ O ₃ Magnetic iron oxide (FeO
x, 4/3 <x ≦ 3/2), Co-deposited magnetite, other Co-containing ferromagnetic iron oxide, Co-containing magnetite,
Ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, and other ferrites such as hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite or solid solutions or ion substitutes thereof can be used. Co-deposited ferromagnetic iron oxide such as γ-Fe ₂ O ₃ having a Fe ²⁺ / Fe ³⁺ ratio of 0 to 10% is preferable from the viewpoint of transmission density.

The shape of the ferromagnetic material may be needle-like, rice-like, spherical, cubic, plate-like or the like, but needle-like is preferable in terms of electromagnetic conversion characteristics. In the case of needle-shaped particles, the major axis is 0.01 to 0.8 μm, and the major axis / minor axis ratio is 2-1.
00 is more preferable, the major axis is more preferably 0.05 to 0.3 μm, and the major axis / minor axis ratio is more preferably 4 to 15. S in specific surface area
_{The BET} is preferably 20 m ² / g or more, and more preferably 30 m ² / g or more. The larger the saturation magnetization (σ s) of the ferromagnetic material, the more preferable it is, but 50 emu / g or more, more preferably 70
It is more than emu / g, and is 100 emu / g or less in practice. The squareness ratio (σr / σs) of the ferromagnetic material is preferably 40% or more, more preferably 45% or more. If the coercive force (Hc) is too small, it will be easy to erase, and if it is too large, it will not be possible to write depending on the system, so an appropriate value is preferable.
It is 0 Oe or more and 3000 Oe or less, preferably 500 Oe or more and 2000 Oe or less, and more preferably 650 Oe or more and 950 Oe or less.

These ferromagnetic particles are described in, for example, Japanese Patent Laid-Open No.
It may be surface-treated with silica and / or alumina such as 9-23505 and those described in JP-A-4-096052. In addition, JP-A-4-195726 and 4-1.
92116, 4-259911, 5-081652.
A surface treatment with an inorganic and / or organic material as described may be applied. Furthermore, these ferromagnetic particles may be treated on their surface with a silane coupling agent or a titanium coupling agent. Next, the binder in which the magnetic particles of the present invention are preferably used will be described. The binder used in the present invention is a known thermoplastic resin, thermosetting resin, which is conventionally used as a binder for magnetic recording media.
Radiation curable resins, reactive resins, acids, alkali or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above-mentioned resin preferably has a Tg of −40 ° C. to 300 ° C. and a weight average molecular weight of 20,000 to 1,000,000, preferably 0.5.
It is 10,000 to 300,000.

Among the binders, cellulose di (or tri) acetate is preferred. The binder may be used alone or as a mixture of several kinds, and a known crosslinking agent of epoxy type, aziridine type, isocyanate type and / or a radiation curable vinyl type monomer may be added for curing treatment. Particularly preferred are isocyanate cross-linking agents, such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and reaction products of these isocyanates with polyalcohols (for example, 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane). Reaction products), and polyisocyanate produced by condensation of these isocyanates. Further, as the crosslinking agent having an epoxy group, for example, trimethylolpropane, triglycidyl adduct, pentaerythritol tetraglycidyl adduct and the like are preferable. The radiation-curable vinyl monomer is a compound that can be polymerized by irradiation with radiation, and is preferably diethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups,
Polyethylene glycol (meth) acrylates, such as triethylene glycol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, reaction product of polyisisoanate and hydroxy (meth) acrylate compound , Etc. These cross-linking agents are preferably 5 to 45 wt% with respect to the entire binder containing the cross-linking agents.

A hydrophilic binder can also be used in the magnetic recording layer of the present invention, and water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and cellulose esters such as carboxymethyl cellulose and hydroxyethyl cellulose. Is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. The most preferred of these is gelatin. Examples of the gelatin hardener include 2-hydroxy-4,6-dichloro-1,3,5-triazine, divinyl sulfone,
Isocyanates described in US Pat. No. 3,103,437 and the like, aziridine compounds described in US Pat. Nos. 3,017,280 and 2,983,611, US Pat. No. 3,321 No. 313, etc., and a carboxyl group-activating type hardener can be exemplified.
The amount of hardener used is usually 0.01 with respect to dry gelatin.
-30% by weight, preferably 0.05-20% by weight.

Various known means can be used to disperse the above-mentioned magnetic material in the binder, but a kneader, a pin type mill, an annular type mill or the like is preferable, and a kneader and a pin type mill or a kneader is used. A combined use of an annular mill is also preferable. The thickness of the magnetic recording layer is 0.1 μm
It is 10μ, preferably 0.2μ to 5μ, and more preferably 0.3μ to 3μ. The weight ratio of magnetic particles to binder is preferably comprised between 0.5: 100 and 60: 100,
More preferably, it is 1: 100 to 30: 100. The coating amount of the magnetic material is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and more preferably 0.02 to 0.
It is 5 g / m ² .

The magnetic recording layer of the present invention can be provided on the entire back surface of the photographic support by coating or printing or in the form of stripes. This magnetic recording layer can be applied by air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, kiss coating, cast coating, spray coating, dip coating, bar coating. , Extrusion coat, etc. can be used, and other methods are also possible. Specific explanations for these are given in "Coating Engineering" 25 published by Asakura Shoten.
It is described in detail on pages 3 to 277 (published 46.20. Showa). The magnetic recording layer may have functions such as lubricity improvement, curl control, antistatic, adhesion prevention and head polishing, or may be provided with another functional layer to impart these functions. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. For example, inorganic or organic fine particles (eg, silica, SiO ₂ ,
SnO ₂ , Al ₂ O ₃ , TiO ₂ , cross-linked polymethylmethacrylate, barium carbonate, fine silicone particles, etc.) are preferably added.

Next, the polyethylene aromatic dicarboxylate polyester support, which is a support preferably used in the present invention, will be described. The polyester of the present invention is
The dibasic acid is formed by using a diol and an aromatic dicarboxylic acid as essential components, and a dibasic acid that can be often used as a mixture with other dicarboxylic acids is terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, or naphthalenedicarboxylic acid ( Two
6-, 1,5-, 1,4-, 2,7-), diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride,
Succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1 , 4-Cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,1-dicarboxy-2-phenylethylene, 1,4-dicarboxymethylphenol, 1,3-
Examples thereof include dicarboxy-5 phenylphenol, sodium 3-sulfoisophthalate, and the like. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus among the above-mentioned dicarboxylic acids.

Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1, Examples thereof include 1-cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene (PHBA), and bisphenol A. Further, if necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be salicylic acid or the like, which may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule.

Preferred as the polymer formed is
Homopolymers such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate (PCT), and copolymers of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (the mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0. 1 to 0.1: 0.9 is preferable,
It is more preferably 0.8: 0.2 to 0.2: 0.8. ) Is preferred. Particularly preferred is a polyester containing 2,6-naphthalenedicarboxylic acid. Specifically, 2,6-
It is a polyester containing 0.1 to 1.0 of naphthalene dicarboxylic acid. Among them, polyethylene 2 is particularly preferable.
It is 6-naphthalate.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters, and for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition".
(Kyoritsu Shuppan, 1980) 103-136.
The description can be made with reference to the description on pages 187 to 286 of "Synthetic Polymer V" (Asakura Shoten, 1971). The preferred average molecular weight range for these polyesters is about 500.
It is 0 to 200,000. In addition, these polyesters may be partially blended with another polyester to improve adhesion with another type of polyester,
It is possible to copolymerize a monomer constituting another polyester, or to copolymerize a monomer having an unsaturated bond in these polyesters and radically crosslink them. Polymer blends prepared by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482 and JP-A-64-5482.
-4325, JP-A-3-192718, Research Disclosure 283,739-41, 284,77.
It can be easily formed according to the method described in 9-82 and 294,807-14.

The polyester of the present invention has a Tg of 50 ° C.
As described above, the conditions of use are not generally handled with sufficient caution, and the temperature is often exposed to 40 ° C. especially in the midsummer outdoors. From this viewpoint, the Tg of the present invention is safe. The temperature is preferably 55 ° C or higher. More preferably, Tg is 60 ° C. or higher, and particularly preferably 70 ° C. or higher. Further, it is preferable that Tg is 90 ° C. or higher in order to complete the treatment. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature exceeds 40 ° C in summer. Polyesters having a glass transition temperature above the temperature are preferred.

Examples of preferable specific compounds of the polyester used in the present invention are shown below, but the present invention is not limited thereto. Polyester compound example BP-0: [terephthalic acid (TPA) / ethylene glycol (EG) (100/100)] (PET) Tg = 80 ° C. BP-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] (PEN) Tg = 119 ° C. BP-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. BP-3: [TPA / Bisphenol (BPA) (100/100)] Tg = 192 ° C

[0148] BP-4: 2,6-NDCA / TPA / EG (50/50/100)                                                         Tg = 92 ° C BP-5: 2,6-NDCA / TPA / EG (75/25/100)                                                         Tg = 102 ° C BP-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25)                                                         Tg = 112 ° C BP-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C. BP-8: TPA / EG / BPA (100/25/75) Tg = 135 ° C. BP-9: TPA / EG / CHDM / BPA (100/25/25/50)                                                           Tg = 115 ° C

[0149] BP-10: isophthalic acid (IPA) / NDCA / TPA / EG (20/50/3             0/100) Tg = 95 ° C BP-11: NDCA / Neopentyl glycol (NPG) / EG (100/70             / 30) Tg = 105 ° C BP-12: TPA / EG / bisphenol (BP) (100/20/80)                                                         Tg = 115 ° C BP-13: PHBA / EG / TPA (200/100/100)                                                         Tg = 125 ° C BP-14: PEN / PET (60/40) Tg = 95 ° C BP-15: PEN / PET (80/20) Tg = 104 ° C. BP-16: Polyarylate (PAr) / PEN (50/50)                                                         Tg = 142 ° C BP-17: PAr / Polycyclohexanedimethanol terephthalate (PCT)             (50/50) Tg = 118 ° C BP-18: PAr / PET (60/40) Tg = 101 ° C. BP-19: PEN / PET / PAr (50/25/25) Tg = 108 ° C. BP-20: TPA / 5-sulfoisophthalic acid (SIP) / EG (95/5/1             00) Tg = 65 ° C BP-21: PEN / SIP / EG (99/1/100) Tg = 115 ° C

These supports of the present invention have a thickness of 50 μm or more and 300 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, while if it exceeds 300 μm, it is inconsistent with the purpose of reducing the thickness for compactness. More preferably from the strength of the waist, the thicker one is preferably 50 to 200 μm,
Furthermore, 80 to 115 μm is preferable, and 8 is particularly preferable.
It is 5 to 105 μm. Next, the polyester support of the present invention is characterized in that it is subjected to a heat treatment, in which case 40
It is necessary to carry out the treatment at a temperature of not less than 0 ° C and not more than the glass transition temperature for 0.1 to 1500 hours, which results in a film which is hard to curl. More preferably, it is a heat treatment at Tg of -20 ° C or higher and lower than Tg. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. If the time is 0.1 hours or less, a sufficient effect cannot be obtained, and if the time is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. In order to further increase the effect of eliminating the curl, heat treatment is performed at a temperature of Tg or higher and lower than the melting point (melting temperature determined by DSC) before this heat treatment to erase the heat history of the support, and then the above 40 It is preferable to perform the heat treatment again at a temperature of ℃ or more and less than Tg.

The heat treatment of such a support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web. In the case of heat treatment in the form of a roll, any of a method of heat-treating the roll in a constant temperature bath from room temperature and a method of winding and heat-treating the roll in the form of a roll after being brought to a predetermined temperature during web conveyance may be performed. In the heat treatment in a roll, due to the heat shrinkage stress generated during the heat treatment, surface defects such as wrinkles due to winding tightness and cut-out of the core portion are likely to occur.
Therefore, the surface is roughened (for example, SnO ₂ / Sb
Applying conductive inorganic fine particles such as ₂ O ₅ or colloidal silica) to prevent wrinkles due to winding tightness by reducing the squeak between the supports, or to give knurls to the ends of the supports to slightly increase the edges only. It is desirable to take measures such as preventing the cut end of the core from being exposed by increasing the height. When the heat treatment is performed in the form of a web, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the form of roll. These heat treatments may be carried out at any stage after the support film formation, the glow discharge treatment, the back layer application (antistatic agent, slip agent, etc.), and the undercoat application. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, various additives are preferably coexisted. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 20% by weight, preferably 0.05% by weight based on the weight of the polyester film.
It is about 10% by weight to 10% by weight. As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-
4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4
Benzophenone-based compounds such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, benzotriazole compounds such as 2 (2'-hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole, phenyl salicylate, methyl salicylate, etc. Examples include salicylic acid-based ultraviolet absorbers.

Further, in order to avoid the light piping phenomenon, it is preferable to add inert dyes or the like to the support, and it is preferable to add a dye. The dye is not particularly limited. Made of Diar
The object can be achieved by mixing a commercially available dye for polyester such as esin and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more. The polyester film according to the present invention can be imparted with slipperiness according to the use, and SiO ₂ , TiO ₂ , Ba as the inert inorganic particles.
SO ₄ , CaCO ₃ , talc, kaolin, etc. are added.

When any of these polyester films is used as a support, since each of these polyester supports has a hydrophobic surface, a photographic layer (eg, a photosensitive halogen) containing a protective colloid mainly containing gelatin is provided on the support. It is preferable to perform various surface treatments in order to firmly adhere the silver halide emulsion layer, the intermediate layer, the filter layer, etc.). Examples thereof include surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. After these surface treatments, an undercoat layer may be provided or a photographic emulsion layer may be directly coated.

Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. First, the ultraviolet irradiation treatment will be described below. These are Japanese Examined Patent Publication Nos. 43-2603, 43-2604, and 4
It is preferably carried out by the treatment method described in No. 5-3828. The mercury lamp is a high-pressure mercury lamp composed of a quartz tube, and it is preferable that the wavelength of ultraviolet rays is between 180 and 320 nm. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after heat setting. If there is no problem in the performance of the support that the surface temperature of the support is increased to around 150 ° C., a high pressure mercury lamp having a main wavelength of 365 nm can be used. When low temperature processing is required, the dominant wavelength is 254 nm
Low pressure mercury lamps are preferred. It is also possible to use an ozone-less type high pressure mercury lamp and a low pressure mercury lamp.

Next, the corona discharge treatment will be described by any of the conventionally known methods, for example, Japanese Patent Publication No. 48-5043.
47-51905, JP-A-47-28067, 49-83767, 51-41770 and 51-.
It can be achieved by the method disclosed in No. 131576 or the like. The discharge frequency is suitably 50 Hz to 5000 KHz, preferably 5 KHz to several hundred KHz, and particularly preferably 10 Hz to 30 KHz. Regarding the treatment strength of the object to be treated, it is usually 0.001 KV · A · min / m ² ~
5 KV · A · min / m ^2, preferably is 0.01 kV · A · min / m ² ~1KV · A · min / m ² suitably. The gap clearance between the electrode and the derivative roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm. Corona discharge treatment machine is Pillar solid state corona treatment machine 6KV
The A model can be used. Further, as the flame treatment, natural gas, liquefied propane gas, etc. can be used, and the mixing ratio with air is important. A preferable gas / air mixing ratio is a volume ratio of 1/14 to 1/22 for propane, and more preferably 1/16 to 1/19. 1/6 to 1 for natural gas
/ 10, more preferably 1/7 to 1/9. The flame treatment amount is 1 to 50 Kcal / m ² , more preferably 3 to ²
It is 0 Kcal / m ² . Further, it is more effective that the distance between the tip of the internal flame of the burner and the support is less than 4 cm.

The glow discharge treatment is carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1.
No. 0336, No. 45-22004, No. 45-2200
No. 5, No. 45-24040, No. 46-43480,
US Pat. Nos. 3,057,792 and 3,057,795
Issue 3, Issue 3,179,482, Issue 3,288,638
No. 3,309,299, No. 3,424,735
No. 3, 3,462,335, 3,475,307
No. 3,761,299, British Patent 997,093
JP-A No. 53-129262 and the like can be used. There is a method of introducing various gases such as oxygen, nitrogen, helium or argon into the atmosphere of glow discharge treatment, but glow discharge treatment in the presence of water vapor is preferable. The steam partial pressure is preferably 10% or more and 100% or less, and more preferably 40% or more and 90% or less. 10
If it is less than%, it becomes difficult to obtain insufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like. Further, it is preferable to preheat the film to be surface-treated, preferably 50 ° C. or higher and Tg or lower, and 70 ° C. or higher Tg.
The following is more preferable, and 90 ° C or higher and Tg or lower is further preferable. As a method of raising the surface temperature of the support in vacuum,
There are heating by an infrared heater, heating by contact with a hot roll, and the like.

The pressure during glow discharge treatment is 0.005 to 2
It is preferably 0 Torr. More preferably 0.02-
2 Torr. Further, the voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V. The discharge frequency used is, as seen in the prior art, from direct current to several 1000 MHz, preferably 50 Hz to.
20 MHz, more preferably 1 KHz to 1 MHz. Discharge treatment intensity is 0.01KV · A · min / m ^{2 to} 5K
V · A · min / m ² is preferable, more preferably 0.15K
The desired adhesive performance can be obtained at V · A · min / m ^{2 to 1} KV · A · min / m ² . It is preferable that the temperature of the support thus subjected to the glow discharge treatment is immediately lowered by using a cooling roll.

Next, the method of undercoating the surface-treated support will be described. Single layer or multiple layer method may be used, such as vinyl chloride,
Starting with copolymers starting from monomers selected from vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, polyethyleneimine, epoxy resins, grafted gelatin, nitro For many polymers such as cellulose, a binder based primarily on gelatin is preferred for the second subbing layer in the overlay. Examples of the undercoat polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. As the latex polymer, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer, acrylic acid ester-containing copolymer, vinyl acetate-containing copolymer,
For example, a butadiene-containing copolymer. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various gelatin hardeners can be used in the subbing layer of the present invention. As a gelatin hardening agent, a colloidal salt (chrome alum etc.), an aldehyde (formaldehyde, glutaraldehyde etc.), an isocyanate, an active halogen compound (2,4-dichloro-6-hydroxy-S-triazine etc.), an epichlorohydrin resin. And so on.

The subbing layer of the present invention comprises SiO ₂ , Ti
O ₂ and inorganic fine particles such as a matting agent or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. The undercoating liquid according to the present invention is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. No. 2,681. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 294,294. If desired, U.S. Pat. Nos. 2,761,791, 3,508,947, 2,941,898, and 3,526,528, Yuji Harasaki, "Coating Engineering," page 253. (1
Two or more layers can be coated simultaneously by the method described in, for example, Asakura Shoten, 973). In the present invention, the support is preferably polyethylene-2,6-
Naphthalene dicarboxylate is heat treated for 24 hours between 100 ° C and 115 ° C and the thickness of its support is 85μ.
m to 105 μm, the surface of which is subjected to ultraviolet irradiation treatment or glow discharge treatment, the back side non-photosensitive hydrophilic layer is a gelatin layer of 1 to 7 μm, and the non-photosensitive hydrophilic layer is 0 It is characterized in that it is a cellulose binder of 0.5 to 5 μm. At this time, the weight ratio of the gelatin amount of the non-photosensitive hydrophilic layer of the back layer to the gelatin layer of the emulsion layer on the opposite side is preferably 0.1 to 0.5.

There are no particular restrictions on the 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 From its manufacturing method, page 21, lower left column, line 14 and JP-A-2-2236. Page 7, upper right column, line 19 to page 8, lower left column, line 12, Japanese Patent Application No. 3-116573 and Japanese Patent Application No. 3-189532. 2) Spectral sensitizing dyes, from JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8, from JP-A-2-39042, page 7, lower right column, line 8 Page 13, lower right column, line 5. Tokukaihei 2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left column, line 20 Further, JP-A Nos. 1-112235, 2-124560, 3-79928, and Japanese Patent Application Nos. 3-189532 and 3-411064.

[0163] 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7                           From the same right lower column 7th line. 4) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6                           Eye to page 19, upper left column, first line, and 2-553                           No. 49, page 8, lower right column, line 13 to page 11 left                           Upper row, line 8. 5) Antifoggant JP-A-2-103536, page 17, lower right column 19                           From line 1 to page 18, upper right column, line 4 and lower right column, line 1                           From the 5th line, further JP-A-1-237538                           Thiosulfinic acid compounds described in the report. 6) Polyhydroxy JP-A-2-55349, page 11, upper left column, page 9     From benzenes, the same, lower right column, line 17. 7) Sliding agent, plasticizer JP-A-2-103536, page 19, upper right column, line 6                           From the eye, page 15, upper right column, line 15. 8) Hardener JP-A-2-103536, page 18, upper right column, line 5                           17th line from the eye.

[0164] 9) Dye JP-A-2-103536, page 17, lower right column, line 1                           18th to 18th lines, No. 2-39042, page 4                           Upper right column, first line to page 6, upper right column, fifth line, 2-29                           4638 gazette and Japanese Patent Application No. 3-185773.                           Solid dye listed. 10) Tetrazolium compound JP-A-2-39143, page 4, lower left column, line 8     Page 6, lower left column, line 6, JP-A-3-123346.                           Gazette, page 3, upper right column, line 19 to page 5, upper left column, line 20                           Eye. 11) Redox compound Represented by the general formula (I) in Japanese Patent Application Laid-Open No. 2-301743                           (Especially compound examples 1 to 50), 3                           No. 174143, pages 3 to 20                           Of the general formulas (R-1), (R-2), (R-3)                           Compound Examples 1 to 75, and Japanese Patent Application No. 3-69466                           Nos. 3-15648. 12) Monomethine compound Compound of the general formula (II) described in JP-A-2-287532                           Compounds (especially compound examples II-1 to II-25). 13) Colloidal silica Paragraph symbol “0005” described in JP-A-4-214551                           Listed compounds. 14) Developer and developing method JP-A-2-103536, page 19, upper right column 16                           From line 21 to page 21, upper left column, line 8.                           JP-A-2-55349, page 13, lower right column, first line                           To page 16, upper left column, line 10 of the same.

[0165]

【Example】

Example 1 An emulsion layer and a protective layer having the following compositions were simultaneously coated on one side of a biaxially stretched polyethylene terephthalate support (thickness 100 μm) having both surfaces coated with a subbing layer. <Emulsion layer> I solution; water 300 ml, gelatin 9 g II solution; AgNO ₃ 100 g, water 400 ml III _{solution; NaCl 37g, (NH 4)} 3 RhCl 5
1.1 ml and 400 ml of water Solution II and solution III were simultaneously added to solution I kept at 45 ° C. at a constant rate. Soluble salts were removed from this emulsion by a conventional method well known to those skilled in the art, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. This emulsion was a monodisperse emulsion having an average grain size of 0.16 μm. The following compounds were added to the emulsion thus obtained. Compound -4 3 × 10 ^-3 mol / Ag1 mole compound -5 60 mg / m ² Compound -6 9 mg / m ² Compound -3 10 mg / m ² Compound -7 25 mg / m ² of polystyrene sulphonic acid sodium salt 500 mg / m ² N-oleoyl-N-methyltaurine sodium salt 85 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 58 mg / m ² polymer Latex (Table 2) This coating solution was used for silver amount 2.7 g / m ² and gelatin 0.9 g / m ^2.
Was applied so that

[0166]

[Chemical 8]

<Lower layer of protective layer> Gelatin 0.5 g / m ² Lipoic acid 5 mg / m ² Dodecylbenzenesulfonic acid sodium salt 5 〃 Compound-8 20 〃 Polystyrene sulfonic acid sodium salt 10 〃 Compound -5 50 〃 Compound-9 30 〃 Compound-10 5 〃 Polymer latex (Table-2)

[0168]

[Chemical 9]

<Protective Layer Upper Layer> Gelatin 0.60 g / m ² Matting Agent (Table 2) Dodecylbenzenesulfonic acid sodium salt 20 〃 Perfluorooctane sulfonic acid potassium salt 10 〃 N-perfluorooctanesulfonyl-N-propylglycine pota Sodium salt 3〃 Polystyrene sulfonic acid sodium salt 2〃 Poly (degree of polymerization 5) Oxyethylene nonylphenyl ether sulfate sodium salt 20〃 Liquid paraffin 40〃 Colloidal silica (Nissan Chemical's "Snowtex C") 15〃

A conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 250 mg / m ² Gelatin (Ca ⁺⁺ content 3000 ppm) 100 〃 Compound-3 7 〃 Dodecylbenzenesulfonic acid sodium salt 20 〃 dihexyl -α- sulfosuccinates sodium salt 20 〃 polystyrene sulfonic acid sodium salt 20 〃 <back layer> gelatin (Ca ⁺⁺ content 30ppm) 2.8 g / m ² compound -11 280 mg / m ² compound -12 60 〃 compound -13 35 〃 Compound -3 10 〃 Dodecylbenzenesulfonic acid sodium salt 80 〃 Dibenzyl-α-sulfosuccinate sodium salt 20 〃 1,2-bis (vinylsulfonylacetamide) ethane 150 〃 Polymer latex Compound example P-4 280 〃 Lithium perfluorooctane sulfonate 5〃 Silicon dioxide fine powder particles (average particle size 4μ, pore diameter 170Å, surface area 300m ² / g) 35〃 sodium sulfate 230〃

[0171]

[Chemical 10]

The obtained sample was stored in an atmosphere of 25 ° C. and 50% RH for 1 week, and then evaluated as follows. (1) The Beck's smoothness sample was measured in an atmosphere of 25 ° C. and 50% RH using an Oken type smoothness tester (manufactured by Asahi Seiko Co., Ltd.). (JIS
(Method according to P8119) (2) Photographic performance evaluation sample is Fuji Photo Film Co., Ltd.
-800FX (using a Fresnel lens) is exposed through an optical wedge using a fine light filter type B, and a developing solution (I) and a fixing solution (I) having the following compositions are used, and an automatic processor FG-680AG (Fuji Photo) The film was processed under the developing conditions of 38 ° C. and 20 seconds. Sensitivity is the logarithmic value of the exposure amount that gives a density of 3.0
It is shown as a relative value when 0 is set. The γ value indicates the average gradation degree from the density 0.3 to 3.0 of the characteristic curve,
The value obtained by dividing 2.7 by ΔlogE (the difference between the logarithmic value of the exposure amount giving a density of 3.0 and the logarithmic value of the exposure amount giving a density of 0.3) is shown. The larger the value, the higher the contrast of the image characteristics. The Dm value is shown as the maximum density value of the characteristic curve.

The compositions of the developing solution (I) and the fixing solution (I) are shown below. <Developer (I)> Potassium hydroxide 90.0 g Sodium hydroxide 8.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Boric acid 24.0 g Sodium metabisulfite 65.0 g Potassium bromide 10.0 g Hydroquinone 55.0 g 5-Methylbenzotriazole 0.40 g N- Methyl-p-aminophenol 0.50 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.30 g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.20 g Nn-butyl-diethanolamine 14.0 g N, N-dimethyl Amino-6-hexanol 0.20 g Sodium toluenesulfonate 8.0 g 5-Sulfosalicylic acid 23.0 g Potassium hydroxide is added, and water is added to make 1 liter, and the pH is adjusted to 11.9. The replenishment rate of 1 liter was 240 ml / m ² .

[0174] <Hardening solution (I)>   Ammonium thiosulfate 359.1 g   Ethylenediaminetetraacetic acid 2Na dihydrate 0.092g   Sodium thiosulfate pentahydrate 32.8 g   Sodium sulfite 75.0 g   37.2 g NaOH (in pure content)   Glacial acetic acid 87.3 g   Tartaric acid 8.76g   Sodium gluconate 5.2 g   Aluminum sulfate 25.3 g   pH (adjusted with sulfuric acid or sodium hydroxide) 4.85   1 liter with water   The working solution is prepared by adding 2 liters of water to this.

(3) Degree of Pinhole Generation After exposure to an optical density of 4.0 and processing under the developing conditions described above, the state of pinhole generation was examined on a high-intensity light table. (4) Wet film strength sample was immersed in distilled water at 25 ° C for 5 minutes, and the radius was 0.3mm.
The sample was pressed against the surface of the sample film with the sapphire needle, and the load of the needle was continuously changed while moving at a speed of 10 mm / sec, and the load (g) when the film was broken was measured.

The obtained results are shown in Table 2. As is clear from Table 2, the samples of the present invention containing an active methylene group and using the monodisperse matting agent can significantly reduce pinholes and have a high D
It can be seen that the m value and the wet film strength are strong.

[0177]

[Table 2]

Example-2 <Preparation of silver halide light-sensitive material> Emulsion preparation [Emulsion A] 1 part water 750 ml gelatin 20 g sodium chloride 2 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium thiosulfonate 10 mg 2 liquid water 300 ml silver nitrate 150 g 3 liquid water 300 ml sodium chloride 38 g potassium bromide 32 g K ₃ IrCl ₆ 0.25 mg K ₂ Rh (H ₂ O) Cl ₅ 0.07 mg kept at 38 ° C, pH 4.5 90% each of the 2nd and 3rd liquids was simultaneously added to the dropped 1st liquid over 20 minutes with stirring to form 0.19 μm core particles. Subsequently, the following 4 liquids and 5 liquids were added over 8 minutes, and the remaining 10% amounts of 2 liquids and 3 liquids were added over 2 minutes to obtain a silver chloride content of 70 mol% with an average grain size of 0.22 μm.
To obtain silver chlorobromide grains. 4-liquid water 100 ml Silver nitrate 50 g 5-liquid water 100 ml Sodium chloride 14 g Potassium bromide 11 g

Thereafter, 1 × 10 ^-3 mol of KI solution was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added per mol of silver, and benzenethio was added per mol of silver. 7 mg sodium sulfonate and 2 mg benzenesulfinic acid
PH was adjusted to 5.7 and pAg 7.5, and silver 1 was added.
1 mg / molar sodium thiosulfate and compound (CS-
A) and 5 mg of chloroauric acid were added and chemically sensitized at 55 ° C. for optimum sensitivity. Then, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained particles have an average particle size of 0.
The silver iodochlorobromide cubic grains had a size of 22 μm and a silver chloride content of 70 mol%. (Variation coefficient 10%)

[0180]

[Chemical 11]

<Preparation of Coating Sample> On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, a UL layer, an EM layer, and a support layer were sequentially formed from the support side.
A sample was prepared by coating so as to have a PC layer and an OC layer. The preparation method and coating amount of each layer are shown below. (UL) For the UL layer, 0.5 g / m ^{2 of} gelatin, 150 mg / m ^{2 of} polymer latex P-4, the following dye [a]
Was applied at 5 mg / m ² .

(EM) To the above emulsion, a sensitizing dye and 5 × 1 were added per mol of silver.
^0-4 moles added, and 5 mg KBr per mole silver,
3 × 10 ⁻⁴ mol of the mercapto compound represented by the following (a), 4 × 10 ⁻⁴ mol of the mercapto compound represented by the (b), 4 × 10 ⁻⁴ mol of the triazine compound represented by the (c), 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added, 1 × 10 ⁻⁴ mol of a hydrazine nucleating agent was added, and 4 × 10 ⁻⁴ mol of the following compound A-1 as a nucleation accelerator, A -2 was added at 4 × 10 ^-4 mol. Further, hydroquinone 100 mg / m ² , N-oleyl-N-methyltaurine sodium salt 20 mg / m ² , dodecylbenzenesulfonic acid sodium salt 20 mg / m ² , and the compound of (d) 15
² mg / m ² of colloidal silica with an average particle size of 0.02 μm
Was added as 200 mg / m ² coating, a polymer latex P-4 750mg / m ^2, as a further hardening agent 1,3
200 mg / m ^{2 of} divinylsulfonyl-2-propanol
Was added. The pH of the solution was adjusted to 5.5 with acetic acid. Coating them with an amount of silver of 3.5 g / m ² and gelatin of 1.5 g
It was applied so as to be / m ² .

[0183]

[Chemical 12]

(PC) Gelatin 0.5 g / m ² , polymer latex P-4 250 mg / m ² , sodium ethylsulfonate 5 mg / m ² , 1,5-dihydroxy-2-benzaldoxime 10 mg / m ^2. Applied. (OC) gelatin 0.3 g / m ² , matting agent shown in Table 3, 100 mg / m ² of colloidal silica having an average particle size of 0.02 μm,
Polyacrylamide 100 mg / m ² and silicone oil 2
30 mg / m ^{2 of the} compound represented by 0 mg / m ² and (e), 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (f) and 50 mg / m ² of sodium dodecylbenzenesulfonate as a coating aid. Applied.

[0185]

[Chemical 13]

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound [a] 110 mg / m ²

[0187]

[Chemical 14]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [b], dye [c] and dye [d] dye [b] 100 mg / m ² Dyes [c] 30 mg / m ² Dyes [d] 60 mg / m ²

[0189]

[Chemical 15]

[Back protective layer] Gelatin 0.8 g / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfone Sodium acid salt 15 mg / m ² Sodium acetate 40 mg / m ²

<Exposure and Development> (1) Evaluation of photographic performance The above sample was passed through an interference filter having a peak at 488 nm and passed through a step wedge to emit light for 10 ⁻⁵ se.
It was exposed to the xenon flash light of c, and developed (35 ° C. for 30 seconds), fixed, washed with water and dried using an FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd.
As the developing solution and the fixing solution, the developing solution and the fixing solution having the following compositions were used.

[0192] Developer formulation (Developer A)   Potassium hydroxide 35.0 g   Diethylenetriamine-pentaacetic acid 2.0 g   Sodium metabisulfate 40.0 g   Potassium carbonate 40.0 g   Potassium bromide 3.0 g   5-methylbenzotriazole 0.08g   2,3,5,6,7,8-hexahydro-2-thioxo     -4- (1H) -quinazolinone 0.04g   2-Mercaptobenzimidazole-5-sulfonic acid     Sodium 0.15g   Hydroquinone 25.0 g   4-hydroxymethyl-4-methyl-1-phenyl-     3-pyrazolidone 0.45 g   Sodium erythorbate 3.0 g   Diethylene glycol 20.0 g   Add potassium hydroxide, add water to 1 liter,   Adjust the pH to 10.45. 1 liter

[0193] Fixer formulation   Ammonium thiosulfate 359.1 ml   Ethylenediaminetetraacetic acid 2Na dihydrate 2.26g   Sodium thiosulfate pentahydrate 32.8 g   Sodium sulfite 64.8 g   NaOH 37.2 g   Glacial acetic acid 87.3 g   Tartaric acid 8.76g   Sodium gluconate 6.6 g   Aluminum sulfate 25.3 g   pH (adjusted with sulfuric acid or sodium hydroxide) 4.85   1 liter with water

The sensitivity, γ value and Dm value were determined in the same manner as in Example-1. (2) Beck's smoothness and (3) pinhole occurrence were determined in the same manner as in Example-1.

The obtained results are shown in Table 2. As is clear from Table 2, the sample of the present invention has very few matte pinholes and has a high Dm value.

[0196]

[Table 3]

Example-3 Sample No. 2 of Example-2 described in Japanese Patent Application No. 7-46687
The matting agent in the upper layer of the protective layer of 5 to 30 was used in Examples -4 and-
The matting agent in the OC layer of Nos. 5 and 6 was replaced with the compound example Q-1, and the polyethyl acrylate latex of the emulsion layer and the lower layer of the protective layer of Examples-2 and 3 described in JP-A-7-28188 was replaced with a polymer latex. In P-4, the matting agent in the upper layer of the protective layer was replaced with Compound Example Q-1, the polyethyl acrylate latex in the emulsion layer of Example-4 was used as polymer latex P-4, and the matting agent in the protective layer was Q-1. In place of each of the samples. The obtained sample was evaluated in the same manner as in Example-1. As a result, as in Example-1, the number of matte pinholes was small and the Dm value was high.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kentaro Shirato 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fujisha Shinfilm Co., Ltd. (72) Inventor Hidetoshi Watanabe, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fujisha Shinfilm Co., Ltd. ( 56) References JP-A-1-281443 (JP, A) JP-A-7-168322 (JP, A) JP-A-7-104411 (JP, A) JP-A-2-54249 (JP, A) Japanese Patent Laid-Open No. 2-24649 (JP, A) Japanese Patent Laid-Open No. 5-249586 (JP, A) Japanese Patent Laid-Open No. 8-76309 (JP, A) Japanese Patent Laid-Open No. 5-289225 (JP, A) Japanese Patent Laid-Open No. 2-135335 (JP , A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/04 501 G03C 1/95 G03C 1/76 501 G03C 1/047 G03C 1/053

Claims (4)

(57) [Claims] 1. A silver halide photographic material comprising a layer of light-sensitive silver halide emulsion layer the at least name rather on a support, the small Do Kutomo one layer of hydrophilic colloid layer, having an active methylene group It contains a latex-like polymer having a shell / core / shell structure, and has an average particle diameter of 1 μm or more in the protective layer and a coefficient of variation of particle diameter distribution.
A silver halide photographic light-sensitive material comprising a particulate alkali-insoluble polymer of 0.2 or less . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the latex polymer having an active methylene group has a repeating unit derived from an ethylenically unsaturated monomer represented by the following general formula (I). . General formula (I) 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 CO
_{^{O-, 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, and 1 to 12 carbon atoms
Of a substituted amino _{^{group), R 9 -CO-CH 2}} CON
(R ⁶ )-(R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁹ is a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms, Carbon number 1
To an alkoxy group, an amino group, and a substituted amino group having 1 to 12 carbon atoms), and L is bonded to X in the form of alkylene, aralkylene or arylene. 3. The glass transition temperature of the latex polymer is 50 ° C. or lower, and the glass transition temperature of the monodisperse particulate alkali-insoluble polymer is 60 ° C. or higher. 2. The silver halide photographic light-sensitive material described in 2. 4. The silver halide photograph according to claim 1, wherein the total hydrophilic colloid layer on the side having the silver halide emulsion layer has a total gelatin amount of 3.0 g / m ² or less. Photosensitive material. The above object of the present invention has been achieved by the following means. (1) A silver halide photographic material comprising a layer of light-sensitive silver halide emulsion layer the at least name rather on a support, a latex-like having a small Do Kutomo one layer to the active methylene group of the hydrophilic colloid layer The protective layer contains a polymer and has an average particle size of 1 μm or more and a coefficient of variation of particle size of 0.
A silver halide photographic light-sensitive material comprising a granular alkali-insoluble polymer of 2 or less . [0050] Further polymers having an active methylene group of the present invention, a core having a shell having an active methylene group /
Adopt shell polymer latex. More specifically, the core constituting the core / shell latex is specifically a polymer composed of one or more repeating units of various polymerizable ethylenically unsaturated monomers, and specifically, the above-mentioned polymer. It is a polymer composed of monomers selected from the same group as the ethylenically unsaturated monomers described in A. [0065] an active methylene group that put in the present invention are set forth below Yes
Latec with core / shell structure, with shell to
An example is a polymer having a stripe shape. It is also used as a comparative example.
Listed in the order of non-core / shell latex. The ratio of each component represents a weight ratio, and in the case of the core / shell polymer, the core polymer structure, the shell polymer structure, and the core / shell ratio are described in this order. [Table 2]