JP2670864B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, particularly, an excellent dimensional stability and adhesion between a support and a photographic layer coated thereon under a high humidity atmosphere. Relates to an improved silver halide photographic light-sensitive material.

(Prior art and its problems) In general, a silver halide photographic material has a photographic layer using a hydrophilic colloid as a binder. It has the disadvantage of causing dimensional changes. This dimensional change of the silver halide photographic light-sensitive material is a very serious disadvantage in the silver halide photographic light-sensitive material for printing which requires reproduction of halftone images and precise line drawings for multicolor printing. Become.

Conventionally, various means have been known for improving the dimensional stability of a silver halide photographic light-sensitive material.

For example, in U.S. Pat.No. 3,201250, a technique for defining the thickness ratio of a hydrophilic colloid layer and a support, Japanese Patent Publication No. 394-272,
39-17702, 43-13482, 45-5331, U.S. Pat.No. 237600, 2763625, 2772166, 2852386.
No. 2853457, 3397988, 3411911, 34119
Japanese Patent Publication No. 12 describes a method in which a polymer latex is added to a hydrophilic colloid photographic layer.

Certainly, by using these techniques, the dimensional stability of the silver halide photographic light-sensitive material due to changes in temperature and humidity can be improved.

However, these techniques cannot prevent a dimensional change due to the development processing of a silver halide photographic light-sensitive material. The phenomenon of dimensional change due to the development processing is that the elongation of the silver halide photographic material due to water absorption of the support during the development processing,
Even after a drying step, the silver halide photographic light-sensitive material does not recover by the time of use, and as a result, the dimensions of the silver halide photographic light-sensitive material differ before and after development processing.

In the art, this phenomenon is described as "poor dimensional stability upon processing", which is a very serious drawback especially in silver halide photographic light-sensitive materials for printing.

To improve the dimensional stability associated with this treatment, a technique using an undercoat layer containing a vinylidene chloride copolymer is disclosed in Japanese Patent Application No.
62-94133.

However, this method does have a drawback that the dimensional stability associated with the treatment is improved, but the adhesion between the support and the undercoat layer is not sufficient. It is necessary to add a swelling agent for the support and to perform strong pretreatment such as glow discharge treatment on the surface of the support in advance.

When a polyester support is used, examples of the swelling agent include phenol, resorcin, o-cresol, m-cresol, trichloroacetic acid, dichloroacetic acid, monochlorocreacetic acid, chloral hydrate, benzyl alcohol and the like. The thing is resorcin.

However, resorcin has the disadvantage that it often causes spot failures in the manufacturing process.

In addition, the glow discharge treatment was performed using a polyester support at 1 Torr.
Processing must be performed in a vacuum of a certain degree, which is complicated and disadvantageous in terms of manufacturing cost.

Further, JP-A-63-122537 discloses a technique of providing a polyester film with a primer layer of an aqueous melamine compound, an aqueous epoxy compound, an aqueous aziridine compound or a vinylidene resin crosslinked with a polyvalent metal.

However, in this method, sufficient adhesion between the silver halide photographic emulsion layer and the polyester support, particularly in the wet state, cannot be obtained, or the dimensional stability is improved by developing the silver halide photographic light-sensitive material. It had a drawback of impairing the effect.

Therefore, a technique for improving the adhesion between the polyester support and the silver halide photographic emulsion layer, which does not have the above-mentioned drawbacks, has been desired.

(Object of the Invention) It is an object of the present invention to provide a silver halide photographic material having improved dimensional stability upon processing. A second object of the present invention is to halogenate a polyester swelling agent such as resorcin, a halogenated layer having improved adhesion between a polyester support and a vinylidene chloride subbing layer without using a complicated pretreatment such as glow discharge treatment. It is to provide a silver photographic sensitizer.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having sufficient adhesion between a polyester support and a vinylidene chloride undercoat layer even when exposed to a high humidity atmosphere for a long time. is there.

(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 a polymer latex on at least one side of a polyester support,
The polyester support comprises a vinylidene chloride copolymer comprising at least 70-99.9% by weight of vinylidene chloride monomer and 0.1-5% by weight of vinyl monomer having one or more carboxyl groups. A silver halide photographic light-sensitive material having the above-mentioned undercoat layer, wherein the undercoat layer contains a compound represented by the following general formula I or II. (In the formula, R ¹ , R ² , R ³ and R ⁴ are chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -OH group (M
Represents a monovalent metal atom. ), -NR'R "group, -NHCO
R groups (R ', R ", and R each represent a hydrogen atom, an alkyl group, or an aryl group), and may be the same or different. Q ¹ and Q ² are each-
It represents an O-, -S-, or -NH- linking group, and L represents an alkylene group, an arylene group, or a divalent linking group obtained by combining them. l and m are 0 or 1 respectively
It is.

Achieved by the silver halide photographic light-sensitive material according to claim 1, which contains colloidal silica in the undercoat layer.

(Specific Structure of the Invention) First, the vinylidene chloride copolymer of the present invention will be described. The vinylidene chloride copolymer of the present invention contains 70 to 99.9% by weight, more preferably 85 to 99% by weight of vinylidene chloride. Acrylonitrile as an example of these monomers,
Methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, methyl acrylamide, methyl methacrylamide, methyl vinyl ether, styrene, etc. it can. These monomers may be used alone or in combination of two or more kinds.

Examples of vinyl monomers having one or more carboxyl groups used in the vinylidene chloride copolymer of the present invention include acrylic acid, methacrylic acid, itaconic acid, citraconic acid and the like.

The vinylidene chloride copolymer of the present invention is preferably an aqueous dispersion of latex.

In this case, a so-called core shell type latex having different structures of the core portion and the shell portion of the latex particles may be used in addition to the ordinary latex having a uniform structure.

Specific examples of the vinylidene chloride copolymer used in the present invention include the following. Numbers in parentheses indicate% by weight.

V-1 Vinylidene chloride: Acrylic acid: Methyl acrylate (90: 1: 9) V-2 Vinylidene chloride: Acrylic acid: Methyl methacrylate (90: 1: 9) V-3 Vinylidene chloride: Methacrylic acid: Methyl methacrylate (90: 0.5: 9.5) V-4 Vinylidene chloride: Methacrylic acid: Ethyl acrylate: Methyl methacrylate (90: 0.5: 5: 4.5) V-5 Vinylidene chloride: Acrylic acid: Methyl acrylate: Methyl methacrylate (90: 0.5: 5: 4.5) V-6 Vinylidene chloride: Acrylic acid: Methyl methacrylate: Acrylonitrile (90: 0.3: 8: 1.7) V-7 Vinylidene chloride: Methacrylic acid: Methyl methacrylate: Methacrylonitrile (80: 3: 10: 7) V-8 Chloride Vinylidene: Acrylic acid: Methyl acrylate: Glycidyl methacrylate (90: 0.3: 6.7: 3) V-9 Vinylidene chloride: Methacryl : Methyl methacrylate: 2-hydroxyethyl methacrylate (90: 0.
5: 5.5: 4) V-10 Vinylidene chloride: Methacrylic acid: Methyl methacrylate: Butyl methacrylate: Acrylonitrile (75: 5: 10: 5: 5) V-11 Vinylidene chloride: Acrylic acid: Methyl acrylate: Ethyl acrylate: Acrylonitrile ( 90: 0.
3: 3: 3: 3.7) V-12 vinylidene chloride: methacrylic acid: methyl acrylate: methyl methacrylate: methacrylonitrile (80: 5: 5: 5: 5) V-13 vinylidene chloride: methacrylic acid: methyl acrylate: methyl Methacrylate: Acrylonitrile (9
V-14 vinylidene chloride: acrylic acid: methyl acrylate: methyl methacrylate: acrylonitrile (90: 0.3: 4: 4: 1.7) V-15 vinylidene chloride: methacrylic acid: methyl methacrylate: glycidyl Methacrylate: acrylonitrile (90: 0.5: 3.5: 3: 3) V-16 (core shell type latex aqueous dispersion: 90% by weight of core, 10% by weight of shell) Core: vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile : Acrylic acid (93:
3: 3: 0.9: 0.1) Shell part Vinylidene chloride: Methyl acrylate: Methyl methacrylate: Acrylonitrile: Acrylic acid (9
0: 3: 3: 2: 2) Next, the compound represented by formula I or II used in the present invention will be described.

R ¹ , R ^{2 of} the compounds represented by the general formula I and the general formula II,
Examples of the alkyl group represented by R ³ and R ⁴ include a methyl group,
Examples thereof include an ethyl group and a butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. The -NR'R "-NH ₂ group Specific examples of the groups, -NHCH ₃ group, -
Specific examples of the -NHCOR group such as NHC ₂ H ₅ group include -NHCOCH.
₃ group, -NHCOC ₆ H ₅ group, and the like. Furthermore, R ¹ , R ² ,
M of the —OM group of R ³ and R ⁴ is, for example, a sodium atom or a potassium atom.

R ¹ is preferably a chlorine atom. R ² , R ³ and R ⁴ are preferably an alkoxy group, an —OM group and a —NR′R ″ group, particularly preferably an —OM group. R ² , R ³ and R ⁴ are an alkoxy group or —NR′R ″.
In the case of a group, R ² , R ³ and R ⁴ may be substituted, and examples of the substituent include a sulfo group and a salt thereof, a carboxyl group and a salt thereof, an alkoxy group and the like.

Examples of the divalent group represented by L of the compound represented by the general formula II include —CH ₂ —, CH _{2 2} , CH _{2 3} and C.
H _{2 2} OCH _{2 2} , (Any of o-, m-, p- is possible), (Any of o-, m-, and p- is acceptable) and the like. L
Is preferably an alkylene group. Q ¹ and Q ² are preferably —O— and —NH—, and both 1 and m are preferably 1.

For compounds of general formula I see US Pat.
No. 743, Japanese Patent Publication No. 47-6151, No. 47-33380, No. 51-9607
No. 48, 19220, 51-78788, 52-60612
No. 52-128130, No. 52-130326, No. 56-1043, etc., the compound represented by the general formula II, Canadian Patent 89
5,808, JP-B-58-33542, JP-A-57-40244 and the like describe the synthesis method and the like.

Typical examples of the compounds represented by formula I or II are shown below, but the invention is not limited to these.

The compounds represented by formula I or II of the present invention may be used alone or in combination of two or more kinds.

The addition amount of the compound represented by the compound 1 or II of the present invention is preferably 0.1 to 10% by weight of the vinylidene chloride copolymer.

It is preferable to add a koirodo-like silica to the undercoat layer of the present invention because the adhesion between the support and the undercoat layer is significantly improved. In particular, the adhesiveness is improved when the silver halide photographic light-sensitive material is left for a long time in a high humidity atmosphere.

The coiled silica used in the present invention has an average particle size of 7 m.
μ to 120 mμ, the main component is silicon dioxide, and may include alumina or sodium aluminate as a minor component. Further, these colloidal silica may contain, as a stabilizer, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia, or an organic base such as tetramethylammonium ion. For these colloidal silica, for example, Egon Matijevic ′
Ed., Surface and Colloid Science, Volume 6, pp. 3-100 (1973, John Wiley & Sons).

EI du Pont is a concrete example of colloidal silica.
de Nemours & Co. (USA) from Ludox AM, Ludox AS, Ludox
Nissan Chemical (Japan, under the trade name of LS, Ludox TM, Ludox HS, etc.
From Tokyo), product names such as Snowtex 20, Snowtex C, Snowtex N, Snowtex O, Snowtex S, Snowtex SS, Snowtex XS, Snowtex ZL, and Snowtex YL are available from Monsanto Co.
(USA) with trade names such as Syton C-30, Syton 200, and Nalco Chem, Co. (USA) with Nalcoag 1030, Nalcoag.
Examples thereof include those marketed under the trade name of 1060, Nalcoag ID-21-64.

The preferred amount of colloidal silica used in the present invention is 0.1 in terms of dry weight with respect to the vinylidene chloride copolymer.
% To 10%, particularly preferably 1% to 5%.

The thickness of the undercoat layer of the present invention is preferably 0.3 μm or more and 5 μm or less, and more preferably 0.4 to 1.5 μm.

In the undercoat layer of the present invention, in addition to the vinylidene chloride copolymer and the compound represented by the general formula I or II, if necessary, a matting agent, a surfactant, an acid or alkali for pH adjustment,
A dye or the like may be added.

There is no limitation on the means for forming the undercoat layer of the present invention,
Preferred is a method in which an aqueous coating solution containing an aqueous dispersion of a vinylidene chloride copolymer, a compound represented by the general formula I or II, etc. is coated on a polyester support by a known method and dried.

In this case, as a method of applying the aqueous coating solution to the polyester support, an air knife coater, a bar coater,
A known method such as a roll coater can be used.

At the time of coating, the aqueous coating solution may be cooled to 5 to 15 ° C if necessary.

When the undercoat layer of the present invention is formed by coating and drying the aqueous coating solution, the drying is preferably performed in the range of 80 ° C to 190 ° C for 20 seconds to 5 minutes.

The polyester used in the support of the present invention is an aromatic dibasic acid and a polyester containing glycol as a main component. Typical dibasic acids are terephthalic acid, isophthalic acid and p-β-oxyethoxybenzoic acid. , Diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenylenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like. Is 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.

Of 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.

Before applying the first undercoat layer, the polyester support of the present invention may be subjected to a pretreatment such as a corona discharge treatment on the surface of the support.

However, in the present invention, a complicated process such as a glow discharge process for performing the process in a vacuum and a chromium mixed acid process which is greatly restricted in preventing pollution is not required.

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, oxygen-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 carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alkynate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N- Vinylpyrrolidone polyacrylic acid copolymer, polyacrylamide or their derivatives and partial hydrolysates can be used. If desired, mixtures of two or more of these colloids can be used.

The polymer latex used in the present invention has an average particle size.
20mμ ~ 200mμ aqueous dispersion of water-insoluble polymer, the preferred amount is gelatin used as a binder
The dry weight ratio with respect to 1.0 is preferably 0.01 to 1.0, and particularly preferably 0.1.
1 to 0.8.

Preferred examples of the polymer latex used in the present invention are alkyl esters of acrylic acid, hydroxyalkyl esters or glycidyl esters, or
Having an alkyl ester of methacrylic acid, a hydroxyalkyl ester, or a glycidyl ester as a monomer unit, and having an average molecular weight of 100,000 or more, particularly preferably 30
10,000 to 500,000 polymers, and specific examples are shown by the following formula.

Furthermore, regarding polymer latex,
45-5331, U.S. Pat.Nos. 2,852,386, 3,062,674, and
It is possible to refer to the description in the specifications of 3,411,911 and 3,411,912.

The polymer latex used in the present invention is contained in at least one of 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, 4,241,164
No. 4,272,606, JP-A-60-83028, JP-A-60-2186
No. 42, No. 60-258537, No. 61-223738 and the like.

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. Image forming methods using a tetrazolium compound are described in JP-A Nos. 52-18317, 53-17719, 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 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 their 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 Magazine, 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.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

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, the composition contains a thickener such as potassium polystyrene sulfonate, a gelatin hardener, a surfactant, a sliding agent, a UV absorber and the like.

The backing 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 backing layer is 0.1μ to 10μ, and if necessary, a gelatin hardening agent, a surfactant, a matting agent, colloidal silica, a slipping agent, a UV absorbing agent as well as the silver halide emulsion layer and the surface protective layer. , Dyes, thickeners and the like.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically, a photographic material of a type using silver halide as a photosensitive component such as a photosensitive material for printing and a photosensitive material for X-rays. , 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.

Further, as described in JP-A-60-258537, U.S. Pat. No. 4,269,929, etc., it is also possible to increase the developing speed and shorten the developing time by adding amines to the developing solution. it can.

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

Example 1 Undercoat samples 101 to 119 were prepared by applying the following undercoat first layer and undercoat second layer to both sides of a 100 μm-thick biaxially stretched polyethylene terephthalate support in order from the side closer to the support. did.

(1) Undercoat first layer formulation Vinylidene chloride latex (type is as shown in Table 1) 15 parts by weight Exemplified compound H-1 The addition amount is as shown in Table 1 Polystyrene fine particles (average particle size 3 μ) 80 mg / m ² Add to the coating amount Add distilled water 100 parts by weight Add 10% by weight KOH to adjust to pH 6 Coating solution temperature 10 ℃ Dry film thickness as shown in Table 1 Drying conditions 180 ℃ 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 Acetic acid 0.2 parts by weight H ₂ O was added to 100 parts by weight Coating solution temperature 25 ° C Dry film thickness 0.1μ Drying 170 ° C for 2 minutes Similarly, undercoating in which the following compound was added instead of Exemplified compound H-1 in the undercoating 1st layer Samples 116-119 were made.

Then, a silver halide emulsifier layer 1, a silver halide emulsion layer 2, a protective layer 1, and a protective layer 2 were coated on one surface of this undercoat sample in the order of proximity to the support and dried. On the opposite side, a back layer and a protective layer 3 were applied in order from the side closer to the support and dried to give a sample 10
Created 1-119.

(1) Formulation of silver halide emulsion layer 1 liquid I: water 300 ml, gelatin 9 g II liquid; AgNO ₃ 100 g, water 400 ml III liquid A; NaCl 37 g, (NH ₄ ) ₃ RhCl ₆ 1.1 mg, water 400 ml kept at 45 ° C. Solution II and solution IIIA were simultaneously added to solution I at a constant rate. After removing soluble salts from the emulsion by a conventional method well known 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.
It was a 20 μ monodisperse emulsion, and the amount of gelatin contained per 1 kg of the finished emulsion was 60 g.

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

Polystyrene sulfonic acid sodium salt 30 mg / m ² N-oleoyl-N-methyltaurine sodium 50 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 70 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.1 μm) 40 mg / m ^{2 The} coating solution thus obtained was coated so that the coating silver amount was 2 g / m ² .

(2) Formulation of silver halide emulsion layer 2 solution I: water 300 ml, gelatin 9 g II solution; AgNO ₃ 100 g, water 400 ml III B solution; NaCl 37 g, (NH ₃ ) RhCl ₆ 2.2 mg, water 400 ml The same method as emulsion A Emulsion B was prepared using III B solution instead of III A solution. This emulsion has an average grain size of 0.20μ
It was a monodisperse emulsion of.

To the emulsion B thus obtained, the following compounds a) to e) which were the same as those used in the preparation of the emulsion A and other compounds were added.

Compound-a 5 × 10 ^-3 mol / Ag 1 mol Compound-b 120 mg / m ² compound-c 100 mg / m ² compound-d 100 mg / m ² compound-ho 9 mg / m ² Polystyrenesulfonic acid sodium salt 50 mg / m ² N -Oleoyl-N-methyltaurine sodium salt 40 mg / m ² 1,2-bis (vinylsulfonylacetamido) ethane 85 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.1 μ) 40 mg / m ^{2 The} coating solution thus obtained was coated so that the coating silver amount was 2 mg / m ² .

(3) Protective layer 1 formulation Gelatin 1.0 g / m ² Lipoic acid 5 mg / m ² Dodecylbenzenesulfonic acid sodium salt 5 mg / m ² Compound-ha 20 mg / m ² Poly (degree of polymerization 5) Sulfate ester of oxyethylene nonylphenol ether Sodium salt 5 mg / m ² Polystyrenesulfonic acid sodium salt 10 mg / m ² Ethyl acrylate latex (average particle size 0.1μ) 200mg / m ² (4) Protective layer 2 formulation Gelatin 1.0g / m ² Polymethylmethacrylate fine particles (average particle size 3
μ) 60 mg / m ² dodecylbenzene sulfonic acid sodium salt 20 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potassium salt 3 mg / m ² poly (degree of polymerization 5) oxyethylene nonylphenol ether sulfate sodium salt 15mg / m ² Polystyrenesulfonic acid sodium salt 2mg / m ² (5) Back layer formulation Gelatin 2.5g / m ² Sodium dodecylbenzene sulfonate 50 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 20 mg / m ² Polystyrene sulfonic acid sodium salt 40 mg / m ² 1,3-Divinylsulfonyl-2-propanol 150 mg / m ² Ethyl acrylate latex ( Average particle size 0.1μ) 500mg / m ² (6) Protective layer 3 formulation (back layer protection layer) Gelatin 1g / m ² Polymethylmethacrylate fine particles (average particle size 3μ) 40mg / m ² Dodecylbenzenesulfonic acid sodium salt 15mg / m ² Dihexyl-α-sulfosuccinate sodium salt 10 mg / m ² Polystyrene sulfonic acid sodium salt 20 mg / m ² Sodium acetate 40 mg / m ² Samples 101 to 119 thus obtained were placed in an atmosphere of 25 ° C. and 60% RH. Stored below for 2 weeks.

After that, the “dimensional change with treatment”, “wearability when dry” and “adhesion when wet” of these samples were evaluated by the following methods.

[Evaluation method of dimensional change due to processing]

Two holes with a diameter of 8 mm are opened at intervals of 200 mm for the sample, and 25
After leaving it in a room of 30% RH for 30 ° C, 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, after development, fixing, washing with water and drying with an automatic processor, the dimension after 5 minutes is set to 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 process was carried out using an FG-66-0 automatic developing machine manufactured by Fuji Photo Film Co., Ltd., and using GRD-1 and GRF-1 manufactured by Fuji Photo Film Co., Ltd. as developing solutions and fixing solutions under processing conditions of 38 ° C. for 20 seconds. . The drying temperature at that time was 45 ° C.

[Adhesion evaluation method during drying]

Make 7 cuts with a razor on the surface of the sample at intervals of 5 mm each to make 36 squares, and stick adhesive tape (Nitto tape manufactured by Nitto Denki Kogyo Co., Ltd.) on this and stick it in the 180 ° direction. Peel off quickly. In this method, 95% or more of the unpeeled portion is class A, 90% or more is class B, 60% or more is class C, and less than 60% is class D.
Adhesive strength sufficient for practical use as a photographic material is classified into Class A among the above four-grade evaluation.

[Adhesion evaluation method when wet]

At each stage of development, fixing, and washing, scratch marks were made on the emulsion surface of the film in the processing liquid with an iron brush to mark X, and this was rubbed strongly with the fingertips 5 times. The adhesive strength is evaluated by.

When the emulsion layer does not peel more than the scratch, it is classified as Class A, when the maximum peel width is 2 mm or less, B class, when the maximum peel width is 5 mm or less, C class, and others are D class. 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.

Development GRD1 (manufactured by Fuji Photo Film Co., Ltd.) 38 ° C. for 20 seconds Fixing GRF1 (manufactured by Fuji Photo Film Co., Ltd.) 38 ° C. for 20 seconds Water washing 25 ° C. for 20 seconds Samples 101 to 119 were evaluated as described above.

 The results are shown in Table 1.

(Example-2) An undercoat first layer was applied to both sides of a biaxially stretched polyester support having a thickness of 100 [mu] which was subjected to a corona discharge treatment under the following conditions.

[Corona treatment conditions]

Support width 30 cm Support transport speed 30 m / min Support electrode gap 1.8 mm Power 200 W [Undercoat 1st layer formulation] Vinylidene chloride latex (kind is as shown in Table 2) 15 parts by weight Exemplified Compound H-1 Second As shown in the table, polystyrene fine particles (average particle size 3μ) are added to achieve a coating amount of 80 mg / m ² . Add distilled water to 100 parts by weight, then 10% by weight KOH
To adjust to pH 6 Coating solution temperature 15 ° C Dry film thickness as shown in Table 2 Drying conditions 150 ° C for 2 minutes, followed by corona discharge treatment on the first layer of the undercoating under the above conditions to prepare the second undercoating of Example 1. The layers were applied.

Thus, the support screen had an undercoat first layer and an undercoat second layer. Undercoat samples 201-215 were made.

On one surface of each of the undercoat samples 201 to 215, a silver halide emulsion layer and a protective layer 1 were applied in the order closer to the support, and on the other surface, a back layer and a protective layer 2 were applied in the order closer to the support. 215
It was created.

(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. This emulsion is a monodisperse emulsion having an average grain size of 0.15μ, and the yield of the emulsion is
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 (vinylsulfonylacetamido) ethane 100 mg / m ² Ethyl acrylate latex (average particle size 0.1 μ) 500 mg / 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 Dodecylbenzenesulfonic acid sodium salt 25 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 10 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potassium salt 2 mg / m ² Polystyrenesulfonic acid sodium salt 3 mg / m ² Ethyl acrylate latex (average particle size 0.1μ) 200mg / m ² Colloidal silica 350mg / m ² Lipoic acid 8mg / m ² (3) Back layer formulation Gelatin 2g / m ² Dihexyl-α-sulfosuccinate sodium salt 20 mg / m ² Sodium dodecylbenzenesulfonate 30 mg / m ² Polystyrene sulfonic acid sodium salt 30 mg / m ² 1,3-Divinylsulfonyl-2-propanol 100 mg / m ² Ethyl acrylate latex ( Average particle size 0.1μ) 200mg / m ² (4) Protective layer 2 formulation Gelatin 1g / m ² Polymethylmethacrylate fine particles similar to those used in emulsion protective layer 40mg / m ² Dihexyl-α-sulfosuccinate sodium salt 10mg / m ² Dodecylbenzene sulfonic acid sodium salt 30 mg / m ² Polystyrene sulfonic acid sodium salt 25 mg / m ² Sodium acetate 30 mg / m ^{2 After the} finished 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) Backcoating samples 101 to 115 of Example 1 were backed with silver halide emulsion layers, protective layer 1 and protective layer 2 on one side in the order closer to the support and on the other side in the order closer to the support. Layer, protective layer 2 is applied,
Samples 301-315 were prepared.

(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.

To this emulsion, 1 × 10 5 of the compound Q-1) was added as a contrast-increasing agent.
^-3 mol / Ag 1 mol, and compound Q-2) at 1 × 10 ^-4 mol / A
g1 mol was added, and polyethyl acrylate was added as solid content of 50 wt% per gelatin, Was added in an amount of 35 mg / m ² and 2-bis (vinylsulfonylacetamido) ethane in an amount of 145 mg / m ^{2 was} added as a curing agent.

(2) Protective layer 1 formulation Gelatin 1g / m ² Thioctic acid 6mg / m ² 1,5-dihydroxy-2-benzaldoxime 35 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² of polystyrene sulphonic acid sodium salt 20 mg / m ² of ethyl acrylate Latte try (average particle size 0.05 .mu.m) 0.2 g
/ m ² (2) Protective layer 2 formulation Gelatin 0.6g / m ² Polymethylmethacrylate fine particles (average particle size 2.5μ) 20mg / m ² Silicon dioxide fine particles (average particle size 2.8μ) 30mg / m ² N-perfluorooctanesulfonyl-N-propyroglycine potadium salt 3mg / m ² dodecylbenzene Sodium sulfonate 20 mg / m ² Hydroquinone 150 mg / m ² Compound R was prepared by adding a gelatin dispersion by the following procedure.

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

C₁₁H_{twenty three}CONH (CH_Two)_ThreeN (CH_Three)₂(CH_Two)_FourSO_Three  (Compound-S) (4) Back layer formulation Gelatin 2.5g / m^Two  Dihexyl-α-sulfosuccinate sodium salt 30 mg / m^Two Dodecylbenzenesulfonic acid sodium salt 35mg / m^Two 1,3-divinylsulfonyl-2-propanol 130 mg / m^Two Ethyl acrylate latex (average particle size 0.05μ) 0.5g / m^Two (5) Protective layer 3 formulation Gelatin 0.8g / m^Two Polymethylmethacrylate fine particles (average particle size 3.4μ) 40mg / m^Two Dihexyl-α-sulfosuccinate sodium salt 9 mg / m^Two Dodecylbenzenesulfonic acid sodium salt 10 mg / m^Two Sodium acetate 40 mg / m^Two Samples 301 to 315 obtained in this manner were placed in an atmosphere of 25 ° C and 60% RH.
Stored in the atmosphere for 2 weeks and evaluated in the same manner as in Example 1.
Was.

 The results are shown in Table 3.

(Example-4) In one of the undercoat samples 201 to 215 of Example 2, the silver halide emulsion layer 1 and the protective layer 1 were arranged on one surface of the undercoat samples 201 to 215 in the order closer to the support, and the back layer and the protective layer were arranged on the other surface in the order closer to the support. Apply Layer 2 and sample
401-415 were created.

(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 chlorobromide monodispersed emulsion having an average particle 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 heat-induced fogging was performed 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 sulfonic acid 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 applied with a coating 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 4 μ) 50 mg / m ² Dodecylbenzenesulfonic acid sodium salt 50 mg / m ² 5-nitroindazole 15 mg / m ² 1,3-divinylsulfonyl-2-propanol 50 mg / m ² N-perfluorooctanesulfonyl-N-propyroglycine potadium salt 2 mg / m ² ethyl acrylate latex (average particle size 0.1 μ) 300 mg / m ² (3) Back layer formulation Gelatin 2.5g / m ² 1,3-Divinylsulfonyl-2-propanol 150 mg / m ² Ethyl acrylate latex (average particle size 0.1 μm) 900 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 35 mg / m ² Dodecylbenzenesulfonic acid sodium salt 35 mg / m ² (4) Protective layer 2 formulation Gelatin 0.8 g / m ² Polymethylmethacrylate fine particles (average particle size 3 μ) 20 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 10 mg / m ² Dodecylbenzenesulfonic acid sodium salt 10 mg / A sample prepared by adding 40 mg / m ^{2 of} sodium m ² acetate was stored in an atmosphere of 25 ° C. and 60% RH for 2 weeks, and then evaluated in the same manner as in Example 1.

 The results are shown in Table 4.

Example-5 Undercoat Samples 501 to 522 were prepared by applying the following undercoat first layer and undercoat second layer to both sides of a biaxially stretched polyethylene terephthalate support having a thickness of 100 μm in this order from the side closer to the support. did.

(1) Undercoat 1st layer formulation Vinylidene chloride latex (kind is as shown in Table 5) 15 parts by weight Exemplified compound H-1 Addition amount is as shown in Table 5 Colloidal silica Addition amount is as shown in Table 5 Polystyrene fine particles ( Add an average particle size of 3μ) to a coating amount of 80 / m ² Add 100 parts by weight of distilled water and adjust to pH 6 by adding 10 parts by weight of KOH Coating solution temperature 10 ℃ Dry film thickness as shown in Table 5 Minute (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 Acetic acid 0.2 parts by weight H ₂ O was added to 100 parts by weight Coating solution temperature 25 ° C Dry film thickness 0.1μ Drying 170 ° C for 2 minutes Similarly, undercoating in which the following compound was added instead of Exemplified compound H-1 in the undercoating 1st layer Samples 523-526 were made.

Then, on one side of this undercoat sample, silver halide emulsion layer 1, silver halide emulsion layer 2, protective layer 1 and protective layer 2 disclosed in Example 1 were applied in that order close to the support and dried. A back layer and a protective layer 3 were applied to the opposite surface in the order of being closer to the support and dried to prepare samples 501 to 526.

The samples 501 to 526 thus obtained were stored for 2 weeks in an atmosphere of 25 ° C. and 60% RH.

After that, these samples were evaluated for "dimensional change due to treatment", "adhesiveness when dried", "adhesiveness in a high humidity atmosphere" and "adhesiveness when wet".

[Adhesion evaluation method under high humidity atmosphere]

The sample is left to stand in an atmosphere of 25 ° C and 80% RH for 24 hours, and then 7 nicks are made on the surface of the sample with a razor to form 7 cuts at intervals of 5 mm to make 36 squares, and an adhesive tape (Nitto Denki Kogyo) Attach a knit tape made by K.K. and leave for 1 hour 30 minutes or longer. Peel quickly in the direction of 180 ℃ in an atmosphere of 25 ℃ and 80% RH. In this method
Class A for 95% or more, B for 90% or more and less than 95%
Class, 60% or more and less than 90% is C class, and less than 60% is D class.
Adhesive strength sufficient for practical use as a photographic material is classified into Class A among the above four-grade evaluation.

 The results are shown in Table 5.

Example 6 An undercoat first layer was applied to both sides of a 100 μm-thick biaxially stretched polyester support which had been subjected to corona discharge treatment under the following conditions.

[Corona treatment conditions]

Support width 30 cm Support transport speed 30 m / min Support electrode gap 1.8 mm Power 200 W [Undercoat first layer formulation] Vinylidene chloride latex (type is as shown in Table 6) 15 parts by weight Exemplified compound H-1 Table 6 Colloidal silica As shown in Table 6 Polystyrene fine particles (average particle size 3μ) Added to a coating amount of 80 mg / m ² . Add distilled water to 100 parts by weight, then 10% by weight KOH
To adjust the pH to 6 Coating solution temperature 15 ° C Dry film thickness as shown in Table 6 Drying conditions 150 ° C for 2 minutes, followed by corona discharge treatment on the first undercoating layer under the above conditions, and then undercoating second example of Example 1 The layers were applied.

Thus, the undercoating first layer and the undercoating second layer were provided on both surfaces of the support. Undercoat samples 601 to 616 were prepared.

The silver halide emulsion layer and the protective layer 1 were formed on one surface of each of the subbing samples 601 to 616 in the order close to the support in the same manner as in Example 2.
The back layer and the protective layer 2 were applied to the other surface in the order of being closer to the support to prepare samples 601 to 616.

The prepared sample was stored in an atmosphere of 25 ° C. and 60% RH for 1 week, and then evaluated in the same manner as in Example-5.

 The results are shown in Table 6.

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic coirod layer containing a polymer latex on at least one side of a polyester support, wherein the polyester support comprises at least 70-99.9% by weight of vinylidene chloride. Having an undercoat layer having a thickness of 0.3 μm or more containing a vinylidene chloride copolymer composed of a monomer and 0.1 to 5% by weight of a vinyl monomer having one or more carboxyl groups, the undercoat layer having the following general formula: A silver halide photographic light-sensitive material comprising a compound represented by I or II. In the formula, R ¹ , R ² , R ³ and R ⁴ are chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -OM group (M represents a monovalent metal atom), -NR'R. ″ Group, -NHCOR
And R ', R ", and R each represent a hydrogen atom, an alkyl group, or an aryl group, and they may be the same or different. Q ¹ and Q ² are -O.
Represents a-, -S-, or -NH- linking group, and L represents an alkylene group, an arylene group, or a divalent linking group obtained by combining them. l and m are 0 or 1, respectively. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the undercoat layer contains colloidal silica.