JPH02266934A - Antistatic layer - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic photosensitive material having no haze and excellent in transparency and antistatic properties by containing a hydrophobic polymer particle having one or more group out of a sulfonic acid group, a sulfuric ester group or a salt thereof in an antistatic layer. CONSTITUTION:A plastic film has an antistatic layer composed of a reaction product of a water-soluble conductive polymer, a hydrophobic polymer particle and a curing agent and the hydrophobic polymer particle has at least one of a sulfonic acid group, a sulfuric ester group or a salt thereof and is contained in a latex form not dissolved in water. One or more group out of an N-methylol group and a derivative thereof, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinylsulfone group and a block isocyanate group is contained in the hydrophobic polymer pref. in an amount of 1wt.% or more, especially, 5wt.% or more per one molecule. Further, the water-soluble conductive polymer has a conductive group selected from a sulfonic acid group, a sulfuric ester group, a quaternary or tertiary ammonium salt, a carboxyl group and a polyethylene oxide group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antistatic layer for a plastic film, and more particularly to a silver halide photographic material with excellent antistatic ability.

[Background of the invention]

Generally, plastic films have strong electrostatic properties, and this often imposes many restrictions on their use.

For example, supports such as polyethylene terephthalate are generally used in silver halide photographic materials, but they tend to become electrically charged, especially at low humidity such as in winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.

When a photosensitive material is charged, static marks appear due to the discharge, or foreign matter such as dust adheres to it, which causes pinholes and significantly degrades the quality, making it extremely difficult to repair. I'll put it down. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfonic acid Alternatively, a polymer having a phosphoric acid group in the molecule is used.

In particular, fluorosurfactants are used to adjust the charge series, and conductive polymers are used to improve conductivity.
No. 21523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.

However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.

This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for printing, such as with printing photosensitive materials, problems such as pinholes occur due to adhesion of dust.

For this reason, for example, JP-A Nos. 55-84658 and 61-1
No. 74542 proposes an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine. According to this method, it is possible to retain the antistatic ability even after geolysis, but it has the disadvantage that the fractional stability of the hydrophobic polymer particles is poor, causing aggregation in the film, and impairing the transparency of the antistatic layer. Ta.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide an antistatic layer for a glass film with excellent transparency and no haze. An object of the present invention is to provide a silver photographic material.

[Structure of the invention]

The above object of the present invention is to provide a plastic film having an antistatic layer consisting of a reaction product of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) a curing agent, in which the hydrophobic polymer particles have a sulfonic acid group, This is achieved by an antistatic layer characterized by having at least one group selected from sulfate ester groups or salts thereof.

The details of the present invention will be explained below.

About the water-soluble conductive polymer of the present invention 1. Examples include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. Among these groups, sulfonic acid groups, sulfuric acid ester groups, and quaternary ammonium bases are preferred. The amount of conductive groups required is 5% by weight or more per polymer molecule. The water-soluble conductive polymer preferably contains a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group. Requires at least 5% by weight per molecule.

The molecular weight of the polymer is 3000-100000,
Preferably it is 3500-5oooo.

Examples of water-soluble conductive polymer compounds used in the present invention are listed below, but the present invention is not limited thereto.

Homopolymer Homopolymer SO, Na CHl 5O3N & vl, 6ka (lO) MQ10,000 (23) Degree of dextran sulfate substitution 2.0 M-100,000 Father, Tsutomu, in (1) to (31) above! sF*'IF represents the mole % of the monomer component, and M represents the average molecular weight (in this specification, the average molecular weight refers to the number average molecular weight).

These polymers can be synthesized by polymerizing monomers that are commercially available or obtained by conventional methods.

Next, the hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are so-called latex particles that have at least one of a sulfonic acid group, a sulfuric acid ester group, or a salt thereof, and are substantially insoluble in water. Contained in the form of This hydrophobic polymer contains at least one of N-methylol groups and derivatives thereof, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, vinyl sulfone groups, and blocked incyanate groups. It is necessary to contain a large amount of hydrophobic polymer, and preferably it is contained in an amount of 1 weight or more per molecule of hydrophobic polymer, especially 5%.
The above is preferable. This hydrophobic polymer includes styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives,
It is obtained by polymerizing heptamers selected from vinyl ester derivatives, acrylonitrile, etc. in any combination. In particular, the content of styrene derivatives, alkyl acrylates, and alkyl methacrylates is preferably at least 30 mol %, particularly preferably 50 mol % or more.

As the monomer for introducing a sulfonic acid group, a sulfuric acid ester group, or a salt thereof, those represented by the following are preferable.

General formula (1) %formula% General formula (1) below [In the formula, R is an alkyl group having 1 to 4 carbon atoms, a hydrogen atom 2゜ 3゜ 4.

C1l-rich-C1 ωQC, Hδ-Na Ct+S αh-rich C α-power csaaso3, represents a divalent group having 1 to 6 carbon atoms, an aryl group, or a substituted aryl group, and A is an alkyl group having 1 to 12 carbon atoms. ,
a and b representing an alkenyl group or an aryl group represent 0 or l.

X represents -305M, -O3OiM-, and noodles represent a cation or a hydrogen atom. ] Specific examples of preferable seven-termers represented by the general formula (1) are given below.

l.

HI-CI SO, Na 5.

The content of the hepatomer having a sulfonic acid group, a sulfuric acid ester group, or a salt thereof is preferably 20 mol % or less.

There are two methods to make a latex from a hydrophobic polymer: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent and finely dispersing it, followed by distilling off the solvent. It is preferable to add emulsification because it allows the production of

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
A large amount of surfactant, preferably 0% by weight or less, causes clouding of the conductive layer.

The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.

2゜ 3゜ 4.

5゜ 9・ C.I.

6.

10° 7.

11° 8.

12°13°14°15° In the present invention, a conductive layer is coated on a transparent support. Although any photographic transparent support can be used, polyethylene terephthalate or cellulose triacetate, which is made to transmit 90% or more of visible light, is preferable.

These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, a slight amount of dye may be added to give them a blue tint so as not to substantially inhibit light transmission. good.

The support of the present invention may be coated with a subbing layer containing a latex polymer after being subjected to a corona discharge treatment.
■“win” is particularly preferably applied.

Particularly preferably, the corona discharge treatment is performed again before applying the conductive layer using a latex subbing layer coater.

As the compound for curing the conductive layer of the present invention, polyfunctional aziridine is preferred. Particularly preferred are those having bifunctional or trifunctional properties and a molecular weight of 600 or less.

The conductive layer of the present invention may be located closer to the support than the photosensitive layer, or may be located on the opposite side of the support to the photosensitive layer, ie, on the back surface.

The present invention can be applied to photosensitive materials formed on a support. For example, silver halide color photosensitive materials,
These include photosensitive materials for X-rays and photosensitive materials for plate making.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any commonly used silver halide grains can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is formed mainly inside the particle.

The silver halide emulsions used in the present invention are, for example, U.S. Pat. No. 2.444.607, U.S. Pat.
No. 89.380, No. 2.058.626, No. 2.
No. 118゜411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342.596, Japanese Patent Publication No. 4417-1987, West German Publication No. 2,149,789, Japanese Patent Publication No. 39-2
Compounds described in specifications or publications such as No. 825 and Japanese Patent Publication No. 49-13566, preferably, for example, 5°6-drimethylene-7-hydroxyne-S-triazolo (1,5-a)pyrimidine, 5. 6-Titramethylene-7-hydroxy-S-triazolo (l.5-a) Pyrimidine, 5-methyl-7-hydroxy-3-)riazolo (l.5-a) Pyrimidine, 5-methyl-7-hydroxy-5-triazolo (1,5-a)pyrimidine, 7
-Hydroxyne-s-triacylon(1,5-a)pyrimidine, 5-methyl-6-bromo-hydroxy-s
- triazolo(1,5-a)pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate,
propyl gallate, sodium gallate), mercaptans (l-722-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazole (6-nidropenzimidazole), etc. can be used for stabilization.

The silver halide photographic material and/or developer according to the present invention may contain an amino compound.

Further, in order to improve the developability, a developing agent such as phenidone or noihydroquinone, or an inhibitor such as benzotriazole may be contained in the emulsion. Alternatively, the backing layer may contain a developing agent or an inhibitor in order to increase the geographical ability of the Tsuta solution.

A hydrophilic colloid used with particular advantage in the present invention is gelatin.

The gelatin used in the present invention can be either alkali gelatin, acid gelatin, or alkaline gelatin, but when using ossein gelatin, it is preferable to remove the calcium or iron content.The calcium content is preferably 1 to 99%.
The iron content is 9 ppm, more preferably 1 to 500 ppm, and the iron content is 0. O is preferably 1 to 50 ppm, more preferably 0.140 ppm. In this way, the amount of calcium and iron can be adjusted by passing an aqueous gelatin solution through an ion exchange device.

Developing agents used in developing the silver halide photographic material according to the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2
．． 3-dibromo-11hydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4
-phenyl-catechol, 3-methoxy-catechol,
Examples include 4-acetyl-pyrogallol and sodium ascorbic acid.

In addition, typical ortho and rose aminophenols are used as first base developers, including 4-aminophenol, 2-amino-6-phenylphenol, and 2-aminophenol. -4-chlorophenylphenol, N-methyl-p-aminophenyl, and the like.

Furthermore, examples of the tlJ-(CH-CH)-NH* base developer include doamino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline,
Examples include N-(4-amino-3-methylphenyl)-7ulfoline and p-phenylenediamine.

Examples of the heterocyclic cleft developer include 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-virazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -Pyrazolidore 11
．． Examples include 1-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

The Theory of the Photographic Process, 4th Edition, by T. H. James.
ic Process Fourth Edition)
pp. 291-334 and Journal of the American Chemical Society.
he Ainawate erioan Chemical 5ooi
Ety) Vol. 73, p. 3.100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Furthermore, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used to develop the photosensitive material according to the invention, the effects of the invention will not be impaired, and the preservative will not be impaired. Hydroxylamine or a hydrazide compound can be used as a constant agent, and in this case, the amount used is preferably 5 to 500 g per 11 parts of the developer.
More preferably, it is 20 to 200 g.

Further, the developer may contain glycols as an organic solvent, and such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol,
Although examples include 1,5-bentanediol, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g per developing solution la. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material according to the present invention can be developed with a developer containing the above-mentioned development inhibitor to obtain a light-sensitive material with extremely excellent storage stability.

The DH value of the developer having the above composition is preferably 9 to 1.
3, but from the viewpoint of preservation and photographic properties, the 9H value is 10-
A range of 12 is more preferred. Regarding cations in the developer, it is preferable that the ratio of potassium ions is higher than that of sodium because the activity of the developer can be increased.

The silver halide photographic material according to the present invention can be processed under various conditions. For example, the development temperature is preferably 50°C or lower, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds to 50°C. It is optional to adopt processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, pre-hardening and neutralization. can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as I development or D development, or mechanical development such as roller development, color development, or hanger development.

〔Example〕

The present invention will be specifically explained below with reference to Examples.

It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example-1 After corona discharge was applied to subbed-treated polyethylene terephthalate, an antistatic liquid having the following composition was applied to the polyethylene terephthalate using a roll-fit coating pan and an air knife at a rate of 33 rises/in to 10a4/da''. It was applied.

Water-soluble conductive polymer (A) 6 glQ
Latex of the present invention (B) 4 g/Q
Hardener (H) It was dried at 90° C. for 2 minutes and heat treated at 140”o for 90 seconds.

Gelatin was coated on this antistatic layer at a concentration of 2.0 g/m'' and an adhesion test was conducted.As a hardening agent for gelatin, formalin, 2,4-dichloro-6-hydroxy s-triazine, Sodium was used.The results are shown in Table-1.

(1) Transmittance test Turbidity meter Model T-260OD manufactured by Tokyo Denshoku Co., Ltd.
Table 1 shows the transmittance as a percentage by measuring the film support using The growth of 0 particles, which produced particles containing 10-' moles per mole, was carried out in a system containing 3 og of benzyladenine per 11 of a 1% aqueous gelatin solution. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a,7tetrazaindene was added per mole of silver halide, followed by washing with water and desalting.

Next, 60 mg of 6-methyl-4-hydroxy-1,3,3m,7-tetrazaindene per mole of silver halide was added, followed by sulfur sensitization. 6-methyl-4-hydroxy-1,3°31. as a stabilizer after sulfur sensitization.
7-Tetrazaindene was added.

(Silver halide emulsion layer) Additives were added to each of the above emulsions in the amounts shown below, and layered on a polyethylene terephthalate support (100 μm thick) that was subbed with poly(vinylidene chloride-itaconic acid) latex. Coated.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer polymer 1.0 gam"Tetraphenylphosphonium chloride 30 yag/-3 Saponin 200 mg/s"
Polyethylene glycol 1GG am/s+
"Sodium dodecylbenzenesulfonate 100
mg/-■ Hydroquinone 200 mg/1 phenidone 100 B/a
“Styrene sulfone forged sodium-maleic acid polymer (
My-250,000) 200 mg/
m” gallic acid butyl ester 500 mg/
s”5-methylbenzotriazole 30 mg/
m”2-mercagutobenzimidazole-5-sulfone ml
3G mg/Kamokura inato-7ine gelatin (isoelectric point 4.9) 1.5 gam3 1(p-acetylamidophenyl)-5 mercaptotetrazole 30 ag/is the amount of silver
2.8 gam" (emulsion layer protective film) As an emulsion layer protective film, prepare the following amount I!1
I went to market.

Fluorinated dioctyl sulfosuccinate 300mg/
m" Matting agent: Polymethyl methacrylate (average particle size 3°5"
”)100 ・,/,・ Lithium nitrate salt 30 mg/m”
Acidic gelatin (isoelectric point 7.O) 1.2 ga
m” Colloidal Silica 50 mg/
s" Sodium styrene sulfonate-maleic acid copolymer 100 sg/m" Mordant dye (backing layer) After corona discharge with a power of 301/■ snow sin on the support opposite to the emulsion layer. , a poly(butyl acrylate-styrene-t-butyl acrylate-hydroxyethyl methacrylate) latex polymer was applied in the presence of a hexamethylene aziridine hardener, and an antistatic layer of the present invention was further applied in the same manner as in Example-1. Then, on this layer, a backing layer containing a backing dye having the following composition was applied.

The gelatin layer contains glyoxal and l-oxy-3,5-
Hardened with dichloro-5-triazine sodium salt.

(Backing layer) Hydroquinone 100 mg/1 phenidone 30 g/
Latex polymer: Butyl acrylate-styrene-acrylic acid copolymer 0.5 g/3 styrene-maleic acid 1t & 100 as/ugly 2
Citric acid 40 mg/-
3benzotriazole 100 v*g/
Teng 1 Styrene sulfonic acid under maleic acid copolymer
200 g/1 lithium nitrate salt 30 mg/II” Backing dye (b). (c) Ossein gelatin
2.0 g/s” (a) (b) (c) So, Na After the entire surface of the sample obtained as above was exposed and developed using the developer and fixer shown below, a film was formed. A transmittance test was conducted.

Developer formulation> Hydroquinone 25 gl-phenyl-4,4dimethyl-3-pyrazolidone 0.4M sodium bromide 3g5-methylbenzotriazole 0.3g5-nitroindazole 0
．． 05g5gdiethylaminopropane-2-diol0
g Potassium sulfite 90 g Sodium 5-sulfosalicylate 75 g Sodium ethylenediaminetetraacetate g Finished up with water to HE.

pa was set to 11.5 with caustic soda.

(ml composition A) Ammonium thiosulfate (72.5w% Sodium sulfite Sodium acetate, trihydrate boric acid, sodium citrate, dihydrate acetic acid (90w% aqueous solution) (Composition) Pure water (ion exchange) Water) Aqueous solution) 240 mG 7 g 6.5 g 6 g 6 g 13.61a 7 -Q Sulfuric acid (50% aqueous solution) 3.0 g Aluminum sulfate (Aqueous solution with All, O, converted content of 8.1 w%) 20 g Fixing Water 50% when using liquid
0m! The above-mentioned composition A5 was dissolved in the order of composition A5, and the composition was finished to 1a and used. The pH of this fixer was about 5.6.

Development geographical conditions> (Process) (Temperature) (Time) Development
Fixing at 40°C for 8 seconds, washing at 35°C for 8 seconds, and 10 seconds at room temperature. Evaluation was performed as follows, and the results are shown in Table 2.

Table-2 Ω/C-.

Furthermore, similar effects were obtained by replacing the hydrazine compound in the emulsion layer with the following tetrazolium salt.

From the results of tetrazolium compound Table 2, it can be seen that the samples according to the present invention show less deterioration in antistatic ability after development, are excellent in haze, and are significantly improved compared to the comparison.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material that does not deteriorate in antistatic performance even after processing such as development and has excellent haze.

The amount of polymer added is g/ugly 3 , the surface resistivity is

Claims (1)

[Claims] In a plastic film comprising an antistatic layer comprising a reaction product of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (3) a curing agent, the hydrophobic polymer particles have a sulfonic acid group, An antistatic layer having at least one group selected from a sulfate ester group or a salt thereof.