JPH037934A - Antistatic layer - Google Patents

Abstract

PURPOSE:To prevent the deterioration of an antistatic layer even after photographic processing and to improve the adhesive property to a hydrophilic colloidal layer by forming the antistatic layer with specified polymer particles and a specified hardening agent. CONSTITUTION:An antistatic layer is formed on a plastic film with a product obtd. by allowing a water soluble electrically conductive polymer such as a compd. represented by formula I to react with particles of a hydrophobic polymer and a hardening agent represented by formula III (where R1 is H, <=20C alkyl, etc., and R2 is H or <=10C alkyl). The hydrophobic polymer has one or more prescribed groups such as N-methylol (deriv.), amino and epoxy groups and may be a compd. represented by formula II. The hardening agent may be a compd. represented by formula IV.

Description

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

[Background of the invention]

Generally, plastic film supports 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.
It is easy to be charged especially in low humidity such as 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, adjusting the charge series using fluorine-based surfactants or improving conductivity using conductive polymers has been widely used, for example, in JP-A-49-91165 and JP-A-49-1.
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, antistatic properties can be maintained even after processing, but this antistatic layer has poor adhesion to the hydrophilic colloid layer coated on top of this layer, making it difficult for the film to peel off during the development process. There was a problem that occurred.

[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 plastics that does not deteriorate even after processing such as development and has excellent adhesive properties. The object of the present invention is to provide a silver halide photographic material having excellent antistatic properties.

[Structure of the invention]

The above object of the present invention is to provide a plastic film having an antistatic layer consisting of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) a reaction product of a hardening agent, in which the hydrophobic polymer particles are N- Methylol group and its derivatives, amino group, epoxy group, aziridine group, active methylene group, sulfine group, aldehyde group, vinyl sulfone group,
This can be achieved by an antistatic layer having at least one group of blocked isocyanate groups and containing the following binding agent CI) as a hardening agent.

[In the formula, R1 represents a hydrogen atom, an alkyl group or aryl group having up to 20 carbon atoms, a hydroxy group, or a halogen atom. R7 represents a hydrogen atom or an alkyl group having up to IO carbon atoms. ] The details of the present invention will be explained below.

The water-soluble conductive polymer according to claim 1 of the present invention has 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. Examples include polymers with 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. Water-soluble conductive polymers contain N-methylol groups and derivatives, hydroxy groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, vinyl sulfone groups, and blocked isocyanate groups. is preferable.

These groups are required in an amount of 5% by weight or more per polymer molecule. The molecular weight of the polymer is 3,000 to 100,000, preferably 3,500 to 50,000.

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

(1) Homopolymer (2) Homopolymer (4) (5) So , Na (lO) (11) (12) (13) (6) (7) (8) (9) (14) (15) (16 ) (17) (18) (19) (20) (21) 5υ3L1 (26) (27) o3Na (28) (29) MSpec 10,000M#06,000 (22) (23) Dextran sulfate substitution degree 2.0 M=100,000 (24) SO, Na (25) M#100,000 (30) (31) In the above (1) to (31), Xt3' and Z are the monomer components, respectively. 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 heptamers 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 contained in a so-called latex form that is substantially insoluble in water. This hydrophobic volize contains at least one group selected from N-methylol groups and derivatives, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, vinyl sulfone groups, and blocked isocyanate groups. The content is preferably 1% by weight or more per molecule of the hydrophobic polymer. Particularly preferred is 5% or more.

This hydrophobic polymer is obtained by polymerizing seven polymers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. . In particular, it is preferred that the composition contains at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates.

Particularly preferred is 50 mol% or more.

There are two methods to make a hydrophobic polymer into a latex form: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then distilling off the solvent. Emulsion polymerization is preferable because it can produce a product.

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferably 0% by weight or less.

A large amount of surfactant 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.

Specific examples of the hydrophobic polymer of the present invention will be given below.

l.

The curing agent used in the present invention is represented by the following general formula [I].

14° Here, R1 represents a hydrogen atom, an alkyl or aryl group having up to 20 carbon atoms, a hydroxy group, or a hydrogen atom, and R2 represents a hydrogen atom or an alkyl group having up to IO carbon atoms.

The following are preferably used, but the invention is not limited thereto.

(1) (2) (5) (6) (7) 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 latex or polymer after being subjected to corona discharge treatment.

The energy value of corona discharge treatment is l mW” l
KW/m"min is particularly preferably applied.

Particularly preferably, corona discharge treatment is performed again after applying the latex undercoat layer and before applying the conductive layer.

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. 47-4417,
West German Application Publication No. 2,149.789, Special Publication No. 1973-
Compounds described in specifications or publications such as No. 2825 and Japanese Patent Publication No. 49-13566, preferably, e.g.
゜6-Drimethylene-7-hydroxyne-S-triazolo(1,5-a)pyrimidine, 5,6-titramethylene-7-hydroxy-S-triazolo, (1,5-a)pyrimidine, 5-methyl-7-hydroxy-3 -) Riazolo(1,5-a)pyrimidine, 5-methyl-hydroxy-S-triazolo(1,5-a)pyrimidine, 7-
Hydroxine-5-) Riazolone (l, 5-a) Pyrimidine, 5-methyl-6-promorph-hydroxy-S
- triazolo(1,5-a)pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate,
propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2
-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazolemidazole (6-nidropenzimidazole), etc.).

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 hydroquinone or an inhibitor such as benzotriazole may be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the backing layer may contain a developing agent or an inhibitor.

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

The gelatin used in the present invention can be treated with either alkali treatment or acid treatment, but when using ossein gelatin, it is preferable to remove calcium or iron. The preferred calcium content is 1-99
9 ppm, more preferably 1 to 500 ppm
The iron content is preferably 0.01 to 50 ppm, more preferably 0.1 to 10 ppm. The amount of calcium and iron can be adjusted in this way 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-dibromohydroquinone, 2.5-diethylhydroquinone, catechol, 4-chlorocatechol, 4
-7enylcatechol, 3-methoxy-catechol,
Examples include 4-acetyl-pyrogallol and sodium ascorbic acid.

In addition, as HO- (CH-, CH), -NH, type developers, ortho and rose aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-aminophenol, etc. -4-chloro-6-phenylphenol, N-methyl-p-aminophenyl and the like.

Furthermore, examples of HzN (CH- CH)-NHz type developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, and N-(4-amino-diethylaniline). -3-methylphenyl)-
Examples include p-7 ruforine, p-7 22-diamine, and the like.

Examples of the heterocyclic base developer include 3-pyrazolidone such as 1-7enyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-virazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -pyrazolidones,
Examples include l-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

The Theory of the Photographic Process, 4th Edition, by T. H. James.
ofPhotographic Process Fo
urth Edition) pages 291-334 and Journal of the American Chemical Society ((Journal of the American
Chemical 5ociety) Volume 73, No. 3.
Developers such as those described on page 100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more, but
It is preferable to use a combination of two or more species. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the invention, the effects of the invention will not be impaired. In addition, hydroxylamine and hydrazide compounds can be used as preservatives, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 2 g per tQ of developer.
00g.

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 preferred amount of these glycols used is 5 to 500 g per 112 grams of developer.
The amount is more preferably 20 to 200 g. 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 pH value of the developer having the above composition is preferably 9 to 13.
However, from the viewpoint of storage stability and photographic properties, the pH value is 1O~1
A range of 2 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. As for the processing temperature, 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. Seconds often have a positive effect. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments include plate development,
It may be a so-called manual development process such as frame development, or a mechanical development process such as roller development or hanger development.

〔Example〕

EXAMPLES 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 performing corona discharge on polyethylene terephthalate treated with subbing, an antistatic liquid having the following composition was applied at 10 mff/dm.
The coating was carried out using a roll-fit coating pan and an air knife at a speed of 33 m/min so that the coating amount was as follows.

Water-soluble conductive polymer (A) 6 glQ Latex of the present invention (B) 4 gIQ-Hardening agent (C) 1.5 g #290
It was dried at 140°C for 2 minutes and heat treated at 140°C for 190 seconds.

Gelatin was coated on this antistatic layer at a concentration of 2.0 g/m' and a haze test was conducted. Formalin and 2,4-dichloro-6-hydroxy S-) lyazine sodium were used as gelatin hardeners. The results are shown in Table-1.

(1) Adhesion test/dry film test> Make shallow scratches on the emulsion surface of the sample with a razor in the shape of the substrate.
The remaining rate of the emulsion film relative to the adhesive area of the cellophane tape when the cellophane adhesive tape was pressure-bonded thereon and then rapidly peeled off was expressed as a percentage.

Treatment film test> In a processing bath, the emulsion surface of the sample was scratched in the shape of a substrate with a sharp end, and the surface was rubbed, and the residual rate of the emulsion film was expressed as a percentage. In practice, there is no problem if this percentage is 8.0% or more.

Example 2 Particles containing 10 moles of rhodium per mole of silver were prepared by a controlled double jet method in an acidic atmosphere with a pH of 3.0. Particle growth was carried out in a system containing 30 mg of benzyladenine per 1Q of 1% aqueous gelatin solution. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a,7tetrazaindene per mole of silver halide was added, followed by washing with water and desalting.

Next, 60 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene per mole of silver halide was added, followed by sulfur sensitization. 6-methyl-4-hydroxy-1,3,3a 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 coated on a polyethylene terephthalate support (100 μm thick) that had been subbed with poly(vinylidene chloride-itaphonic acid) latex. did.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer 1.0 g/m"Tetraphenylphosphonium chloride 30 +ig/a"Saponin 200 mg7m"
Polyethylene glycol 100 mg/+”
Sodium dodecylbenzenesulfonate 100-g/
m”Hydroquinone 20On+g/m”Phenidone 100 mg/m”Sodium styrene sulfonate-maleic acid polymer (My
-250,000) 200 mg/m"Gallic acid butyl ester 500 mg/la"5-
Methylbenzotriazole 30 mg/va”
2-Mercaptobenzimidazole-5-sulfonic acid
30 wig/m' Inatoossein gelatin (isoelectric point 4.9) 1.5 g/m" 1-(p-acetylamidophenyl)-5 mercaptotetrazole 30 mg/+a" Silver amount 2.8 g/m (Emulsion layer protective film) An emulsion layer protective film was prepared and coated in the following amount.

Fluorinated dioctyl sulfosuccinate 300mg/
m” Matting agent: polymethyl methacrylate (average particle size 3.5 p m) 100 B
/+”Lithium nitrate salt 30!!
Ig7m” acid-treated gelatin (isoelectric point 7.0) 1
．． 2 g/m” colloidal silica 50
mg/m” Sodium styrene sulfonate-maleic acid copolymer 100 rag/
a" mordant (backing layer) 30 W/m" in advance on the support opposite to the emulsion layer
After corona discharge with a power of min., a poly(butyl acrylate-styrene-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 as an example. Coating was carried out in the same manner as in -1, and then a backing layer containing a backing dye having the following composition was coated on this layer. The gelatin layer contains glyoxal and 1-
hardened with oxy-3,5-dichloro-S-triazine sodium salt;

(Backing layer) Hydroquinone! 00 a+g/m
“Phenidone 30 rag/
m" Latex polymer: Butyl acrylate-styrene-acrylic acid copolymer 0.5 g/m" Styrene-malein H co-11 combination 100 mg/m" Citric acid 40 mg/m" Benzotriazole 100 mg/m2 Styrene sulfonic acid soda maleic acid copolymer
200 mg7m” lithium nitrate salt
30 mg/m” backing dye (a), (
b), (c) Ossein gelatin 2.0
g/m2CI! So.

Developer formulation> Hydroquinone 25 gl-phenyl-4,4dimethyl-3-pyrazolidone 0.4g Sodium bromide 3g 5-methylbenzotriazole 0.3 g5-nitroindazole
0.05 g 5 g Diethylaminopropane-2-diol 0 g Potassium sulfite 90 g Sodium 5-sulfosalicylate 75 g Sodium ethylenediaminetetraacetate g Finished to 1Q with water.

pn was set to 11.5 with caustic soda.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5w% aqueous solution) 240
mQ Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g Sodium citrate dihydrate
2g acetic acid (90w% aqueous solution) 13.6
n+72 (composition) Pure water (ion-exchanged water) 17 mQ sulfuric acid (50w% aqueous solution) 3.0g aluminum sulfate (A (2203 equivalent content: 8.1v% aqueous solution)
When using 20g of fixer, the above compositions were dissolved in 500mff of water in the order of composition A1 and finished to 1Q before use. The pH of this fixer was about 5.6.

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

The unit of the surface resistivity after treatment is 0 cm.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material whose antistatic performance does not deteriorate even after processing such as development.

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 hardening agent, the hydrophobic polymer particles are N- It has at least one group selected from a methylol group and its derivatives, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfine group, an aldehyde group, a vinyl sulfone group, and a blocked isocyanate group, and has the following as a hardening agent: An antistatic layer characterized by containing general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a hydrogen atom, an alkyl group or aryl group having up to 20 carbon atoms, a hydroxy group, or a halogen atom. R_2 represents a hydrogen atom or an alkyl group having up to 10 carbon atoms. ]