JPH04184431A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve dimensional stability at the time of processing by forming an undercoat layer of a specified thickness contg. a vinylidene chloride copolymer contg. a vinylidene chloride monomer and a vinyl monomer contg. a carboxyl group on a polyester base and incorporating N-methylpyrrolidone into the undercoat layer. CONSTITUTION:An undercoat layer of >=0.3mum thickness contg. a vinylidene chloride copolymer contg. 70-99.9 wt.% vinylidene chloride monomer and 0.1-5 wt.% vinyl monomer contg. a carboxyl group is formed on at least one side of a polyester base and N-methylpyrrolidone is incorporated into the undercoat layer. The vinylidene chloride copolymer preferably contains 85-99 wt.% vinylidene chloride monomer and 0.2-3 wt.% vinyl monomer contg. a carboxyl group. Dimensional stability can be improved at the time of processing.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, particularly a silver halide photographic material having excellent dimensional stability. The present invention relates to a silver halide photographic material with improved properties.

(Prior Art) Silver halide photographic materials generally have the disadvantage that their dimensions change during development.

This is because the elongation of the silver halide photographic light-sensitive material due to water absorption by the support during development processing does not recover until the time of use of the silver halide photographic light-sensitive material, even after the subsequent drying process. This is a phenomenon in which the dimensions of silver halide photographic materials change. In the art, this phenomenon is expressed as "poor dimensional stability associated with one processing", and this is an extremely important drawback, especially in silver halide photographic materials for printing.

In order to improve the dimensional stability associated with this treatment, a technology using an undercoat layer containing vinylidene chloride copolymer was developed in JP-A No. 6.
It is described in No. 4-538.

This method certainly improves the dimensional stability associated with processing. However, this method has the disadvantage that the adhesion between the support and the subbing layer is not sufficient.

As a means to improve the adhesion between the polyester support and the undercoat layer, a method of adding a polyester swelling agent to the undercoat layer is known, for example, as described in US Pat. No. 3,143,421, dihydric phenols are added to the undercoat layer. The method is described.

Among dihydric phenols, the most preferred one is resorcin, and the use of resorcin improves the adhesiveness to some extent. However, this method has the drawback that it not only has insufficient adhesion under an extremely high temperature atmosphere, but also spot failures often occur during the manufacturing process. In addition, dihydric phenols are highly irritating to the skin and eyes, and are not preferred in the production of silver halide photographic materials.

As a means of improving the adhesion between the polyester support and the undercoat layer, a method is known in which 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 process must be carried out under a vacuum of about I Torr, which is extremely complicated and disadvantageous in terms of cost.

Therefore, a means of improving adhesion between a polyester support and a subbing layer that does not have these drawbacks is desired.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic material with improved dimensional stability during processing.

The second object of the present invention is that it is highly irritating to the skin and eyes;
In addition, without using polyester swelling agents such as resorcinol, which tend to cause spot failures during the manufacturing process, or complicated means such as glow discharge treatment, it is possible to improve the adhesion between the polyester support and the silver halide emulsion layer. An object of the present invention is to provide a silver halide photographic material with improved adhesiveness in a humid atmosphere.

(Means for Solving the Problems) This object of the present invention is to provide at least 70 to 99.9% by weight of vinylidene chloride monomer and 0.1 to 5% by weight of vinylidene chloride monomer on at least one side of the polyester support. A halogenated product comprising an undercoat layer having a thickness of 0.3μ or more containing a vinylidene chloride copolymer containing a carboxyl group-containing vinyl monomer, and the undercoat layer containing N-methylpyrrolidone. Silver photosensitive material.

(2) The weight average molecular weight of the vinylidene chloride copolymer is 5
This was achieved by the silver halide photographic material described in (1) above, which is characterized in that it has a molecular weight of 0,000 or less.

(Specific Structure of the Invention) The vinylidene chloride copolymer of the present invention will be briefly described.

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

The carboxyl group-containing vinyl monomer used in the vinylidene chloride copolymer of the present invention has one specific example in the molecule:
Acrylic acid, methacrylic acid, itaconic acid, citraconic acid, etc. can be mentioned.

The vinylidene chloride copolymer of the present invention may contain, in addition to vinylidene chloride monomers and carboxyl group-containing monomers, monomers copolymerizable with these monomers.

Specific examples of these monomers include acrylonitrile, methacrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, styrene, and the like. 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 5000
It is preferably 0 or less, more preferably 45,000 or less.

The vinylidene chloride copolymer of the present invention is preferably in the form of an aqueous latex dispersion. In this case, a so-called core-shell structure latex having a different composition in the round part may be used.

Specific examples of the vinylidene chloride copolymer of the present invention include the following. However, the numbers in parentheses () represent weight ratios, and the hexagonal average molecular weight represents weight average molecular weights.

V-1 Latex of vinylidene chloride: methyl acrylate: acrylic acid (90:9:1) (average molecular weight
42000) v-2 vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic flic
81:4:4:4:l) latex (average molecular weight 40,000) V-3 vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90:6:2:2
) latex (average molecular weight 38,000) V-4 vinylidene chloride: ethyl methacrylate: 2-hydroxyethyl methacrylate: acrylic # (90:8
:1. sho.

5) latex (average molecular weight 44,000) V-5 core-shell type latex (core part 90% by weight, shell part 10% by weight) Core part, vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile, acrylic acid (93:3: 3:Q, 9:0.1) Shell part Vinylidene chloride dimethyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (88: 3:3:3:3) (average molecular weight 38000) V-6 core shell type latex (core core part vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (92°5=3:11:0.5) shell part vinylidene chloride: methyl acrylate dimethyl methacrylate: Acrylonitrile: methacrylic acid (90:3:3:1:3) (average molecular weight 20,000) The amount of N-methylpyrrolidone added is 0% of the coating solution for the undercoat layer.
．． A range of 2 to 20% by volume, preferably 1 to 10% by volume is preferred.

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

In addition to the vinylidene chloride copolymer and N-methylpyrrolidone, it is preferable to add a crosslinking agent to the undercoat layer of the present invention. As the crosslinking agent, a triazine compound such as 2.
Examples include 4-dichloro-6-hydroxy-1,3,5 triazine sodium salt, blocked isocyanate compounds such as BNII manufactured by Daiichi Kogyo Seiyaku ■, and melamine compounds such as Heckamine J-101 manufactured by Dainippon Ink ■. A matting agent, a surfactant, a dye, an inorganic fine particle, and a pH adjusting acid or alkali may be added.

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 constituents are aromatic dibasic acids such as isophthalic acid and terephthalic acid, and glycols such as ethylene glycol and 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
00. It is preferable to use a material with a diameter of about 100 mm in terms of ease of handling and versatility.

The silver halide photographic light-sensitive material of the present invention may be coated with one or more layers on the undercoat layer of the present invention, if necessary, and in this case, there are no particular restrictions on the binder for these undercoat layers, but the binder used is usually used. The thing is gelatin.

In addition to the binder, a crosslinking agent for the binder, a surfactant, a dye, a polymer latex, a mantle agent, a slipping agent, inorganic fine particles, an acid or alkali for adjusting pH1i, a preservative, etc. may be added to these undercoat layers.

The thickness of these undercoat layers is not particularly limited, but is preferably 0.
．． It is in the range of 0.02 to 2μ, more preferably 0.03 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 hack 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 hydroxyethyl cellulose; sugar derivatives such as agar, sodium alkinate, and starch derivatives; and 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 milk used in the silver halide photographic light-sensitive material used in the present invention is usually prepared by adding a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution to a water-soluble material such as gelatin. It is made by mixing in the presence of a polymer solution.

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 antifoggant, a hydrophilic colloid (especially gelatin), a gelatin hardener, a surfactant, a film physical property improver, It can contain a thickener, 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 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 capping 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 hex 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.

C. The thickness of the layer is 0.1μ to 10μ, and if necessary, like the silver halide emulsion layer and surface protection layer, gelatin hardener, surfactant, mantle agent, colloidal silica, slip agent, etc. It may contain UV absorbers, 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. , -i 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.

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

Hiroshi jl [l-1 Undercoat samples 101 to 109 were prepared by coating a first undercoat layer and a second undercoat layer on both sides of a biaxially stretched polyethylene terephthalate support having a thickness of 100 a in order from the support.

At this time, as shown in Table 1, the type of vinylidene chloride latex, the amount of N-methylpyrrolidone added, and the first
Created by changing the layer thickness.

(1) Undercoat 1st layer prescription Vinylidene chloride latex (types are as shown in Table 1) 20 parts by weight N-methylpyrrolidone Addition amount is as shown in Table 1 Colloidal silica (Snowtex ZL 8 Sankagaku tS>1, 5 Part by weight Polystyrene fine particles (average particle size 3 μ) 5a+g/m” (7) Coating Addition to make 1 ton Add distilled water 100 parts by weight Add 4% by weight KOH Adjust to pH 6 Dry film thickness Dry as shown in Table 1
180°C 3 minutes (2) 2nd undercoat
Layer formulation Gelatin 1 part by weight Methyl cellulose 0.05 part by weight HO+C(CH,
+, C-NH(C)If)2-N-(C)12)2N
H÷, HCIII II 10
0 (H.

Tobi HOII H2C1 0.02 parts by weight Cl28□0 (CH2CH2O) r. Ho, 03 parts by weight Add distilled water 100 parts by weight Dry film thickness 0. 1μ dry
At 170°C for 3 minutes, one side of this undercoat sample was coated with a back layer and a protective layer 1 in order from the support, and silver halide emulsion layer 1, silver halide emulsion layer 2, protective layer 2, and a protective layer 1 on the other side in order from the support. Samples 101 to 109 were prepared by coating the protective layer 3.

(1) Hack layer formulation (conductive layer) SnOz/Sb (9/1 weight ratio, average particle size 0.2
5μ) 300a+g/s+2 Gelatin 17o Compound-1
7 Dodecylbenzenesulfonate sodium salt 1o Dihexyl-α-sulfosuccinate sodium salt 4o Polystyrene sulfonate sodium salt 9 (2) Protective layer 1 prescription gelatin 2.9 g/m” compound-2 300 mg/m” compound- 3 SO3, S03 50IIg/II12 Compound-1 (above) 10 Dodecylbenzenesulfonic acid sodium salt 70 Dibenzyl-α
-Sulfosuccinate sodium salt 15 〃1.3-divinylsulfonyl-2-propatol 150 〃Ethyl acrylate latex (average particle size 0.05 μ) 500 〃Perfluorooctane sulfonic acid potassium salt 〃O 〃Silicon dioxide fine powder particles (Average particle size 3.5 μ, pore diameter 170, surface area 300 m”/g) 35 〃 (3) Silver halide milk layer-1 prescription ■ Solution: 300 ml of water, 9 g of gelatin II Solution: 100 g of AgNO, water 40011II solution; NaC] 37 g, (N)Ia)zRhcI
1.Al water 40 (1+1) Solution TI and solution III were added simultaneously at a constant rate to solution I kept at 45°C.The soluble salts were removed from this emulsion by a conventional method well known to those skilled in the art. After that, gelatin was added and 6-methyl-4-hydroxy-1,3,3a was added as a stabilizer.
7-thitraazaindene 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.

Compound-5 (postscript) 6X10-3 mol/Ag 1
Mol compound-6 (see below) 60 mong/garden 2
Compound-7 (described later) 96/m" Compound-1 (above) 101187m" Polystyrene sulfonic acid sodium salt 40 g/■2N-
Oleoyl-N-methyltaurine sodium salt 50mg/m”1.2
-Bis(vinylsulfonylacetamido)ethane 70s+g/Sono21-
Phenyl-5-mercaptotetradules 3 towns/m 2 Ethyl acrylate latex (average particle size 0.05 μ) 460 mg/m 2 The coating solution thus obtained was coated with an amount of silver of 2. Qg/,
, 2.

Compound-5 OJ Compound-7 2C1○ (4) Silver halide emulsion layer-2 formulation I Solution: 300 ml of water, 9 g of gelatin Solution II: 3100 g of AgNO, 400 ml of water III
Liquid; NaC137g, (NHa)3RhCI62.2m
g water 40 liters n+1 Prescription - In the same manner as the emulsion (3), add liquid II and liquid I to liquid I.
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 X10-'' mole/Ag 1 mole.

Compound-660mg/m2 Compound-79B/Il"Compound-110mg/m" Polystyrene sulfonic acid sodium salt 50mH/m2N-
Oleoyl-N-methyltaurine sodium salt 405g/+sz1.
2-bis(vinylsulfonylacetamido)ethane 80mg/a+”1-
Phenyl-5-mercaptotetrasol 3sg/s + ethyl acrylate latex (average particle size 0.05μ) 400sg/m The coating solution thus obtained was coated with a silver amount of 1. It was coated at a rate of 3 g/s''.

(5) Protective layer-2 prescription gelatin 1. Og/■2α-riboic acid 10mg/s"Dodecylbenzenesulfonic acid sodium salt 5-g/,!Compound-6 (above) 40+g/■2Compound-8 (postscript) 20-87m"Polystyrenesulfonic acid sodium salt 10mg/ m”1-
Phenyl-5-mercaptohydrazole 5mg/m" Compound-9 (see below) 20mg/m2 Ethyl acrylate latex (average particle size 0.05μ) 200mg/m2 (6
) Protective layer - 3 prescription Gelatin 1.0g/m2 Silicon dioxide fine powder particles (average particle size 3.5μ, pore diameter 25, surface area 700112/g) 50Il1g/w12 Liquid paraffin (gelatin dispersion) 43mg/m2 Dodecyl Sodium benzenesulfonate salt 20mg/side2 Potassium salt of perfluorooctanesulfonate 10+g/m2N-perfluorooctanesulfonyl-N-propylglycine potassium salt 3mg/m"Sodium salt of polystyrenesulfonate 2mg/s"Polymerization degree 5) Sodium sulfate ester of oxyethylene nonylphenyl ether 20++g/mz Colloidal silica (particle size 15 μm) 20a+g/s+
"Compound-8 Compound-9 <Method for preparing emulsified dispersion of hydrazine derivative>"
. , 12.1 The mixture was heated to 65°C and dissolved uniformly to form a liquid.

[Gelatin 12g□ The mixture was heated to 65° C. to uniformly dissolve it, and a liquid II was obtained.

Solution (1) and Solution II were mixed and stirred at high speed using a homogenizer (Nippon Seiki Seisakusho type) 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 was 0.2%.

Compound-10 The sample thus obtained was stored at 25° C. under an atmosphere of 160% RH for two weeks. Afterwards, the following evaluations were conducted.

1. Adhesiveness under normal humidity atmosphere] Using a razor, make 7 cuts in length and width at 5 mm intervals on the surface of the sample stored for 3 days in an atmosphere of 25°C and 55% RH to form 36 squares. 18.
Peel off quickly in the 0° 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 humidity atmosphere] Using a razor, make 7 cuts vertically and horizontally at intervals of 5+ m on the surface of the sample stored for 3 days at 25°C and 85% RH to form 36 squares. 1. Then attach adhesive tape (Made by Nitto Electric Industry ■ - Tape) on top of this.
Peel off quickly in an 80° 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 water washing, mark the emulsion surface of the film in the processing solution with a scratch mark (X) using an iron pen, and rub it firmly with the tip of your finger (Rub 5 times). Adhesion is evaluated during maximum peeling along the line.

Class A is when the emulsion layer does not peel beyond the scratches, and Class B is when the maximum peeling is within 2111111, and the maximum peeling is 5mm.
If it is within t, it is grade 0, and if it is less than t, it is grade D. Adhesive strength that is sufficient for practical use as a photographic material is A in the above four-level evaluation.
It is classified into a class.

[Evaluation method of dimensional change due to treatment] Two holes with a diameter of 81 mm were drilled in the sample at an interval of 20011I11, and after leaving it in a room at 25°C and 30% RH,
The distance between the two holes was accurately measured using a pin gauge with an accuracy of /10001 m/1 m. The length at this time is X1111
Set to 1. Next, an automatic developing machine is used to develop, fix, wash, and
After drying, the dimension after 5 minutes is defined as Ymm. In the industry, it is considered that there is no practical problem if the dimensional change rate (%) due to processing is less than ±0.01%.

The development process was done using Fuji Photo Film Co., Ltd.'s FG-660 automatic processor, and the developer and fixer were GR-D 1 and GR made by the same company.
The treatment was carried out using -F1 at 38°C for 20 seconds. The drying temperature at that time was 45°C.

As can be seen from Table 1, samples 102 to 105 of the present invention have good adhesion and dimensional stability due to processing.

Sample 1O1 to which N-methylpyrrolidone was not added;
Sample 108, which used a vinylidene chloride copolymer containing no carboxyl group, had poor adhesion, and a vinylidene chloride copolymer with a low vinylidene chloride content and a vinylidene chloride copolymer with an acrylic acid content of more than 5% were used. Sample 1
07.109 and sample 106 in which the thickness of the first undercoat layer was less than 0.2μ had poor dimensional stability during processing.

Furthermore, the coating liquid for the first undercoat layer of the present invention had extremely low irritation to the skin and eyes.

Example-2 Example-1 except that the first layer formulation of the undercoat was changed as follows.
Undercoat samples 201 to 204 were created in the same manner. At this time, as shown in Table 2, the thickness of the first undercoat layer and the amount of N-methylpyrrolidone added were varied.

(1) Undercoat 1st layer prescription Vinylidene chloride latex v-6 20 parts by weight Polystyrene fine particles (average particle size 2.5μ) Coating amount Lo
The amount of N-methylpyrrolidone added is as shown in Table 2. Add 1 part by weight of distilled water, add 1 part by weight of distilled water, add 100 parts by weight, 41% KOH, pH 5. , dry film thickness adjusted to 5
Dry at 190°C for 3 minutes as shown in Table 2. On one side of this undercoat sample, coat the silver halide emulsion layer and protective layer 1 in the order closest to the support, and on the other side coat the pack layer and protective layer 2 in the order closest to the support. Samples 201 to 204 were prepared.

This sample was then evaluated in the same manner as in Example 1.

The results are shown in Table 2.

(1) Silver halide emulsion layer prescription 1. Emulsion A was prepared using the TI and III solutions in the following manner.

Liquid I: 300ml of water, 79g of gelatin II @; AgN (100g of water, 400ml of water)
1III solution; NaC137g, (NH4)3RHC16
0.66 mg, water 400+I+1 The rr solution and the Ill solution were simultaneously added at a constant rate to the solution (2) maintained at 40°C. 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.
7-thitraazaindene and 4-hydroxy-5,6-
) Rimethylene-1°3.3a,7-titraazaindene was added.

The average grain size of this emulsion is 0.15 μm, which is a monodisperse backside, and the amount of gelatin contained per 1 kg of emulsion yield is 60 μm.
It was g.

The following compounds were added to the emulsion thus obtained.

Polystyrene sulfonic acid sodium trilam salt 10mg/m”II
2-bis(vinylsulfonylacetamido)ethane 100mg/m” Ethyl acrylate latex (average particle size 0.1μ) 500mg/m2
0.3 mg/m2 The coating solution thus obtained was coated to give a coated silver amount of 3'g/m2.

(2) Protective layer 1 prescription gelatin 1.5g/m2 Dodecylhenzensulfonic acid sodium salt 25II1g/Il
t-dihexyl-α-sulfosacnate sodium salt 110ll1/w1
2 Polymethyl methacrylate fine particles (average particle size 3μ) 601mg/m”N
-Perfluorooctanesulfonyl-N-probylglycine potassium salt 2mg/2m salt
3□g/m Z ethyl acrylate latex (average particle size 0.1μ) 200mg/m
2 Colloidal swell force 350mg/m” Riboic acid 8n+g/m2 (
3) Pack layer prescription gelatin 2g/m230mg
/m2 180 mg/la2 50I1g/m" Dibenzyl-α-sulfosacnate sodium salt 20+g/m2 Sodium dodecylbenzenesulfonate 305g/+++"
Polystyrene sulfonic acid sodium salt 30B/a+”1.
3-divinylsulfonyl-2-propertool 100mg/m” Ethyl acrylate latex (average particle size 0.1#) 20 (1+g/
s'' (4) Protective layer 2 prescription gelatin Ig/s+''Polymethyl methacrylate fine particles similar to those used in protective layer 1 4 (1+g/■2 dihexy-α-sulfosacnate sodium salt lo-g/, 1
Dodecylbenzenesulfonic acid sodium salt 30mg/m" Polystyrene sulfonic acid sodium salt 25+sg/m" Sodium acetate 30mg/m2 Example-3 Example-1 except that the first layer formulation of the undercoat was changed as follows.
Undercoat samples 301 to 303 were created in the same manner.

At this time, as shown in Table 3, the amount of N-methylpyrrolidone added was varied.

(1) Undercoat 1st layer prescription Vinylidene chloride latex V-4 20 parts by weight Polystyrene fine particles (average particle size 3μ) Added to give coating amount ioIIg/m2 N-methylpyrrolidone Addition amount is as shown in Table 3 Block isocyanate compound NB -11 (Daiichi Kogyo Seiyaku ■) 0.2 parts by weight Colloidal silica (Snowtex C (8 San Kagaku ■) Add 0.4 parts by weight of distilled water and add 100 parts by weight of 4% by weight of NaOH p) Adjust to 16 and dry Film thickness 3rd
Dry at 185°C for 3 minutes as shown in the table. On one side of this undercoat sample, in the order closest to the support, silver halide back layer, protective layer 1, and protective layer 2. On the opposite side, in the order closest to the support, hack layer, protective layer 3. Sample 301
~303 was created. This sample was then evaluated in the same manner as in Example-1.

The results are shown in Table 3.

(1) Silver halide hole side prescription Into a gelatin aqueous solution kept at 35°C, simultaneously add a silver nitrate aqueous solution and a sodium chloride aqueous solution containing 1.3 x 10-' mol of rhodium (III) hexachloride compound ammonium per 1 mol of silver. 2 minutes, and the potential during that time was set to 200
By controlling the mV, monodisperse cubic silver chloride grains with an average grain size of 0.08 μm were prepared. After particle formation, soluble salts are removed by flocculation methods well known in the art, and stabilizers 4-hydroxy-6-methyl-1,3,3a, 7-titraazaindene and l-phenyl- 5-mercapto'e-)razole was added.

A compound represented by the following (Q-1) is placed on the back side of this
10-3 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) In addition, polyethyl acrylate was added as a solid content at 50 t% per gelatin, So, Na was added at 35 mg/m2, and 2-bis(vinylsulfonylacetamido)ethane was added at 145 mg/m2 as a hardening agent. Added.

(2) Protective layer-1 prescription gelatin Ig/m2 Thioctic acid 6mg/m"1,5-dihydroxy-2-henzaldoxime 35mg/m"Dodecylbenzenesulfonic acid sodium salt 10mg/m"Polystyrenesulfonic acid sodium salt 20B/m m” Ethyl acrylate latex (average particle size 0.05 μ) 0.2 g/m2 (4) Protective layer-2 prescription gelatin 0. 6tsg/m2
(Compound R) 0.1g/a+” Polymethyl methacrylate fine particles (average particle size 2.5μ) 20+g/lI” Silicon dioxide fine particles (average particle size 2.8u) 30mg/m
"N-perfluorooctanesulfonyl-N-propylglycine potassium salt 3mg/m2 Dodecylhenzenesulfonic acid sodium salt 20mg/m2 Hydroquinone L 50mg/+112
In addition, the above-mentioned compound R was added after preparing a gelatin dispersion according to the following procedure.

A solution of 9 g of compound R1B dissolved in 25 ml of N,N-dimethylsulfamide was added to 536 g of a 6.5 wt% aqueous gelatin solution containing 313 g of the following compound at 45°C.
The mixture was mixed with stirring to obtain a dispersion.

(Compound 5) (4) Bank layer formulation gelatin 2.25g/e”0.2
6g/m" 30kg/■2 40mg/rin2 Dihexyl-α-sulfosacnate sodium salt 30s+g/m"Dodecylbenzenesulfonic acid sodium salt 35■g/m"1.3
-Divinylsulfonyl-2-propanol 130 mong/m"Ethyl acrylate latex (average particle size 0.05μ) 0.5g/m" (5)
Protective layer-3 formulation gelatin 0.8g/-2 polymethylmethactalate fine particles (average particle size 3.4 μ) 40mg/m”
Dihexyl α-sulfosacnate sodium salt 9 mg/m” Dodecylhenzenesulfonic acid sodium salt 10 g/m
Sodium acetate salt 40 steel g/m2 Example-4 Undercoat samples 401 to 403 were prepared in the same manner as in Example-1, except that the formulation of the first undercoat layer was changed as follows. The hair of N-methylpyrrolidone was changed as shown in the table.

(1) Undercoat 1st layer prescription Vinylidene chloride latex v-2 20 parts by weight Polystyrene fine particles (average particle size 3μ) Added to give a coating amount of 10+g/m” Melamine compound BECKAMINE The amount of N-methylpyrrolidone added is as shown in Table 4. J-101 (Dainippon Ink & Chemicals ■) 0.2 parts by weight Colloidal silica (Snowtex C (8san Kagaku ■) 0.4 parts by weight Add distilled water, add 100 parts by weight 4% by weight NaOH, adjust to pH 6 and dry. Film thickness: Dry as shown in Table 3. Dry at 180°C for 3 minutes. On one side of this undercoat sample, silver halide emulsion layer and protective layer I are applied in order from the support, and on the other side, back layer and protective layer are applied in order from the support. Apply layer 2 and sample 401-4
03 was created. This sample was then evaluated in the same manner as in Example-1. The results are shown in Table 4.

(1) 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.
A 2μ silver chlorobromide monodisperse emulsion was prepared. (CI composition 95
(mol%) This emulsion was desalted by the flocculation method, 1 mg of thiourea dioxide and 0.6 mg of chloroauric acid were added per mole of silver, 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+Jzs 2X10-"mol/Ag1mol〇'IXIO-"%/Lz/Ag1
Mol 4XIQ-4 mol/Ag 1 mol KB r 20μg7'a
Polystyrene sulfonate sodium salt 40+g/month 22.
6-Dichloro-6-hydrone sodium salt 30 mg 1/2 This coating solution was coated at a coating silver amount of 3.5 g/s.

(2) Protective layer l prescription gelatin 1, 5 g/s
"Sin, fine particles (average particle size 4#) 5 (1+g/m
"Dodecylbenzenesulfonic acid sodium salt 50μ+g/@"H 5-nitroindazole 15mg/s"1.
3-divinylsulfonyl-2-propatol 50mg/■2N-perfluorooctanesulfonyl-N-pro and luglycine botadium salt 2mg/*"Ethyl acrylate latex (average particle size 0.1 #) 300mg/m"
100ag/s" (3) Hack layer prescription gelatin 2.5g/e230mg/1I2 SO3Na 140ng/m"40ng
/m2 1.3-divinylsulfonyl-2-propatol 150mg/m" Ethyl acrylate latex (average particle size 0.1 μ) 900mg/m"
Dihexyl-α-sulfosacuna monosodium salt 35mg/m2 Dodisylbenzenesulfonic acid sodium salt 35+sg/m2 (
4) Protective layer 2 prescription gelatin 0.8 g/m" polymethyl methacrylate fine particles (average particle size 3 μ) 20 mg/m2 dihexyl-α-sulfosacnate sodium salt 10+wg/m2 dodisylbenzenesulfonic acid sodium salt l10l11/11
12 Sodium acetate 40a+g/
m2 procedural amendment February 1, 1991 ゛

Claims (2)

[Claims] (1) Vinylidene chloride copolymer containing at least 70 to 99.9% by weight of vinylidene chloride monomer and 0.1 to 5% by weight of carboxyl group-containing vinyl monomer on at least one side of the polyester support. Thickness 0.3 including coalescence
1. A silver halide photographic light-sensitive material having an undercoat layer having a particle size of μ or more, and the undercoat layer containing N-methylpyrrolidone. (2) The weight average molecular weight of the vinylidene chloride copolymer is 5
2. The silver halide photographic material according to claim 1, wherein the silver halide photosensitive material has a molecular weight of 0,000 or less.