JP2614122B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic material having excellent dimensional stability, and has improved film physical properties, particularly improved adhesion to a binder. It is about.

(Prior art and its problems) A silver halide photographic material generally has a layer having a hydrophilic colloid such as gelatin as a binder on at least one side of a support. Such a hydrophilic colloid layer has a disadvantage that it easily expands and contracts with changes in humidity and temperature.

The dimensional change of the photographic material due to the expansion and contraction of the hydrophilic colloid layer is extremely important in a photographic material for printing which requires the reproduction of a halftone image or a precise line drawing for multicolor printing. Disadvantages.

Dimensional Stab with small dimensional change (Dimensional Stab
U.S. Pat. No. 3201 discloses a technique for defining the thickness ratio between a hydrophilic colloid layer and a support in order to obtain a photographic material having excellent ility).
Japanese Patent Publication Nos. 39-4272 and 39-1770 disclose a technique for incorporating a polymer latex into a hydrophilic colloid layer in the specification of Japanese Patent Publication No. 250-250.
No. 2, No. 43-13482, No. 45-5331, U.S. Pat.
Nos. 2763625, 2772166, 2852386, 28534
Nos. 57, 3397988, 3411911 and 3411912. Further, the theoretical support of the above technology is described by JQ Umberger in Photograph Science and Engineering (Phot. Sci. And Eng.) (1957), pp. 69-73. .

However, the incorporation of these polymer latexes in the hydrophilic colloid layer often adversely affects the film strength in a developing solution, abrasion resistance and adhesion of these layers to a support.

U.S. Pat.Nos. 3,459,790, 3,488,708, 3,554,987
Nos. 3,700,456 and 3,939,130, UK Patent 1,491,70
No. 1, etc. describe a technique for improving the adverse effect of the polymer latex by using a polymer having an active methylene group which reacts with a conventional gelatin hardener. By these techniques, a certain degree of improvement in dimensional stability was obtained without impairing the film strength or abrasion resistance in the developing solution. However, in the printing field where multicolor printing and precise line drawing reproduction are required, further improvement in dimensional stability is strongly desired. Japanese Patent Application Laid-Open No. 60-3627 discloses a technique for improving dimensional stability by using a support in which a polyester film is coated on both sides with a polyolefin, but it is still insufficient for practical use.

Also, as a method of obtaining high contrast photographic characteristics,
U.S. Pat.Nos. 4,224,401, 4,168,977, and 4,166,
No. 742, No. 4,311,781, No. 4,272,606, No. 4,21
There is a method using hydrazine derivatives described in 1,857, 4,243,739 and the like.

According to this method, high-sensitivity photographic characteristics can be obtained with ultra-high contrast. However, for the purpose of improving dimensional stability, the use of a large amount of polymer latex inhibits the high-contrast effect of the hydrazine derivative, resulting in high contrast. However, there is an inconvenience that the amount of the polymer latex used is limited and sufficient dimensional stability cannot be obtained.

The technique of defining the thickness ratio between the hydrophilic colloid layer and the support can also reduce the amount of expansion and contraction of the untreated film and the treated film with respect to a change in humidity. However, the processing steps (development, fixing, washing,
The dimensional stability before and after drying) cannot be improved.
This results in that the support elongates due to water absorption during the treatment step, but the elongation of the base does not return to the original state until a long time elapses even after the subsequent drying step, resulting in practically remaining elongation. Therefore, when the dimensions of the unprocessed film and the processed film are compared, the latter is often in a stretched state. The art describes this development as having poor dimensional stability with processing, which is sometimes a significant drawback in photographic light-sensitive materials for printing.

The technique of incorporating the polymer latex into the hydrophilic colloid layer can also reduce the amount of expansion and contraction due to a change in humidity, but the above-mentioned disadvantages cannot be avoided in the treatment step because the treatment liquid permeates the support.

In order to improve such disadvantages, Japanese Patent Application No. 62-94133 discloses a technique using a polyester support coated with a copolymer containing vinylidene chloride. This technique is particularly excellent for improving the dimensional stability associated with the processing of photographic light-sensitive materials for printing, but the coating thickness of the vinylidene chloride-containing copolymer is difficult to be uniform, resulting in uneven coating. Or adversely affect the adhesion to the support and the binder. In this situation, no effective means has been found.

Further, when applying the vinylidene chloride-containing copolymer, a strong shearing force often acts between the application surface and the application machine, a check valve in a coating solution feeding pump, and the like, and often the polymer is used. Agglomerates are generated, causing problems such as deterioration of the coated surface and the necessity of cleaning the manufacturing process.

(Object of the Invention) A first object of the present invention is to provide a silver halide photographic material having excellent dimensional stability due to environmental changes and dimensional stability due to processing.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in dimensional stability due to environmental changes and processing in a super-hardened light-sensitive material using a hydrazine derivative.

A third object of the present invention is to improve the film strength, abrasion resistance and adhesion to a support and a binder in a developing solution, and furthermore, to provide a silver halide photograph having excellent dimensional stability due to environmental changes and processing. Provided is a photosensitive material.

A fourth object is to provide a silver halide photographic material in which a polyester film support and a hydrophilic colloid layer are firmly adhered.

Fifth, a silver halide photographic light-sensitive material having a uniform coating thickness and a coated surface of a vinylidene chloride-containing copolymer, excellent adhesion to a support and a binder, and excellent dimensional stability due to environmental changes and processing. To provide.

(Constitution of the Invention) An object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer containing at least one polymer latex on a polyester film support, wherein the polyester film support has an average molecular weight of 45,000 or less. Coated with a vinylidene chloride copolymer layer, wherein the vinylidene chloride copolymer comprises a core-shell type latex, and the core comprises at least one of repeating units represented by the following general formulas (I) and (II): And the shell has at least one of the repeating units represented by the following general formulas (I), (III) and (IV).

In the above formula, A ¹ represents a hydrogen atom, a methyl group or a halogen atom, A ² represents a substituted or unsubstituted alkyl group or a phenyl group, A ³ represents a hydrogen atom or a methyl group, A ⁴ represents a hydrogen atom, represents a methyl group or -CH ₂ COOM group, a ⁵ represents a hydrogen atom, a methyl group or -COOM group, a ⁶ is substituted by a -COOM group, a -COOM group, an alkoxycarbonyl group, phenyl group or N- Represents an alkylcarbamoyl group, and M represents a hydrogen atom or an alkali metal atom.

(Concrete Configuration of the Invention) The vinylidene chloride copolymer in the present invention is defined by adding at least one kind of each of the monomers represented by the general formulas (II) to (IV) and optionally 0 to 10 Weight average molecular weight of 45000 made by combining species
The following, preferably weight average molecular weight 4000
It is 0 or less and 3000 or more, most preferably 35000 or less and 6000 or more. Here, the weight average molecular weight refers to a weight average molecular weight calculated in terms of polystyrene by a gel permeation chromatogram method.

The molecular weight distribution of the vinylidene chloride copolymer of the present invention is not particularly limited, and may be any of a monodispersed one, a broadly distributed one and a polydispersed one.

The core portion of the vinylidene chloride copolymer latex of the present invention accounts for 60 to 95% by weight, particularly 70 to 90% by weight of the whole latex particles.
Preferably, the shell portion is 5 to 40 wt%, particularly
It is preferably 10 to 30% by weight.

The ratio (w) of the portion composed of the repeating unit represented by the general formula (I) in the whole latex particles is 70 to 98.5 wt.
%, Preferably 85-97 wt%, most preferably 88-94 wt%
%.

The ratio (x) of the portion composed of the repeating unit represented by the general formula (II) is 1.0 to 20% by weight, preferably 2 to 12% by weight, particularly preferably 5 to 10% by weight.

The proportion (y) of the portion composed of the repeating unit represented by the general formula (III) is 0.1 to 5.0% by weight, preferably 0.3 to 3.5% by weight, particularly preferably 0.5 to 2.5% by weight.
V) Ratio of the part consisting of the repeating unit represented by (z)
Represents 0.05 to 3.0% by weight, preferably 0.1 to 1.5% by weight, particularly preferably 0.1 to 0.8% by weight.

In the general formulas (II) to (IV), A ¹ is preferably a hydrogen atom, a methyl group or a Cl or F atom, and more preferably a hydrogen atom or a methyl group.

A ² preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.

A ³ represents a hydrogen atom or a methyl group.

A ⁴ preferably represents a hydrogen atom, a methyl group or a —CH ₂ COOH group, particularly preferably a hydrogen atom or a methyl group.

A ⁵ preferably represents a hydrogen atom.

A ⁶ preferably represents an alkoxycarbonyl group or an N-alkylcarbamoyl group having a —COOH group or a —COOH group, and particularly preferably represents a —COOH group.

Examples of the substituent of the substituted alkyl group or the phenyl group represented by A ² include an alkoxy group (which may be further substituted with some alkoxy groups), a halogen atom, a nitro group, a cyano group, and an alkyl group (a phenyl group). ), A carbonamido group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonic acid group, and the like.

Next, specific examples of the monomers of the general formulas (II) to (IV) will be given, but the present invention is not limited thereto.

Other specific examples of the general formula (II) include, for example, the following.

n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 3-acryloylpropanesulfonic acid, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2- (methoxyethoxy) ethyl acrylate, 2-methane sulfone Amidoethyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, dimethylethylamino methacrylate.

Other optional monomers used in the present invention include, for example, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, and the like. Can be

Further, monomers of the general formulas (III) and (IV) may be used for the core portion, and monomers of the general formula (II) may be used for the shell portion.

Specific examples of these monomers will be given below. Examples of the crotonic acid ester include butyl crotonate and hexur crotonate. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumaric acid diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate, and the like. Examples of the itaconic acid diester include diethyl itaconate, dimethyl itaconate, and dibutyl itaconate. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, hydroxymethylacrylamide, diacetoneacrylamide, acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and the like. Examples of methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxyethyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide and the like. Examples of vinyl ethers include methyl vinyl ether, bunyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, chloromethyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, and vinyl benzoate. Acid methyl ester, 2-methylstyrene, styrenesulfonic acid, vinylbenzoic acid, trimethylaminomethylstyrene and the like.

Examples of other monomers include allyl compounds (eg, allyl acetate, etc.), vinyl ketones (eg, methyl vinyl ketone, etc.), vinyl heterocyclic compounds (eg, vinyl pyridine), unsaturated nitriles (eg, acrylonitrile, methacrylonitrile, etc.) Is raised.

It may be a monomer having a group that binds to a binder directly or via a curing agent, such as an active methylene group, a (poly) hydroxyphenyl group, a sulfinic acid group, or an amino group (substituted with an alkyl group or a phenyl group). And an active ester group, an active halogen atom, an active vinyl group and its precursor, an epoxy group, an ethyleneimine group and the like.

Although the synthesis of the vinylidene chloride copolymer of the present invention can be obtained by using an emulsion polymerization method, the emulsion polymerization method includes the techniques disclosed so far, for example, U.S. Pat.
No. 4,401,788, No. 4,446,273, No. 4,535,120, JP-A-6
1-1108650, 62-256871, 62-246913, 62
-246912, 57-139136, 61-236669, 57-
A synthesis method according to 137109 can be applied. According to these synthesis methods (for example, synthesis according to JP-A-62-256871),
The present invention has been achieved by a vinylidene chloride latex obtained by synthesizing a polymer having excellent adhesion or shear stability in a shell portion and a polymer ensuring a barrier property in a core portion, and synthesizing the polymer.

Here, the polymer excellent in adhesion and the like of the present invention is obtained by using at least one of each of (I), (III) and (IV), and the polymer ensuring the barrier properties is at least (I) , And (II).

The emulsifier used in the synthesis of the present invention may be any of anionic, nonionic, cationic, betaine or polymeric surfactant or a mixture thereof, but anionic emulsifiers are preferred. Among the anionic emulsifiers, those containing at least one alkylbenzene sulfonate are particularly preferred. For example (N is a positive integer and averages about 11-16), Mixture of C _n H _{2n + 1} SO ₃ Na or And C _m H _{2m + 1} OSO ₃ Na (m is 10, 12, 14, 16 or 18).

Hereinafter, specific examples of the compound of the present invention are shown, but the compound of the present invention is not limited thereto.

[Synthesis Example 1] Synthesis of compound 1 of the present invention In a glass pressure-resistant reactor, 440 ml of water, 5 g of sodium alkylbenzenesulfonate and 0.7 g of sodium persulfate were charged and replaced with nitrogen. Then, while stirring, 39 g of vinylidene chloride and methyl methacrylate were stirred at 50 ° C. 4.5 g of the monomer mixture were injected. After confirming the completion of the reaction by lowering the internal pressure, a monomer mixture of 351 g of vinylidene chloride and 39 g of methyl methacrylate was further injected. After confirming the completion of the reaction by reducing the internal pressure, 0.15 g of sodium persulfate and 0.075 g of sodium sulfite were used.
g was dissolved in 25 ml of water and poured into a container. Thereafter, a monomer mixture of 60 g of vinylidene chloride, 5 g of acrylonitrile and 1.75 g of methacrylic acid was injected. After confirming the completion of the reaction by lowering the internal pressure, 30 ml of a 10% aqueous sodium alkylbenzene sulfonate solution was added to obtain the desired latex.

Solid content concentration 50.2%, average particle size 148nm, weight average molecular weight 2
It was 3,600.

Elemental analysis and NMR revealed that Compound 1 of the present invention showed the following structure.

[Synthesis Example 2] Synthesis of compound 2 of the present invention 200 ml of water, 0.80 g of sodium bisulfite and 4.8 g of sodium alkylbenzenesulfonate (a mixture having an alkyl group having 12 carbon atoms as a main component) were replaced with nitrogen, and then stirred. 216 g of vinylidene chloride purged with nitrogen in a closed system, 24 g of methyl methacrylate, and an aqueous solution of potassium persulfate (1.9 g / 80 g)
ml) was added dropwise at 55 ° C. for 12 hours. After the dropwise addition, the mixture was stirred at 55 ° C. for 3 hours.
6g / 20ml) was added dropwise at 55 ° C for 4 hours. After the dropwise addition, the mixture was stirred at 55 ° C. for 3 hours, and then unreacted monomers were removed by bubbling with nitrogen to obtain the desired latex.

Solids concentration 49.8%, average particle size 76nm, weight average molecular weight 3
It was 6,200. Compound 2 of the present invention from elemental analysis and NMR
Has the following structure:

[Synthesis Example 3] Synthesis of Compound 3 of the Present Invention The desired latex was obtained by changing the emulsifier from sodium alkylbenzenesulfonate to sodium lauryl sulfate in Synthesis Example 1. The solid component concentration was 49.2%, the average particle size was 83 nm, and the weight average molecular weight was 31,000.

Elemental analysis and NMR revealed that Compound 3 of the present invention had the following structure.

[Synthesis Example 4] Compounds 4 to 5 of the present invention according to Synthesis Examples 1 and 2
20 was synthesized.

However, in the above table, D ₁ ; sodium alkylbenzene sulfonate D ₂ ; sodium lauryl sulfate D ₃ ; C _n H _{2n + 1} SO ₃ Na [Synthesis Example 5] Comparative Compounds 101 to 103 were synthesized according to Synthesis Examples 1 and 2 while halving the amount of potassium persulfate used.

Comparative compound 101 Solid content concentration 48.9%, average particle size 89 nm, weight average molecular weight 79600, comparative compound 102 Solid content concentration 45.5%, average particle size 78nm weight average molecular weight 58800 Comparative compound 103 Solid content concentration: 48.3%, average particle diameter: 83 nm, weight average molecular weight: 84000 [Synthesis Example 6] Synthesis of comparative compound 104 After water of 200 ml, sodium alkylbenzenesulfonate (2.8 g) and potassium persulfate (0.75 g) were replaced with nitrogen, sealed while stirring. 270 g of vinylidene chloride substituted with nitrogen in the system, 25 g of methyl methacrylate, 3.0 g of acrylonitrile and IV-21.5 g
Of a monomer mixture and an aqueous solution of sodium bisulfite (0.
65g / 100ml) was added dropwise at 50 ° C for 16 hours. After the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours, unreacted monomers were removed by bubbling with nitrogen, and 2.0 g of sodium alkylbenzenesulfonate was further added to obtain the desired latex.

Solids concentration 50.8%, average particle size 87nm, weight average molecular weight 68
It was 400. Elemental analysis and NMR revealed that Comparative Compound 104 had the following structure.

As a method for coating the vinylidene chloride copolymer latex on the polyester support in the present invention, generally known coating methods, for example, a tape coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method The coating can be performed by a gravure coating method or an extrusion coating method using a hopper described in US Pat. No. 2,681,294.

The coating solution of the vinylidene chloride copolymer in the present invention may contain a compound generally referred to in the art as a curing agent. For example, U.S. Patent No. 3,325,287
No. 3,288,775, No. 3,549,377, Belgian Patent No. 6,
No. 602,226, etc .; triazine compounds; U.S. Pat.
3,291,624, 3,232,764, French Patent 1,543,69
No. 4, dialdehyde compounds described in British Patent No. 1,270,578, etc .; U.S. Pat. No. 3,091,537, epoxy compounds described in Japanese Patent Publication No. 49-26580, etc .; vinyl compounds described in U.S. Pat. No. 3,642,486; Aziridine compounds described in Patent No. 3,392,024; ethyleneimine compounds described in U.S. Patent No. 3,549,378; and methylol compounds.

Of these curing agents, triazine-based compounds, dialdehyde-based compounds, and epoxy-based compounds are preferably used.

The amount of these curing agents added is 0.001 to 30 g per coating liquid of the vinylidene chloride copolymer.

The thickness of the vinylidene chloride copolymer layer in the present invention is preferably large in order to suppress the elongation of the base due to water absorption during the development step. However, if the thickness is too large, the adhesion to the silver halide emulsion layer is disadvantageously caused.

Therefore, the thickness is 0.3 μm or more and 5 μm or less, preferably 0.5 μm or more and 2.0 or less.

In the present invention, polyester is a polyester containing aromatic dibasic acid and glycol as main constituents. Representative dibasic acids are terephthalic acid, isophthalic acid, p
-Β-oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenylenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid And glycols such as ethylene glycol, propylene glycol, butanediol, neopentylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4
-Bisoxyethoxybenzene, bisphenol A, diethylene glycol, polyethylene glycol and the like.

Among the polyesters composed of these components, polyethylene terephthalate is the most convenient in terms of availability.

The thickness of the polyester is not particularly limited, but is about 12μ.
Those having a size of about 500 μm, preferably about 40 μm to 200 μm are advantageous in terms of ease of handling and versatility. In particular, those biaxially stretched and crystallized are advantageous in terms of stability, strength and the like.

In order to improve the adhesive strength between the polymer layer and the emulsion layer, a layer having adhesiveness to either of them can be provided as an undercoat layer. In order to further improve the adhesiveness, the surface of the polymer layer may be subjected to a conventional pretreatment such as corona discharge, ultraviolet irradiation, or flame treatment.

The hydrophilic colloid layer of the photographic light-sensitive material of the present invention includes a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer and the like, and a hydrophilic colloid is used for these layers. Gelatin is most preferred as the hydrophilic colloid, and gelatin that is commonly used in the art, such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, and gelatin derivatives and denatured gelatin, can be used. Among them, lime-processed gelatin and acid-processed gelatin are preferably used.

In addition to gelatin, proteins such as colloidal albumin and casein; cellulose compounds such as carboxymethylcellulose and hydroxyethylcellulose; sugar derivatives such as agar, sodium alginate and starch derivatives: synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-vinyl A pyrrolidone polyacrylic acid copolymer, polyacrylamide or a derivative or partial hydrolyzate thereof can be used. If desired, mixtures of two or more of these colloids can be used.

Polymer latex is used in the hydrocolloid of the present invention. The polymer latex preferably used is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 μm to 700 μm,
The preferred amount of use is from 0.01 to 1.0, particularly preferably from 0.1 to 0.8, as a dry weight ratio to 1.0 of gelatin used as a binder.

As a preferred example of this polymer latex And the like.

The polymer latex used in the hydrophilic colloid layer of the present invention can be contained in at least one of the hydrophilic colloid layers such as a silver halide emulsion layer, a back layer, a protective layer and an intermediate layer.

The present invention is particularly effective in a super-high contrast material containing a hydrazine derivative.

Regarding such a hydrazine derivative-containing ultra-high contrast material and an image forming method using the same, US Pat. No. 4,224,401
Nos. 4,168,977, 4,166,742, 4,241,1649
No. 4,272,606, JP-A-60-83028, JP-A-60-2186
No. 42, No. 60-258537, No. 61-223738 and the like.

When a hydrazine derivative is used in the present invention, the hydrazine derivative is preferably represented by the following general formula (Q).

General formula (Q) In the formula, A ″ represents an aliphatic group or an aromatic group,
B "represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfanyl group or a heterocyclic group. X and Y both represent a hydrogen atom or one of a hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

Representative compounds among the compounds represented by formula (Q) are shown below.

Further, the present invention provides a photosensitive material containing a tetrazolium compound in a PQ type containing a relatively high concentration of sulfite or
The effect can also be exerted in a method of obtaining high contrast by processing with an MQ type developer. The image forming method using a tetrazolium compound is described in JP-A-52-18317, JP-A-53-17719 and JP-A-53-17720.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble silver salt (eg, silver nitrate) solution and a water-soluble halogen salt (eg, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing.

As silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used, and the grain morphology and size distribution are not particularly limited.

The silver halide emulsion layer comprises a film physical property improver such as a photosensitive silver halide, a chemical sensitizer, a spectral sensitizer, an antifoggant, a hydrophilic colloid (especially gelatin), a gelatin hardener, and a surfactant. It may contain a thickener and the like. These are described in Research Disclosure, Volume 176 1
Description of paragraph 7643 (December 1978) and JP-A-52-108130
No. 52-114328, No. 52-121321, No. 53-3217,
Reference can be made to the description in the specification of JP-A-53-44025.

The surface protective layer is a layer having a thickness of 0.3 to 3 μm, particularly 0.5 to 1.5 μm, using a hydrophilic colloid such as gelatin as a binder, in which a matting agent such as fine particles of polymethyl methacrylate, colloidal silica, And, if necessary, a thickener such as potassium polystyrene sulfonate, a gelatin hardener, a surfactant, a sliding agent, a UV absorber and the like.

Examples of gelatin hardeners include chromium salts, aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), and active vinyl compounds (1,3,5-triacryloyl-
Hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β-
(Vinylsulfonyl) propionamide]), an active halogen compound (2,4-dichloro-6-hydroxy-s)
-Triazines, etc.), mucohalic acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like, and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium and 2-naphthalenesulfonate) can be used alone or in combination. Among them, JP-A-53-41220 and JP-A-53-5
Preferred are the active vinyl compounds described in 7257, 59-162546 and 60-80846 and the active halides described in U.S. Pat. No. 3,325,287.

The back layer is a layer using a hydrophilic colloid such as gelatin as a binder, is non-photosensitive, and may have a single-layer structure or a multilayer structure having an intermediate layer, a protective layer, and the like.

The thickness of the back layer is from 0.1 μm to 10 μm, in which gelatin hardeners, surfactants, matting agents, colloidal silica, sliding agents, UV absorbers are used as necessary, as with the silver halide emulsion layer and the surface protective layer. , A dye, a thickener and the like.

Although the method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, typically, a photographic material using silver halide as a photosensitive component, for example, a photographic material for printing and a photographic material for X-ray It can be used as a general negative photosensitive material, a general reversal photosensitive material, a general positive photosensitive material, a direct positive photosensitive material and the like. The effect of the present invention is particularly remarkable in a photosensitive material for printing.

There are no particular restrictions on the exposure method, development processing method, and the like of the photosensitive material of the present invention. For example, JP-A-52-108130,
Reference can be made to the specifications of JP-A Nos. 52-114328 and 52-121321 and the descriptions in the above-mentioned Research Disclosure Magazine.

(Specific Effects of the Invention) According to the present invention, at least one side of a polyester support has a hydrophilic colloid containing a polymer latex, and the support has a core shell type latet having an average molecular weight of 45,000 or less on both sides. By coating with a vinylidene chloride copolymer layer made of tux, a silver halide photographic light-sensitive material having excellent dimensional stability due to environmental changes and dimensional stability due to processing can be obtained.

In addition, due to the presence of a monomer having a group that binds to the binder directly or via a hardener in the vinylidene chloride copolymer, the vinylidene chloride copolymer layer is bonded to the support, and the vinylidene chloride copolymer layer is bonded to the adjacent binder layer. Thus, a silver halide photographic light-sensitive material having excellent properties, particularly the latter adhesive property, can be obtained.

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

(Example-1) The undercoating first layer and the undercoating second layer described below were applied on both sides of a biaxially stretched polyethylene terephthalate support having a thickness of 100 µm in the order of distance from the support to prepare undercoat samples 101 to 110.

(1) Undercoat first layer formulation Vinylidene chloride latex (types are as shown in Table 1) 15
Parts by weight 2,4-dichloro-6-hydroxy-S-triazine sodium salt 0.15 parts by weight Polystyrene fine particles (average particle size 2.5μ) added so that the coating amount becomes 80 mg / m ² Distilled water The total amount becomes 100 parts by weight Addition After adding 10% KOH to the coating solution to adjust the pH to 6, the coating solution having a dry film thickness as shown in Table 1 was applied, and dried at 185 ° C. for 2 minutes.

(2) Undercoat second layer formulation Gelatin 1 part by weight Methylcellulose 0.05 part by weight C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 parts by weight Distilled water 98.9 parts by weight This coating solution was applied to a dry film thickness of 0.1 μm and dried at 170 ° C. for 2 minutes to prepare an undercoat sample. .

A backing layer (conductive layer) and a protective layer 1 were arranged on one side of the undercoated sample in order from the support, and a silver halide emulsion layer 1, a silver halide emulsion layer 2, and
Protective layer 2 and protective layer 3 were applied to prepare samples 101 to 110.

(1) Back layer 1 formulation (conductive layer) SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 300 mg / m ² gelatin 170 化合物 Compound-1 7 mg / m ² Dodecylbenzenesulfonic acid sodium salt 10〃Dihexyl-α-sulfosuccinate sodium salt 40
ナ ト リ ウ ム Sodium salt of polystyrene sulfonic acid 9 〃 (2) Protective layer 1 formulation Gelatin 2.9 g / m ² Compound-2 Compound-1 10 mg / m ² Dodecylbenzenesulfonic acid sodium salt 70 mg / m ² Dibenzyl-α-sulfosuccinate sodium salt 15
mg / m ² 1,3-divinyl-sulfonyl-2-propanol 0.99 mg / m
² Ethyl acrylate latex (average particle size 0.05μ) 500
mg / m ² Perfluorooctanesulfonic acid potassium salt 10 mg / m ² Silicon dioxide fine powder particles (average particle size 3.5μ, pore diameter 170
(Å, surface area 300 m ² / g) 35 mg / m ² (3) Silver halide emulsion layer-1 formulation I solution; water 300 ml, gelatin 9 g II solution; AgNO ₃ 100 g, water 400 ml III solution; NaCl 37 g, (NH ₄ ) ₃ RhCl 1.1 ml, water 400 ml Solution II and solution III were simultaneously added at a constant rate to solution I kept at 45 ° C. After removing soluble salts from the emulsion by a conventional method well known to those skilled in the art, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer. The average grain size of this emulsion is 0.20
It was a monodisperse emulsion of μ, and the amount of gelatin contained per kg of the emulsion was 60 g.

 The following compounds were added to the emulsion thus obtained.

Compound-5 6 × 10 ^-3 mol / Ag1 mol Compound-6 60 mg / m ² Compound-7 9 mg / m ² Compound-1 10 mg / m ² Polystyrenesulfonic acid sodium salt 40 mg / m ² N-oleoyl -N-methyltaurine sodium salt 50
mg / m ² 1,2-bis (vinylsulfonylacetamido) ethane 70
mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 0.46
g / m ² The coating solution thus obtained was coated so that the coated silver amount was 2.0 g / m ² .

(4) Silver halide emulsion layer-2 formulation I solution; water 300 ml, gelatin 9 g II solution; AgNO ₃ 100 g, water 400 ml III solution; NaCl 37 g, (NH ₃ ) RhCl ₆ 2.2 mg, water 400 ml In the same manner as the emulsion, the solution I and the solution II
The emulsion was prepared by simultaneously adding the solution I. This emulsion was a monodisperse emulsion having an average grain size of 0.20μ.

 The following compounds were added to the emulsion thus obtained.

As an emulsified dispersion compound -5 hydrazine derivative 5 × 10 ^-3 mol / Ag1 mole compound -6 60 mg / m ² Compound -7 9 mg / m ² Compound -1 10 mg / m ² of polystyrene sulphonic acid sodium salt 50 mg / m ² N-oleoyl-N-methyltaurine sodium salt 40
mg / m ² 1,2-bis (vinylsulfonylacetamido) ethane 80
mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 0.40
g / m ² The coating solution thus obtained was applied so that the coated silver amount was 1.3 g / m ² .

(5) Protective layer-2 formulation Gelatin 1.0 g / m ² α-lipoic acid 10 mg / m ² Dodecylbenzenesulfonic acid sodium salt 5 mg / m ² Compound-6 40 mg / m ² Compound-8 20 mg / m ² Polystyrenesulfonic acid sodium salt 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m
² Compound-9 20 mg / m ² Ethyl acrylate latex (average particle size 0.05μ) 200
mg / m ² (6) Protective layer-3 formulation Gelatin 1.0 g / m ² Silicon dioxide fine powder particles (average particle size 3.5μ, pore diameter 25
Å, surface area 700 m ² / g) 50 mg / m ² liquid paraffin (gelatin dispersion) 43 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² potassium perfluorooctanesulfonate 10 mg / m ² N- Perfluorooctanesulfonyl-N-propylglycine potadium salt 3 mg / m ² Sodium polystyrene sulfonate 2 mg / m ² Sodium sulfate sodium salt of poly (degree of polymerization 5) oxyethylene nonylphenyl ether 20 mg / m ² Colloidal Silica (particle size 15mμ) 20 mg / m ² <Method for preparing emulsified dispersion of hydrazine derivative> The mixture was heated to 65 ° C. and uniformly dissolved to obtain a solution I.

The solution was heated to 65 ° C. and uniformly dissolved to obtain a solution II.

The liquids I and II were mixed and stirred at a high speed with a homogenizer (manufactured by Nippon Seiki Seisakusho) to obtain a fine particle emulsified dispersion. This emulsion was heated under reduced pressure to remove ethyl acetate, and then water was added to make 250 g. The residual ethyl acetate was 0.2%.

The sample thus obtained was stored in an atmosphere of 25 ° C. and 60% RH for 2 weeks, and then evaluated for “dimensional change due to treatment”, “adhesion when dry”, and “adhesion when wet”.

[Evaluation method of dimensional change due to processing]

Drill two holes with a diameter of 8mm at 200mm intervals on the sample,
After standing in a room at 25 ° C. and 30% RH, the distance between the two holes was accurately measured using a pin gauge with an accuracy of 1/1000 mm. The length at this time is Xmm. Then, with an automatic developing machine, development,
After fixing, washing and drying, the size 5 minutes later is defined as Ymm. Dimensional change rate (%) due to processing Was evaluated.

In the art, it is considered that there is no practical problem if the dimensional change rate is ± 0.01% or less.

The development was carried out using a FG-660 automatic developing machine manufactured by Fuji Photo Film Co., Ltd., and using GR-D1 and GR-F1 manufactured by Fuji Photo Film Co., Ltd. under processing conditions of 38 ° C. for 20 seconds. The drying temperature at that time was 45 ° C.

(Evaluation method of adhesiveness during drying)

A razor is used to make 7 vertical and horizontal cuts on the surface of the sample conditioned for 3 days in an atmosphere of 25 ° C. and 55% RH to form 36 squares, and an adhesive tape (NEC)
And nip-tape) and quickly peel off in the 180 ° direction. In this method, the case where the unpeeled portion is 95% or more is class A, the case where it is 90% or more and less than 95% is class B,
% And C are less than C and D respectively. Adhesive strength sufficient for practical use as a photographic material is classified into the above class A.

(Evaluation method of wet adhesion)

At each stage of development, fixing, and washing, a scratch was marked on the emulsion surface of the film with a pencil in the processing solution using a pencil, and this was rubbed five times strongly with a fingertip. To evaluate the adhesive strength.

When the emulsion layer does not peel more than the scratches, it is class A, when the maximum peel width is 2 mm or less, class B, when the maximum peel width is 5 mm or less, class C, and other class D. Adhesive strength sufficient for practical use as a photographic material is classified into Class A among the above four-grade evaluation.

 The development was performed under the following conditions.

Developing GR-D1 (Fuji Photo Film Co., Ltd.) 30 ° C for 20 seconds Fixing GR-F1 (GR) 38 ° C for 20 seconds Rinse at 25 ° C for 20 seconds The evaluation results are shown in Table 1.

(Example-2) Undercoat samples 201 to 210 were prepared in the same manner as in Example-1 except that the type of vinylidene chloride latex used for the first layer of undercoat was changed as shown in Table 2.

Samples 201 to 210 were prepared by applying a silver halide emulsion layer and a protective layer 1 on one surface of each of the undercoat samples 201 to 210 in the order from the support, and a back layer and a protective layer 2 on the opposite surface in the order from the support. .

(1) Formulation of silver halide emulsion layer Emulsion A was prepared by the following method using the following solutions I, II and III.
Was prepared.

Solution I: 300 ml of water, 9 g of gelatin II solution; 100 g of AgNO ₃ , 400 ml of water III solution; 37 g of NaCl, 0.66 mg of (NH ₄ ) ₃ RhCl ₆ , 400 ml of water It was added at a constant rate. After removing soluble salts from the emulsion by a conventional method well known in the art, gelatin was added thereto, and 6-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene and 4-hydroxy −5,6-trimethylene-1,
3,3a, 7-Tetraazaindene was added. The average inhibition size of this emulsion was a monodisperse emulsion of 0.15μ, and the yield of the emulsion was
The amount of gelatin per kg was 60 g.

 The following compounds were added to the emulsion thus obtained.

Polystyrenesulfonic acid sodium salt 10 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 100
mg / m ² ethyl acrylate latex (average particle size 0.1μ) 500mg
/ m ² The coating solution thus obtained was coated so that the coated silver amount was 3 g / m ² .

(2) Protective layer 1 formulation Gelatin 1.5 g / m ² Sodium dodecylbenzenesulfonate 25 mg / m ² dihexyl -α- sulfo succinate inert sodium 10mg /
m ² N-Perfluorooctanesulfonyl-N-propylglycine potadium salt 2 mg / m ² Sodium polystyrene sulfonate 3 mg / m ² Ethyl acrylate latex (average particle size 0.1 μ) 200 mg
/ m ² Colloidal silica 350 mg / m ² Lipoic acid 8 mg / m ² (3) Back layer formulation Gelatin 2 g / m ² Dihexyl-α-sulfosacnate sodium salt 20 mg /
m ² Sodium dodecylbenzenesulfonate 30 mg / m ² of polystyrene sulphonic acid sodium salt 30 mg / m ² 1,3-divinyl-sulfonyl-2-propanol 100 mg / m ² of ethyl acrylate Latte try (average particle size 0.1 [mu]) 200 mg
/ m ² (4) Formulation of protective layer 2 Gelatin 1 g / m ² Polymethyl methacrylate fine particles similar to those used in emulsion protective layer 40 mg / m ² Dihexyl-α-sulfosacnate sodium salt 10 mg / m
² Dodecylbenzenesulfonic acid sodium salt 30 mg / m ² Polystyrenesulfonic acid sodium salt 25 mg / m ² Sodium acetate 30 mg / m ^{2 The} resulting sample was stored at 25 ° C. and 60% RH for 2 weeks. The same evaluation as in Example 1 was performed.

 The results are shown in Table 2.

(Example-3) Undercoat samples 301 to 310 were prepared in the same manner as in Example-1, except that the type of vinylidene chloride latex used for the undercoat first layer was changed as shown in Table 3.

One of the undercoat samples 301 to 310 was coated with a silver halide emulsion layer, a protective layer 1 and a protective layer 2 in the order from the support, and a back layer and a protective layer 3 were coated on the other surface in the order from the support.
Created 301-310.

(1) Silver halide emulsion formulation Silver nitrate aqueous solution and silver 1 in gelatin aqueous solution maintained at 35 ° C
1.3 × 10 ^-4 mol of hexasalt compound rhodium (III) per mol
Simultaneously with aqueous sodium chloride solution containing ammonium acid
By controlling the potential during this period to 200 mV, monodispersed silver chloride cubic grains having an average grain size of 0.08 μm were prepared. After the particles are formed, the soluble salts are removed by the flocculation method well known in the art,
As a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7
-Tetraazaindene and 1-phenyl-5-mercaptotetrazole were added.

A compound represented by the following formula (Q-1) was added to this emulsion at 1 ×
10 ^-3 mol / Ag 1 mol, the compound represented by (Q-2)
× 10 ^-4 mol / Ag 1 mol was added.

In addition, 50% by weight of polyethyl acrylate as solids per gelatin, 145 mg / m ^{2 of} 2-bis (vinylsulfonylacetamido) ethane was added as a curing agent.

(2) Protective layer-1 formulation Gelatin 1 g / m ² Thioctic acid 6 mg / m ² 1,5-dihydroxy-2-benzaldoxime 35 mg / m ² dodecylbenzenesulfonic acid sodium salt 10 mg / m ² polystyrenesulfonic acid sodium salt 20 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 0.2
g / m ² (3) Protective layer-2 formulation Gelatin 0.6 g / m ² Polymethyl methacrylate fine particles (average particle size 2.5μ) 20
mg / m ² Silicon dioxide fine particles (average particle size 2.8μ) 30 mg / m ² N-Perfluorooctanesulfonyl-N-propylglycine potadium 3 mg / m ² Dodecylbenzenesulfonic acid sodium salt 20 mg / m ² Hydroquinone 150 mg / m ² Compound R was prepared and added as a gelatin dispersion according to the following procedure.

A solution obtained by dissolving 18.9 g of the compound R in 25 ml of N, N-dimethylsulfamide was mixed with 536 g of a 6.5 wt% aqueous gelatin solution to which 13 g of compound-S was added at 45 ° C. while stirring to obtain a dispersion.

(4) Back layer formulation Gelatin 2.5 g / m ² Dihexyl-α-sulfosacnate sodium salt 30 m
g / m ² sodium dodecylbenzenesulfonate 35 mg / m ² 1,3- divinyl sulphonyl-2-propanol 130 mg / m
² Ethyl acrylate latex (average particle size 0.05μ)
0.5 g / m ² (5) Protective layer-3 formulation Gelatin 0.8 g / m ² Polymethyl methacrylate fine particles (average particle size 3.4 μ) 40
mg / m ² Dihexyl-α-sulfosacnate sodium salt 9 mg
/ m ² dodecylbenzenesulfonic acid sodium salt 10 mg / m ² sodium acetate 40 mg / m ² Samples 301 to 310 thus obtained were stored at 25 ° C. and 60% RH for 2 weeks. The same evaluation as in Example 1 was performed. The results are shown in Table 3.

(Example-4) Undercoat samples 401 to 410 were prepared in the same manner as in Example-1 except that the type of vinylidene chloride latex used for the first layer of undercoat was changed as shown in Table 4.

Samples 401 to 410 were prepared by applying a silver halide emulsion layer and a protective layer 1 on one side of the undercoating samples 401 to 410 in order from the support, and a backing layer and a protective layer 2 on the opposite side in order from the support. .

(1) Silver halide emulsion layer formulation In a gelatin aqueous solution maintained at 50 ° C., 2 ×
An aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes in the presence of 10 ^-5 mol of rhodium chloride to prepare a silver chlorinated monodispersed emulsion having an average grain size of 0.2 μm. (Cl composition: 95 mol%) The emulsion was desalted by the flocculation method to obtain 1 mg of thiourea dioxide per 1 mol of silver and
0.6 mg of chloroauric acid was added and aged fog was produced at 65 ° C until the best performance was obtained.

 The following compounds were further added to the emulsion thus obtained.

KBr 20 mg / m ² Polystyrene sulfonate sodium salt 40 mg / m ² 2,6-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg / m ² This coating solution was coated with a silver amount of 3.5 g / m ^2. It was applied so that

(2) Protective layer 1 formulation Gelatin 1.5 g / m ² SiO ₂ fine particles (average particle size 4μ) 50 mg / m ² Dodecylbenzenesulfonic acid sodium salt 50 mg / m ² 5-nitroindazole 15 mg / m ² 1,3- divinyl sulphonyl-2-propanol 50 mg / m
² N-Perfluorooctanesulfonyl-N-propylglycine potadium salt 2 mg / m ² Ethyl acrylate latex (average particle size 0.1 μ) 300
mg / m ² (3) Back layer formulation Gelatin 2.5 g / m ² 1,3-divinylsulfonyl-2-propanol 150 mg / m
² Ethyl acrylate latex (average particle size 0.1μ) 900
mg / m ² Dihexyl-α-sulfosacnate sodium salt 35 m
g / m ² Dodecylbenzenesulfonic acid sodium salt 35 mg / m ² (4) Protective layer 2 formulation Gelatin 0.8 g / m ² Polymethyl methacrylate fine particles (average particle size 3μ) 20
mg / m ² dihexyl-α-sulfosacnate sodium salt 10 mg
/ m ² Dodecylbenzenesulfonic acid sodium salt 10 mg / m ² Sodium acetate 40 mg / m ^{2 The} resulting sample was stored in an atmosphere of 25 ° C. and 60% RH for 2 weeks, and evaluated in the same manner as in Example 1. Carried out. The results are shown in Table 4.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer containing a polymer latex on a polyester film support, wherein the polyester film support has a vinylidene chloride having an average molecular weight of 45,000 or less. Coated with a polymer layer, wherein the vinylidene chloride copolymer comprises a core shell type latex,
And the core has at least one of the repeating units represented by the following general formulas (I) and (II), and the shell has a repeating unit represented by the following general formulas (I), (III) and (IV). A silver halide photographic material comprising at least one kind. In the above formula, A ¹ represents a hydrogen atom, a methyl group or a halogen atom, A ² represents a substituted or unsubstituted alkyl group or a phenyl group, A ³ represents a hydrogen atom or a methyl group, A ⁴ represents a hydrogen atom, represents a methyl group or -CH ₂ COOM group, a ⁵ represents a hydrogen atom, a methyl group or -COOM group, a ⁶ is substituted by a -COOM group, a -COOM group, an alkoxycarbonyl group, phenyl group or N- Represents an alkylcarbamoyl group, and M represents a hydrogen atom or an alkali metal atom.