JPH0224649A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the dimensional stability, film strength and wear resistance associated with an environmental change and the adhesiveness to a polyester film base and binder by coating the base with a specific vinylidene chloride copolymer layer. CONSTITUTION:The base of the silver halide photographic sensitive material having a hydrophilic colloidal layer contg. a polymer latex on the polyester film base is coated with the vinylidene chloride copolymer. The copolymer consists of the latex type of a core shell type and the core and shell thereof have at least one kind each of the repeating units respectively expressed by the formulas I and II and I, III and IV. In the formulas, A<1> is a hydrogen atom, methyl group, halogen atom; A<2> denotes an alkyl group, phenyl group; A<3> is a hydrogen atom, methyl group, halogen atom; A<4> is a hydrogen atom, methyl group, -CH2COOM group; A<5> is a hydrogen atom, methyl group, -COOM group; A<6> is a -COOM group, an alkoxycarbonyl group in which the -COOM group is substd., phenyl group, N-alkyl carbamoyl group; M is a hydrogen atom, alkaline metal atom.

Description

Detailed Description of the Invention (Technical Field) The present invention relates to a silver halide photographic material with excellent dimensional stability, and which has improved film thickness uniformity and film physical properties, especially adhesion to a binder. This invention relates to silver halide photographic materials.

(Prior art and its problems) Silver halide photographic materials generally include a layer containing a hydrophilic colloid such as gelatin as a binder on at least one side of a support. Such a hydrophilic colloid layer has the disadvantage that it easily expands and contracts due to changes in humidity and temperature.

Dimensional changes in photographic materials due to expansion and contraction of the hydrophilic colloid layer are a problem in photographic materials for printing, which require the reproduction of halftone images and precise lines for multicolor printing. This is a serious drawback.

Dimensional stability with little dimensional change
In order to obtain a photographic light-sensitive material with excellent stability, a technique for regulating the thickness ratio of a hydrophilic colloid layer and a support is disclosed in US Pat. -4272, 39-17702, 43-1
No. 3482, No. 54-5331, U.S. Patent No. 2376
No. 00, No. 2763625, No. 2772166, No. 2852386, No. 2853457, No. 33979
No. 88, No. 3411911, and No. 3411912. In addition, the theoretical basis for the above technology is
J, Q, tlmberger
) by Photographic Science and Engineering (Photo, Sci, and Eng, )
(1957) pp. 69-73.

However, the inclusion of these polymer latexes in hydrophilic colloid layers often has an adverse effect on film strength in processing solutions, abrasion resistance, and adhesion of these layers to the support.

U.S. Patent No. 3,459.790, U.S. Patent No. 3.488708, U.S. Patent No. 3,554.987, U.S. Patent No. 3,700.456,
No. 3,939,130, British Patent No. 1,491,701
No. 1, et al. describe a technique for improving the above-mentioned adverse effects of polymer latex by using a polymer having active methylene groups that reacts with conventional gelatin hardeners. These techniques have made it possible to improve the dimensional stability to some extent without impairing the film strength or abrasion resistance in a developing solution. However, in the printing field where multicolor printing and precise reproduction of line drawings are required, further improvement in dimensional stability is strongly desired.

Furthermore, JP-A-60-3627 discloses a technique for improving dimensional stability using a support in which both sides of a polyester film are coated with polyolefin, but this technique is still insufficient for practical use.

Also, as a method for obtaining high contrast photographic characteristics, US Pat. No. 4,224,401 and US Pat.
No. 7, No. 4,166.742, No. 4,311.7
No. 81, No. 4,272,606, No. 4.211,
There is a method using a hydrazine derivative described in No. 857, No. 4.243.739, and the like.

With this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, but by using a large amount of polymer latex for the purpose of improving dimensional stability, the high contrast effect of the hydrazine derivative is inhibited, resulting in high contrast. This has the disadvantage that the amount of polymer latex used is limited, and sufficient dimensional stability cannot be obtained.

The technology for regulating the thickness ratio between the hydrophilic colloid layer and the support is
The amount of expansion and contraction of the untreated film and the treated film due to changes in humidity can also be reduced.

However, it is not possible to improve the dimensional stability before and after the processing steps (developing, fixing, washing, drying) that ordinary photographic films necessarily undergo. This is because the support stretches due to water absorption during the treatment process, but even after the subsequent drying process, the elongation of the haze does not return to its original state until a long period of time has elapsed, resulting in some elongation remaining in practical use. Therefore, when comparing the dimensions of an untreated film and a treated film, the latter is often in an elongated state.

In the art, this development is referred to as poor dimensional stability due to processing, and this is a particularly serious drawback in photographic materials for printing.

A technique in which a hydrophilic colloid layer contains a polymer latex can also reduce the amount of expansion and contraction due to changes in humidity, but the above-mentioned drawbacks cannot be avoided because the treatment liquid permeates into the support during the treatment process.

In order to improve this drawback, Japanese Patent Application No. 62-94133 discloses a technique using a polyester support coated with a vinylidene chloride-containing copolymer. Although this technology is particularly excellent for improving the dimensional stability associated with the processing of photosensitive materials for printing, it is difficult to achieve a uniform coating thickness of the vinylidene chloride-containing copolymer, resulting in uneven coating. In many cases, the adhesion to the support and binder was not adversely affected. No effective means have yet been found in this regard.

Furthermore, when applying vinylidene chloride-containing copolymers, strong shearing forces often act between the coating surface and the coating machine, or at the check valves in the coating liquid pumps, and the polymer often Aggregates are generated, causing problems such as deterioration of the coating surface condition and the necessity of cleaning the manufacturing process.

(Object of the Invention) The first object of the present invention is to provide a silver halide photographic material that has 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 material that uses a hydrazine derivative and has excellent dimensional stability due to environmental changes and processing.

The third object of the present invention is to improve film strength, abrasion resistance, and adhesion to a support and binder in a developing solution;
Another object of the present invention is to provide a silver halide photographic material that has excellent dimensional stability due to environmental changes and processing.

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 to each other.

Fifth, the silver halide photographic material has a uniform coating thickness and coating surface condition of the vinylidene chloride-containing copolymer, has excellent adhesion to supports and binders, and has excellent dimensional stability due to environmental changes and processing. It is about providing.

(Structure of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one polymer latex on a polyester film support, wherein the polyester film support is a vinylidene chloride copolymer. coated with a coalescing layer, the vinylidene chloride copolymer consisting of a core Soel type latex, and the core comprising:
Each has at least one type of repeating unit represented by Noshiro (1) and (II), and the shell has the following general formula (1).
, (ffl) and (IV), each of which has at least one type of repeating unit.

In the above formula, Nl + CH2-C/→-(II) COOA" (Specific structure of the invention) The vinylidene chloride copolymer in the present invention is represented by the - formation of II) to (rV) with respect to vinylidene chloride. It can be made by combining at least one type of each of the seven monomers and zero to several types of arbitrary monomers as necessary.

The core portion of the tolylidene chloride copolymer latex of the present invention preferably accounts for 60 to 95 wt% of the total latex particles, and the shell portion accounts for 5 to 40 wt%, particularly 10 to 3 wt%.
Preferably, it is 0 wt%.

The ratio (W) of the portion consisting of repeating units represented by general formula (1) in the entire latex particle is 70 to 98.5.
wt%, preferably 85-97wt%, most preferably 88-94wL%.

The ratio (x) of the portion consisting of repeating units represented by the general formula (■) is 1. O~20wL%, preferably 2~1
2 wt%, particularly preferably 5 to 10 wt%.

The ratio (y) of the portion consisting of repeating units represented by the general formula ([[) is 0.1 to 5.0 wt%, preferably 0.
3 to 3.5% by weight, particularly preferably 0.5 to 2.5% by weight, and the proportion (z) of the portion consisting of repeating units expressed as -formation (It/) is 0.105 to 3.0% by weight. % by weight, preferably 0.1-1.5% by weight, particularly preferably 0.1% by weight
~0.8% by weight.

In general formulas (n) to (IV), AI is preferably a hydrogen atom, a methyl group, or a C2, F atom, and more preferably a hydrogen atom or a methyl group.

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

A3 represents a hydrogen atom or a methyl group.

A4 is preferably a hydrogen atom, a methyl group, -C)l, C0
It represents an OH group, particularly preferably a hydrogen atom or a methyl group.

A5 preferably represents a hydrogen atom.

A6 preferably represents an -COOH group, an alkoxycarbonyl group having a -Cool group, or an N-alkylcarbamoyl group, particularly preferably a -COOH group.

Examples of the substituted alkyl group, substituted alkoxy group, or ffl* group of the phenyl group represented by A2 and A6 include a thehaalkoxy group (which may be further substituted with several alkoxy groups), a halogen atom, a nitro group, and a cyano group. group, an alkyl group (in the case of a phenyl group), a carbonamide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonic acid group, and the like.

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

CH□=C,/ ■ 1! :0OCH,CH20C11゜ -t CH=　CH Otori 11I-2 CH□=C-CH.

Feng (Cis or trans) Uruguay 00 H Cl1. Other specific examples of =C11COOCH,CH,00CCH□CH2C00H- formation (1'l) include the following.

n-propyl acrylate, isopropyl acrylate, n-butyl acrylate-1, 3-acryloylpropanesulfonic acid, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2(methoxyethoxy)ethyl acrylate, 2-methane Sulfonamide ethyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, dimethylethylaminomethacrylate.

Other arbitrary monomers used in the present invention include, for example, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, etc. It will be done.

Furthermore, monomers of the general formula (III) or (rV) may be used for the core part, and monomers of the general formula (II) may be used for the shell part.
Monomers may also be used.

More specific examples of these monomers include butyl crotonate, hexyl crotonate, and the like as crotonate esters. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, hydroxymethylacrylamide, diacetone acrylamide, acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and the like.

Examples of methacrylamide include methylmethacrylamide,
Examples include ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2-methoxyethylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, and the like. Examples include vinyl ether vinyl ether, butyl vinyl ether, xyl vinyl ether, xyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, fromstyrene, and vinylbenzoin. Examples include acid methyl ester, dimethylstyrene, styrene sulfonic acid, vinylbenzoic acid, trimethylaminomethylstyrene, and the like.

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

It may also be a monomer having a group that binds to the binder directly or via a curing agent, such as an active methylene group, a (poly)bidrotosiphenyl group, a sulfinic acid group, or an amine group (substituted with an alkyl-1 or phenyl group). Examples include monomers having active ester groups, active halogens, active vinyl groups and their precursors, epoxy groups, ethyleneimine groups, etc.

The vinylidene chloride copolymer of the present invention can be synthesized using an emulsion polymerization method, but as an emulsion polymerization method, techniques disclosed so far, such as US Pat.
No. 4,401,788, No. 4.446.273, No. 4,535.120, JP-A-61-108650
No. 62256871, No. 62-246913,
Synthesis methods similar to those disclosed in 62-246912, 57-139136, 6m-236669, 57-137109, etc. can be applied. According to these synthesis methods (for example, synthesis based on JP-A No. 62-256871), a polymer with excellent adhesion or shear stability is used in the shell part.
Furthermore, the present invention was achieved using a vinylidene chloride latex obtained by synthesizing a polymer that ensures barrier properties by distributing it in a portion of the core.

Here, the polymer excellent in adhesion, etc. of the present invention is one obtained using at least one of each of (1), (III), and (■), and the polymer ensuring barrier properties is one obtained by using at least one of (1), (III), and (■). , (II).

The emulsifier used in the synthesis of the present invention may be anionic, nonionic, cationic, hetain, polymeric surfactant, or a mixture thereof, but anionic emulsifiers are preferred. Among anionic emulsifiers, those containing at least one type of alkylbenzene sulfonate are particularly preferred (a mixture of integers, with an average of about 11 to 16)
, (m is 10.12.14.16or1B).

Specific examples of the compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[Synthesis Example 1] 440 ml of water, 5 g of sodium alkylbenzenesulfonate, and 0.4 g of sodium persulfate were placed in a synthetic glass pressure-resistant reactor for compound 1 of the present invention.
After replacing the mixture with nitrogen, a monomer mixture of 39 g of vinylidene chloride and 4.5 g of methyl methacrylate was injected at 50° C. with stirring.

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 lowering the internal pressure, 0.05 g of sodium persulfate and 0.025 g of sodium sulfite were dissolved in 25 ml of water and poured into the container. Then 60g of vinylidene chloride, 5g of acrylonitrile
and 1.75 g of methacrylic acid were injected. After confirming the reaction drop by lowering the internal pressure, 10% alkylbenzene sulfone was added to obtain the target latex.

The solid content concentration was 50.2%, and the average particle size was 148 mm.

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

Cβ C113 Clh(
C It z C )y+ry(Ctl z C 11
h coHc II z C II hry(C If
z (JπIrC Q COOCII 3
CN COOII [Synthesis Example 2] Synthesis of compound 2 of the present invention 200g of water, 0.40g of sodium bisulfite and 4.8g of sodium alkylhenzenesulfonate (a mixture whose alkyl group has 12 carbon atoms as a main component) were added to nitrogen. After the substitution, 216 g of vinylidene chloride, 24 g of methyl methacrylate, and an aqueous potassium persulfate solution (0°8 g/8 (ltl) was heated to 55°C, 1
It was added dropwise over 2 hours.

After stirring at 55°C for 3 hours, add 40g of vinylidene chloride, 3g of acrylonitrile, and 1.5g of methacrylic acid.
5g and potassium persulfate aqueous solution (0°2g/20mff
1) was added dropwise at 55°C for 4 hours. 3 at 55°C after dropping
After stirring for a period of time, unreacted monomers were removed by nitrogen bubbling to obtain the desired latex.

The solid content concentration was 49.8%, and the average particle size was 76 nm. Elemental analysis and NMR revealed that Compound 2 of the present invention had the following structure.

The desired latex was obtained by changing sodium sulfonate to sodium lauryl sulfate. The solid content concentration was 49.2%, and the average particle size was 83 nm.

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

CI Cl1z Cl13
IC1l□C斤Ro→CII z CII h7HCII
□C11 斤Go (-CIl□C 斤了-CI C
00CII3 CN COO11 [Synthesis Example 4] Compounds 4 to 20 of the present invention were synthesized according to Synthesis Example 1.2.

10C11□C-)-,-(-11hmom -H+rv廿CI C00CHs CN
C00f+ [Synthesis Example 3] Synthesis of Compound 3 of the Present Invention In Synthesis Example 1, the emulsifier was alkylbenzene. However, in the above table, Dl; Sodium alkylbenzenesulfonate D2; Sodium lauryl sulfate D3; Cn Ilz++, +5OJa D,; C 1hi CIl□000 lh Ds; C+□11□, SbeC11□011)
C11, C11 CN C00II [Synthesis Example 5] Same as Synthesis Example 1.2 Comparative Compounds IO1-1
03 was synthesized.

Comparative compound 101 l +c+hc->1°, 1 moM M A +a, * +
A N +-+.

l Solid content concentration 48.9%, average particle size 89 nm Comparison compound 1
02 C7! -(-CIl, Csv-o, + (-M A +-1
1,8-(-M A A→-1,0 Solid content concentration 45.5
%, average particle size 78 nm Comparative compound 103 +C11□C-)-To, z + M M A +-
+, sl Solid content concentration 48.3%, average particle size 83 nm [Synthesis Example 6]
200 ml of synthetic water of comparative compound 104, 2 of sodium alkylbenzenesulfonate
．． After replacing 8g and 0.75g of potassium persulfate with nitrogen, vinylidene chloride 2 was replaced with nitrogen in a closed system while stirring.
70 g, methyl methacrylate 25 g, acrylonitrile 3.0 g and [V-21.5 g monomer mixture and sodium bisulfite aqueous solution (0.65 g/100 m2
) was added dropwise at 50°C for 116 hours. After 0 dropwise addition, the mixture was incubated at 50°C for 2 hours, unreacted monomers were removed by nitrogen bubbling, and 2.0 g of sodium alkylbenzenesulfonate was added to obtain the desired product. Got latex.

The solid content concentration was 50.8% and the average particle size was 87 nm. Elemental analysis and NMR revealed that Comparative Compound 104 had the following structure.

The method of coating the polyester support with the vinylidene chloride copolymer latex in the present invention includes generally well-known coating methods, such as dip coating, air knife coating, curtain coating, roller coating, and wire barcoding. , gravure coating, or extrusion coating using a homper described in US Pat. No. 2,681,294.

In order to further improve the adhesive strength between the polyester support and the above polymer layer, the surface of the polyester support is subjected to chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, and activated plasma. process,
High pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment,
There is no problem with treatment such as ozone oxidation treatment.

Further, in order to firmly adhere the polymer layer used in the present invention to the polyester base, US Pat. No. 3,245.
No. 937, No. 3,143,421, No. 3,501.3
No. 01, same 3. 271. 178, polyester swelling agents such as phenol, resorcin, 0-cresol, m-cresol, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid IW, chloral hydrate, and benzyl alcohol can be added. It becomes necessary. As these swelling agents, resorcinol is preferably used, but resorcinol has the drawback of often inducing spont failure during the manufacturing process.

A particularly preferred method for avoiding such drawbacks is to apply the polymer layer used in the present invention after subjecting the surface of the polyester support to glow discharge treatment.

The glow discharge treatment in the present invention refers to any conventionally known method, for example, Japanese Patent Publication No. 35-7578, No. 3
No. 6-10336, No. 45-22004, No. 45-2
No. 2005, No. 45-24040, No. 46-4348
No. 0, U.S. Patent No. 3057.792, U.S. Patent No. 3,057.7
No. 95, 3.179 No. 482, 3.28 f3.6
No. 313, No. 3 309 299, No. 3,424.7
No. 35, No. 3,462,335, No. 3,475.30
No. 7, No. 3,761.299, British Patent No. 997.09
No. 3, JP-A-53-129262, etc. can be used.

The pressure during glow discharge is 0.　OO5~20Torr.

Preferably, 0.02 to 2 Torr is appropriate. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may even destroy the object to be treated. Discharge is generated by applying a high voltage between one or more pairs of metal plates or metal rods spaced apart from each other in a vacuum tank.

This voltage can take various values depending on the composition and pressure of the atmospheric gas, but usually within the above pressure range, it is 50
Stable fixing glow discharge occurs between 0 and 5000V.

A particularly suitable pressure range for improving adhesion is 20
00 to 4000V.

Furthermore, as seen in the prior art, the discharge frequency ranges from DC to several 1000100 O, preferably 50 Hz to 2
0MHz is appropriate. Regarding the discharge treatment strength, 0.0 IKV-A・min/min since the desired adhesive performance can be obtained.
rrr ~5 KV・A・min/r+(, preferably 0.05KV・A・min/rr!−IKV−A・min/n
A is appropriate.

Furthermore, in order to improve the adhesive strength between the polyester support and the above polymer layer, a layer having adhesive properties to both may be provided as an undercoat layer.

As such an undercoat, water-soluble polyester, urethane compounds, etc. can be used.

Also, commercially available anchor coating agents such as Vylon (manufactured by Toyobo Co., Ltd.), Jurimer (manufactured by Hiki Junyaku Co., Ltd.), Polysol (manufactured by Showa Kobunshi Co., Ltd.), etc. may be used.

The coating solution of vinylidene chloride copolymer in the present invention includes:
Compounds commonly referred to in the art as curing agents can be included. For example, U.S. Patent No. 3,325,28
No. 7, No. 3,288.775, No. 3,547,377
Triazine compounds described in Belgian Patent No. 6.602.226, etc.; US Patent No. 3.291.624;
Dialdehyde compounds described in French Patent No. 3.232.764, French Patent No. 1.543.694, British Patent No. 1.270,578; US Patent No. 3,091.537
Epoxy compounds described in U.S. Patent No. 3,642.486; Azilidene compounds described in U.S. Pat. Examples thereof include ethyleneimine compounds described in No. 3,549.378 and the like; and methylol compounds.

Among these curing agents, triazine compounds, dialdehyde compounds, and epoxy compounds are preferably used.

The amount of these curing agents added is 0.001 to 30 g per 11 coating liquid of vinylidene chloride copolymer.

The thickness of the vinylidene chloride copolymer layer in the present invention is preferably thick in order to suppress elongation of the base due to water absorption during the development process. However, if it is too thick, there will be problems in adhesion to the silver halide emulsion layer.

Therefore, the thickness is 0.3μ or more and 5μ or less, preferably 0.3μ or more and 5μ or less. A material having a diameter of 5μ or more and 2.0 or less is used.

In the present invention, polyester refers to polyester whose main components are aromatic dibasic acid and glycol. Typical dibasic acids include terephthalic acid, isophthalic acid, p-
β-oxyethoxybenzoic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, etc. Glycols include ethylene glycol, propylene glycol, butanediol, neopentylene gelicol, ■.

4-cyclohexanediol, 1,4-cyclohexane dimetatool, 1,4-bisoxyethoxybenzene,
Bisphenol A1 diethylene glycol, polyethylene glycol, etc.

Among polyesters made of these components, polyethylene terrescrete is the most convenient from the standpoint of availability.

There is no particular limit to the thickness of polyester, but it is approximately 12μ.
A thickness of about 500 μm, preferably about 40 μm to 200 μm is advantageous in terms of ease of handling and versatility. In particular, biaxially stretched crystallized materials 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 adhesive properties to both may be provided as an undercoat layer. In order to further improve the adhesion, the surface of the polymer layer may be subjected to conventional pretreatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The hydrophilic colloid layers of the photographic window optical material of the present invention include a silver halide emulsion layer, a bank layer, a protective layer, an intermediate layer, etc., and hydrophilic colloids are used in these layers. Gelatin is most preferred as the hydrophilic colloid, and examples of the gelatin include so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivatives, modified gelatin, etc.
Any of those used for -C in the art can be used, but lime-treated gelatin and acid-treated gelatin are preferably used.

In addition to gelatin, proteins such as colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; $1 derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N- Vinylpyrrolidone polyacrylic acid copolymer, polyacrylamide, or derivatives and partial hydrolysates thereof, etc. can be used. Mixtures of two or more of these colloids can be used if desired.

It is preferable to use a polymer latex in the hydrocolloid of the present invention. The preferably used polymer latex is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 mμ to 700 mμ, and the preferable amount used is gelatin used as a binder. 0 in dry weight ratio to 1.0
．． 01 to 1.0, particularly preferably 0.1 to 0.8.

Preferred examples of this polymer latex include those having monomers represented by the following formulas (P-■) to (P-Bl) as repeating units, but the present invention is of course not limited thereto.

CH2=CH ○P+OR3+2 In the formula, R1 represents a hydrogen atom, a carboxyl group, or a salt thereof, R2 represents a hydrogen atom, an alkyl group, a substituted alkyl group, a rogen atom, a cyano group, and R3 represents a hydrogen atom, an alkyl group, Substituted alkyl group, arylene group, substituted arylene group R4, R5 may be the same or different, hydrogen atom, alkyl group, substituted alkyl group, carboxyl group or salt thereof, -COOR
3 groups (R3 has the same meaning as above), no-rogen atom, hydroxyl group or its salt, cyano group, carbamoyl group, m represents Q, /, J, n represents "% '%, R6 and R7 may be the same They may also be different, and R8H represents a hydrogen atom, an alkyl group, a substituted alkyl group, a 7-enyl group, a substituted phenyl group, and R8H represents an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, and R9 is an alkyl group or a substituted phenyl group. ?″i substituted alkyl fund representation Rl
oXRll, R12, R13'd, rL) hydrogen atom, alkyl group, substituted alkyl group,
Halogen atom, cyanide foundation, R14 is hydrogen atom,
Alkyl group...Represents Rogen Atsuko, R15 represents all alkenyl groups, R16 represents a hydrogen atom, an alkyl group, or a substituted alkyl group, R and 7 are an alkyl group or a substituted alkyl group'f = eagle, R18 is a hydrogen atom, All alkyl group, alkenyl group, R19, R20 may be the same or different, hydrogen atom, alkyl group, R21'rl alkylene group, substituted alkylene group, 1,000 CH
2+xO-1-+-Cl:++, 0-)-f-CH2+
-g (x, ylwlv respectively represent no or l) represents metal (R6 has the same meaning as above), q represents O or l sound quality 1 When Q = 0, R21-N forms a pyridine ring R22, R23, R24n are the same, or R26 represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and Ll and R2 may be the same or different -O--
S--〇oc--co-, represents a phenylene group, r represents O or / (synonymous), -0OC-, R27 represents a hydrogen atom, an alkyl group, a substituted alkyl group, t is 3 or a , C28 represents a carbon atom, -CH-1 or a heterocycle, R4 is replaced with -ooc--co-, R5 is -Co-R1□ (R17 is the same as above), (-
COOR171R17 has the same meaning as above), cyan group, -5
02-R17 (R17 has the same meaning as above), R29
represents a hydrogen atom, -Co-R17 (R17 has the same meaning as above) represents gold, R6 represents -NHCNHC- -N- (R16 has the same meaning as above), R7 represents an oxygen atom or a nitrogen atom, and R30 represents It represents an alkylene group or a triazole ring, and A represents a halogen atom or an amino group; however, when R3° is a triazole ring, A may represent all of a plurality of halogen atoms.

R31 and R32 may be opposite or different; a hydrogen atom, an alkyl group, a substituted alkyl group, a hydroxyl group and a salt thereof;
It represents an amine group, a carboxyl group, a salt thereof, or a cyan group, and Z is bonded to N to represent a complete heterocyclic element having 3 to 3 carbon atoms.

Specific examples of the monomer n represented by the monomer formula [P-1) include those in the table below.

- Specific examples of monomers represented by the formula (P-■) include the following: ○0H P-α m-α P-SO2CH3 0-3O3C2H5 -CH5 SO3N a SO2K m-CH20CCH3 Specific examples of the monomer represented by the general formula (P-111) include the following.

-Specific monomer of n represented by the property (P-■) -The character formula (
Specific examples of P-■) include the following.

I'll give it to you.

M- from CH2CH2=CH-3-CH2CH2CH2SCH3
゜CH2=CH-3-CH2SCH3 - Specific examples of the role formula (P-■) include the following n
Ru.

M-1,l CH2=CHCN CH2CH2=CQ! z Specific examples of the general formula (P-■) include the following:

General formula (p-v ) are as follows: M-4≠ CH2=CHCH=CH2 I'll give it to you.

CH2=CH ○CH3 M-t. CH2=CHCHCH=CHCH=CH2-jtr CH2=CH-OC4Hq(n) Specific examples of (P-■) include the following.

-Ay CH2=CHCOCH3 CH3 Specific examples of (P-X) include the following.

Specific examples of (P-XI) include the following.

Specific examples of (P-kari) include the following.

-7F fart Coo/\/ death (P-XIV) The following are specific examples: Agency 0CH2CH20 Ran.

(P-XIII The following are specific examples: Ran.

M-Takoichi 23 C4H9(t) CH2=CH Co0CH2CH2NHCNHCH2CH2CH2αM
Specific examples of -ta0 CH2=CH \ (P-XV) include the following.

(P-X■) The following are specific examples: (P-X■) The following are specific examples: Ran.

Ran.

126 M-1o.

CH2=CH M-7O/ CH2=CH vinegar CH2=CH (P-X■) The following are specific examples: Ran.

Furthermore, regarding polymer latex, U.S. Pat.
．． RifA, r77, same! ,j/l,! No. 30, Jin] 3
1j33+723, R, D, /rt Hiroori, 3,1,
No. 36, 7/3, No. 3,327゜71g, No. 3.6μ
7. ≠! ri No. 3,607, λri No. 0, Mukai 3,672
．． ri gj issue, same 3゜j3I! l, ≠ri No. 7, same 3.7t
No. 9,020, 3.7 Otsuhiro, No. 327, 2.37
t, No. 006, 2.7AI, C#0, 2.77
．． 2, / 4 Otsu No. 2,101.3♂, Mukai 2
, 13! , Jr, No. 2, same j, Ijt2.3rA
No., Mukai, 2, 163.

Guj No. 7, same co, Itj, 7yo No. 3, British patent tube 1.3
! I, No. 116, I/, /It, & Tata No.,
U.S. Patent No. 3. 2. T! ; No. 3, same 3. Hiro //.

No. 777, 3. ≠//, ri/, No. 2, No. 3. Hiro? ,
790, fB33.1711.701, 43.

700, Hiroshi! 3. Ri3ri, No. 730, same J,
jolt, 91'7, 3,607, 1rt1
No. J, 608', 926, British patent cylinder 1, 3
/l.

! ≠/No., same/, 33t, No. 061, British patent tube 1.4
No. 91,701, British Patent No. 1,498゜697, R
D14739, U.S. Patent No. 3,620.751, RD
15638, U.S. Patent No. 3,635.715, British Patent No. 1,401,768, U.S. Patent No. 3,967.9
No. 66, No. 3゜142.568, No. 3,252,80
No. 1, No. 3,625,689, No. 3,632,342
No. 2,887,380, British Patent No. 1.623゜522, U.S. Patent No. 2,721,801, No. 2.8
No. 75.054, No. 3,021,214, RD119
06, U.S. Patent No. 3,793,029, RD1523
5. The description of RD16250 can be referred to.

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 ultra-high contrast sensitive materials containing hydrazine derivatives.

Regarding ultra-high contrast sensitive materials containing such hydrazine derivatives and image forming methods using the same, US Pat. No. 4,224,4
No. 01, No. 4,168,977, No. 4,166.7
No. 42, No. 4,241.164, No. 4,272.6
No. 06, JP 60-83028, JP 60-2186
No. 42, No. 60-258537, No. 61-22373
It is described in No. 13, etc.

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

General formula (Q) A'-N-N-B' Y In the formula, A# represents an aliphatic group or an aromatic group, and 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 sulfaniyl group or a heterocyclic group. In the formula, both X and Y represent a hydrogen atom, one 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 (α) are shown below.

C11 O-2) Q-5) Q-7) Q-8) Furthermore, the present invention provides a method for processing a photosensitive material containing a tetrazolium compound in a PQ type or MQ type developer containing a relatively high concentration of a sub-@ oligosalt. This effect can also be achieved in a method of obtaining high contrast through processing. Image forming methods using tetrazolium compounds are described in Jikai No. 52-18317, Jikai No. 53-17719, Jikai No. 53-17720, and the like.

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

As the silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used, and there are no particular limitations on the grain form and size distribution.

The silver halide emulsion layer contains photosensitive silver halide, chemical thickeners, spectral worsening agents, antifoggants, hydrophilic colloids (especially gelatin), gelatin hardeners, film physical property improvers such as surfactants, and thickeners. It can contain agents, etc. Regarding these, please refer to Research Disclosure magazine, Vol. 176, Section 17643 (December 1978), and Japanese Patent Application Laid-open No. 52-108130, No. 52-114328, No. 5
No. 2-121321, No. 53-3217, No. 53-4
The description in the specification of No. 4025 can be referred to.

The surface protective layer is a layer with a thickness of 0.3 to 3 μm, particularly 0.5 to 1.5 μm, containing a hydrophilic colloid such as gelatin as a binder, and contains a matting agent such as fine particles of polymethyl methacrylate, It contains colloidal silica and, if necessary, a thickener such as potassium polystyrene sulfonate, a gelatin hardening agent, a surfactant, a slip agent, a UV absorber, and the like.

Examples of gelatin hardening agents include chromium salts, aldehydes (formaldehyde, glitaraldehyde, etc.),
N-methylol compounds (dimethylol urea, etc.), active vinyl compounds (1,3゜5-triacryloyl-hexahydro-3-toIJ azine, bis(vinylsulfonyl) methyl ether, N N'-methylenebis-[β-
(vinylsulfonyl)propionamide], active halogen compounds (2,4-dichloro-6-hydroxy-
S-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1
-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salt in-(+-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A No. 53-41220, No. 53-57257, No. 59-162546, No. 60-8
0846 and U.S. Pat.
325,287 are preferred.

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 including an intermediate layer, a protective layer, etc.

The thickness of the back layer is 0.1μ to 10μ, and if necessary, it contains a gelatin hardener, a surfactant, a matting agent, a colloidal silica, a slip agent, and a UV ray as well as a silver halide emulsion layer and a surface protective layer. It may contain absorbents, dyes, thickeners, etc.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically photographic materials using silver halide as a photosensitive component, such as photosensitive materials for printing and photosensitive materials for X-ray. , -IG negative photosensitive materials, general reversal photosensitive materials, general positive photosensitive materials, direct positive photosensitive materials, etc. The effects of the present invention are particularly remarkable in photosensitive materials for printing.

There are no particular limitations on the exposure method, development method, etc. of the photosensitive material of the present invention;
No. 52-114328, No. 52-121321, etc., and the descriptions in the above-mentioned Research Disclosure magazine can be referred to.

(Specific Effects of the Invention) According to the present invention, a polyester support has a hydrophilic colloid containing polymer latex on at least one side, and both sides of the support are made of vinylidene chloride having a thickness of 0.3μ or more. By coating with a copolymer layer, it is possible to obtain a silver halide photographic material that has excellent dimensional stability due to environmental changes and dimensional stability due to processing.

In addition, due to the presence of a monomer in the vinylidene chloride copolymer that has a group that binds directly to the binder or through a hardening agent, the vinylidene chloride copolymer layer and the support as well as the vinylidene chloride copolymer layer and the adjacent binder layer are bonded to each other. A silver halide photographic material having excellent adhesive properties, especially the latter adhesive property, can be obtained.

Example-1 Four semicircular rod electrodes with a length of 40 cm and a diameter of 3 (Jl) were fixed on an insulating plate at 10 clI intervals. This electrode plate was fixed in a vacuum tank, and from this electrode surface A biaxially stretched polyethylene terephthalate film with a thickness of 100 μ and a width of 30 cm was placed on a rod 15 cm apart and directly facing the electrode surface.
I ran it at a speed of 1 minute. Immediately before the film passed over the electrode, a heating roll with a temperature controller having a diameter of 50 CIm was set at 100° C., and the heating roll was arranged so that the film was in contact with the film for 3/4 of a turn. Glow discharge brings the inside of the tank to 0.
This was carried out by applying a voltage of 2000 V to the electrodes while maintaining the ITorr. At this time, the electrode current is 0.
It was 58. At this time, the PET support is 0.125K
This means that the processing amount is VA min/m'. In this way, on top of the glow discharge treated polyethylene terephthalate, the vinylidene chloride shown in Table 1 was further applied as a second undercoat layer on the undercoat 1N made of this vinylidene chloride copolymer. 'l Q d /
It was coated on both sides to give a weight of 1.5 g and dried at 170°C.

Next, a silver halogenide emulsion layer of the following formulation (2) was coated on one side of the support, and an emulsion protective layer of the following formulation (3) was further coated thereon. On the opposite side, in order from the support side, a back layer of the following formulation (4) and a hack protective layer of the following formulation (5) were applied, giving samples 1 to 7. Sample 8 was primed directly onto the glow discharge treated polyethylene terephthalate.

(1) Prescription gelatin for second layer of undercoat 1.0 parts by weight Epichlorohydrin of polyamide made of diethylenetriamine and adipic acid 0.07 parts by weight Saponin
Add 0.01 parts by weight of water
100 parts by weight (2) Silver halide emulsion layer formulation 2X per mole of silver in an aqueous gelatin solution kept at 50°C.
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-' moles of rhodium chloride to obtain an average particle size of 0.2.
A silver chlorobromide monodisperse emulsion of μ was prepared. ((:2 composition 95
(mol%) This emulsion was desalted by the flocculage run method, lag of thiourea dioxide and 0.6 μg of chloroauric acid per mole of silver were added, and the emulsion was aged at 65°C until the highest performance was obtained. It caused a fog.

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

n-C+zHzs 2X10-'' mol/Ag1 mol lXl0-3 mol/Ag1 mol 4X10-' mol/Ag1 mol Br Polystyrene sulfonic acid sodium salt 2.6-dichloro-6-hydride 20 ■/d 40 ■/Ifxy 1.3 .5-triazine sodium salt 30 %/% This coating solution was coated to give a coated silver amount of 3.5 g/n.

(3) Emulsion protective layer formulation gelatin 1.5g/Sing-resistant fine particles (average particle size 4μ) 50mg/m dodecylbenzenesulfonic acid sodium salt 50μ/mH (average particle size 0.1μ) Bank layer formulation gelatin 300μ/m d 2゜5g/m 5-nitroindazole 13-divinylsulfonyl 2-propatol N-perfluorophthanesulfonyl-N-probylglycinepotadium salt ethyl acrylate tratic 15■/m 50■/, (2■/M SO: +40■/Bow/m 1.3-Divinylsulfonyl-2-propateurethyl acrylate latix (average particle size 0.1μ) Dihexyl α-sulfosacnate sodium salt 150■/, 1900■ /M 35■/1 Sodium dodecylbenzenesulfonate salt 35■/Resistance (5) Back protective layer prescription gelatin 0.8g/Resistant polymethyl methacrylate fine particles (average particle size 3μ) 20■/d Sodium dihexyl-α-sulfosacnate Salt 10■/M Dodecylbenzenesulfonic acid sodium salt 10■/m + Sodium acetate 40■/Resistant sample at 25℃50
After being left in an atmosphere of %RH for two weeks, dimensional changes due to development were measured using the following method.

(6) Evaluation method for dimensional changes due to development processing
Drill two holes with a diameter of 8N at a distance from each other and heat at 25℃30.
After being left in a room with %RH for 2 hours, the distance between the two holes was accurately measured using a bottle gauge with an accuracy of 1/1000n. The length at this time is defined as Xfl. Then, after developing, fixing, washing, and drying using an automatic developing machine, the dimension after 5 minutes is defined as Y. In the industry, it is considered that there is no practical problem if the dimensional change rate (%) due to treatment is ±0.01% or less.

The processing was done using Fuji Photo Film Co., Ltd.'s FC-660 automatic processor, and the developer and fixer were GRD-1 and GRF made by the same company.
-1 under the treatment conditions of 38° C. for 20 seconds.

The drying temperature at that time was 45°C.

Adhesion tests were conducted on samples 1 to 8. The adhesion here refers to the adhesion between the support and the emulsion layer and back layer, and the test method is as follows.

1. Adhesion test method for dry film On the emulsion surface to be tested, make 36 squares by making 7 cuts at 51 intervals vertically and horizontally. Attach the knit tape) and quickly peel it off in the 180＠ direction. In this method, if the unpeeled portion is 90% or more, it is graded A, if it is 60% or more, it is graded B, and if it is less than 60%, it is graded 0. Adhesive strength sufficient for practical use as a photographic material is one that is classified as grade A of the above three-level evaluation.

2. Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the emulsion side of the film in the processing solution at the X mark using a steel pen, and then rub it strongly with the tip of your finger 5 times to make the X line. The adhesive strength is evaluated during the maximum peeling.

If the emulsion layer does not peel off after scratching, it is graded A, if the maximum peeling is within 511, it is graded B, and in other cases it is graded 0.

Adhesive strength sufficient for practical use as a photographic material is one classified as B or higher, preferably grade A, of the above three-level evaluation.

3. Shear stability of the polymer The shear stability of the polymer was evaluated using a Colon type measuring device. 100 cc of a 15% by weight dispersion of polymer
After the test was carried out for 10 minutes while applying a load of 10 kg, the aggregates generated were collected and dried, and the weight of the aggregates was measured. The shear stability was judged to be good if the weight of the aggregate was 5 cm or less.

4. The undercoated support before coating with the planar silver halide photographic emulsion of the vinylidene chloride-containing copolymer coating film was immersed in a 1% aqueous solution of brilliant blue to be dyed, and the degree of dyeing was visually evaluated.

Example 2 Polyethylene terephthalate to be subjected to glow discharge treatment similar to Example 1 was coated with an aqueous dispersion of vinylidene chloride copolymer shown in Table 2 on both sides and dried at 120°C.

Furthermore, a second undercoat similar to that in Example 1 was applied on both sides and dried at 150°C.

Next, on one side of the support, (1) a silver halide emulsion layer and (2) an emulsion protective layer of the following formulation are coated, and on the opposite side, (3) a bank layer of the following formulation is applied in order from the support side. ,(4)
A back FM preservation layer was applied to prepare samples 1 to 5.

(1) Silver halide emulsion layer prescription below! Emulsion A was prepared by the following method using solutions , (1) and (2).

Solution I: 300 d of water, 9 g of gelatin Solution ■: 100 g of AgN0*, 400-111? (I
;NaC1!37g, (NH4)! Rh(/!60.6
6.) Solution] and Solution 2 were simultaneously added at a constant rate into Solution 6, which was kept at 400°C to 40°C. After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin was added and stabilizers such as 6-methyl-4-hydroxy-1,3,3a, 7-titraazaindene and 4-hydroxy -5,6-drimethylene-1.33a,7-titraazaindene was added. This emulsion was a monodispersed emulsion with an average grain size of 0.15 μm, and the amount of gelatin contained per 1 kg of emulsion yield was 60 g.

The following compounds were added to the emulsion thus obtained.

OJa Polystyrene sulfonic acid sodium salt 1.2-bis(vinylsulfonylacetamide)ethaneethyl acrylate dry 10/Poly 100/M (average particle size 0.1μ) 500/d0, 3/
M The coating liquid thus obtained was coated to a coating weight of 51 ml and 13 g.

(2) Emulsion protective layer formulation gelatin 1.5 g/polymethyl methacrylate resistant fine particles (average particle size 3 μ) 50 μ/g sodium salt N-perfluorophthanesulfonyl-N-propylglycine bokdium salt polystyrene sulfonate sodium salt Ethyl acrylate latix (average particle size 0.1μ) Colloidal silicalipoic acid (3) Back layer prescription gelatin 10 / d 2 / , 1 3 / d 200IIv / n ( 350 / 11 ( 8 / 2g / Resistance to S (1+Na Dodecylbenzenesulfonic acid sodium salt dihexyl-α-sulfosacnate 25 μ/d 30 ov/% SO3 to S03 Dihexyl-α-sulfosacnate sodium salt Dodecylbenzenesulfonate sodium polystyrene sulfonate sodium salt 180 μ/m 50 tt/m 20■/d 30■/d 30tt/rd 1.3-divinylsulfonyl-2-propanol 100 units/d Ethyl acrylate latex (average particle size 0.1μ) 200■71 (4) Back protective layer prescription gelatin 1 g/rd polymethyl methacrylate fine particles (average particle size 3μ) 40■/dihexyl sulfosacnate sodium salt 10■/rd dodecylbenzenesulfonic acid sodium salt 30■/d polystyrene sulfonate sodium salt 25■/sodium polyacetate 30IIW/ Example 3 Polysol di-2,6-dichloro-6- manufactured by Showa Kobunshi Co., Ltd.
A solution containing hydroxy-t,3.5-triazine sodium salt at 3% based on the weight of the polymer was coated on both sides with a dry film thickness of 0.
．． It was coated to a thickness of 3 .mu.m and dried at 150"C. On top of that, an aqueous dispersion of vinylidene chloride copolymer for the first layer of undercoat shown in Table 3 was coated on both sides and dried at 120"C.

Furthermore, a second undercoat layer similar to that in Example 1 was applied on both sides and dried at 170°C. Next, the following silver halide emulsions N1 and 2 were placed on one side of the support in order from the support side.
, protective layers 1 and 2 were applied and dried. Next, a back layer and a protective layer 3 were applied to the opposite side and dried.
．． I got 7-9. In addition, without using polysol, on polyethylene terephthalate treated with glow discharge, the same undercoat tube 1, second layer, silver halide emulsion layer 1.2, and a preservative a! Samples 4 to 6 were obtained by applying the i-layer 1.2 and the back layer and protective layer 3 on the opposite side.

(1) Silver halide emulsion Fil formulation solution I; 300 d of water, 9 g of gelatin; Solution (2); AgN0+ 100 g - 400 d of water;
NaCj237g, (NH4)s RhCebl, 1■
, water 400d kept at 45°C! Solution (2) and Solution A were simultaneously added to the solution at a constant rate. After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin was added and 6-methyl-4-hydroxy-1,3,3a was added as a stabilizer.
? - Tetraazaindene was added. This emulsion was a monodispersed emulsion with an average grain size of 0.20 μm, and the amount of gelatin contained per 1 kg of emulsion yield was 60 g.

The following compounds were added to the emulsion thus obtained.

5 X 10-3 mol/^g1 mol (compound-portion) Polystyrene sulfonic acid sodium salt N-oleoyl-N-methyltaurine sodium salt 1.2-bis(vinylsulfonylacetamido)ethane 1-phenyl-5-methikabuto Chitrazole 40mg/po 50mg/nia 0mg/bo 3tng/lag Ethyl acrylate tratics (average particle size 0.1μ) 40cm/lag The coating solution thus obtained was coated to give a coated silver i of 12g/rrf.

(2) Silver halide emulsion N2 formulation I solution; water 300m, gelatin 9g solution ■; AgN0z 100g, water 400d11 IB solution;
NaCj! 37g, (NHff)RhCfi&2.
Emulsion B was prepared in the same manner as Emulsion A, using Solution IIIB instead of Solution IIA. This emulsion has an average grain size of 0.
It was a 20μ monodisperse emulsion.

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

Compound Q-85XlO-3 mol/Ag1 mol -i
60mg/boro
9■/ivorystyrenesulfonic acid sodium salt 50■/BoN-oleoyl-N-methyltaurine sodium salt 40■/nfl, 2
-Bis(vinylsulfonylacetamido)ethane 85 +ng/ +d
3 mg of l-phenyl-5-mercaptotitrazole/40 mg of boethyl acrylate latex (average particle size: 0.1 .mu.m) The coating solution thus obtained was coated at a coating weight of 12 g of silver/polymer.

(3) Protective layer 1 prescription gelatin 1.0g/bolipoic acid
5 mg/n (dodecylbenzenesulfonic acid sodium salt 5 mg/po20
/Polystyrenesulfonic acid sodium salt 10mg/n ((Compound-2) 20■/Ethyl acrylate latix (average particle size 0.1μ) (4) Protective layer 2 prescription gelatin 200/Bo 1.0g/Polymethyl Mekkuri Rate fine particles (average particle size 3μ) 60■/m' Dodecylbenzenesulfonic acid sodium salt 20■/, dN-perfluorophthanesulfonyl-N-propylglycine potassium salt 3yt/m Poly (degree of polymerization 5) oxyethylene nonylphenol Ethyl sulfate ester sodium trilam salt 15IIN/m polystyrene sulfonate sodium salt 2mg/rd (5)
Back layer prescription gelatin 2. 5g/rr+U
Go h SO3 50ov/m 50■/sodium idodecylbenzenesulfonate dihexyl-alpha-sulfosacnate sodium salt polystyrenesulfonic acid sodium salt 50■/r+(20n/1ri 40■/d 1.3-divinylsulfonyl-2 -Propatool 150■/d Ethyl acrylate latex 7x (average particle size 0.1μ) 500w/n?
(6) Protective N3 formulation (protective layer for grasshopper wear) gelatin
Ig/m polymethyl methacrylate particles (average particle size 3 μ) 40 / r + (dodecylbenzenesulfonic acid sodium salt 15 / idihexyl α-sulfosacnate sodium salt 10 / M polystyrene sulfonate sodium salt 20 / m acetic acid Sodium 40ag/n?f Threshold, Samples 4 to G using the compounds of the present invention have better adhesion than Samples 7 to 9 using comparative compounds even if the thickness of the first undercoat layer is the same.However, Even when the compound of the present invention is used, when the thickness of the first undercoat layer becomes thicker, although it is practically satisfactory, the adhesion tends to be poor (Sample-6). It can be seen that the adhesion is improved when polysol is provided between the layers. (Sample 3) Patent applicant: Fuji Photo Film Co., Ltd. Target of amendment: "Detailed description of the invention" section of the specification Description of the Hisji case 1988 Patent Application No. 77≠62r Name of the invention Relationship with the case concerning persons who correct silver halide photographic light-sensitive materials

Claims (1)

[Scope of Claims] 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 is coated with a vinylidene chloride copolymer layer. is,
The vinylidene chloride copolymer is made of a core-shell type latex, and the core has at least one type of repeating unit represented by the following general formulas (I) and (II), and the shell has a repeating unit represented by the following general formula (I). ), (III) and (IV), each of which contains at least one type of repeating unit. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( 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 phenyl group, A^3 represents a hydrogen atom or a methyl group, A^4 represents a hydrogen atom, methyl group or -CH_2COOM group, A^5 represents a hydrogen atom, methyl group or -COOM group,
A^6 represents a -COOM group or an alkoxycarbonyl group substituted with a -COOM group, a phenyl group or an N-alkylcarbamoyl group, and M represents a hydrogen atom or an alkali metal atom. ]