JPH1020475A - Silver halide photographic sensitive material having glass support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce occurrence of pressure fog and to improve adhesion between the glass support and a silver halide emulsion layer by incorporating a polymer latex having active methylene groups in the silver halide emulsion layer or another hydrophilic colloidal layer and to provide a dry glass plate for a photomask. SOLUTION: The silver halide emulsion layer is formed on the glass support and this layer or another hydrophilic colloidal layer contains the polymer latex having the active methylene groups and this polymer is represented by the formula in which C is one of repeating units derived form an ethylenically unsaturated monomer; A is one of repeating units derived from another ethylenically unsaturated monomer having a glass transition point of its homopolymer <=35 deg.C; and each of x, y, z is a weight percentage of each component; x is 0.5-40, y is 60-99.5, and z is 0-50, and x+y+z=100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic material having a silver halide emulsion layer on a glass support. More specifically, the present invention relates to a photographic light-sensitive material which has a low fog and a low adhesion between the glass support and the emulsion layer. The present invention relates to an improved silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A glass dry plate having a silver halide photographic emulsion layer on a glass support is excellent in dimensional stability, and therefore, a photomask for ICs, a shadow mask of a CRT, a lead frame, various displays which require high precision are required. It is used as a related photomask. Such a glass dry plate is used to bake a fine pattern to form an original pattern, and then use it as a mask to contact and expose another glass dry plate to reproduce the pattern, or to contact and expose a substrate having a photoresist layer to expose the original pattern. It is used to transfer and obtain a large number of photoresist patterns.

However, according to the prior art, when an original image pattern is transferred by contact exposure, if there is a correction portion such as an opaque or a smear on a master mask having the original pattern, the correction is made when the original mask is brought into close contact with a vacuum printer. Vacuum pressure concentrates on a slight protrusion at a location, and fog due to pressure may occur in a photosensitive material to be copied. Such fog (crimp fog)
When this occurs, that part becomes a serious defect. Similar press fog also occurs when there is minute foreign matter between the master mask and the photosensitive material to be copied. The occurrence of pressure fog peculiar to the silver halide photographic light-sensitive material having such a glass support is a major obstacle in producing a high-definition photomask. Such a silver halide photographic light-sensitive material is formed by coating a silver halide emulsion layer on a sufficiently washed glass support. However, if the adhesion between the support and the emulsion layer is insufficient, development processing is performed. The emulsion layer peels off the support during or after drying.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass dry plate for a photomask in which the generation of pressure fog is reduced and the adhesion between the glass support and the emulsion layer is improved.

[0005]

An object of the present invention is to provide a polymer having at least one silver halide emulsion layer on a glass support and having an active methylene group in the emulsion layer or another hydrophilic colloid layer. This was achieved by a silver halide photographic material characterized by containing latex.

[0006] The glass support used in the present invention is not particularly limited in the glass composition, but is preferably soda-lime glass, soda-lime aluminum glass, or the like. It is preferable that the surface of the support is degreased in advance before the application of the coating liquid for a hydrophilic colloid layer, and is subjected to a pretreatment for improving hydrophilicity. The end face of the support is preferably polished for handling.

The light-sensitive material of the present invention has at least one silver halide emulsion layer on a glass support, and if necessary, a protective layer above the emulsion layer and an undercoat layer below the emulsion layer. Can be. Further, an antihalation layer can be provided between the emulsion layer and the undercoat layer.

The polymer latex having an active methylene group in the present invention is a polymer represented by the following general formula (I). General formula (I)

[0009]

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

X, y, and z each represent a weight percentage ratio of each component, x is 0.5 to 40, y is 60 to 99.5,
z takes a value of 0 to 50. Where x + y + z = 10
Represents 0.

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

[0013]

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In the formula, R ¹ represents a hydrogen atom, a carbon atom having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl) or a halogen atom (for example, chlorine atom or bromine atom); Represents an 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.

[0015]

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

[0017]

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

[0019]

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

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

X represents a monovalent group containing an active methylene group, and preferred examples thereof include R ⁸ —CO—CH ₂ —COO— and NC—CH
^{_{2 -COO-, R 8 -CO-CH}} 2 -CO-, R 8 -CO-CH 2 -CON (R 5) - , and the like. Here, R ⁵ is the same as above, and R ⁸
Is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, n-propyl, n-butyl,
t-butyl, n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl and the like, and substituted or unsubstituted aryl groups (for example, phenyl, p-methylphenyl, p-methoxyphenyl,
o-chlorophenyl and the like), alkoxy groups (for example, methoxy, ethoxy, methoxyethoxy, n-butoxy and the like),

Cycloalkyloxy groups (eg, cyclohexyloxy), allyloxy (eg, phenoxy, p-
Methylphenoxy, o-chlorophenoxy, p-cyanophenoxy, etc.), an amino group, and a substituted amino group (eg, methylamino, ethylamino, dimethylamino, butylamino, etc.).

Hereinafter, in the polymer represented by the general formula (I) of the present invention, an ethylenically unsaturated monomer having an active methylene group represented by C will be exemplified, but the 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-13 Ethyl acryloyl acetate M-14 Acryloyl methyl acetate M-15 N-Methacryloyloxymethyl acetoacetamide M-16 Ethyl methacryloylacetoacetate M-17 N-Allyl cyanoacetamide M-18 Methyl acryloylacetoacetate

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

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

More preferred monomers are those having a homopolymer having a glass transition temperature of 10 ° C. or lower. Examples of such monomers include alkyl acrylates having an alkyl side chain having 2 or more carbon atoms (eg, ethyl acrylate, n- Particularly preferred examples include butyl acrylate, 2-ethylhexyl acrylate, etc., alkyl methacrylates having an alkyl side chain having 6 or more carbon atoms (eg, n-hexyl methacrylate, 2-ethylhexyl methacrylate, etc.), and dienes (eg, butadiene, isoprene). Can be mentioned.

Regarding the value of the glass transition temperature of the above polymer, see “Polymer Ha,” edited by J. Brandrup. EH Immergut.
ndbook "3rd edition (John Wily & Sons, 1989) VI / 209 ~
It is described on page VI / 277.

The repeating unit represented by B is a repeating unit other than A, that is, the homopolymer has a glass transition temperature of 3
It represents a repeating unit derived from a monomer having a temperature exceeding 5 ° C.

Specifically, acrylates (for example, t-butyl acrylate, phenyl acrylate,
2-naphthyl acrylate, etc.), methacrylic esters (for example, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, phenyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate, ethylene glycol) Dimethacrylate),

Vinyl esters (eg, vinyl benzoate, pivaloyloxyethylene, etc.), acrylamides (eg, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide) , Hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide,
Diacetone acrylamide),

Methacrylamides (for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide Amide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide,
Diethyl methacrylamide, β-cyanoethyl methacrylamide, etc.),

Styrenes (for example, styrene, methylstyrene, dimethylstyrene, trimethylenestyrene, ethylstyrene, isopropylstyrene, chlorostyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate) Etc.), divinylbenzene,

Acrylic nitrile, methacrylonitrile, N-vinyl pyrrolidone, N-vinyl oxazolidone, vinylidene chloride, phenyl vinyl ketone and the like can be mentioned.

Further, in the polymer represented by the general formula (I) of the present invention, Japanese Patent Publication Nos.
No.-3822, No.53-28086, U.S. Pat.
A monomer having an anionic functional group (for example, a carboxyl group or a sulfonic acid group) as described in Japanese Patent No. 700,456 or the like may be copolymerized for the purpose of improving the stability of the latex.

The following compounds can be mentioned as such monomers. Acrylic acid; methacrylic acid;
Monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate; citraconic acid; styrene sulfonic acid; vinylbenzyl sulfonic acid; Vinylsulfonic acid; acryloyloxyalkylsulfonic acid,
For example, acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc .; methacryloyloxyalkylsulfonic acid, for example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc .; acrylamidoalkyl Sulfonic acid, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-
2-methylpropanesulfonic acid, 2-acrylamide-
2-methylbutanesulfonic acid and the like; methacrylamide alkylsulfonic acid, for example, 2-methacrylamide-2
-Methylethanesulfonic acid, 2-methacrylamide-2
-Methylpropanesulfonic acid, 2-methacrylamide-
Such acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

X, y, and z each represent a percentage by weight of each monomer component in the polymer, and x is 0.5 to 40, preferably 0.1 to 0.4.
5 to 30, particularly preferably 1 to 20, and y is 60
To 99.5, preferably 70 to 99.5, particularly preferably 75 to 99, and z is 0 to 50, preferably 0 to 35, particularly preferably 0 to 25.

The above-mentioned monomer having an anionic functional group can be used as required, for example, for imparting stability to a latex, irrespective of the glass transition temperature of the homopolymer. Preferred amounts are 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the total weight of the polymer.

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

I-1 Ethyl acrylate / M-1 / acrylic acid copolymer (85/10/5) I-2 n-butyl acrylate / M-1 / methacrylic acid copolymer (85/5/10) -3 to 7 n-butyl acrylate / M-1 / acrylic acid copolymer (x / y / z) I-3 x / y / z = 95/2/3 I-4 x / y / z = 92 / 5/3 I-5 x / y / z = 89/8/3 I-6 x / y / z = 81/16/3 I-7 x / y / z = 72/25/3

I-8 n-butyl acrylate / styrene / M-1 / methacrylic acid copolymer (65/20/5/10) I-9 methyl acrylate / M-4 / methacrylic acid copolymer (80/15 / 5) I-10 n-butyl acrylate / M-5 / acrylic acid copolymer (85/10/5) I-11 n-butyl acrylate / M-7 / methacrylic acid copolymer (85/10/5) ) I-12 2-ethylhexyl acrylate / M-9 copolymer (75/25)

I-13 n-butyl acrylate / M-14
/ Polystyrene styrene sulfinate copolymer (75/20/5) I-14 n-hexyl acrylate / methoxyethyl acrylate / M-2 copolymer (70/20/10) I-15 2-ethylhexyl acrylate / M- 15 / methacrylic acid copolymer (90/5/5) I-16 n-butyl acrylate / M-1 / M-17 / acrylic acid copolymer (75/5/15/5)

The polymer latex of the present invention is prepared by a generally well-known emulsion polymerization method, and the preferred range of the particle size is 0.01 to 1.0 μm. The emulsion polymerization method is preferably carried out by emulsifying a monomer in water or a mixed solvent of water and an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.) using at least one emulsifier, and using a radical polymerization initiator. Generally 30 ° C
It is carried out at a temperature of from about 100 ° C to about 100 ° C, preferably from 40 ° C to about 90 ° C. The amount of the organic solvent miscible with water is from 0 to 100%, preferably from 0 to 50%, by volume relative to water.

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

As the emulsifier, anionic, cationic,
In addition to amphoteric and nonionic surfactants, there are water-soluble polymers and the like. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfosanoate, sodium lauryl naphthalene sulfonate, sodium lauryl benzene sulfonate, sodium lauryl phosphate,
Cetyltrimethylammonium chloride, dodecyltrimethyleneammonium chloride, N-2-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan laurate ester, polyvinyl alcohol, JP-B-53
And emulsifiers and water-soluble polymers described in US Pat.

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

In the polymer represented by the general formula (I) of the present invention, the type of the monomer having an active methylene group represented by C and the polymer latex and the method of synthesizing the same are described in US Pat. 790, 3,61
9,195, 3,929,482, 3,70
No. 0,456, West German Patent No. 2,442,165, European Patent No. 13,147, JP-A-50-73625, and JP-A-50-73625.
It can be performed with reference to the description of 146331 or the like.

Further, the polymer latex having an active methylene group is preferably a polymer latex having a core / shell structure. The core of the core / shell polymer latex of the present invention is specifically a polymer comprising one or more kinds of repeating units of various polymerizable ethylenically unsaturated monomers.

As such monomers, acrylic esters, methacrylic 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 be preferably used.

More specifically, examples of acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate and tert-butyl acrylate. , Amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 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-methoxy polyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2
-Methoxyethyl acrylate, 1,1-dichloro-2
-Ethoxyethyl acrylate and the like.

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

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

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

Olefins: for example, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylylene chloride and the like; styrenes such as styrene, methyl styrene, ethyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro Styrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester and the like; vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether and the like;

Others include butyl crotonate, hexyl crotonate, dimethyl itaconate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxy vinyl ketone, N-vinyl pyrrolidone , Acrylonitrile, methacrylonitrile, methylenemalononitrile, vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, vinylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and the like. Can be mentioned.

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

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

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

The shell part 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 (C) in the general formula (I).

In the polymer constituting the shell part of the present invention, an ethylenically unsaturated monomer other than the above-mentioned ethylenically unsaturated monomer containing an active methylene group may be copolymerized. 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. Can be listed,
Of these, acrylic esters, methacrylic esters, vinyl esters, and styrenes are particularly preferred.

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

The ratio of the core polymer to the shell polymer in the core / gel polymer latex of the present invention can be arbitrarily changed.
90-95 / 5, preferably 20 / 80-95
/ 5, particularly preferably 30/70 to 90/10. This means that if the core is too small, the effect of concentrating the active methylene monomer on the shell decreases, and if the shell is too small, it becomes difficult to form a clear core / shell structure. The particle diameter of the core / shell polymer latex is 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less, as in the case of the copolymer particles. And 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, a combination in which the core polymer and the shell polymer have close polarities and are compatible with each other may have a desired core / shell structure. May not be formed sufficiently. In order to form a more effective core / shell structure, it is preferable to select a polymer in which the polymer forming the shell and the polymer forming the core are hardly compatible.

One of the very useful aspects in this regard is to use a polymer having a conjugated diene monomer component as a core. When the conjugated diene monomer is used in a certain amount or more, the core particles have extremely low polarity, so that it is possible to form an effective core / shell structure with most of the monomers used for the shell portion. The standard for forming a core having such performance is that the conjugated diene monomer is contained in an amount of 25% or more by weight, and a preferred example is a styrene-butadiene copolymer (commonly referred to as SBR, and solution-polymerized SBR). The solution-polymerized SBR includes the above-mentioned block copolymers (eg, butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer) in addition to the random polymer. Butadiene homopolymer (for example, cis-1,4-butadiene, trans-1,2-butadiene, or a rubber in which these are mixed with trans-1,4-butadiene structure), isoprene homopolymer (an example of the steric structure is: , Butadiene polymer), styrene-isoprene copolymer (random copolymer, block copolymer), d Ren - propylene -
Diene copolymers (diene monomers include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, etc.), acrylonitrile-butadiene copolymer, chloroprene copolymer, isobutylene-isoprene copolymer Butadiene-acrylate copolymer (eg, ethyl acrylate, butyl acrylate, etc. as acrylate) and butadiene-acrylate-acrylonitrile copolymer (the same as acrylate). it can.

Also, by selecting a polymer having a large polarity difference between the polymer constituting the core and the shell, the effective core /
A shell structure can be formed, for example, poly (n-dodecyl methacrylate) core / poly (methyl acrylate-
Co-2-acetoacetoxyethyl methacrylate) shell, poly (ethyl acrylate) core / poly (styrene-co-2-acetoacetoxyethyl acrylate) shell, and the like. However, these indicate that the effect of the core / shell polymer latex of the present invention can be selected depending on the magnitude of the effect. Even in the case of a combination of polymers having similar polarities, the non-core / shell type polymer latex can be selected. In contrast, the core / shell latex of the present invention shows better film strength properties.

Further, even when a monomer having close polarity is used for the core and the shell, the core must be three-dimensionally cross-linked using the cross-linking monomer (a monomer having two or more ethylenically unsaturated groups in the molecule). Thereby, an extremely effective core / shell polymer latex can be obtained. As described above, in the present invention, it is possible to form a useful core / shell polymer latex structure irrespective of the type of monomer used.

The core / shell latex of the present invention has a glass transition temperature of the core or shell portion, or both of the core portion and the shell portion, in terms of the brittleness improving effect when added to a gelatin film separately from the film strength characteristics. Tg) is suitably 50 ° C. or less, and preferably Tg of the core portion is lower than Tg of the shell portion, and more preferably Tg of the core portion is lower than 0 ° C. (the lower limit is −10 ° C.) from the viewpoint of improving shear stability. 110 ° C),
The Tg of the shell portion is preferably 0 ° C. or higher (the upper limit is 150 ° C.).

The Tg of the polymer is described, for example, in J. Brandrup, E.
H. Immergut, Polymer Hondbook, 2nd Edition, II
I-139 to III-192 (1975) ". In the case of a copolymer, it can be determined by the following formula.

[0072]

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

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

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

P-13,14 core: styrene / butadiene copolymer (22/78) P-13 shell = styrene / M─2 (84/16) core / shell = 50/50 P-14 shell = n- Butyl acrylate / M-8 (84/16) core / shell = 50/50

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

P-21 to 23 Core: Polyisoprene homopolymer (100) P-21 shell = styrene / acrylonitrile / M-1 (63/21/16) Core / shell = 90/10 P-22 shell = methyl Methacrylate / ethyl acrylate / M ／ 2 / 2-acrylamide-2-methylpropanesulfonate sodium (15/65/15/5) Core / shell = 75/25 P-23 Shell = styrene / M-1 (84/16 ) Core / shell = 20/80

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

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

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

P-37-40 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-methyl sodium propane sulfonate (80 / 15/5) core / shell = 75/25 P-40 shell = n-butyl acrylate / M─1 (84/16) core / shell = 50/50

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

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

P-50 Core: Poly (ethylene glycol dimethacrylate / vinyl palmitate / n-butyl acrylate) copolymer (20/20/60) Shell: Ethylene glycol dimethacrylate / styrene / n-butyl methacrylate / M- 1 (5/40/40/15) core / shell = 50/50 P-51 core: poly (trivinylcyclohexane / n-butyl acrylate / styrene) copolymer (10/55/35) shell: methyl acrylate / M-1 / 2-acrylamide-2-methylpropanesulfonic acid sodium (88/7/5) Core / shell = 70/30 P-52,53 Core: Poly (divinylbenzene / styrene / methyl methacrylate) 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 (6 0/30/10) Core / shell = 50/50

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

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

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

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

In order to form a latex having an effective core / shell structure, the polymerization of the core particles at the time of addition of the shell-forming monomer is preferably as complete as possible, and the polymerization rate is 90% or more, preferably 95%. As described above, the content is particularly preferably substantially 100%.

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

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

The amount of the polymer latex having an active methylene group of the present invention is optional, but is preferably 10 mg.
/ M ^{2 to} 10 g / m ² , especially 100 mg / m ^{2 to} 1.5 g / m ² . The content of gelatin in the additive layer is 5 to 5.
400% by weight, especially 10-200% by weight is preferred.

It is advantageous to use gelatin as a binder for the protective layer used in the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin oxygen-decomposed product can also be used.

The protective layer used in the present invention may contain, in addition to the binder, a matting agent such as silica, magnesium oxide and polymethyl methacrylate. For preventing static charge, a fluorine-containing surfactant described in JP-A-60-80849 or the like can be contained. In order to lower the surface Masatsu's coefficient, a slipping agent may be contained.

Representative examples of the slip agent used in the present invention include, for example, US Pat. No. 3,042,522, British Patent No. 955,061, and US Pat. No. 3,080,31.
No. 7, 4,004,927 and 4,047,958
No. 3,489,567 and British Patent No. 1,143.
No. 118, etc., US Pat. Nos. 2,454,043, 2,732,305, 2,976,148, 3,206,311 and German Patent No. 1 Fatty acid-based, alcohol-based, acid amide-based slip agents described in, for example, U.S. Patent Nos. 1,263,722 and 3,933,516. Metal soaps described in U.S. Pat. Nos. 2,588,765 and 3,121,060; and esters described in British Patent No. 1,198,387,
Ether slip agents, U.S. Pat. No. 3,502,473,
And a taurine-based slip agent described in JP-A-3,042,222. Of these sliding agents, particularly preferred are alkylpolysiloxanes and liquid paraffin described in JP-A-60-188945.

EDTA for the purpose of preventing black spots
A chelating agent such as 5-chloro-8-hydroxyquinoline and 1,5-dihydroxy-2-benzaldoxime may be contained. Further, a part or all of an antifoggant, an anti-irradiation dye, a surfactant, a hardener, a poorly soluble synthetic polymer and the like may be contained in the protective layer.

The thickness of the protective layer used in the present invention is preferably from 0.05 to 5 μm, more preferably from 0.2 to 2 μm.
μm. The protective layer used in the present invention may have a multilayer structure of two or more layers.

The silane coupling agent used in the present invention is preferably a compound represented by the following general formula. General formula [S]

[0101]

Embedded image

In the formula, X represents an oxygen atom or —O—CO—. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a halogen atom or a hydrocarbon group, and at least one of R _{11 to} R ₁₄ is a double bond, a halogen atom, an epoxy group, an acid anhydride residue, an alkoxy group. Contains carbonyl or amino groups.
n, n 'and n "each represent 0 or 1, and n + n'
+ N ″ is at least 1. In the general formula [S], examples of the halogen atom represented by R _{11 to} R ₁₄ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Each of which includes a saturated or unsaturated chain or ring, and includes, for example, an alkyl group (eg, methyl, ethyl, propyl, etc.), an alkenyl group (eg, vinyl, allyl, etc.), an aryl group (eg, phenyl, tolyl, etc.) The double bond of at least one of R _{11 to} R ₁₄ is a C ＝ C bond, for example, an alkenyl group, an acryloyl group, a methacryloid group, a vinylcarbonylamino group,
Introduced as an isopropenylcarbonylamino group and the like,
Examples of the acid anhydride residue include a group such as a methylcarbonyloxycarbonylethyl group, and a halogen atom may be introduced in a form such as a haloacylamino group. Preferred specific examples of the compound represented by the general formula [S] are shown below, but it should not be construed that the invention is limited thereto.

[0103]

Embedded image

The compound represented by the general formula [S] is described in
It can be synthesized by the method described in JP-A-8-3565, and can also be obtained as a commercial product from Toray Silicon Co., Ltd. or Chisso Corporation. The shiraka coupling agent may be added to any hydrophilic colloid layer such as a silver halide emulsion layer, an undercoat layer and a protective layer. Preferred is a mode in which a silane coupling agent is contained in a silver halide emulsion and coated, or a silane coupling agent is contained in an undercoat layer and applied, and more preferably, the silane coupling agent is contained in the undercoat layer. This is a mode in which it is contained and applied. When the compound is added to a hydrophilic colloid layer such as a silver halide emulsion layer, it is preferable to add the compound by dissolving it in water, lower alcohol, acetone or the like. The coating amount of the compound is 1 to 50
Ranges preferably 0 mg / m ^2, more preferably in the range of 10-100 mg / m ^2.

The colloidal silica used in the present invention has an average particle diameter of 30 μm or less, preferably 5 to 20 μm. These colloidal silicas can be easily obtained as commercial products from, for example, Nissan Chemical Industries, Ltd.
Colloidal silica may be added to any of the hydrophilic colloid layers of the silver halide emulsion layer and the protective layer. A more preferred embodiment is one in which both the protective layer and the silver halide emulsion layer are contained and coated.

When the protective layer is contained in the protective layer, the hydrophilic colloid of the protective layer is preferably gelatin, and the weight ratio of gelatin to colloidal silica is preferably in the range of 50: 1 to 5: 1. The coating amount of colloidal silica is 5 to 5
00 mg / m ² , preferably 30-300 mg / m ² . The thickness of the protective layer is preferably in the range of 0.1 to 5 μm,
The range of 0.5 to 2 mμ is more preferable. When it is contained in the silver halide emulsion layer, gelatin is preferable as the hydrophilic colloid of the silver halide emulsion layer, and the weight ratio of gelatin to colloidal silica is preferably in the range of 50: 1 to 5: 1. Coating amount of colloidal silica is 3 ~ 3
000mg / m ^2, preferably 100-1000 mg / m ^2. The thickness of the silver halide emulsion layer is preferably in the range of 1 to 20 μm, more preferably 4 to 10 μm.

In the silver halide emulsion of the silver halide emulsion layer of the present invention, a conventional silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide or silver chloride is used. Any of those used for silver emulsions can be used, and there is no limitation on the grain size and grain size distribution of the silver halide grains. The silver halide composition is 50 mol% or more of silver chloride and 10 mol of silver iodide. % Of silver chlorobromide or silver chloroiodobromide having a grain size of 0.1 to 1.0 μm, and silver iodobromide having a silver iodide content of 8 mol% or less having a grain size of 0.1 μm or less. Emulsions can also be used. The silver halide grains used in the silver halide emulsion layer of the present invention may be cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), A metal ion is added using at least one selected from a rhodium salt (including a complex salt), a ruthenium salt (including a complex salt), and an iron salt (including a complex salt), and the metal ion is added to the inside and / or the surface of the particle. An element can be contained, and a reduction sensitizing nucleus can be imparted to the inside and / or the surface of the grain by placing the element in an appropriate reducing atmosphere.

In the silver halide emulsion of the silver halide emulsion layer of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. The silver halide emulsion of the present invention is a sulfur sensitization method,
A selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination. The silver halide emulsion of the present invention can be spectrally sensitized. The sensitizing dye may be used alone or in combination of two or more. In the silver halide emulsion of the present invention, during the production process of the light-sensitive material, during chemical ripening for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance, at the end of chemical ripening,
And / or after the completion of chemical ripening and before the silver halide emulsion is coated, compounds known in the photographic art as antifoggants or stabilizers can be added.

A plasticizer can be added to the silver halide emulsion layer and / or another hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. The photographic emulsion layer of the light-sensitive material of the present invention has increased sensitivity, increased contrast,
Or a polyalkylene oxide or a derivative thereof such as an ether, ester, or amine, a thioether compound, a thiomorpholine, a quaternary ammonium compound for the purpose of accelerating development,
It may contain urethane derivatives, urea derivatives, imidazole derivatives and the like. The silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention has a particle size of 0.5 to 1
Matting agents such as 0 μm silica or polymethyl methacrylate particles can be used. An antistatic agent for the purpose of preventing static charge can be added to the light-sensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used for the protective layer other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. May be used.

The binder for the backing layer used in the light-sensitive material of the present invention is preferably a polymer that is insoluble in an acid or neutral aqueous solution and soluble in an alkaline solution, preferably an alkaline solution having a pH of 9 or more. Particularly preferred among such alkali-soluble polymers are copolymers containing a carboxyl group in the molecule, such as methyl methacrylate / methacrylic acid copolymer, ethyl methacrylate / methacrylic acid copolymer, and methyl Methacrylate / ethyl methacrylate / methacrylic acid copolymer; As the dye for the backing layer used in the present invention, any dye may be used as long as it has low solubility in water, is decolorized with alkali or sodium sulfite, and is compatible with the binder.

Known processing solutions such as a developing solution used in the present invention are used. Specifically, PQ
This is a developing solution, an MQ developing solution, or a developing solution for forming a hard image at a stage used for photolithography. The present invention can be applied to any of the following systems which are used as a method of forming a hard gradation image used for photolithography. One such system is the so-called squirrel developing system,
A method of obtaining an ultra-high contrast image by processing a single solution of hydroquinone containing a relatively low concentration of sulfite with a developer, for example, THJames the Theory of the Pho
tographic Process (Fourth Edition) 1977, Macmii
an Publishing Co., Inc., pp. 420-426.

The squirrel-type silver halide light-sensitive material was used as a hydroquinone developer to have a considerably high sulfite ion concentration (0.
(2 mol / l or more) High pH (10.5 or more) Using a developer containing a nitroindazole compound, a system capable of obtaining a high-contrast image
No. 190943) is also known. Another system is a method of obtaining a high contrast by processing a light-sensitive material containing a tetrazolium compound with a PQ type or MQ type developer containing a relatively high concentration of sulfite. -18317, 5
Nos. 3,177,719 and 53-17720. Yet another system is a hydrazine derivative (eg, US Pat. Nos. 4,166,742;
7,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
As described in JP-A Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added can be used at pH 11.0 to 1
This is a method of obtaining a super-high contrast image by processing with a developer containing 0.15 mol / l or more of sulfite in 2.3.

The light-sensitive material of the present invention may be a light-sensitive material which can be handled substantially in a light room. In order to make the light-sensitive material substantially light-light-sensitive material that can be handled in a light room, an inorganic desensitizer such as a rhodium salt, an iridium salt, or cupric chloride that extremely lowers the sensitivity of the silver halide emulsion is used. Addition of grains to the emulsion, addition of organic desensitizers such as pinacryptol yellow and phenosafranine to the emulsion, and insensitivity to the wavelength region of safelight light that can be felt as a substantially bright room. As described above, there is a method in which a dye (safelight dye) having a long-wave end of silver halide in its region is absorbed in a light-sensitive material.

These inorganic desensitizers are preferably contained in an amount of 10 ^-6 mol / mol-Ag or more. Especially 10 ^-6 to 1
0 ^-3 mol / mol -Ag are preferred. It is preferable that the organic desensitizer is contained in an amount of 10 ^-5 mol / mol-Ag or more. Particularly, 10 ^-5 to 10 ^-2 mol / mol-Ag is preferable. About the method of lightening using these desensitizers,
For details, see JP-A-58-190943 and JP-A-59-1.
No. 57630, and the like. In addition, a method for making a room bright by using a dye can be carried out by incorporating a dye having an absorption maximum at 400 to 550 nm into a photosensitive material. This method is described in detail in JP-A-62-67554.

Hereinafter, embodiments of the present invention will be described. However, needless to say, the present invention is not limited to the embodiments described below.

[0116]

【Example】

Example 1 Preparation of Coating Solution and Processing Solution (Preparation of Emulsion A) A Lippmann type silver halide emulsion composed of 2 mol% of silver iodide and 98 mol% of silver bromide and having an average grain size of 0.06 μm was physically ripened according to a conventional method. After desalting, sodium thiosulfate and chloroauric [III] acid were added for chemical ripening. The following compounds A-1 as sensitizing dyes, and the following compounds A-2, A-3, A-4 and A as irradiation inhibitors
-5, 1,2-bis (vinylsulfonylacetamido) ethane as a hardener, and 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole as an antifoggant, the following compound A-6 as a surfactant and the following compound A-7 as a thickener were added. Thus, emulsion A was prepared.

[0117]

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[0118]

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(Preparation of Emulsion B) A double jet method comprising 30 mol% of silver bromide and 70 mol% of silver chloride, 2 × 10 ⁻⁶ g of potassium hexabromorhodate per mol silver and 3 × 10 ⁻ A monodispersed cubic silver halide emulsion containing ⁵ g of potassium hexachloroiridate and having an average particle size of 0.25 μm was physically ripened and desalted according to a conventional method, and sodium thiosulfate and chloroauric [III] acid were added. Chemically aged. The following compound B-1 is used as a sensitizing dye, the compound A-3 is used as an irradiation inhibitor, 1,3-divinylsulfonyl-2-propanol is used as a hardening agent, and 4-hydroxy-6-methyl-1 is used as a stabilizer. 3,3a,
Emulsion B was prepared by adding 7-tetrazaindene, hydroquinone, and 1-phenyl-5-mercaptotetrazole as an antifoggant.

[0120]

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(Preparation of Emulsion C) 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 2.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml chloride Sodium 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachlorodium (III) (0.001% aqueous solution) 7 ml

Solution 1 and Solution 3 were added simultaneously to Solution 1 maintained at 40 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate were added and chemically sensitized at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride,
Silver chloroiodobromide cubic grains having an average grain size of 0.23 μm were obtained. Further, sensitizing dye 2.0 × 10 ⁻⁴ mol / mol Ag,
Spectral sensitization was performed by adding 7.0 × 10 ⁻⁴ mol / mol Ag of the sensitizing dye. Furthermore, 3.4 × 10 ⁻⁴ mol / mol Ag of Kbr, 5.0 × 10 ⁻⁴ mol / mol Ag of compound, 8.0 × 10 ⁻⁴ mol / mol Ag of compound, and hydroquinone 1.
2 × 10 ⁻² mol / mol Ag, compound was 1.8 × 10 ⁻⁴
Emulsion C was prepared by adding 3.5 × 10 ^-4 mol / mol Ag of the compound and 4 wt% of the compound to gelatin.

[0124]

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(Preparation of Undercoating Solution) An undercoating solution having the following composition was prepared. Gelatin 4.5 g Lithium silicate (30% aqueous dispersion) 45 g Methanol 300 ml Water 650 ml (Preparation of backing solution) Binder (compound C-1 below) 30 g Dye (compound C-2 below) 5 g (〃C-3) 5 g ( 〃 C-4) 6 g (〃 C-5) 1.2 g ethanol 420 ml methanol 550 ml

[0126]

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[0127]

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(Preparation of Protective Layer Liquid) A liquid for a protective layer having the following composition was prepared. Gelatin 65 g Polymethyl methacrylate fine particles 3 g Surfactant (compound A-6) 3 g Thickener (〃A-7) 0.5 g Spot inhibitor (compound D-1 below) 1.2 g Antifoggant (compound D below) -2) 0.6 g (Compound D-3 below) 0.8 g Water 900 ml

[0129]

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Preparation of Photosensitive Material (Application of Backing Layer) A backing solution was applied on a glass support with a bar coater so as to have an application amount of 15 cc / m ² to provide a backing layer. (Application of Undercoating Solution) An undercoating solution was applied to the opposite side of the backing layer of the glass support provided with the backing layer with a napkin coater so that the application amount was 10 cc / m ^2. Provided.

(Coating of Emulsion Layer and Protective Layer) Emulsion A
Gelatin was added to B and C, and coated so that the coated silver amount was 5.1 g / m ² and the gelatin amount was 4.9 g / m ² . In some samples, 180 mg / m ^{2 of} polymer latex P-4 having an active methylene group and 80 mg of colloidal silica or silane coupling agent S-3 having an average particle diameter of 20 μm, respectively.
/ M ² , 280 mg / m ² . Some samples were further provided with a protective layer on the emulsion layer. Table 1 summarizes the layer structure of each sample, the presence or absence of polymer latex, colloidal silica, and silane coupling agent.

[0132]

[Table 1]

Evaluation of photosensitive material (Evaluation of compression fog) The photosensitive materials 1 to 15 were brought into close contact with 50 opaque-corrected master masks, and vacuumed for 2 minutes and 30 seconds with a vacuum printer for dry glass plates (Kuranami Manufacturing Honeycomb Printer PH). I did a pull. Thereafter, the photosensitive materials 1 to 5 were exposed to the developing solution-1 without exposure.
The photosensitive materials 6 to 10 are developer 2 and photosensitive materials 11 to 1
No. 5 was developed, fixed, and washed with a developing solution-3. The obtained photosensitive materials A to L were observed on a light table, and the number of pressure fog generated at the opaque correction portion of the master mask was examined. The formulas of the developer and the fixer are shown below.

<Developer-1> Hydroquinone 5 g N-methyl-p-aminophenol 1/2 sulfate 1 g Anhydrous sodium sulfite 50 g Potassium hydroxide 20 g Potassium bromide 0.5 g Water was made up to 1000 ml with water. <Developer-2> Hydroquinone 20 g Potassium sulfite 5 g Sodium ethylenediaminetetraacetate 1 g Potassium carbonate 35 g Sodium carbonate 15 g Potassium bromide 3 g 5-Nitroindazole 4 mg Triethylene glycol 30 g Diethanolamine 20 g Sodium bisulfite adduct 50 g Polyethylene glycol (average molecular weight 1500 9.) 0.2 g to 1 liter with water and pH adjusted with sodium hydroxide to 10.
Adjusted to 2. <Developer-3> Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium metabisulfate 40.0 g Potassium carbonate 40.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.08 g 2,3,5 , 6,7,8-Hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.15 g Hydroquinone 25.0 g 4-hydroxymethyl-4-methyl- 1-phenyl-3-pyrazolidone 0.45 g sodium erythorbate 3.0 g diethylene glycol 20.0 g potassium hydroxide was added, and water was added to make up to 1 liter.
Adjust H to 10.45.

<Fixing Solution Formulation> Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 3 L with water

(Evaluation of Adhesion Property)
After the seasoning for 6 hours at 60 ° C. and a relative humidity of 60%, photosensitive materials 1 to 5 are at 20 ° C. for 5 minutes with developer-1, and photosensitive materials 6 to 10 are at 20 ° C. for 3 minutes with developer 2 for 3 minutes. 11
Nos. 15 to 15 were immersed in developer-3 at 20 ° C. for 3 minutes, and the emulsion film was wet with the developer, the emulsion film was scratched with the tip of tweezers, and the surface was rubbed with a finger to evaluate the adhesion to glass. did. The results are summarized in Table 1.

As is clear from the results shown in Table 1, the sample containing the polymer latex having an active methylene group has a small number of pressure fog and good adhesion of the emulsion layer.
Further, the sample containing colloidal silica and the sample having a protective layer have a smaller number of press fogs, and the sample containing a silane coupling agent has better adhesion of the emulsion layer.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 1/76 501 G03C 1/76 501 5/00 5/00 B

Claims (4)

[Claims] 1. A halogen having at least one silver halide emulsion layer on a glass support and containing a polymer latex having an active methylene group in the emulsion layer or another hydrophilic colloid layer. Silver halide photographic material. 2. The silver halide photographic material according to claim 1, further comprising at least one non-photosensitive protective layer on the emulsion layer. 3. The silver halide photographic material according to claim 1, wherein the emulsion layer or the other hydrophilic colloid layer contains a silane coupling agent. 4. The silver halide photographic material according to claim 1, wherein said emulsion layer or another hydrophilic colloid layer contains colloidal silica having an average particle diameter of 30 mμ or less.