JPH04184335A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve adhesion property between a supporting body and photographic layers by providing a base coating layer containing polymers having carboxylic groups in the molecular chain and a water-soluble or water- dispersible block isocyanate on at least one side of a polyester supporting body. CONSTITUTION:A vinylidene copolymer is preferable for the polymer containing carboxylic groups, and this copolymer contains 70-99.9wt.% vinylidene monomers and 0.1-5wt.% carboxylic group-contg. vinyl monomers. The polyester supporting body has 40-200mum thickness and is biaxially oriented and crystallized. Thereby, both adhesion property and dimensional stability for treatment can be obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to silver halide photographic materials, particularly silver halide materials having improved adhesion between a support and a photographic layer coated thereon. Regarding photographic materials.

The present invention further relates to a silver halide photographic material with improved dimensional stability.

(Prior art) In silver halide photographic light-sensitive materials, a photographic layer containing a hydrophilic colloid such as gelatin as a binder is usually provided on a hydrophobic support such as polyester or triacetylcellulose. Techniques are required to achieve good adhesion between the photographic layer and the photographic layer.

In order to obtain good adhesion between the support and the photographic layer, a method is known in which the surface of the support is subjected to strong pretreatment such as glow discharge treatment or flame treatment.

The most preferred of these pretreatments is glow discharge treatment, but this method requires treatment under a vacuum of about I Torr, is extremely complicated, and is disadvantageous in terms of cost.

Another known means for improving the adhesion between the support and the photographic layer is to provide a subbing layer on the support.

As the undercoat layer, styrene-butadiene copolymer,
Materials such as vinyl chloride copolymers, acrylic ester copolymers, polyester copolymers, salt-vinyl acetate copolymers, maleic anhydride copolymers, and polyacetal copolymers may be used as binders. I can do it.

In this case, it is known to add a support swelling agent or a subbing layer crosslinking agent to the subbing layer in order to obtain sufficient adhesion between the support and the photographic layer.

For example, when the support is polyester, phenols are known as swelling agents, and a specific example is US Pat.
43421, resorcinol was published in Japanese Patent Publication No. 46-80
Publication No. 291 describes phenol.

Resorcinol is the most preferred swelling agent for polyester supports, but resorcinol has the drawback of often causing spot failures during the manufacturing process.

Specific examples of crosslinking agents include epoxy compounds described in JP-A-51-103422, JP-A-51-11412;
Examples include triazine compounds described in Publication No. 0.

A preferred example of the crosslinking agent is 2,4-dichloro-6-hydroxy-1,3,5) riazine sodium salt. It is certainly possible to obtain fairly good adhesion by using this crosslinking agent. However, in this case as well, sufficient adhesion cannot be obtained under extreme conditions (for example, high temperature atmosphere).

Furthermore, silver halide photographic materials have the disadvantage that their dimensions change due to development processing.

This phenomenon is caused by elongation of the silver halide photographic material due to water absorption by the support during development.

In the industry, this phenomenon is referred to as ``poor dimensional stability due to processing.''
This is an extremely serious drawback, especially in silver halide photographic light-sensitive materials for printing.In order to improve the dimensional stability associated with this treatment, a technology using an undercoat layer containing vinylidene chloride copolymer has been developed. It is described in Japanese Patent Application Laid-Open No. 64-538.

It is true that this method can improve the ``dimensional stability associated with processing,'' but this system has the problem that the adhesion between the vinylidene chloride copolymer undercoat layer and the support is not perfect. There is.

Therefore, there has been a demand for a technique to improve the adhesiveness of silver halide photographic materials using this technique.

(Problem to be solved by the present invention!!l) The purpose of the present invention is to create a solution between the polyester support and the photographic layer without using complicated means such as resorcinol, a polyester swelling agent, or glow discharge treatment. It is an object of the present invention to provide a silver halide photographic material with improved adhesive properties, especially adhesive properties under a high humidity atmosphere.

A second object of the present invention is to provide a silver halide photographic material which has good dimensional stability during processing and improved adhesion between a polyester support and a photographic layer.

(Means for Solving the Problems) The object of the present invention is to (1) have an undercoat layer containing a polymer having a carboxyl group in its molecular chain on at least one side of a polyester support; A silver halide photographic light-sensitive material, wherein the undercoat layer contains a water-soluble or water-dispersible blocked isocyanate.

(2) The polymer contains a vinylidene chloride copolymer containing at least 70 to 99.9% by weight of a vinylidene chloride monomer and 0.1 to 5% by weight of a carboxyl group-containing vinyl monomer; The silver halide photographic material as described in (1) above, wherein the layer thickness is 0°3μ or more.

(3) This was achieved by the silver halide photographic material described in (2) above, characterized in that the undercoat layer is applied after biaxially stretching the polyester support.

(Specific structure of the invention) First, the polymer of the present invention will be described.

The polymer of the present invention is a polymer containing a carboxyl group in the molecular chain, and may be a polymer obtained by polymerizing a carboxyl group-containing monomer (homopolymer), or a polymer containing a carboxyl group and a monomer containing no carboxyl group. A polymer (copolymer) obtained by copolymerizing monomers may also be used.

In this case, the carboxy group-containing monomer is acrylic acid,
Examples include methacrylic acid, itaconic acid, and citraconic acid.

The polymer of the present invention may be a water-soluble polymer or a latex in which a water-insoluble polymer is dispersed in water, but latex is preferred.

Examples of the polymer of the present invention include vinylidene chloride copolymers copolymerized with carboxyl group-containing monomers, styrene-butadiene copolymers, acrylic acid ester copolymers, vinyl acetate copolymers, chlorobrene copolymers, etc. Of these, the most preferred is vinylidene chloride copolymer. Specific examples of these copolymers include the following. The numbers in parentheses represent weight ratios, and the molecular weights represent average molecular weights.

Styrene: Butadiene: Acrylic # (65:27:8)
latex (average molecular weight 48,000) styrene:butadiene:itaconic acid (30:67:3) latex (
Average molecular weight 60,000) Styrene: Butadiene: Divinylbenzene: Methacrylic acid (60:30=5:5) Latex (average molecular weight 50,000) Methyl acrylate: Methyl methacrylate: Butyl acrylate: Acrylic M (50:30:15:5) latex (average molecular weight 460 methyl acrylate: methyl methacrylate: styrene: methacrylic acid (35:5)
0:10:5) latex (average molecular weight 38,000)
Vinyl acetate: styrene: methacrylic acid (80:12:8
) latex (average molecular weight 4500 vinyl acetate dimethyl methacrylate: acrylonitrile: Itacon! 1I
(70:15:12:3) latex (average molecular weight 6
0000) Latex of chlorobrene: methyl methacrylate: methacrylic acid (80:10:10) (average molecular weight 40000) Latex of chlorobrene: styrene: divinylbenzene: acrylonitrile: acrylic acid (60:20:5:5:10) (average molecular weight 40 Vinylidene chloride: Methyl acrylate: Methyl methacrylate: Acrylonitrile: Acrylic acid (55:15:15:5:10) latex (average molecular weight 61,000) Vinylidene chloride: Methyl acrylate Dimethyl methacrylate: Acrylonitrile: Methacrylic acid (80:5:
5:3 (near) latex (average molecular weight 31,000) Next, vinylidene chloride copolymer, which is preferred among the polymers of the present invention, will be described.

The vinylidene chloride copolymer of the present invention contains 70 to 99.9% by weight of vinylidene chloride monomer, more preferably 85 to 99% by weight, and 0.1 to 5% by weight, more preferably 0.2 to 3% by weight. It is a copolymer containing a carboxyl group-containing vinyl monomer.

The carboxyl group-containing vinyl monomer used in the vinylidene chloride copolymer of the present invention is a vinyl monomer having one or more carboxyl groups in the molecule, and specific examples include acrylic acid, methacrylic acid, itaconic acid, and citraconic acid. Examples include acids.

In addition to vinylidene chloride monomers and carboxyl group-containing monomers, the vinylidene chloride copolymer of the present invention may contain monomers copolymerizable with these monomers. Specific examples of these monomers include: Examples include acrylonitrile, methacrylaterile, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, and styrene. These monomers may be used alone or in combination of two or more.

The molecular weight of the vinylidene chloride copolymer of the present invention is 4sooo
The following are preferred.

The vinylidene chloride copolymer of the present invention is preferably in the form of an aqueous latex dispersion. In this case, it may be a latex with a uniform structure or a so-called core-shell structure latex in which the core and shell portions have different compositions.

Specific examples of the vinylidene chloride copolymer of the present invention include the following. However, the numbers in ) represent the weight ratio, and the average molecular weight represents the weight average molecular weight.

Vinylidene chloride: Methyl acrylate: Acrylic acid (9
0:9:1) latex (average molecular weight 42,000) vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (87:4:
4:4:1) latex (average molecular weight 40,000) vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90:6: 2:
2) Latex (average molecular weight 380 vinylidene chloride:
Ethyl methacrylate: 2-hydroxyethyl methacrylate: acrylic acid (90:8:1.5:0.5) latex (average molecular weight 44,000) Core-shell type latex (core part 90% by weight, shell part 10% by weight) Core part Vinylidene chloride dimethyl acrylate: Methyl methacrylate: Acrylonitrile: 7')'J @C9
3:3:3:0. q: o, 1) Shell part vinylidene chloride; methyl acrylate methyl methacrylate: acrylonitrile: acrylic acid (88:3:3:3:3) (average molecular weight 38,000) Core-shell type latex (core part 70% by weight, shell part 30%) Weight%) Core part Vinylidene chloride: Methyl acrylate: Methyl methacrylate: Acrylonitrile: Methacrylic acid (92
, 5:3:3:1:0° Shell part vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90:3:3:1:3) (average molecular weight 20,000) Such vinylidene chloride copolymer A silver halide photographic light-sensitive material using this material has good dimensional stability and can achieve both dimensional stability and adhesion.

Next, the blocked isocyanate compound of the present invention used as a crosslinking agent will be described. (Blocked isocyanate compounds are also called masked isocyanates and capped isocyanates.) The blocked isocyanates of the present invention refer to the isocyanate groups of isocyanate compounds having two or more isocyanate groups in the molecule, including alcohols, phenols, etc. ,ε−
It is a compound stabilized in an aqueous system by blocking with caprolactam, oximes, active methylene compounds, bisulfite, etc.

The blocked isocyanate compound may be one in which all the isocyanate groups of the isocyanate compound are blocked or one in which some of the isocyanate groups are blocked. In the latter case, the unblocked isocyanate group is used to create a hydrophilic group (for example, -COO -) may be introduced.

There is no particular restriction on the isocyanate compound used to create the blocked isocyanate compound of the present invention. Blocked isocyanate compounds are described, for example, in ``Latest Advances in Coating Technology'' (published by Sogo Technological Center).

Examples of commercially available blocked isocyanate compounds include Coronate 2523, Coronate 2507 (all manufactured by Nippon Polyurethane Co., Ltd.), CR-6ON (Dainippon Ink Chemical Co., Ltd.), Elastron BN69, and Elastron BN.
II, Elastron BN08, Elastron BN44,
Examples include Elastron H-38, Elastron H-37, Elastron MF-9, Elastron TP-16 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

The blocked isocyanate compounds of the present invention may be used alone or in combination of two or more.

The amount of the blocked isocyanate compound of the present invention added is 0.000% relative to the polymer used as the binder for the first undercoat layer.
A range of 0.01 to 20% by weight, preferably 0.1 to 10% by weight is suitable.

The thickness of the undercoat layer of the present invention is preferably 0.3 layers or more and 3p or less, and more preferably 0.5 layers or more and 1.5μ or less.

In addition to the vinylidene chloride copolymer and the blocked isocyanate compound, a matting agent, a surfactant, a dye, an inorganic fine particle, and an acid or alkali for pH adjustment may be added to the undercoat layer of the present invention, if necessary. .

Furthermore, there are no particular limitations on the means for applying the undercoat layer of the present invention, and known methods can be used.

The polyester used in the support of the present invention is a polyester whose main component is an aromatic dibasic acid such as isophthalic acid or terephthalic acid, glycol such as ethylene glycol or propylene glycol. Among these polyesters, polyethylene terephthalate is the most convenient in terms of availability. In particular, biaxially stretched crystallized polyethylene terephthalate is most preferred in terms of strength and stability.

There is no particular limit to the thickness of the polyester support, but it is 40 to 2
A material of about 00 μm is preferable from the viewpoint of ease of handling and versatility.

Further, a uniaxially stretched polyester film can be used as the support of the present invention. In this case, after applying the undercoat layer of the present invention, it is preferable to stretch in a direction perpendicular to the l-axis stretching.

In the silver halide photographic material of the present invention, one or more other undercoat layers may be provided on the undercoat layer of the present invention, if necessary.

In this case, the binder for these undercoat layers is not particularly limited, but gelatin is commonly used.

In addition to the binder, a crosslinking agent for the binder, a surfactant, a dye, a polymer latex, a matting agent, a slipping agent, inorganic fine particles, an acid or alkali for pH adjustment, a preservative, etc. may be added to these undercoat layers.

The thickness of these undercoat layers is not particularly limited, but is preferably in the range of 0.02 to 2μ, more preferably in the range of O103 to 1μ.

There are no restrictions on the method of applying these layers, and known methods can be used.

Examples of the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention include a silver halide emulsion layer, a back layer, a protective layer, and an intermediate layer. Gelatin is most preferably used as the binder for these hydrophilic colloid layers.

Gelatin includes lime-processed gelatin, acid-processed gelatin,
Enzyme-treated gelatin, gelatin derivatives, etc. can be used, and among these, 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 droxyethyl cellulose; sugar 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.

The silver halide emulsion used in the silver halide photographic light-sensitive material used in the present invention usually contains a water-soluble silver salt (for example, nitric acid 1j) solution and a water-soluble halide salt (for example, potassium bromide).
solution in the presence of a water-soluble polymer solution such as gelatin.

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, a chemical sensitizer, a spectral sensitizer, an anti-capri side, a woody colloid (especially gelatin), a gelatin hardener, a film physical property improver such as a surfactant, Thickeners, etc. can be included. Regarding these, the description in Research Disclosure magazine, Vol. 176, No. 17643 (December 1978), and Japanese Patent Application Laid-open Nos. 52-108130, 52-114328, and 5
No. 2-121321, No. 53-3217, No. 53-4
The description in Japanese Patent 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.

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 0.1 to 10μ, and if necessary, it contains a gelatin hardening agent, a surfactant, a matting agent, a colloidal silica, a slipping agent, and a UVWllL as well as a silver halide emulsion layer and a surface protective layer. It can contain astringents, 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 of the type that use silver halide as a photosensitive component, such as photosensitive materials for printing, bad light for X-ray, etc. The effects of the present invention are particularly remarkable in photosensitive materials for printing.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this.

Example 1 A first undercoat layer and a second undercoat layer were coated on both sides of a biaxially stretched polyethylene terephthalate support having a thickness of 100 μm in order from the support. At this time, as shown in Table 1, undercoat sample 101 was prepared by changing the type of binder and the amount of crosslinking agent added.
~117 was created.

(1) Undercoat 1st layer prescription Undercoat 1st layer binder (types are as shown in Table 1) 20 parts by weight Elastron BNII (Daiichi Kogyo Seiyaku Co., Ltd.) The amount added is as shown in Table 1. (Nissan Chemical Co., Ltd.) 0.4 parts by weight Polystyrene fine particles (average particle size 3μ) Add distilled water to give 10 g/-1 Add 100 parts by weight 4% KOH and adjust to pH 6 Dry film thickness 0. 6 μ Drying 18013 minutes (2) Undercoat 2nd layer prescription gelatin 1 part by weight Methyl cellulose 0.05 part by weight o o
C1! ■ HOII ■ lICl 0.02 parts by weight C, lH□0 (CHICI+20) 1°II
Add 0.03 parts by weight of distilled water, add 100 parts by weight, dry film thickness: 0.1 μm, dry for 170 minutes and then coat one side of this undercoat sample with the back layer and protective layer 1 in order from the support to the support on the opposite side. Samples 101-117 were prepared by coating silver halide emulsion layer 1, silver halide emulsion layer 2, protective layer 2, and protective layer 3 in order from the closest to the top.

(1) Back layer formulation (conductive layer) Snow/Sb (9/1 weight ratio, average particle size 0.2
5μ) 300mg/m”gelatin
170 #Compound-17# Sodium dodecylbenzenesulfonate salt 10jF dihexyl α-sulfosuccinate sodium salt 40 Sodium polystyrene sulfonate salt 9 #(2) Protective layer 1 prescription gelatin 2.9g/■8 Compound-2 SOIK 5ost+ 5 (1+g/m" Compound-1 (above) 10-g/m" Dodecylbenzenesulfonic acid sodium salt 70 #dibenzyl-α-sulfosuccinate sodium salt 15 -1.3-divinylsulfonyl-2-propatol 150 #ethyl Acrylate latex (average particle size 0.05μ) 500-Perfluorooctane sulfonic acid potassium salt 10 Silicon dioxide fine powder particles (average particle size 3.5μ, pore diameter 170, surface area 300m”/g) 5 I (3 ) Silver halide emulsion layer-1 recipe I solution; water 300 ml 11 gelatin 9 g 11 solution; AgNOs 100 g, water 400 ml III
Liquid iNac 137g, (NHa)JhCl 1 ,
1 ml of water in solution I kept at 4001 456C! Solution (1) and solution III were added simultaneously at a constant rate. After removing soluble salts from this emulsion by a conventional method well known to those skilled in the art, gelatin was added and 6-methyl-4-hydroxy-1,3,3a was added as a stabilizer.
7-tetraazaindene was added. This emulsion was a monodispersed emulsion with an average grain size of 0.20 μm, and the yield of the emulsion was 60 g of gelatin per 1 kg.

The following compounds were added to the emulsion thus obtained.

Compound-5 (postscript) 6X10-”Mo I/Ag 1
Mol compound-6 (described later) 60wg/m
"Compound-7 (see below) 9 mg/+
w” Compound-1 (above) 10 mg/
m"Polystyrene sulfonic acid sodium salt 4Qs+g/m"N
-Oleoyl-N-methyltaurine sodium salt 1,2-bis(vinylsulnylacetamide)ethyl-phenyl-5-mercaptotitrazole 3mg/m'' Ethyl acrylate latex (average particle size 0.05μ) 46 Osg/- ``The coating solution obtained in this way was coated with a coating silver amount of 2. 0g/s”
I applied it to make it look like this.

Compound-5 Compound-6 Compound-7 C1e (4) Silver halide emulsion layer-2 Prescription Solution I; 300 μl of water, 9 g of gelatin, Solution II HAgNOx 100 g, 400 μl of water, 1 III
Solution: 7 g of NaCl3, (NHa)JhCI
m2. 2 mg water 400 ml Prescription - In the same way as the emulsion (3), add the II solution and I solution to the I solution.
Solution II was added at the same time to prepare an emulsion. This emulsion was a monodisperse emulsion with an average grain size of 0.20μ.

The following compounds were added to the emulsion thus obtained.

Compound-5 is an emulsified dispersion of the hydrazine derivative described below.
Add so that the ratio is 10-3 mol of X/1 mol of Ag.

Compound-6 (above) 60g/- Compound-7 (above) 9-g/-2 Compound-1 (above) 10mg/m" Polystyrene sulfonic acid sodium salt 50g/-1N
-Oleoyl-N-methyltaurine sodium salt 405g/w"1.
2-bis(vinylsulfonylacetamido)ethane 130wg/m”■
-Phenyl-5-mercaptotetrazo-J 3 So 747
71” ethyl acrylate latex (average particle size 0.05μ) 400mg/m
``The coating solution obtained in this way was coated with a silver amount of 1.3 g/1.
It was applied to a total weight of 1 g.

(5) Protective layer-2 prescription gelatin 1.0 g/m" α-lipoic acid 10 g/-2 Dodecylbenzenesulfonic acid sodium salt 5-g/2 Compound-6 (above) 40 mg/m" Compound-8 (Postscript) 20wg/s+"Polystyrene sulfonic acid sodium salt 10ng/m"1-
Phenyl-5-mercaptotetrasol 5mg/s" Compound-9 (see below) 20g/mist 2 Ethyl acrylate latex (average particle size 0.05μ) 200g/s2 (6
) Protective layer-3 prescription gelatin 1.0 g/- silicon dioxide fine powder particles (average particle size 3.5 μ, pore diameter 25, surface area 700 m”/g) 50+ g/
m"Liquid paraffin (gelatin dispersion) 43m1/s"Dodecylbenzenesulfonic acid sodium salt 20mg/-1Perfluorooctanesulfonic acid potassium salt 10mg/m"N-
Perfluorooctanesulfonyl-N-probyl glycitubotadium salt 3゜g/, polystyrene sulfonic acid sodium salt 21/, Tomopoly(
Degree of polymerization 5) Oxyethylene nonylphenyl ether sulfate ester sodium salt 20+g/■! Colloidal silica (particle size 15 μm) 20 mg/s” Compound-8 Compound-9 Method for preparing emulsified dispersion of hydrazine derivative> Heated to 65@C and uniformly dissolved to form a liquid.

Ta.

Solution (1) and Solution II were mixed and stirred at high speed using a homogenizer (Nippon Seiki Seisakusho) to obtain a fine particle emulsified dispersion. After removing ethyl acetate from this emulsion by heating and vacuum distillation, water was added to give a total volume of 250 g.

Residual ethyl acetate is 0. It was 2%.

Compound-10 The sample obtained from this camphor was stored for two weeks in an atmosphere of 25% RH and 60% RH. Afterwards, the following evaluations were conducted. The results are shown in Table 1.

[Adhesion under normal humidity atmosphere] Using a razor, make 7 cuts vertically and horizontally at 5-square intervals on the surface of the sample stored for 3 days in a 25"C 155% RH atmosphere to make 36 incisions. Make a square, apply adhesive tape (Ninto Tape manufactured by Nitto Electric Industry Co., Ltd.) on top of the square, and quickly peel it off in a 180° direction.

At this time, 95% or more of the unpeeled part is A grade, 90% or more 95%
Less than 60% is grade B, 60% or more and less than 90% is grade 0, and less than 60% is grade D.

The adhesive strength that is sufficient for practical use as a photographic material is classified as A class among the above four classes.

[Adhesiveness under high temperature atmosphere]

Using a razor, make 7 cuts vertically and horizontally at 5 mm intervals on the surface of the sample, which had been stored for 3 days at 25 °C and 185% RH, to create 36 squares. Denki Kogyo Co., Ltd. Seiji.

Attach the totebe and quickly peel it off in a 180° direction.

At this time, 95% or more of the unpeeled part is A grade, 90% or more 95%
Less than 60% is grade B, 60% or more and less than 90% is grade 0, and less than 60% is grade D.

The adhesive strength that is sufficient for practical use as a photographic material is classified as A class among the above four classes.

(Wet adhesion evaluation method) At each stage of development, fixing, and washing with water, scratch the emulsion surface of the film in the processing solution at the X mark using a steel pen, and rub it strongly with the tip of your finger 5 times on the X line. Evaluate the adhesion strength by during maximum peeling along.

If the milk layer does not peel off more than the scratches, it is graded A. If the maximum peeling is within 21111, it is grade B. If the maximum peeling is within 51, it is grade 0. Otherwise, it is graded D. Adhesive strength sufficient for practical use as a photographic material is one classified as A grade in the above four-level evaluation.

Table 1 P-101 Styrene: Butadiene: Divinylbenzene (65:30
:5) latex (average molecular weight 50 methyl acrylate: methyl methacrylate: styrene (40:50:1)
0) latex (average molecular weight 40,000) Vinyl acetate: methyl methacrylate: acrylonitrile (70: 15: 15) latex (average molecular weight 5
5000) Chloroprene: Styrene: Divinylbenzene: Acrylonitrile (60:20:10:10) latex (average molecular weight 41000) Vinylidene chloride: Methyl acrylate: Methyl methacrylate: Acrylonitrile (60
:15:15:10) latex (average molecular weight 6
As can be seen from the table, Samples 101 to 107 of the present invention have good adhesive properties, while Samples 108 to 112 to which Elastron BNII is not added and Samples 113 to 117 which use latex without carboxyl groups as a binder have good adhesive properties. is defective.

Example-2 Samples 201 to 201 were prepared in the same manner as in Example-1, except that V-5 was used as the binder for the first undercoat layer and the thickness of the first undercoat layer and the amount of Elastron BNII added were changed as shown in Table 2.
204 was created. At this time, as shown in Table 2, the thickness of the first undercoat layer and the amount of crosslinking agent added were varied.

The adhesiveness of this sample in Example-1 and the dimensional stability described below were evaluated.

[Evaluation method of dimensional change due to treatment]

Two holes with a diameter of 81 mm were made at a distance of 200 mm in the sample, and after leaving it in a 25"C 130% RH room,
The distance between the two holes was accurately measured using a pin gauge with 00m+-accuracy. The length at this time is defined as X-.0 Next, after developing, fixing, washing, and drying using an automatic developing machine, the dimension after 5 minutes is defined as Y-, and the dimensional change rate C due to processing.
%) in the industry, 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 Fuji Photo Film Co., Ltd.'s FC-660 automatic processor, and the developer and fixer were GR-DI and GR-
The treatment was carried out using Fl at 38° C. for 20 seconds. The drying temperature at that time was 45°C. Second result
Shown in the table.

As can be seen from Table 2, samples 201 to 203 of the present invention have good adhesion, whereas sample 204 has poor adhesion.

Furthermore, the sample of the present invention has good dimensional stability due to processing, and has both adhesion and dimensional stability.

Example-3 Example-1 except that the first layer formulation of the undercoat was changed as follows.
Undercoat samples 301 to 304 were prepared in the same manner as above. At this time, as shown in Table 3, the thickness of the first undercoat layer and the type and amount of crosslinking agent added were varied.

(1) Undercoat first layer prescription Undercoat first layer binder V-620 parts by weight CR-6O
N (Dainippon In Seikagaku Co., Ltd.) Addition amount is as shown in Table 3 2.4dichloro-6-hydroxy-1,3,5) riazine sodium salt colloidal silica (Snowtex ZL (Nissan Chemical Co., Ltd.) ) 1.5 parts by weight Polystyrene fine particles (average particle size 3μ) Added leather distilled water to make 8 mg/m'' 100 parts by weight 4% by weight Add KC)H and adjust to pH 6 Dry film thickness Dry as shown in Table 3 Then, on one side of this undercoat sample, a silver halide emulsion layer and a protective layer 1 were coated in the order closest to the support, and on the other side, a hack side and a protective layer 2 were coated in the order closest to the support.
1 to 304 were created. This sample was evaluated by the method of Example-2. The results are shown in Table 3.

(1) Silver halide hole side layer formulation Emulsion A was prepared by the following method using the following solutions (1), (2), and (1).

Solution I: 300ml of water, 9g of gelatin Solution II: 100g of AgNOs, 400ml of water
Liquid: 137g of NaC, (Nl(a)JhCli 0.
66 mg of water and 4001 of water were added at a constant rate to Solution II and Solution III maintained at 40'''C.This emulsion was prepared as described in the art (after removing soluble salts by a conventional method known in the art). Add gelatin and 6-methyl-4-hydroxy-1,3,3a as a stabilizer
, 7-tetraazaindene and 4-hydroxy-5,6
-Drimethylene-1°3.3a,7-tetraazaindene was added.

This emulsion is a monodisperse emulsion with an average grain size of 0.15μ, and the amount of gelatin contained per 1 kg of emulsion yield is 6
It was 0g.

The following compounds were added to the emulsion thus obtained.

5OJ8 5mg/m” Polystyrene sulfonic acid sodium salt 10-g/1121.
2-bis(vinylsulfonylacetamido)ethane 100 mg/a" Ethyl acrylate latex (average particle size 0.1 μm) 5005 g/m" The coating liquid thus obtained was coated to give a coated silver amount of 3 g/m.

(2) Protective layer l prescription gelatin 1.5g/m”5OJ
a 5 mg/a” Dodecylbenzenesulfonic acid sodium salt 25 g/■! Dihexyl α-sulfosacnate sodium salt 10 mg/■ Thickness polymethyl methacrylate fine particles (average particle size 3 μ) 60 g/m Thickness N-perfluorooctane Sulfonyl-N-propylglycine potassium salt 2 g/■2 Sodium polystyrene sulfonate salt 3 g/■2 Ethyl acrylate latex (average particle size 0.1μ) 200 B/s" Colloidal silica 350 g/mist 8 lipoic acid
8-g/Ugly 3 (3) Back layer prescription gelatin 2g/m”305
g/■1 180mg/s"50mg/m" Dibenzyl-α-sulfosacnate sodium salt 20mg/m" Sodium dodecylbenzenesulfonate 3 (leg/■2 Polystyrene sulfonate sodium salt
3Q+sg/m”1.3-divinylsulfonyl-
2.Proper tool 100 g/1 Ethyl acrylate latex (average particle size 0.1μ) 200 g/-1 (4)
Protective layer 2 prescription gelatin Ig/m"Polymethyl methacrylate fine particles similar to those used in protective layer 1 40mg/s"Dihexyl-α-sulfosacnate sodium salt 10mg/m'Dodecylbenzenesulfonic acid sodium salt 30g/garden 2 Polystyrene sulfonic acid sodium salt 25-g/-1 Sodium acetate 30 g/-1 As can be seen from Table 3, samples 301 to 303 of the present invention had good adhesion, whereas samples 304.305 has poor adhesion.

Furthermore, the sample of the present invention has good dimensional stability due to processing, and has both adhesion and dimensional stability.

Example-4 Example-1 except that the formulation of the first undercoat layer was changed to camphor as shown below.
Undercoat samples 401 to 404 were created in the same manner as above. At this time, as shown in Table 4, the thickness of the first undercoat layer and the amount of crosslinking agent added were varied.

(1) Undercoat 1st layer prescription Undercoat 1st layer binder V-520 parts by weight Elastron BN69 (Daiichi Kogyo Seiyaku Co., Ltd.) Addition amount is as shown in Table 4. ) 1 part by weight polystyrene fine particles (average particle size 3μ) Add distilled water to give lO-g/-2 Add 100 parts by weight 4% KOH p) Adjust to 16 Dry film thickness Dry as shown in Table 4 180603 Then, on one side of this undercoat sample, a silver halide emulsion layer, protective layer 1, and protective layer 2 were coated in order from the support, and on the other side, a back layer and protective layer 3 were coated in order from the support. 401 to 404 were created.

This sample was evaluated in the same manner as in Example-3.

The results are shown in Table 4.

(1) Silver halide emulsion formulation 35 Silver nitrate aqueous solution and sodium chloride aqueous solution containing the large salt compound ammonium rhodium (DI) in an amount of 1.3×10-' mol per 1 mol of silver were simultaneously added over 10 minutes to an aqueous gelatin solution kept in water. and set the potential between them to 200mV
After forming silver chloride cubic grains with an average grain size of 0.08μ in a monodisperse manner by controlling
Soluble salts are removed and 4-hydroxy-
6-Methyl-1,3,3a, 7-tetraazaindene and 1-phenyl-5-mercaptotetrazole were added.

A compound represented by the following (Q-1) was added to this emulsion.
10'' mol/1 mol of Ag, and the compound represented by (Q-2) was added in an amount of 1X10-' mol/1 mol of Ag.

(Q-1) (Q-2) Furthermore, 2-bis(vinylsulfonyl-leacetamido)ethane was added as a hardening agent at 145 g/edge of polyethyl acrylate at a solid content of 50 wt% based on gelatin at 935 mg/s. .

(2) Protective layer-1 prescription gelatin Ig/s"thioctic acid 6ag/m"90mg/
s" l,5-dihydroxy-2-benzaldoxime 35 mg/m" Dodecylbenzenesulfonic acid sodium salt 10 g/■8 Polystyrene sulfonic acid sodium salt
20mg/m" Ethyl acrylate latex (average particle size 0.05μ) 0.2g/m" (4)
Protective layer-2 prescription gelatin 0.6B/m" (Compound R) Polymethyl methacrylate fine particles (average particle size 2.5μ) 20mg/■Full silicon dioxide fine particles (average particle size 2.8μ) 305g/■FuN-
Perfluorooctanesulfonyl-N-probylglycinobotadium salt 3-g/-blocked dodecylbenzenesulfonic acid sodium salt 20 g/sr
“Hydroquinone 150+g/■
2. Compound R was added after preparing a gelatin dispersion according to the following procedure.

Compound R1B, 9g, was added to N,N-dimethylsulfamide 2
A dispersion was obtained by mixing the solution dissolved in 5-1 with 536 g of a 6.5 wt % aqueous gelatin solution containing 513 g of the following compound while stirring.

(Compound S) C11H13CONH(Cut) 5N(CHs) x
(CHz) ashs e (4) Back layer prescription gelatin 2.5g/m”0.2
6g/m"3Qmg/m" SO,K SO, 40+g/■2 SOJ 9
011g/”enriched dihexyl-α-sulfosacnate sodium salt 30a+g/m”dodecylbenzenesulfonic acid sodium salt 35mg/-21,
3-divinylsulfonyl-2-propertool 130s+g/-2 Ethyl acrylate latex (average particle size 0.05μ) 0.5g/m” (5
) Protective layer - 3 prescription gelatin 0.8 g/m" Polymethyl methacrylate fine particles (average particle size 3.4 μ) '40 mg/-8 dihexyl-α-sulfosacnate sodium salt 9 g/1 m" Dodecylbenzenesulfonic acid sodium salt 10 mg/m" Sodium Acetate Salt 40+g/So1 As can be seen from Table 4, samples 401 to 403 of the present invention have good adhesion, whereas sample 404 has poor adhesion.

Furthermore, the sample of the present invention has good dimensional stability due to processing, and has both adhesion and dimensional stability.

Example 5 Undercoat samples 501 to 504 were prepared in the same manner as in Example 1, except that the formulation of the first undercoat layer was changed as shown below. At this time, as shown in Table 5, the thickness of the first undercoat layer and the amount added on the crosslinking side were varied.

(1) Undercoat 1st layer prescription Undercoat 1st layer binder V-620 parts by weight Elastron BN44 (Daiichi Kogyo Seiyaku Co., Ltd.) The amount added is as shown in Table 5. Colloidal silica (Snowchix C (Kaguchi Kagaku Co., Ltd.) 0.4 parts by weight polystyrene fine particles (average particle size 3 μ) 5 g/-: Add distilled water and add 100 parts by weight 4% KOI (adjust to pH 6) Dry film thickness as shown in Table 5 18013 Then, on one side of this undercoat sample, a silver halide emulsion layer and a protective layer 1 were coated in order from the support, and on the other side, a back layer and a protective layer 2 were coated in order from the support.
~504 was created.

This sample was evaluated by the method of Example-3. The results are shown in Table 5.

(1) Silver halide emulsion layer formulation In the presence of 2×10-' mol of rhodium chloride per s 1 mol in a gelatin aqueous solution maintained at 50 @C, a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide are simultaneously added at a constant rate. for 30 minutes to reduce the average particle size to 0.
．． A 2μ silver chlorobromide monodisperse emulsion was prepared. (C1 composition: 95 mol%) This back side was desalted by the flochieracin method, and 1 g of thiourea dioxide and 0.6 mg of chloroauric acid were added per 111 moles, and the highest performance was achieved at 65% addition. It was left to ripen until it was obtained.

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

2X10-''mol/Ag1mol■ lXl0-3mol/Ai1mol4X10-'mol/Ag1molKB r 20mg/m
``Polystyrene sulfonate sodium salt 40mg1■32.
6-Dichloro-6-hydroxy-1,3,5-) riazine sodium salt 30 mg/s The coating solution was coated with a silver coating amount of 3.5 g/2.

(2) Protective layer l prescription gelatin 1.5g/-”Sto
w Fine particles (average particle size 4 μ) 50 g/Kabiyi dodecylbenzenesulfonic acid sodium salt 50 mg/-2H 5-nitroindasol 15 g/s”1
．． 3-Divinylsulfonyl-2-propatol 5Q+sg/-”p
J-berfluorooctanesulfonyl-N-propylglycine potadium salt 2 g/-8 Ethyl acrylate latex (average particle size 0.1 μ) 300 mg/garden 11
0 0+g/@” (3) Back layer prescription gelatin 2.5g/-39m
g/-” 5O2K 5osK40+g/amount 1 SOxK 5OffK80
s+g/m" 1.3-divinylsulfonyl-2-propatol 150 mg/m" Ethyl acrylate latex (average particle size 0.1 μ) 900 mg/m"
Dihexyl-α-sulfosacuna monosodium salt 35 mg/■ Dodecylbenzenesulfonic acid sodium salt 35-g/-1 (4
) Protective layer 2 prescription Gelatin 0.8 g/1 Polymethyl methacrylate fine particles (average particle size 3 μ) 20 g/, Z dihexyl α-sulfosacna monosodium salt 10 g/2 Dodecylbenzenesulfonic acid sodium salt 10 mg/ g+'Sodium acetate 40 g/Kaku 2 No. 5
As can be seen from the table, samples 501 to 503 of the present invention have good adhesion, whereas sample 504 has poor adhesion.

Furthermore, the sample of the present invention has good dimensional stability due to processing, and has both adhesion and dimensional stability.

Example-6 Polyethylene terephthalate extruded from a gooey to a thickness of 1
A 300 μm film was prepared, stretched 3.5 times in the longitudinal direction, and the following first undercoat layer was applied to both sides of the single film. At this time, as shown in Table 6, the first undercoat
Samples 601 to 60 were prepared by changing the layer thickness and type of crosslinking.
4 was created.

(1) Undercoat 1st layer prescription Vinylidene chloride latex (types are as shown in Table 5) 20 parts by weight Elastron BNII (Daiichi Kogyo Seiyaku Co., Ltd.) Colloidal silica Snochix ZL (Enza) in amounts added as shown in Table 6 Kagaku Co., Ltd.) 1.5 parts by weight of polystyrene fine particles (average particle size 3II) Added camphor-added distilled water such that the coating amount after biaxial stretching was 5-g/s'', and added 100 parts by weight of 4% by weight of KOH. Adjusted to pH 6 Dry film thickness The film thickness after biaxial stretching is as shown in Table 6.
After drying at 180''C for 3 minutes, this sample was stretched 4 times in the transverse direction at 120@C and further heat-set at 240°C to obtain a biaxially stretched polyethylene terephthalate film having a thickness of 100μ.

Subsequently, the following second undercoat layer was applied to both sides of this film to obtain undercoat samples 601 to 604.

(2) Undercoat second layer prescription Gelatin 1 part by weight Methyl cellulose 0.05 part by weight 0 0
CHx CHOI+ dict 0.02 parts by weight C+1F4isO(CEItCH*O)+J
0. Added 03 parts by weight of distilled water and added 100 parts by weight Dry film thickness: 0.1μ Dry time: 170163 minutes Silver halide back side layer, back layer, and protective layer similar to Example 1 were coated on both sides of this undercoat sample, and Samples 601 to 601 were prepared. 6
04 was created.

This sample was evaluated in the same manner as in Example-3.

The results are shown in Table 6.

As can be seen from Table 6, samples 602 to 604 of the present invention have good adhesion, whereas sample 601 has poor adhesion.

Furthermore, the sample of the present invention has good dimensional stability due to treatment, and exhibits both adhesion and dimensional stability due to treatment.

Claims (3)

[Claims] (1) An undercoat layer containing a polymer having a carboxyl group in the molecular chain is provided on at least one side of the polyester support, and the undercoat layer contains a water-soluble or water-dispersible blocked isocyanate. A silver halide photographic material characterized by: (2) the polymer contains a vinylidene chloride copolymer containing at least 70 to 99.9% by weight of a vinylidene chloride monomer and 0.1 to 5% by weight of a carboxyl group-containing vinyl monomer; The silver halide photographic material according to claim 1, wherein the layer thickness is 0.3 μm or more. (3) The silver halide photographic material according to claim 2, wherein the undercoat layer is applied after biaxially stretching the polyester support.