JP3441861B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 latex polymer. More specifically, it relates to a silver halide photographic light-sensitive material having a film-like physical property improved by containing the latex-like polymer 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 extremely 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, and 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 hydrophilic colloid film is prepared by incorporating a latex polymer into the hydrophilic colloid layer such as a silver halide emulsion layer, a protective layer, a back layer and an intermediate layer. Attempts have been made to improve film physical properties such as dimensional stability against humidity, 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 latex-like polymers composed of 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 the latex.

For example, Japanese Patent Publication Nos. 45-5819 and 46
-22507 and Japanese Patent Laid-Open No. 50-73625 disclose a latex obtained by copolymerizing a monomer having an active methylene group such as 2-acetoacetoxyethyl methacrylate or 2-cyanoacetoxyethyl methacrylate with a monomer such as an alkyl acrylate in a photographic light-sensitive material. It is disclosed that the abrasion resistance and the hardness (especially in a wet state) of the latex-containing gelatin film are improved by coexisting a polymer in the form of gelatin in the gelatin film.

However, in order to improve the abrasion resistance and hardness of the gelatin film by these latexes, it is necessary to copolymerize the active methylene monomer in a certain amount or more. In addition, when the ratio of latex to gelatin is high, or when the absolute amount of gelatin is small, the strength of the gelatin film in the wet state remarkably decreases. There is a problem that the required film strength cannot be obtained only by increasing the amount of methylene 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 case of the conventional simple active methylene monomer copolymerized latex, the film strength may not be sufficiently improved, and the production cost of the latex polymer by using a large amount of active methylene monomer having a relatively complicated structure. A rise problem was raised, and further improvement was desired.

As a latex-like polymer composed of fine particles having a core / shell double structure, there is disclosed in Japanese Patent Application Laid-Open No. 58/1983.
No. 42044 discloses a silver halide color photographic light-sensitive material having a core / shell latex having a polymer containing a coupler unit capable of forming a dye by coupling with an oxidized form of a developing agent in the shell portion. Specifically, as the yellow coupler, a pivaloyl acetanilide type or a benzoyl acetanilide type is described.

However, the latex-like polymer comprising core / shell type fine particles described in the patent has the following problems. The proportion of the core composed of the non-color-forming monomer is extremely small (about 10% at maximum among the exemplified compounds). Therefore, the above-mentioned various merits by concentrating the active methylene moiety on the shell side by the core / shell formation are small. In the field of polymer couplers, it is advantageous to increase the number of coupler monomer units as much as possible from the viewpoint of thinning the light-sensitive material, and also in this patent, as a result, the core portion is extremely small. The reactivity of the active methylene structure sterically crowded to a certain extent such as pivaloylacetanilide or benzoylacetanilide is not always sufficient, and further improvement is desired in terms of, for example, the effect of improving the strength of gelatin film.

[0012]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel latex polymer. 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.

[0013]

The above objects of the present invention have been achieved by the following means. (1) A halogen containing a latex-like polymer comprising core / shell type fine particles having a shell having a repeating unit derived from an ethylenically unsaturated monomer represented by the following general formula (I) Silver halide photographic light-sensitive material. General formula (I)

[0014]

[Chemical 2]

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X is R ² COCH ₂ COO-, NC-
_{^{CH 2 COO-, R 2 COCH 2}} CO-, NC-CH 2 C
O- (R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, or 1 to 1 carbon atoms. 12 representing a substituted amino group), R ⁹ —CO—CH ₂ C
ON (R ⁶ )-(R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁹ represents 1 to 12 carbon atoms.
Substituted or unsubstituted primary or secondary alkyl group, alkoxy group having 1 to 12 carbon atoms, amino group, 1 to 12 carbon atoms
Of an active methylene group selected from the representative) a substituted amino group
Represent

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 of the latex polymer is 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:

The latex-like polymer comprising fine particles having a core / shell structure of the present invention (hereinafter referred to as polymer latex or core / shell latex for simplicity) 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 monomers, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, dienes, acrylamides, methacrylamides, vinyl ethers, and various other ethylenically unsaturated monomers are used. In addition, a monomer having two or more ethylenically unsaturated groups can also be preferably used.

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

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

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

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

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

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

Further, at least two monomers having a copolymerizable ethylenically unsaturated group can be used in the core of the latex of the present invention. Examples of such monomers include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Examples thereof 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 ease of polymerization and ease of core / shell structure formation, acrylic acid esters, methacrylic acid esters, vinyl esters, conjugated dienes, and the like are preferably used among the above monomer groups. 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 is present 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 this polymer affects the physical properties of the film mixed with gelatin, the water dispersion stability of itself, and the film-forming property, and is not preferable if it is too large. From the above points, the number average particle diameter of the core polymer is 1.0 μm or less, preferably 0.7 μm or less, and particularly preferably 0.5 μm or less. The lower limit is preferably 0.00001 μm or more.

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

[0029]

[Chemical 3]

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X is R ² COCH ₂ COO-, NC-
_{^{CH 2 COO-, R 2 COCH 2}} CO-, NC-CH 2 C
O- (R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, or 1 to 1 carbon atoms. 12 representing a substituted amino group), R ⁹ —CO—CH ₂ C
ON (R ⁶ )-(R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁹ represents 1 to 12 carbon atoms.
Substituted or unsubstituted primary or secondary alkyl group, alkoxy group having 1 to 12 carbon atoms, amino group, 1 to 12 carbon atoms
Of an active methylene group selected from the representative) a substituted amino group
Represent

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

[0032]

[Chemical 4]

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

[0034]

[Chemical 5]

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

[0036]

[Chemical 6]

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

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

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

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

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

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

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

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

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

M-15 N-methacryloyloxymethylacetoacetamide M-16 ethylmethacryloylacetoacetate M-17 N-allylcyanoacetamide M-18 2-cyanoacetylethyl acrylate

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

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

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

The amount ratio of the core polymer 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 to 95/5, preferably 20/80 to 95
/ 5, particularly preferably 30/70 to 90/10. This means that if the number of cores is too small, the concentration effect of the active methylene monomer on the shell part is reduced, and if the number of shells is too small, it becomes difficult to form a clear core / shell structure. The particle size of the core / shell polymer latex is 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less, like the core polymer particles. The lower limit is preferably 0.00001 μm or more.

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

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

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

Even when a monomer having a similar polarity is used for the core and the shell, the core is the above-mentioned crosslinking monomer (a monomer having two or more ethylenically unsaturated groups in the molecule).
It is possible to obtain a very effective core / shell polymer latex by three-dimensionally crosslinking with. As described above, in the present invention, it is possible to form a useful core / shell polymer latex structure regardless of the kind of the monomer used.

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

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

[0057]

[Equation 1]

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

The preferred 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 latex compound described below is described in the order of the core polymer structure, the shell polymer structure, and the core / shell ratio, and the copolymerization composition ratio and the core / shell ratio in each polymer are expressed as weight percentage ratios. .

[0060] P-1 to 12   Core: styrene / butadiene copolymer (37/63)   P-1 shell = styrene / M-1 (98/2) core / shell = 50/50   P-2 Shell = Styrene / M-1 (96/4) Core / Shell = 50/50   P-3 Shell = Styrene / M-1 (92/8) Core / Shell = 50/50   P-4 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50   P-5 Shell = Styrene / M-1 (68/32) Core / Shell = 50/50   P-6 Shell = Styrene / M-1 (84/16) Core / Shell = 67/33   P-7 Shell = Styrene / M-1 (84/16) Core / Shell = 85/15   P-8 shell = n-butyl acrylate / M-1 (96/4)                                               Core / shell = 50/50   P-9 shell = n-butyl acrylate / M-1 (92/8)                                               Core / shell = 50/50   P-10 shell = n-butyl acrylate / M-1 (84/16)                                               Core / shell = 50/50   P-11 Shell = Methyl acrylate / M-7 (84/16)                                               Core / shell = 50/50   P-12 Shell = Styrene / Methyl acrylate / M-3 (21/63/16)                                               Core / shell = 50/50

[0061] P-13,14   Core: styrene / butadiene copolymer (22/78)   P-13 Shell = Styrene / M-2 (84/16) Core / Shell = 50/50   P-14 shell = n-butyl acrylate / M-8 (84/16)                                               Core / shell = 50/50

[0062] P-15-20   Core: Polybutadiene homopolymer (100)   P-15 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50   P-16 shell = ethyl acrylate / M-7 / methacrylic acid (65/15/20)                                               Core / shell = 75/25   P-17 shell = n-butyl acrylate / M-1 (84/16)                                               Core / shell = 50/50   P-18 shell = n-butyl acrylate / M-2 (84/16)                                               Core / shell = 50/50   P-19 shell = 2-ethylhexyl acrylate / M-24 (84/16)                                               Core / shell = 50/50   P-20 shell = n-butyl acrylate / M-18 (84/16)                                               Core / shell = 50/50

[0063] P-21-23   Core: Polyisoprene homopolymer (100)   P-21 Shell = Styrene / Acrylonitrile / M-1 (63/21/16)                                               Core / Shell = 90/10   P-22 shell = methyl methacrylate / ethyl acrylate / M-2 / 2-           Sodium acrylamido-2-methylpropane sulfonate (15/65/15/5)                                               Core / shell = 75/25   P-23 Shell = Styrene / M-1 (84/16) Core / Shell = 20/80

[0064] P-24 to 26   Core: styrene / butadiene copolymer (49/51)   P-24 Shell = Styrene / Butyl acrylate / M-1 (25/60/15)                                               Core / shell = 50/50   P-25 shell = M-1 (100) core / shell = 90/10   P-26 Shell = lauryl methacrylate / butyl acrylate / M-7             (30/55/15) Core / Shell = 40/60 P-27   Core: Acrylonitrile / styrene / butadiene copolymer (25/25/50)   Shell: Butyl acrylate / M-1 (92/8) core / shell = 50/50 P-28   Core: ethyl acrylate / butadiene copolymer (50/50)   Shell: Styrene / divinylbenzene / M-1 (79/5/16)                                               Core / shell = 50/50

[0065] P-29 ~ 33   Core: poly (n-dodecyl methacrylate) homopolymer   P-29 Shell = Styrene / M-1 (92/8) Core / Shell = 50/50   P-30 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50   P-31 shell = ethyl acrylate / M-1 (96/4)                                               Core / shell = 50/50   P-32 shell = ethyl acrylate / M-1 (92/8)                                               Core / shell = 50/50   P-33 Shell = Styrene / Methyl Acrylate / M-3 (21/63/16)                                               Core / shell = 50/50

[0066] P-34   Core: poly (n-butyl acrylate) homopolymer   Shell: Styrene / M-2 (84/16) Core / shell = 50/50 P-35,36   Core: Poly (ethylene glycol dimethacrylate / n-butyl acrylate)         Copolymer (10/90)   P-35 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50   P-36 shell = methyl acrylate / M-7 / methacrylic acid (65/15/20)                                               Core / shell = 75/25

[0067] P-37-40   Core: Poly (ethylene glycol dimethacrylate / n-butyl acrylate)         Copolymer (20/80)   P-37 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50   P-38 Shell = Styrene / M-1 (84/16) Core / Shell = 75/25   P-39 shell = methyl acrylate / M-8 / 2-acrylamido-2-me           Sodium chill propane sulfonate (80/15/5)                                               Core / shell = 75/25   P-40 shell = n-butyl acrylate / M-1 (84/16)                                               Core / shell = 50/50

[0068] P-41 to 43   Core: Polyvinyl acetate homopolymer (100)   P-41 Shell = Styrene / M-1 (84/16) Core / Shell = 50/50   P-42 Shell = Styrene / Divinylbenzene / M-24 (79/5/16)                                               Core / shell = 50/50   P-43 shell = n-dodecyl methacrylate / butyl acrylate / M-7                                                                                    (30/55/15) Core / Shell = 40/60

[0069] P-44 to 46   Core: poly (divinylbenzene / 2-ethylhexyl acrylate) copolymer         (10/90)   P-44 shell = methyl acrylate / M-1 (84/16)                                               Core / shell = 50/50   P-45 shell = methyl acrylate / styrene / M-1 (74/10/16)                                               Core / shell = 50/50   P-46 Shell = M-1 (100) Core / Shell = 90/10 P-47 to 49   Core: Poly (divinylbenzene / styrene / 2-ethylhexyl acrylate)         Copolymer (10/23/67)   P-47 Shell = Methyl acrylate / M-1 (84/16)                                               Core / shell = 50/50   P-48 Shell = Methyl Acrylate / Styrene / M-1 (74/10/16)                                               Core / shell = 50/50   P-49 shell = ethyl acrylate / 2-hydroxyethyl methacrylate             / M-5 (65/15/20) Core / Shell = 85/15

[0070] P-50   Core: Poly (ethylene glycol dimethacrylate / vinyl palmitate / n         -Butyl acrylate) copolymer (20/20/60)   Shell: ethylene glycol dimethacrylate / styrene / n-butylmethac         Relate / M-1 (5/40/40/15) Core / Shell = 50/50 P-51   Core: Poly (trivinylcyclohexane / n-butyl acrylate / styrene)         Copolymer (10/55/35)   Shell: Methyl acrylate / M-1 / 2-acrylamido-2-methylpropane         Sodium sulfonate (88/7/5) core / shell = 70/30 P-52, 53   Core: Poly (divinylbenzene / styrene / methylmethacrylate) copolymer         (10/45/45)   P-52 shell = n-butyl acrylate / M-1 (84/16)                                             Core / shell = 50/50   P-53 shell = n-dodecyl acrylate / ethyl acrylate / M-21           (60/30/10) Core / Shell = 50/50

[0071] P-54, 55   Core: poly (p-vinyltoluene / n-dodecyl methacrylate) copolymer         (70/30)   P-54 shell = methyl acrylate / n-butyl methacrylate / M-2 /             Acrylic acid (30/55/10/5) core / shell = 50/50   P-55 shell = n-butyl acrylate / M-19 (84/16)                                             Core / shell = 70/30

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 preferably uses a radical polymerization initiator by emulsifying a monomer in water or a mixed solvent of water and an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.) using at least one emulsifier. Generally from 30 ° C to about 100 ° C, preferably 40
C. to about 90.degree. C. The amount of the organic solvent miscible with water is 0 to 100%, preferably 0 to 50% by volume with respect 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. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrisulfate. Methylene ammonium chloride, N-2-ethylhexyl pyridinium chloride, polyoxyethylene nonyl phenyl ether, polyoxyethylene sorbitan lauryl ester, sodium dodecyl-diphenyl ether disulfonate, sodium 2-tetradecene-1-sulfonate, 3-hydroxytetradecane-1- Sodium sulfonate, gelatin, PVA, etc.
No. 6190, emulsifiers, water-soluble polymers and the like, and of these, anionic or nonionic surfactants and water-soluble polymers are particularly preferable.

The addition of the monomer in the emulsion polymerization is preferably carried out while dropping, from the viewpoint of avoiding heat generation due to the polymerization and forming a more definite core / shell structure. Further, the above initiator, by emulsion polymerization in the presence of an emulsifier,
When the shell monomer is polymerized after forming the core latex particles, an emulsifier may be further added or the emulsifier may be added without being added. Addition of an emulsifier is often necessary from the viewpoint of stability of the produced polymer latex, but conversely, if an excessive amount of emulsifier is present, particles other than the intended shell polymer may be by-produced. Therefore, 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 be as complete as possible, and the polymerization rate is 90% or more, preferably 95%. Above all, it is particularly preferably substantially 100%.

In improving the film strength of the above-mentioned polymer latex / gelatin composite film, the active methylene unit is
Functions as a reactive group. Therefore, the amount of active methylene units present on the latex surface is an important factor for performance. The core / shell latex of the present invention is useful in that the active methylene unit can be basically concentrated on the surface of the latex, which is a necessary site. In addition, by controlling other required functions in the core part, such as controlling the Tg of the whole latex, the film forming ability and the physical properties (eg, brittleness) of the resulting composite film with the film or gelatin can be changed to the shell part. Is also extremely useful in that it can be included independently.

The core / shell latex particles of the present invention are
Although it can be obtained in the form of an aqueous dispersion by the above-mentioned emulsion polymerization method, it can be made into a fine particle powder while maintaining the core / shell structure. As such a method of powdering,
Freeze-drying method, aggregation using strong acid or salt, filtration method, or aggregation by repeated freeze-thawing of latex solution,
A known method such as a filtration method can be used. The synthesis examples of the core / shell latex of the present invention are shown below.

Synthesis Example 1 Core = polybutadiene (homopolymer), Shell = styrene / 2-acetoacetoxyethyl methacrylate (84
/ 16) core / shell latex (core / shell ratio =
50/50) (Synthesis of Exemplified Compound P-15)

A 1-liter three-necked flask equipped with a stirrer and a reflux condenser was charged with 0.28 sodium bisulfite.
g, 1 mol / liter solution of sodium hydrogen carbonate 3.5
After adding 2 g and 454 g of distilled water and stirring and dissolving, polystyrene butadiene latex (particle size 112 nm, solid content 34.3% by weight: Nippon Zeon Co., Ltd. trade name, LX-11)
1J) (294.1 g) was added, and the mixture was heated and stirred at 65 ° C. under a nitrogen stream.

0.32 g of potassium persulfate and 20 g of distilled water
After adding the melted styrene, 84.0 g of styrene, 2
-A mixed solution of 16.0 g of acetoacetoxyethyl methacrylate and 0.16 g of potassium persulfate and 50 g of distilled water.
Dropping was started at a constant speed so that the above-mentioned melted liquid was completed in 1.5 hours.

After completion of dropping, the mixture was heated and stirred for 1 hour, and 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 for further 3 hours. Cool to room temperature and filter to obtain the desired core / shell latex 931.4
g (solid content 21.2%, solid content yield 98.3%, average particle diameter 138 nm: particle diameter measured by Coulter submicron analyzer (Nikkaki)). Further, a part (100 g) of the obtained latex was freeze-dried to obtain 20.2 g of the core / shell fine particle powder of the present invention.

Synthesis Example 2 Core = ethylene glycol dimethacrylate / n-butyl acrylate (20/80), shell = n-butyl acrylate / M-1 (84/16), core / shell = 5
Synthesis of 0/50 (Synthesis of Exemplified Compound P-40) 0.576 g of sodium hydrogen sulfite, sodium succinate di-n-hexyl ester monosulfonate 1. 5
0 g, ethylene glycol dimethacrylate 30.0
g, n-butyl acrylate 120 g, distilled water 510 g
Was charged, and the mixture was heated and stirred at 50 ° C. under a nitrogen stream.

0.5 g of potassium persulfate, 1N sodium bicarbonate water 3.
Add an initiator solution consisting of 7 g and 30 g of distilled water,
After heating and stirring for 1 minute, potassium persulfate 1.0 g, 1N
An initiator solution consisting of 7.4 g of sodium bicarbonate water and 60 g of distilled water was added, and the mixture was heated and stirred at 50 ° C for 2 hours and further at 90 ° C for 3 hours to obtain a core latex (particle size: 126 nm: Coulter submicron analyzer). (Measured using Nikkaki Co., Ltd.).

A solution of 0.65 g of sodium hydrogen sulfite and 250 g of distilled water was added to the obtained core latex to adjust the internal temperature to 70 ° C. 126 g of n-butyl acrylate,
An aqueous solution consisting of a mixed solution of 24 g of 2-acetoacetoxyethyl methacrylate and 1.125 g of potassium persulfate, 8.25 g of 1N sodium hydrogen carbonate solution and 150 g of distilled water was prepared,
The dropping was performed at a constant speed so that the dropping was completed in 1 hour each. After the dropwise addition was completed, the mixture was heated and stirred at 70 ° C. for 1 hour, then, a solution obtained by dissolving 0.375 g of potassium persulfate in 50 g of distilled water was added, and the mixture was heated and stirred at 85 ° C. for 3 hours.

The reaction solution was cooled and filtered to obtain 1355 g of the desired latex P-40 of the present invention. The obtained latex had a solid content of 21.30% (solid content yield 96.2).
%), And the particle size was 159 nm.

Synthesis Example 3 Synthesis of core = n-dodecyl methacrylate, shell = styrene / M-1 (84/16), core / shell = 50/50 (synthesis of exemplified compound P-30) Stirrer, reflux condenser In a 2 liter three-necked flask equipped with, n-dodecyl methacrylate 150 g, succinic acid di-n-hexyl ester sodium monosulfonate 3.
0 g, 1N sodium hydrogen carbonate solution 14.8 g, distilled water 510 g, and methanol 200 ml were added, and the mixture was heated and stirred at 80 ° C. under a nitrogen stream.

An initiator solution consisting of 0.5 g of potassium persulfate and 30 g of distilled water was added every 2 hours for a total of 4 times, and emulsion polymerization was carried out at 80 ° C. After the final addition of the initiator solution,
Methanol was distilled off over 3 hours to obtain a core latex (particle size was 263 nm).

A solution of 0.65 g of sodium hydrogen sulfite and 300 g of distilled water was added to the obtained core latex to adjust the internal temperature to 70 ° C. An aqueous solution consisting of a mixed solution of 126 g of styrene, 24 g of 2-acetoacetoxyethyl methacrylate and 1.125 g of potassium persulfate, 8.25 g of 1N sodium hydrogen carbonate solution, and 150 g of distilled water was prepared, and constant velocity so that the dropping was completed in 1 hour. Dropped. 1 at 70 ° C after completion of dropping
After continuing heating and stirring for an hour, potassium persulfate is further added 0.3
What melt | dissolved 75 g in 50 g of distilled water was added, and heating stirring was continued at 85 degreeC for 3 hours.

The reaction solution was cooled and filtered to obtain 1375 g of the desired latex P-30 of the present invention. The latex obtained had a solid content of 21.45% (solid content yield 98.3).
%), And the particle size was 336 nm. Further, a part (100 g) of the obtained latex was freeze-dried to obtain 20.7 g of core / shell fine particle powder.

Other exemplified polymers could also be synthesized by the method according to Synthesis Example 1.2. In addition, Synthesis Example 1.
In Fig. 2, the particle size of the core latex and the particle size of the core / shell latex show a good agreement with the particle size predicted from the weight ratio of each polymer. It is clear that there is almost no generation.

Gelatin is preferably used as the binder of 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 synthetic hydrophilic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like 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.

Among these, in the preferred 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 of the silver halide emulsion layer, the back layer, and the other hydrophilic colloid layer, 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, grains having twin planes may be used. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes. In the present invention, a monodisperse emulsion is preferred. The monodisperse silver halide grains in the monodisperse emulsion have an average grain size γ
It is preferable that the weight of silver halide contained in the grain size range of ± 10% with respect to is 60% or more of the total weight of silver halide grains.

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

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

The latex of the present invention can also be used in a color silver halide photographic light-sensitive material. The color photographic light-sensitive material may have at least one silver halide emulsion layer of a blue color sensitive layer, a green color sensitive layer and a red color sensitive layer provided on a support. Also, there is no particular limitation on the number and order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. 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 according to the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. 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 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-112751.
No. 62-200350, No. 62-206541.
No. 62-206543, No. 56-25738,
62-63936, 59-202464, JP-B-55-34932, and 49-15495.

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

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

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

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

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252 and the like, and after separation as described in EP 173,302A Couplers that release dyes that recolor, R.I. D. No. 11449, 24
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 higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. The process of latex dispersion method, effects and specific examples of latex for impregnation are described in US Pat.
199,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

[0107] The color light-sensitive material is a total film thickness of all hydrophilic colloid layers on the side having emulsion layers is 28μm or less and the film swelling speed T _^1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured at 25 ° C. 55% relative humidity (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example,
Photographic Science and Engineering (Photogr.Sci.En) by A. Green et al.
g.), 19 Certificates, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _^1/2 is 30 ° C. in a color developing solution, 3 minutes 15 seconds 90% of the maximum swollen film thickness reached when treated with a saturated film thickness, which time defined to reach the thickness of the T _^1/2. Film swelling rate T _^1/2 can be adjusted to gelatin as a binder by adding a hardening agent, or by changing the aging conditions after coating. The swelling rate is 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness.

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

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

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

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

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, 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 processing by a known method, if necessary.

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

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

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

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

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

A hydrophilic binder can also be used in the magnetic recording layer of the present invention, and water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. 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. As a gelatin hardener, for example, 2-hydroxy-4,6-
Dichloro-1,3,5-triazine, divinyl sulfone, isocyanatos described in U.S. Pat. No. 3,103,437, U.S. Pat. No. 3,017,280.
No. 2,983,611 and the like, aziridine compounds described in US Pat. No. 3,321,313, and the like, and carboxyl group-activating type hardeners. The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on dry gelatin.

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

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

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

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

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

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

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

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

[0127] 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

[0128] BP-10: isophthalic acid (IPA) / NDCA / TPA / EG (20/50/3             0/100) Tg = 95 ° C BP-11: NDCA / Neopentyl glycol (NPG) / EG (100/70             / 30) Tg = 105 ° C BP-12: TPA / EG / bisphenol (BP) (100/20/80)                                                         Tg = 115 ° C BP-13: PHBA / EG / TPA (200/100/100)                                                         Tg = 125 ° C BP-14: PEN / PET (60/40) Tg = 95 ° C BP-15: PEN / PET (80/20) Tg = 104 ° C. BP-16: Polyarylate (PAr) / PEN (50/50)                                                         Tg = 142 ° C BP-17: PAr / Polycyclohexanedimethanol terephthalate (PCT)             (50/50) Tg = 118 ° C BP-18: PAr / PET (60/40) Tg = 101 ° C. BP-19: PEN / PET / PAr (50/25/25) Tg = 108 ° C. BP-20: TPA / 5-sulfoisophthalic acid (SIP) / EG (95/5/1             00) Tg = 65 ° C BP-21: PEN / SIP / EG (99/1/100) Tg = 115 ° C

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

The heat treatment of such a support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web. In the case of heat treatment in the form of a roll, any of a method of heat-treating the roll in a constant temperature bath from room temperature and a method of winding and heat-treating the roll in the form of a roll after being brought to a predetermined temperature during web conveyance may be performed. In the heat treatment in a roll, due to the heat shrinkage stress generated during the heat treatment, surface defects such as wrinkles due to winding tightness and cut-out of the core portion are likely to occur.
Therefore, the surface is roughened (for example, SnO ₂ / Sb
Applying conductive inorganic fine particles such as ₂ O ₅ or colloidal silica) to prevent wrinkles due to winding tightness by reducing the squeak between the supports, or to give knurls to the ends of the supports to slightly increase the edges only. It is desirable to take measures such as preventing the cut end of the core from being exposed by increasing the height. When the heat treatment is performed in the form of a web, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the form of roll. These heat treatments may be carried out at any stage after the support film formation, the glow discharge treatment, the back layer application (antistatic agent, slip agent, etc.), and the undercoat application. Preferred is after the 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, benzotriazole compounds such as 2 (2'-hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole, phenyl salicylate, methyl salicylate, etc. Examples include salicylic acid-based ultraviolet absorbers.

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

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

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

Next, the corona discharge treatment will be described in any of the conventionally known methods, for example, Japanese Patent Publication No. 48-5043.
47-51905, JP-A-47-28067, 49-83767, 51-41770 and 51-.
It can be achieved by the method disclosed in No. 131576 or the like. The discharge frequency is suitably 50 Hz to 5000 KHz, preferably 5 KHz to several hundred KHz, and particularly preferably 10 Hz to 30 KHz. Regarding the treatment strength of the object to be treated, it is usually 0.001 KV · A · min / m ² ~
5 KV · A · min / m ^2, preferably is 0.01 kV · A · min / m ² ~1KV · A · min / m ² suitably. The gap clearance between the electrode and the 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
No. 3, 3,462,335, 3,475,307
No. 3,761,299, British Patent 997,093
JP-A No. 53-129262 and the like can be used. There is a method of introducing various gases such as oxygen, nitrogen, helium or argon into the atmosphere of glow discharge treatment, but glow discharge treatment in the presence of water vapor is preferable. The steam partial pressure is preferably 10% or more and 100% or less, and more preferably 40% or more and 90% or less. 10
If it is less than%, it becomes difficult to obtain insufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like. Further, it is preferable to preheat the film to be surface-treated, preferably 50 ° C. or higher and Tg or lower, and 70 ° C. or higher Tg.
The following is more preferable, and 90 ° C or higher and Tg or lower is further preferable. As a method of raising the surface temperature of the support in vacuum,
There are heating by an infrared heater, heating by contact with a hot roll, and the like.

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

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

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

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

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Silver halide emulsion and JP-A-2-97937, page 20, right lower column, line 12 From its production method, page 21, left lower column, line 14 and JP-A-2-2236. Page 7, upper right column, line 19 to page 8, lower left column, line 12, Japanese Patent Application No. 3-116573 and Japanese Patent Application No. 3-189532. 2) Spectral sensitizing dyes, from JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8, from JP-A-2-39042, page 7, lower right column, line 8 Page 13, lower right column, line 5. Tokukaihei 2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left column, line 20 Further, JP-A Nos. 1-112235, 2-124560, 3-79928, and Japanese Patent Application Nos. 3-189532 and 3-411064.

[0142] 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7                           From the same right lower column 7th line. 4) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6                           Eye to page 19, upper left column, first line, and 2-553                           No. 49, page 8, lower right column, line 13 to page 11 left                           Upper row, line 8. 5) Antifoggant JP-A-2-103536, page 17, lower right column 19                           From line 1 to page 18, upper right column, line 4 and lower right column, line 1                           From the 5th line, further JP-A-1-237538                           Thiosulfinic acid compounds described in the report. 6) Polyhydroxy JP-A-2-55349, page 11, upper left column, page 9     From benzenes, the same, lower right column, line 17. 7) Sliding agent, plasticizer JP-A-2-103536, page 19, upper right column, line 6                           From the eye, page 15, upper right column, line 15. 8) Hardener JP-A-2-103536, page 18, upper right column, line 5                           17th line from the eye.

[0143] 9) Dye JP-A-2-103536, page 17, lower right column, line 1                           18th to 18th lines, No. 2-39042, page 4                           Upper right column, first line to page 6, upper right column, fifth line, 2-29                           4638 gazette and Japanese Patent Application No. 3-185773.                           Solid dye listed. 10) Tetrazolium compound JP-A-2-39143, page 4, lower left column, line 8     Page 6, lower left column, line 6, JP-A-3-123346.                           Gazette, page 3, upper right column, line 19 to page 5, upper left column, line 20                           Eye. 11) Redox compound Represented by the general formula (I) in Japanese Patent Application Laid-Open No. 2-301743                           (Especially compound examples 1 to 50), 3                           No. 174143, pages 3 to 20                           Of the general formulas (R-1), (R-2), (R-3)                           Compound Examples 1 to 75, and Japanese Patent Application No. 3-69466                           Nos. 3-15648. 12) Monomethine compound Compound of the general formula (II) described in JP-A-2-287532                           Compounds (especially compound examples II-1 to II-25). 13) Colloidal silica Paragraph symbol “0005” described in JP-A-4-214551                           Listed compounds. 14) Developer and developing method JP-A-2-103536, page 19, upper right column 16                           From line 21 to page 21, upper left column, line 8.                           JP-A-2-55349, page 13, lower right column, first line                           To page 16, upper left column, line 10 of the same.

[0144]

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 〃

[0147]

[Chemical 7]

[0148]

[Chemical 8]

[0149]

[Chemical 9]

Then, 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 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 particles for the core.
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 hardener. 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-propylpyriglycine potassium salt 3〃

The obtained sample was stored in an atmosphere of 25 ° C. and 50% RH for 1 week 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 carried out 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 larger the value, the higher the contrast of the image characteristics. 2) Wet film strength sample was immersed in distilled water at 25 ° C for 5 minutes and then radius 0.3mm
The sample was pressed against the surface of the sample film with the sapphire needle, and the load of the needle was continuously changed while moving at a speed of 10 mm / sec, and the load (g) when the film was broken was measured. 3) After leaving the brittle 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 although the amount of active methylene monomer is small, the wet film strength is significantly improved and the brittleness is also good. 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.

[0154]

[Table 1]

[0155]

[Chemical 10]

Example 2 Biaxially Stretched Polyethylene Terephthalate Support (Undercoat Layer on Both Sides) (thickness 100 μ) 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〃

[0158]

[Chemical 11]

[0159]

[Chemical 12]

Then, an emulsion layer having the following composition, a protective layer lower layer and a protective layer upper layer were simultaneously coated on the surface opposite to 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
Fine particles of μm 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 according to a conventional method. According to the method, it was washed with water and 40 g of gelatin was added.

This emulsion had a pH of 5.3 and a pAg of 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 chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity, and finally 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.

[0163]

[Chemical 13]

<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

[0165]

[Chemical 14]

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.

[0168]

[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 A coating sample was 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 treated 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 61-256344 (JP, A) JP-A 63-218952 (JP, A) JP-A 2-24649 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03C 1/04 501 G03C 1/053

Claims (3)

(57) [Claims] 1. A latex polymer comprising core / shell type fine particles having a shell having a repeating unit derived from an ethylenically unsaturated monomer represented by the following general formula (I). Silver halide photographic light-sensitive material. General formula (I) In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and L represents a single bond or a divalent linking group. X is R ² COCH ₂ COO-, NC-CH ₂ COO
-, R ² COCH ₂ CO-, NC-CH ₂ CO- (R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or 1 carbon atom ~
12 alkoxy groups, amino groups, and substituted amino groups having 1 to 12 carbon atoms), R ⁹ —CO—CH ₂ CON (R ⁶ ) —
(R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁹ is a substituted or unsubstituted primary or secondary alkyl group having 1 to 12 carbon atoms, 1 to 12 carbon atoms. Represents an alkoxy group, an amino group, or a substituted amino group having 1 to 12 carbon atoms) . 2. The weight ratio of each polymer of the latex polymer to the core portion and the shell portion is 20/80 to 95/5.
2. The silver halide photographic light-sensitive material according to claim 1, wherein 3. A silver halide photographic material as claimed in claim 1 or 2 glass transition temperatures of the core and or shell, wherein the at 50 ° C. or less.