JPH0954379A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material improved in the strength and brittleness of a gelatin film without adversely affecting photographic performances by incorporating a core/shell type polymer latex having a shell comprising repeating units derived from at least one kind of ethylenically unsaturated monomer. SOLUTION: The silver halide photographic sensitive material contains the core/shell type polymer latex having the shell comprising repeating units derived from at least one kind of ethylenically unsaturated monomer selected form formulae I-III in which R<4> is an H or halogen atom or an optionally substituted alkyl group; Q is a simple bond or a divalent bonding group; each of L<1> and L<3> is an alkylene or aryl group or the like; L<2> is an alkylene or heteroarylene group or the like; M is an H atom or a cation; X<1> is a halogen atom; R<2> is -CH=CH2 or the like; and X<2> is a group to be substituted by a nucleophilic group or a group to be released in the form of HX<2> by a base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material containing a novel polymer latex. For more details,
By including the polymer latex, the present invention relates to a silver halide photographic light-sensitive material having improved film physical properties without impairing photographic characteristics.

[0002]

2. Description of the Related Art Generally, gelatin is often used as a binder in a hydrophilic colloid layer constituting a photographic light-sensitive material. Gelatin is a binder having excellent properties such as high swelling ability and gelling ability, and easy cross-linking with various hardeners. On the other hand, gelatin as a hydrophilic colloid layer is not always a versatile material in terms of physical properties of the film, for example, deformation due to plasticization of the film under high humidity, elongation of the film due to moisture absorption, or embrittlement of the film under low humidity. It has drawbacks such as

In order to overcome the drawbacks of the gelatin film, the humidity of the hydrophilic colloid film is improved by incorporating a polymer latex into the hydrophilic colloid layer such as silver halide emulsion layer, protective layer, back layer and intermediate layer. Attempts have been made to improve film physical properties such as dimensional stability, scratch strength, brittleness, and dryness.

For example, US Pat. No. 2,763,625,
2,852,382, JP-A-62-115,152.
, JP-A-5-66,512, JP-A-5-80449,
Japanese Patent Publication No. 60-15935, Japanese Patent Publication No. 4-64,058
JP-A-5-45014 and the like disclose the use of polymer latexes containing various monomers such as alkyl acrylate and alkyl methacrylate in the gelatin-containing hydrophilic colloid layer.

However, use of this type of latex is effective for improving some physical properties of gelatin film, but the strength of the gelatin film becomes insufficient especially in high humidity or water containing state. On the other hand, it is known that such a problem can be solved by copolymerizing an active methylene group capable of reacting with gelatin or a coexisting hardener into latex. On the other hand, a reactive group such as a sulfinic acid group, a haloalkyl group, a vinyl sulfone group or a group derived from a vinyl sulfone group, which can react with gelatin or a coexisting hardener, is copolymerized with the latex to It is known that such problems are solved.

For example, JP-A-63-221343 discloses a polymer latex containing a monomer having a sulfinic acid group, and JP-B-4-64058 discloses a polymer latex containing a styrene monomer having a chloromethyl group. JP-A-63-220239, JP-A-2-29
No. 3735 discloses a polymer latex containing a monomer having a vinyl sulfone group or a group derived from a vinyl sulfone group in the gelatin layer of a photographic light-sensitive material, thereby improving the dimensional stability and devitrification It is disclosed that the properties, film strength, adhesive strength, etc. are improved.

However, in order to improve the dimensional stability of the gelatin film and the film strength by these latexes, it is necessary to copolymerize the reactive monomer in a certain amount or more. In addition, when the ratio of latex to gelatin is high or the absolute amount of gelatin is low, the strength of the gelatin film in the wet state is significantly reduced, and it is necessary to copolymerize a larger amount of the reactive monomer. There is a problem that the required film strength cannot be obtained only by increasing the amount of the volatile monomer.

With respect to recent photographic light-sensitive materials, it has been one of the most important issues to reduce the coating amount of gelatin from the viewpoint of high image quality, demand for higher film physical properties, speeding up of processing and the like. For example, in the field of photoengraving, it is strongly desired to improve the dimensional stability by reducing the amount of gelatin coated on the photographic light-sensitive material or reduce the replenishment amount by reducing the amount of processing solution taken out. There is.

Therefore, in the conventional mere reactive monomer copolymerized latex, the film strength may not be sufficiently improved, or the production cost of the polymer latex may be increased by using a large amount of the reactive monomer having a relatively complicated structure. Problems have arisen and further improvements are desired.

[0010]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel polymer latex. A second object of the present invention is to provide a silver halide photographic light-sensitive material containing the above latex, in which the strength and brittleness of the gelatin film are improved without adversely affecting the photographic characteristics. A third object of the present invention is to provide a silver halide photographic light-sensitive material which has a sufficient film strength even with a low amount of gelatin used, is excellent in dimensional stability, and can reduce the replenishing amount of a processing solution. It is in.

[0011]

The above objects of the present invention have been achieved by the following means. (1) Containing a core / shell polymer latex having a shell having a repeating unit derived from at least one ethylenically unsaturated monomer represented by the following general formulas (I), (II) and (III). A characteristic silver halide photographic light-sensitive material.

[0012]

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In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. Q represents a single bond or a divalent linking group. L ¹ and L ³ represent alkylene, aralkylene and arylene, and L ² represents alkylene, aralkylene and heteroarylene. M represents a hydrogen atom or a cation. X ¹ represents a halogen atom. R ² represents either -CH = CH ₂ or -CH ₂ -CH ₂ -X ² ,
X ² is replaced by a nucleophilic group or HX ² by a base
Represents a group capable of leaving in the form of.

Preferred embodiments of the silver halide photographic light-sensitive material of the present invention are the following (2) and (3). (2) The silver halide photographic light-sensitive material as described in (1) above, wherein the weight ratio of each polymer in the core portion and the shell portion of the polymer latex is in the range of 20/80 to 95/5. (3) Glass transition temperature of core and / or shell is 50 ° C
The silver halide photographic light-sensitive material as described in (1) or (2) above, wherein:

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer latex having a core / shell structure of the present invention will be described below. The core constituting the latex of the present invention is specifically a polymer composed of one or more repeating units of various polymerizable ethylenically unsaturated monomers.

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

More specific examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and tert-butyl acrylate. , Amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofur Furyl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate Over DOO, 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-
Examples thereof include (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (addition mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate.

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, octyl methacrylate, stearyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate , Dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate,
Cresyl methacrylate, naphthyl methacrylate, 2
-Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso
-Propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, allyl methacrylate and the like can be mentioned.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl 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-chloro Butadiene, 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 and the like;

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, bromostyrene, methyl vinyl benzoate, etc .; vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether;

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

Further, in the core of the latex of the present invention, at least two monomers having a copolymerizable ethylenically unsaturated group can be used. Examples of such monomers include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Examples include trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol methacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

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

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

The shell portion of the core / shell latex of the present invention will be described below. The shell portion of the present invention is a polymer having a repeating unit derived from at least one ethylenically unsaturated monomer having a reactive group represented by the following general formulas (I), (II) and (III).

[0027]

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In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. Q represents a single bond or a divalent linking group. L ¹ and L ³ represent alkylene, aralkylene and arylene, and L ² represents alkylene, aralkylene and heteroarylene. M represents a hydrogen atom or a cation. X ¹ represents a halogen atom. R ² represents either -CH = CH ₂ or -CH ₂ -CH ₂ -X ² ,
X ² is replaced by a nucleophilic group or HX ² by a base
Represents a group capable of leaving in the form of.

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. Q represents a single bond or a divalent linking group, and is specifically represented by the following formula.

[0030]

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Q 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-,

[0032]

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

[0034]

[Chemical 6]

J ¹ , J ² , J ³ , and J ⁴ may be the same or different, and --CO--, --SO _2- , --CON.
(R ⁶ )-(R ⁶ is a hydrogen atom, an alkyl group (having 1 to 1 carbon atoms)
6), a substituted alkyl group (having 1 to 6 carbon atoms)), -SO ₂ N
(R ⁶ )-(R ⁶ is as defined above), -N (R ⁶ ) -R ⁷
- (R ⁶ is as defined above, R ⁷ is an alkylene group having from about 1 carbon atoms ^{4), - N (R 6} ) -R 7 -N (R 8) - (R 6,
R ⁷ has the same meaning as above, and R ⁸ represents a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms) or a substituted alkyl group (having 1 to 6 carbon atoms). ), - O -, - S -, - N (R 6) -CO-N (R
^{8) - (R 6, R} 8 are as defined ^{above), - N (R 6)} -S
^{_{O 2 -N (R 8) -}} (R 6, R 8 are as defined above), - C
OO -, - OCO -, - N (R 6) CO 2 - (R 6 is as defined ^{above), - N (R 6)} CO- (R 6 is as defined above)
And the like.

P, q and r represent 0 or 1. Y ¹ ,
Y ² , Y ³ and Y ⁴ may be the same or different from each other, and are an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or a phenylene having 6 to 20 carbon atoms. Represents a group, and the alkylene group may be linear or branched. L ¹ and L ³ represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and L ² has 1 to 10 carbon atoms. Represents a substituted or unsubstituted alkylene group, an aralkylene group having 7 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group. The alkylene group may be linear or branched. When L ² is an aralkylene group, it is linked to X ¹ on the alkylene side.

[0037] R ² is -CH = CH _2, represents either ^{_{-CH 2 -CH 2 -X 2, X}} 2 is either replaced by a nucleophilic group, group capable desorbed in the form of HX ² by a base Represents X ² can be a halogen atom, a hydroxyl group, -O ₃ SR ⁹ (R ⁹ is a methyl group, a phenyl group, a methylphenyl group, a halomethyl group), -O ₂ CR ⁹ (R ⁹ is the same as defined above) and the like. .

Examples of the alkylene group include methylene,
Examples of the methylmethylene, dimethylmethylene, methoxymethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene and aralkylene groups include phenylenemethylene, phenyleneethylene, methylenephenylene, ethylenephenylene and arylene groups such as p. -Phenylene, m
-Phenylene, methylphenylene, chlorphenylene,
Heteroarylene groups include, for example, triazinediyl, pyrimidinediyl and the like.

Specific examples of the monomers having a sulfinic acid group, a haloalkyl group, and a vinyl sulfone group, which give the repeating units constituting the shell in the latex of the present invention, will be given below, but the present invention is not limited thereto.

Monomer having sulfinic acid group M-1 Sodium styrenesulfinate M-2 Potassium styrenesulfinate M-3 Styrenesulfinic acid M-4 Sodium α-methylstyrenesulfinate M-5 Sodium α-chlorostyrenesulfinate

[0041]

[Chemical 7]

Monomer having haloalkyl group or haloheteroarylene group M-9 2-chloroethyl acrylate M-10 2-bromoethyl acrylate M-11 2-chloroethyl methacrylate M-12 2-chloropropyl acrylate M-13 3- Chloropropyl acrylate M-14 4-Bromobutyl acrylate M-15 2-Chlorocyclohexyl acrylate M-16 2,2-Dichloroethyl acrylate M-17 2,2,2-Trichloroethyl methacrylate M-18 Chloromethylstyrene M-19 Bromomethylstyrene M-20 2-methyl-4-chloromethylstyrene

[0043]

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Monomers having vinyl sulfone groups or groups derived from vinyl sulfone groups

[0045]

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In the polymer constituting the shell portion of the present invention, an ethylenically unsaturated monomer other than the above-mentioned ethylenically unsaturated monomer having a reactive group may be copolymerized. Examples of such monomers include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers, and other monomers constituting the core particles. Among them, acrylic esters, methacrylic esters, vinyl esters, and styrenes are particularly preferable.

In the core / shell polymer latex of the present invention, the ratio of the monomer unit having a reactive group in the shell polymer can be arbitrarily changed according to the need for performance, and is used in the range of 0.1 to 100% by weight. I can do things. However, while increasing the copolymerization amount of the monomer unit having a reactive group, the various effects described above increase,
If it exceeds a certain amount, the effect may be saturated.
Further, in the case of a monomer having a sulfinic acid group, increasing the copolymerization amount of the monomer unit increases the hydrophilicity, which may increase the difficulty of latex synthesis. Therefore, the proportion of the reactive monomer unit is preferably 0. 0 in the case of the monomer having a sulfinic acid group.
1 to 40% by weight, particularly preferably 1 to 20% by weight, and in the case of a monomer having a haloalkyl group or a haloheteroarylene group, a vinylsulfone group or a group derived from a vinylsulfone group, preferably 0.1 to 40% by weight. It is 60% by weight, particularly preferably 1 to 40% by weight.

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

As is well known in the field of core / shell latex forming technology in emulsion polymerization, the combination of the core polymer and the shell polymer having polarities close to each other and compatibilizing each other results in 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 hardly compatible.

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, so that it is possible to form an effective core / shell structure with most of the monomers used for the shell portion. The standard for forming a core having such performance is that the conjugated diene monomer is contained in an amount of 25% or more by weight. As a preferred example, a styrene-butadiene copolymer (generally called SBR and solution-polymerized SBR) is used.
And emulsion polymerization SBR. As the solution-polymerized SBR, in addition to the random polymer, the above-mentioned block copolymer (for example,
Butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer)), butadiene homopolymer (for example, cis-1,4-butadiene,
Trans-1,2-butadiene, or a rubber in which these are mixed with a trans-1,4-butadiene structure), an isoprene homopolymer (an example of a three-dimensional structure is the same as a butadiene polymer), a styrene-isoprene copolymer (Random copolymer, block copolymer), ethylene-propylene-diene copolymer (diene monomers include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, etc.), acrylonitrile-
Butadiene copolymer, chloroprene 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).

An effective core / shell structure can also be formed by selecting a polymer having a large polarity difference between the polymers forming the core and the shell. However, these show that the effect can be selected in terms of the magnitude of the effect in the core / shell polymer latex of the present invention. On the other hand, the core of the present invention /
Shell latex exhibits better film strength properties.

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

The core / shell latex of the present invention has a glass transition temperature of the core 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 preferred.

The Tg of the polymer is, for example, “J. Brandrup,
E. FIG. 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.

[0055]

[Equation 1]

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

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

P-1 to 3 core: butadiene homopolymer P-1 shell: styrene / M-1 (70/30) core / shell = 50/50 P-2 shell: styrene / M-18 (70/30) ) Core / shell = 50/50 P-3 Shell: Styrene / M-30 (70/30) Core / shell = 50/50

P-4 to 12 core: styrene / butadiene copolymer (37/63) P-4 shell: n-butyl acrylate / M-1 (95/5) core / shell = 50/50 P-5 shell : N-butyl acrylate / M-1 (90/10) core / shell = 50/50 P-6 shell: n-butyl acrylate / M-1 (85/15) core / shell = 50/50 P-7 shell : N-butyl acrylate / M-1 (80/20) core / shell = 50/50 P-8 shell: n-butyl acrylate / M-1 (75/25) core / shell = 50/50 P-9 shell : N-butyl acrylate / M-1 (80/20) core / shell = 67/33 P-10 shell: n-butyl acrylate / M-1 (80/20) core / shell = 80/20 P-11 shell : N-butyl acrylate / M-7 (80/20) core / shell = 50/50 P-12 shell : N-butyl acrylate / M-17 (80/20) core / shell = 50/50

P-13 to 19 Core: Styrene / Butadiene Copolymer (49/51) P-13 Shell: Ethyl Acrylate / M-2 (80/20) Core / Shell = 50/50 P-14 Shell: Ethyl Acrylate / acrylic acid / M-3 (75/5/20) core / shell = 50/50 P-15 shell: methyl acrylate / M-4 (60/40) core / shell = 50/50 P-16 shell: Ethyl acrylate / M-10 (80/20) core / shell = 50/50 P-17 shell: Methyl acrylate / acrylic acid / M-10 (65/5/30) core / shell = 50/50 P-18 shell : Ethyl acrylate / M-25 (80/20) core / shell = 50/50 P-19 shell: Ethyl acrylate / acrylic acid / M-26 (75/5/20) core / shell = 50/50

P-20 to 29 Core: acrylonitrile / styrene / butadiene copolymer (25/25/50) P-20 Shell: ethyl acrylate / M-13 (95/5) Core / shell = 50/50 P- 21 Shell: Ethyl acrylate / M-13 (90/10) Core / Shell = 50/50 P-22 Shell: Ethyl acrylate / M-13 (85/15) Core / Shell = 50/50 P-23 Shell: Ethyl Acrylate / M-13 (80/20) core / shell = 50/50 P-24 shell: ethyl acrylate / M-13 (75/25) core / shell = 50/50 P-25 shell: ethyl acrylate / M- 13 (80/20) Core / Shell = 67/33 P-26 Shell: Ethyl Acrylate / M-13 (80/20) Core / Shell = 80/20 P-27 Shell: Ethyl Acrylate / M-13 (80 / 20) Core / Shell = 50/50 P-28 Shell: Ethyl acrylate To / M-25 (80/20) core / shell = 50/50 P-29 shell: methyl acrylate / 2-acrylamido-2-methylpropanosulfonate sodium / M-25 (70/10/20) core / shell = 50/50

P-30 to 33 Core: n-butyl acrylate / butadiene copolymer P-30 Shell: Styrene / M-7 (80/20) Core / Shell = 50/50 P-31 Shell: Styrene / M- 24 (80/20) Core / Shell = 50/50 P-32 Shell: Styrene / M-29 (80/20) Core / Shell = 50/50 P-33 Shell: Lauryl Methacrylate / M-27 (80/20 ) Core / shell = 50/50

P-34 to 44 Core: divinylbenzene / styrene / methylmethacrylate copolymer (10/45/45) P-34 shell: n-butyl acrylate / M-25 (98/2) core / shell = 50 / 50 P-35 shell: n-butyl acrylate / M-25 (96/4) core / shell = 50/50 P-36 shell: n-butyl acrylate / M-25 (92/8) core / shell = 50 / 50 P-37 shell: n-butyl acrylate / M-25 (84/16) core / shell = 50/50 P-38 shell: n-butyl acrylate / M-25 (68/32) core / shell = 50 / 50 P-39 shell: n-butyl acrylate / M-25 (84/16) core / shell = 67/33 P-40 shell: n-butyl acrylate / M-25 (84/16) core / shell = 80 / 20 P-41 Shell: Ethyl acrylate / 2-acrylamide-2- Methyl propansulfonate sodium / M-25 (74/10/16) core / shell = 50/50 P-42 shell: methyl acrylate / acrylic acid / M-25 (79/5/16) core / shell = 50 / 50 P-43 Shell: Ethyl acrylate / acrylic acid / M-1 (75/5/20) Core / shell = 50/50 P-44 Shell: Ethyl acrylate / acrylic acid / M-9 (75/5/20) Core / shell = 50/50

P-45 to 53 Core: n-dodecyl methacrylate homopolymer P-45 Shell: Styrene / M-4 (70/30) Core / shell = 50/50 P-46 Shell: Methyl acrylate / M-4 (70/30) Core / shell = 50/50 P-47 Shell: Methyl acrylate / methacrylic acid / M-5 (60/10/30) Core / shell = 50/50 P-48 Shell: Vinyl acetate / M- 4 (70/30) core / shell = 50/50 P-49 shell: n-butyl acrylate / M-21 (80/20) core / shell = 50/50 P-50 shell: n-butyl acrylate / acrylic acid / M-21 (70/10/20) core / shell = 50/50 P-51 shell: n-butyl acrylate / methacrylic acid / M-28 (70/10/20) core / shell = 50/50 P- 52 Shell: Styrene / M-37 (84/16) Core / Shell = 50/50 P-53 Shell: Styrene / acrylic acid / M-37 (74/10/16) Core / shell = 50/50

P-54 to 62 Core: Ethylene glycol dimethacrylate / n-butyl acrylate copolymer (10/90) P-54 Shell: Methyl acrylate / acrylic acid / M-8 (70/10/20) core / Shell = 50/50 P-55 Shell: methyl acrylate / styrene / methacrylic acid / M-8 (30/40/10/20) Core / shell = 50/50 P-56 Shell: n-butyl acrylate / 2-acrylamide 2-Methyl propane sulfonic acid sodium / M-8 (65/15/20) core / shell = 50/50 P-57 Shell: methyl acrylate / M-17 (80/20) core / shell = 50/50 P -58 shell: methyl acrylate / acrylonitrile / M-17 (65/15/20) core / shell = 50/50 P-59 shell: ethyl acrylate / acrylic acid / M-17 (70/10/20) core / shell = 50/50 P-60 shell: ethyl acrylate / M-33 (50/50) core / shell = 50/50 P-61 shell: ethyl acrylate / 2-acrylamido-2-methylpropanoic acid soda / M-33 (45/10 / 45) Core / shell = 50/50 P-62 Shell: n-butyl acrylate / methacrylic acid / M-34 (40/20/40) Core / shell = 50/50

P-63 to 67 Core: Vinyl acetate homocopolymer P-63 Shell: Styrene / M-1 (80/20) Core / Shell = 50/50 P-64 Shell: Styrene / M-11 (80 / 20) Core / shell = 50/50 P-65 Shell: Styrene / divinylbenzene / M-11 (70/10/20) Core / shell = 50/50 P-66 Shell: Styrene / M-19 (84 / 16) Core / Shell = 50/50 P-67 Shell: Lauryl Methacrylate / M-22 (80/20) Core / Shell = 50/50

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

The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and, if necessary, 0.1 to 10% by weight of an emulsifier based on the monomers to be polymerized. As the polymerization initiator, azobis compounds, peroxides,
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 and the like. 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.
Nos. 3,839,697, and 5,962,096. Among them, there are emulsifiers, water-soluble polymers and the like, and of these, anionic or nonionic surfactants and water-soluble polymers are particularly preferable.

It is preferable to add the monomer in the emulsion polymerization while adding it dropwise from the viewpoint of avoiding heat generation due to the polymerization and forming a more definite core / shell structure. Also, by the above initiator, emulsion polymerization in the presence of an emulsifier,
After the core latex particles are formed, when the shell monomer is polymerized, an emulsifier may be further added, or the polymerization may be performed without the emulsifier. In many cases, the addition of an emulsifier is necessary from the viewpoint of the stability of the produced polymer latex. However, if an excess emulsifier is present, particles other than the intended shell polymer alone may be by-produced. Therefore, it is preferable that the amount of the emulsifier added after formation of the core polymer is suppressed to about 0.001 to 5% by weight with respect to the core particles, or it is not added at all.

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

The reactive group plays an important function in improving the film strength of the polymer latex / gelatin composite film. That is, the amount of reactive groups present on the latex surface is an important factor for performance. The core / shell latex of the present invention is basically useful in that reactive groups can be concentrated on the latex surface, which is a necessary site. Further, by controlling other required functions in the core, for example, Tg of the whole latex, the ability to form a film and the physical properties (eg, brittleness) of the resulting film or a composite film with gelatin or the like can be controlled by the shell. Is also very useful in that it can be included independently.

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

Synthesis Example 1 Core = styrene / butadiene copolymer (37/63), shell = n-butyl acrylate / potassium styrene sulfinate (80/20) core / shell latex (core / shell ratio = 50/50). ) (Synthesis of Exemplified Compound P-7)

In a 1 liter three-necked flask equipped with a stirrer and a reflux condenser, 539 g of distilled water and polystyrene butadiene latex (particle size 144 nm, solid content 50.2) were added.
%: Nippon Zeon Co., Ltd. trade name, LX-426) 199.
2 g was added, and the mixture was heated and stirred at 65 ° C. under a nitrogen stream.

80.0 g of n-butyl acrylate, and 20.0 g of potassium styrenesulfinate and 4,4'-
Azobis (4-cyano-pentanoic acid) sodium 4.6
A liquid obtained by dissolving 8 g in 100 g of distilled water was started at a constant speed so that the addition was completed in 1.5 hours. After the dropping was completed, heating and stirring were continued for another 4 hours.

After cooling to room temperature and filtering, 921.5 g of desired core / shell latex (solid content 21.4%, solid content yield 96.3%, average particle diameter 177 nm: particle diameter is Coulter submicron analyzer) (Measured by Nikkaki).

Synthesis Example 2 Core = butadiene homocopolymer, shell = styrene / chloromethylstyrene (70/30), core / shell = 50 /
Synthesis of 50 (Synthesis of Exemplified Compound P-2) In a 1-liter three-necked flask equipped with a stirrer and a reflux condenser, 0.28 g of sodium hydrogen sulfite, 3.52 g of 1 mol / liter solution of sodium hydrogen carbonate, and distilled water 4
After adding 54 g and stirring and dissolving, 294.1 g of polybutadiene latex (particle size 112 nm, solid content 34.3 wt%: Nippon Zeon Co., Ltd. trade name, LX-111J) was added and heated to 70 ° C. under a nitrogen stream. It was stirred.

0.16 g of potassium persulfate and 20 g of distilled water
After the melted mixture was added, a mixed solution of 70.0 g of styrene and 30 g of chloromethylstyrene, and a solution of 0.32 g of potassium persulfate in 50 g of distilled water were each added to 2 parts.
The dropping was performed at a constant speed so that the dropping was completed in time.

After completion of the dropping, the mixture was heated and stirred for 1 hour, and then a solution prepared by dissolving 0.10 g of potassium persulfate in 20 g of distilled water was added and the mixture was further stirred for 3 hours while heating. Cool to room temperature and filter to obtain the desired core / shell latex 905.4
g (solid content 22.1 g, solid content yield 99.2%, average particle diameter 140 nm).

Synthesis Example 3 Core = divinylbenzene / styrene / methyl methacrylate copolymer (10/45/45), shell = n-butyl acrylate / M-25 (84/16), core / shell = 50/5
Synthesis of Compound No. 0 (Synthesis of Exemplified Compound P-37) 0.28 g of sodium hydrogen sulfite, 3.52 g of 1 mol / liter sodium hydrogen carbonate solution, and distilled water 56 in a 1-liter three-necked flask equipped with a stirring device and a reflux condenser.
0 g was added and the mixture was heated and stirred at 80 ° C. under a nitrogen stream.

0.16 g of potassium persulfate and 20 g of distilled water
Divinylbenzene 10
g, 45 g of styrene, 45 g of methyl methacrylate, and a solution of 0.32 g of potassium persulfate dissolved in 50 g of distilled water were added dropwise at a constant rate so that the addition was completed in 2 hours.

After completion of the dropping, the mixture was heated and stirred for 1 hour, then a solution prepared by dissolving 0.16 g of potassium persulfate in 20 g of distilled water was added, and the mixture was heated and stirred at 90 ° C. for 3 hours to give a core latex (particle diameter 121 nm). Got

After adjusting the internal temperature of the obtained core latex to 80 ° C., 84 g of n-butyl acrylate, M-25
16g mixed solution, and sodium bisulfite 0.14
g, and a solution of 0.32 g of potassium persulfate dissolved in 50 g of distilled water were added dropwise at a constant rate so that the addition was completed in 2 hours.

At the end of the dropping, sodium bisulfite 0.
After adding 07 g and 0.16 g of potassium persulfate in 20 g of distilled water and heating and stirring for 2 hours, 0.07 g of sodium hydrogen sulfite and 0.1% of potassium persulfate were added again.
Add an initiator solution of 6 g and 20 g of distilled water, and further add 90 ° C.
The heating and stirring was continued for 3 hours.

After cooling to room temperature, the solution was neutralized with a 1 mol / liter sodium hydrogen carbonate solution and filtered to obtain the desired core /
917.6 g of shell latex (solid content 21.7%, solid content yield 98.7%, particle size 149 nm) was obtained.

Other exemplified polymers are also prepared in Synthesis Examples 1, 2, 3
It was possible to synthesize by the method according to. In Synthesis Examples 1, 2, and 3, the particle size of the core latex and the core /
The particle size of the shell latex shows a good agreement with the particle size predicted from the weight ratio of the respective polymers, and it is clear that there is almost no aggregation during polymerization and formation of other particles other than the core / shell.

Gelatin is preferably used as the binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids can be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole 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.

Specific examples of the silver halide photographic light-sensitive material containing the latex of the present invention include X-ray light-sensitive materials, printing light-sensitive materials, black-and-white photographic light-sensitive materials, color negative light-sensitive materials, color reversal light-sensitive materials and color photographic papers. Can be mentioned.

In the preferable embodiment of the photosensitive material for printing and the X-ray photosensitive 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.

The core / shell polymer latex of the present invention is contained in at least one layer of a silver halide emulsion layer, a back layer and other hydrophilic colloid layers, and the addition amount is 0. It is 1 to 200% by weight, preferably 5 to 150% by weight.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as the 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, particles having a twin plane 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 of the present invention, the photographic emulsion may be spectrally sensitized with a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. 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 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 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. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. In the installation, each layer may be sequentially coated, or the coating may be performed in a single layer (so-called simultaneous multilayer coating), which is a manufacturing method which is quite common in the art, and is not particularly specified.

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 JP-A 1-20037 and JP-A 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly 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 described in Research Disclosure (RD) No. 17643, VII-C to G. Examples of yellow couplers include US 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. 3,073,636; U.S. Pat.
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, JP-A-61-72238, and 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-based and naphthol-based couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 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 unwanted 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, 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 can also be 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 imagewise release a nucleating agent or a development accelerator during development, British Patent No. 2,093
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
No. 241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, and a ligand-releasing coupler described in US Pat. No. 4,553,477, 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 light-sensitive 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 more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 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.

[0103] 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. Also, the ionic surfactants have anionic and cationic properties. For example, JP-A-49-85826.
JP-A-49-33630, U.S. Pat.
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.
Further, 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 and after-treated electrical resistances.
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 conductive crystalline oxide or its composite oxide particles or 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 slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when moving at 60 cm / m ² with respect to a stainless ball having a diameter of 5 mm. In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. 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. The slip agent used in the present invention can be dispersed in an organic solvent by various methods. As a method of dispersing in an organic solvent, a lubricant is solid-dispersed in an organic solvent with a ball mill, a sand grinder, or the like, a lubricant is dissolved by heating in an organic solvent, 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 then 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, baryta paper, polyethylene coated paper and the like can be used. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating by a known method as 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 any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like, but needle shape 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.
Surface treatment may be carried out with silica and / or alumina, such as those described in 9-23505 and 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.
10,000 to 300,000.

Among the binders, cellulose di (or tri) acetate is preferred. The binders 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-based 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 polyisisoateate 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. Examples of the water-soluble polymer include gelatin, a gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, a polyacrylic acid copolymer, and a maleic anhydride copolymer. It 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.
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 the 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 diols, 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. 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 the conventionally known methods for producing polyesters, and for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition".
(Kyoritsu Shuppan, 1980) pp. 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 care, 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.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, 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

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.

BP-10: isophthalic acid (IPA) / NDCA / TPA / EG (20/50/30/100) 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 (95/5/100) ) 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 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, the 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 while being conveyed in the form of a web. When the heat treatment is performed in the form of a roll, the heat treatment may be performed in any of a method in which the roll is heat-treated in a constant temperature bath from room temperature, and a method in which the roll is heat-treated after being heated to a predetermined temperature during web transport. 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
₂ ) Conductive inorganic fine particles such as O ₅ and colloidal silica are applied) to prevent wrinkles due to winding tightness by reducing the squeaking between the supports, or to add knurls to the ends of the supports to slightly increase the edges. 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 a 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. Preferably after application of the antistatic agent. 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, it is preferable to coexist with various additives. 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, benzotriazoles 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, and the dye is not particularly limited. Made of Diar
The objective 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 that the color density in the visible light range is measured with a color densitometer manufactured by Macbeth Co., and that it is at least 0.01. 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 composed of a protective colloid mainly containing gelatin is formed on the support (for example, a photosensitive halogen). 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. Irradiation with ultraviolet rays may be carried out during the stretching step of the support, during 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 conventionally known method, 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 dielectric 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
Nos. 3,462,335 and 3,475,307
No. 3,761,299, British Patent 997,093
And JP-A-53-129262 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 intensity is 0.01KV · A · min / m ² ~ 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, etc., 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. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers,
Butadiene-containing copolymers. 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 (chromium 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
Inorganic fine particles such as O ₂ and a matting agent or fine particles of polymethyl methacrylate copolymer (1 to 10 μm) can be contained as a matting agent. The undercoating liquid according to the present invention is a well-known coating method such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or US Pat. 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-105 μm, the surface of which is subjected to ultraviolet irradiation treatment or glow discharge treatment, the non-photosensitive hydrophilic layer on the back side 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. 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 JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; JP-A-2-39042, page 7, lower right column, line 8, Page 13, lower right column, 5th line. Tokukaihei No. 2-12236, page 8, lower left column, line 13 to same, 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.

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

9) Dyes JP-A-2-103536, page 17, lower right column, line 1 to line 18, JP-A 2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 The solid dyes described in JP-A 2-294638 and Japanese Patent Application No. 3-185773. 10) Tetrazolium compound JP-A-2-39143, page 4, lower left column, line 8 to page 6, lower left column, line 6, from JP-A-3-123346, page 3, upper right column, lines 19 to 5 Top left column, line 20. 11) Redox compound A compound represented by the general formula (I) of JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 of JP-A No. 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 12) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-25). 13) Colloidal silica Compounds described in paragraph “0005” of JP-A-4-214551. 14) Developer and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8 JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10

[0140]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 A conductive layer and a back layer having the following compositions were simultaneously coated on one side of a biaxially stretched polyethylene terephthalate support (thickness 100 μm) having undercoat layers on both sides. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ² Gelatin (Ca ^** content 3000 ppm) 77 〃 Compound-6 7 〃 Sodium dodecylbenzene sulfonate 10 〃 Dihexyl -Α-Sulfosuccinate sodium 40〃 Sodium polystyrene sulfonate 9〃

<Back Layer> Gelatin (Ca ^** content 30 ppm) 2.82 g / m ² Polymethylmethacrylate fine particles (average particle size 4.0 μm) 20 mg / m ² Compound-1 3〃 Compound-2 40〃 Compound-3 40 〃 Compound -4 80 〃 Compound -5 150 〃 Sodium dodecylbenzenesulfonate 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound -6 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃 1,2-bis (vinyl sulfonyl) Acetamide) ethane 150 〃

[0143]

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[0144]

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[0145]

[Chemical 12]

Next, the emulsion layer, the lower layer and the upper layer of the protective layer shown below were simultaneously coated on the opposite surface of the support. <Emulsion layer> 5,6-Cyclopentane-4 kept at 40 ° C
In a gelatin aqueous solution containing -hydroxy-1,3,3a, 7-tetrazaindene (5 x 10 ^-3 mol per 1 mol of silver), an aqueous silver nitrate solution and 4 x 10 ^-5 mol per mol of silver were added.
An aqueous sodium chloride solution containing (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was simultaneously added over 7 minutes, and the potential during that period was controlled to 95 mV to prepare 0.12 μm of the core particles.
Then, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per mol of silver were simultaneously added in 14 minutes, and the potential between them was controlled to 95 mV. By doing so, silver chloride cubic grains having an average grain size of 0.15 μm were prepared. C ₁₆ H ₃₃ O (CH ₂ C
H ₂ O) ₂₅ H having a structural formula of 50 mg / m ² , 5,6-
Cyclopentane-4-hydroxy-1,3,3a, 7-
Tetrazaindene is 24 mg / m ² , 5-methyltriazole is 5 mg / m ² , compound-6 is 3 mg / m ² , polymer latex is as shown in Table-1, and 2-bis (vinylsulfonylacetamide) as a hardening agent. 126 mg / m ^{2 of} ethane was added,
It was coated so that the amount of silver was 3.0 g / m ² and the amount of gelatin was 1.1 g / m ² .

<Lower layer of protective layer> Gelatin 0.7 g / m ² 5-nitroindazole 5 mg / m ² lipoic acid 8 〃 C ₂ H ₅ SO ₂ Na 6 〃 hydroquinone 50 〃 1-hydroxy-2-benzaldoxime 15 〃 Polymer latex Table-1 <Upper layer of protective layer> Gelatin 0.5 g / m ² Silicon dioxide fine particles (average particle size 3.5 μm) 55 mg / m ² Colloidal silica (average particle size 0.02 μm) 135 〃 Sodium dodecylbenzenesulfonate 25 〃 Poly (Polymerization degree 5) Sulfate sodium salt of oxyethylene nonyl phenyl ether 20〃 N-perfluorooctanesulfonyl-N-propylpyricin potassium salt 3〃

The obtained sample was stored for 1 week in an atmosphere of 25 ° C. and 50% RH, and then evaluated as follows. 1) Sensitivity and γ value Meituro Printer P-627F manufactured by Dainippon Screen Co., Ltd.
M (mercury lamp light source) is used to expose through an optical wedge. The developer and fixer are Fuji Photo Film SR-
Using D2 and GR-F1, automatic developing machine FG-680
Processing was performed with AG (manufactured by Fuji Photo Film Co., Ltd.) under the developing conditions of 38 ° C. and 20 seconds. Sensitivity was expressed as a relative value when the sample number -15 was set to 100 as a logarithmic value of the exposure amount giving a density of 3.0. The γ value indicates the average gradation degree from the density 0.3 to 3.0 of the characteristic curve, and 2.7 is ΔlogE (density 3.0
The difference between the logarithmic value of the exposure amount which gives the density and the logarithmic value of the exposure amount which gives the density of 0.3). The higher the numerical value, the higher the contrast image characteristics. 2) Wet film strength After immersing the sample in distilled water at 25 ℃ for 5 minutes, the radius is 0.3mm
The sample was pressed against the surface of the sample film with the sapphire needle of, 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. 3) Brittleness After leaving the sample in an atmosphere of 25 ° C and 10% RH for 2 hours, IS
The average value of the points where cracks first occurred on the side containing the silver halide emulsion layer was determined by the same method as O6077 “Wedge brittleness test”.

The results are shown in Table 1. As is clear from Table 1, the samples of the present invention have no adverse effect on the photographic properties, and the wet film strength is significantly improved and the brittleness is also good despite the small amount of the reactive group-containing monomer. . In addition, the total amount of gelatin in the emulsion layer and protective layer should be 3g and 4g.
The same excellent result was obtained.

[0150]

[Table 1]

[0151]

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Example 2 Biaxially Stretched Poly (ethylene terephthalate) Support (Thickness 100 μm) with Undercoat Layer on Both Sides A conductive layer and a back layer having the following compositions were coated on one side of the support. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ² Gelatin (Ca ^** content 3000 ppm) 77 〃 Compound- (1) 7 〃 Sodium dodecylbenzene sulfonate 10 〃 Sodium dihexyl-α-sulfosuccinate 40 〃 Sodium polystyrene sulfonate 9 〃 The surface resistivity of the conductive layer is 3.0 at 25 ℃ and 20% RH.
It was × 10 ⁹ Ω.

<Back Layer> Gelatin (Ca ^** content 30 ppm) 2.82 g / m ² compound- (1) 3 mg / m ² polymethylmethacrylate fine particles (average particle size 3.4 μm) 50 〃 compound- (2) 40 〃 Compound- (3) 40 〃 Compound- (4) 80 〃 Sodium dodecylbenzenesulfonate 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound- (5) 5 〃 N-perfluorooctanesulfonyl-N-propyl glycine Potassium 7〃 Sodium sulfate 50〃 Sodium acetate 85〃 1,2-Bis (vinylsulfonylacetamide) ethane 150〃

[0154]

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[0155]

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Then, an emulsion layer having the following composition, a protective layer lower layer and a protective layer upper layer were simultaneously coated on the opposite surface of the support. <Emulsion layer> Emulsion preparation Liquid I Water 1000 ml Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidin-2-thione 20 g Sodium benzenesulfonate 6 mg Liquid II 400 ml Silver nitrate 100 g Liquid III water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g Potassium hexachloroiridium (III) (0.001% aqueous solution) 15 ml Ammonium hexabromorhodium (III) (0.001% aqueous solution) 1.5 ml 38 ° C., pH = 4. Solution I and solution III were added to solution I kept at 5 at the same time for 10 minutes while stirring to give 0.16
μm fine particles were formed. Then, the following IV liquid and V liquid 10
Added over minutes. Further potassium iodide 0.15
g was added to complete the grain formation.

Liquid IV water 400 ml Silver nitrate 100 g V liquid water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag After that, flocculation was carried out according to a conventional method. According to the method, it was washed with water and 40 g of gelatin was added.

This emulsion was adjusted to pH = 5.3, pAg = 7.
Adjusted to 5, sodium thiosulfate 5.2mg, chloroauric acid 1
0.0 mg and 2.0 mg of N, N-dimethylselenourea were added, 8 mg of sodium benzenesulfonate and 2.0 mg of sodium benzenesulfinate were added, and chemically sensitized at 55 ° C. so as to obtain an optimum sensitivity. A silver iodochlorobromide cubic grain emulsion containing 80 mol% of silver chloride and having an average grain size of 0.20 μm was prepared. Then, a sensitizing dye was added at 100 mg per mol of Ag to perform panchromatic sensitization. Further, as antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole were added at 2.5 g per 1 mol of Ag, respectively.
50 mg, colloidal silica (Nissan Chemical's Snowtex C, average particle size 0.015 μm) to gelatin to 30
% By weight, and polymer latex as a plasticizer.
In addition to the above, 1,1'-bis (vinylsulfonyl) methane (100 mg / m ² ) was added as a hardener. The coating solution Ag3.3g / m ^2, was coated so as to be gelatin 1.5 g / m ^2.

[0159]

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<Protective layer lower layer formulation> Gelatin per m ² 0.5 g Sodium benzenesulfonate 4 mg 1,5-dihydroxy-2-benzaldoxime 25 mg Polymer latex Table 2 <Protective layer upper layer formulation> Gelatin 0.25 per m ² g Polymethylmethacrylate fine particles (average particle size 2.7 μm) 40 mg Compound- (6) (gelatin dispersion of lubricant) 30 mg Colloidal silica (Nissan Chemical Snowtex C) 30 mg Compound- (7) 5 mg Dodecylbenzene Sodium sulfonate 22 mg

[0161]

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The obtained sample was passed through an interference filter having a peak at 633 nm and a continuous concentration wedge to give an emission time of 1
Exposed with 0 ^-6 sec xenon flash light, using Fuji Photo Film Co. automatic developing machine FG-680AS, performs development processing was likewise determined the sensitivity and γ in Example 1. The developing solution and the fixing solution are S manufactured by Fuji Photo Film Co., Ltd.
Using R-D2 and SR-F1, developing conditions 38 ° C. 11
Done in seconds. The wet film strength and brittleness were the same as in Example 1.

The results are shown in Table 2. As is clear from Table 2, the sample of the present invention is remarkably excellent in that the wet film strength does not decrease even if the content of the polymer latex is increased.

[0164]

[Table 2]

Example 3 Polymer latex as the lower layer of the emulsion layer and protective layer of Example 1 described in JP-A-4-340951, Japanese Patent Application No. 6-4660.
No. 6, the back layer of Example 2, the emulsion layer first layer and the second layer
Layer, polymer latex under protective layer, non-photosensitive layer of Example 6, polymer latex of emulsion layer, UL of Example 7
Layer, EM layer, PC layer polymer latex, emulsion layer polymer latex of Example 8, bottom layer of Example 11, emulsion first layer, intermediate layer, emulsion second layer polymer latex,
The polymer latex of the emulsion layer of Example 1 described in JP-A-6-27590 was replaced with the polymer latex compound example P-4 of the present invention, and the same evaluation as in Example 1 was performed. Moreover, excellent film physical properties were obtained without impairing photographic characteristics.

Example 4 Coating samples were prepared and processed according to Japanese Patent Application No. 4-341005, Examples 1 and 2 of the present invention.
The same effect as that appeared.

Example 5 A coating sample was prepared and processed in accordance with Japanese Patent Application No. 5-33721 Examples 1, 2 and 3, and Example 1 of the present invention was conducted.
The same effect as in 2 appeared.

Example 6 When a coated sample was prepared and treated according to Japanese Patent Application No. 6-272259 Example 2, the same effects as those of Examples 1 and 2 of the present invention were exhibited.

Claims (3)

[Claims] 1. A core having a shell having a repeating unit derived from at least one of ethylenically unsaturated monomers represented by the following general formulas (I), (II) and (III):
A silver halide photographic light-sensitive material comprising a shell polymer latex. Embedded image In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. Q is a single bond or 2
Represents a valent linking group. L ¹ and L ³ represent alkylene, aralkylene and arylene, and L ² represents alkylene, aralkylene and heteroarylene. M represents a hydrogen atom or a cation. X ¹ represents a halogen atom. R ² is-
CH = CH _2, represents either ^{_{-CH 2 -CH 2 -X 2, X}} 2 is either replaced by a nucleophilic group, a group capable of elimination in the form of HX ² by a base. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the weight ratio of each polymer in the core portion and the shell portion of the polymer latex is in the range of 20/80 to 95/5. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the glass transition temperature of the core and / or shell is 50 ° C. or lower.