JPH02298941A - Antistatic layer - Google Patents

Abstract

PURPOSE:To improve transparency and to obviate the degradation in antistatic performance even after processing, such as developing, by using hydrophobic polymer particles having specific groups for the antistatic layer of a plastic film base and incorporating the compd. expressed by general formula as a hardener therein. CONSTITUTION:The hydrophobic polymer particles of the antistatic layer for the plastic film base have at least one of the groups among sulfonic acid sulfonate ester groups or the salts thereof and contain the compd. expressed by the general formula 1 as the hardener. In this formula I, R1, R2 denote up to 4C alkyl groups which may be different from each other; X1, X2, X3, X4 denote hydrogen, up to 3C alkyl groups, and halogen atom which may be different from each other. L denotes a mere bond, up to 4C alkyl groups, alkyleneoxy group. The deterioration in the performance of the antistatic layer which has the excellent transparency and is free from haze and the electrostatic charge after the development processing is obviated.

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 are created due to the discharge, or foreign matter such as dust is attached, which causes pinholes and significantly deteriorates the quality.
The work efficiency is greatly reduced due to the correction. 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-4912.
No. 1523 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-55-84658 and JP-A-61-174542 propose 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, the antistatic ability can be maintained even after treatment, but the dispersion stability of the hydrophobic polymer particles is poor, causing aggregation in the film, which impairs the transparency of the antistatic layer.

[Purpose of the invention]

In view of the above-mentioned problems, an object of the present invention is to provide an antistatic layer for a plastic film support having excellent transparency and no haze.
An 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 support having an antistatic layer comprising a reaction product of (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (3) a hardening agent. the polymer particles have at least one group of a sulfonic acid sulfate group or a salt thereof;
This is achieved by an antistatic layer characterized in that it contains the general formula CI) as a hardening agent.

General formula (1) R,, R, represent an alkyl group having up to 4 carbon atoms, and may be different from each other. X l, X *, X s, X a
represent hydrogen, an alkyl group having up to 3 carbon atoms, or a halogen atom, and may be different from each other. L is just a bond,
Represents an alkyl group or alkyleneoxy group having up to 4 carbon atoms.

The details of the present invention will be explained below.

For the water-soluble conductive polymer of the present invention, sulfone r
lll&, flLm ester group, quaternary ammonium salt,
Examples include polymers having at least one conductive group selected from tertiary ammonium salts, carboxyl groups, and polyethylene oxide groups. 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 carboxy group, 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.

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) Homobolimer (2) Homopolymer (3) Ii, Hs ? 1・ Cα CH.

■ 1 grade 25,000? H・M″q10,000M=tO, 60,000 (23) Degree of dextransal 78 substitution 2.0 M-100,000M”=100,000i#60,000x:y:z-60:10230Mζ60,000 In addition, in the above (1) to (31), X+'l+2 each represents the mol% 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). represent.

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

Next, the hydrophobic polymer particles contained in one layer of the water-soluble conductive polymer 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 includes styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives,
It is obtained by polymerizing heptamers selected from acrylonitrile and the like in any combination. Especially styrene derivatives,
Preferably, the alkyl acrylate or alkyl methacrylate content is at least 30-Tyl%. Particularly preferred is 50 mol% or more.

The monomer having a sulfonic acid group, a sulfuric acid ester group, or a salt thereof is preferably 20 mol % or less.

As the hexamer for introducing a sulfonic acid group, a sulfuric acid ester group, or a salt thereof, those represented by the following general formula [■] are preferable.

(II) R □ <cH2-c)- R: alkyl group having 1 to 4 carbon atoms, hydrogen atom, halogen L: at least one bonding group selected from -C-, -NH-, -0-, 2 having a group and having 1 to 6 carbon atoms
or group aryl group, substituted aryl group A: C1-C12 alkyl group, alkenyl group, aryl group a, b: Q or l X: SO3M, O3OxM, M is a cation or hydrogen General formula (II ) Specific examples of preferred monomers are listed below.

3, 4゜5, 6゜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, finely dispersing it, and then distilling off the solvent. Emulsion polymerization is preferred because it produces particles with fine particle size and uniform grain size.

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.

2゜ KotJ3Na 3.

4.

5, clI3 11° and i3 General formula CI) for curing the conductive layer of the present invention will be explained.

R,,R! : Represents an alkyl group having up to 4 carbon atoms, and may be different from each other.

X,,X2. X , , X 4 represents hydrogen, an alkyl group having up to 3 carbon atoms, or a halogen atom, and may be different from each other.

L: represents a simple bond, an alkylene group having up to 4 carbon atoms, or an alkyleneoxy group.

Next, specific examples of compounds will be given.

I-I CH,O,5-cHz-CI,-SO,CH
3I 2 CHsOsS- (CI2 piece So, CH.

■-3CL (hS CHZ) zCH*5 (hc
Hsl-4CH,O,5-Cl(CH2)0(CH2h
CH25(hcHxI-5CQ CQ CH303S CH(CH2)4CH5O3CH3 These compounds can be synthesized with reference to the description in the specification of US Pat. No. 2,726.162.

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. Corona discharge treatment has an energy value of 1 mW to 1 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. The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver monohalide composition distribution within the grain, or may be core/fel grains in which the silver halide composition differs between the interior and surface layer of the grain, in which the latent image is mainly The particles may be formed on the surface or may be formed primarily inside the particles.

Examples of the silver halide emulsion used in the present invention include U.S. Pat. No. 2,444.607, U.S. Pat.
No. 80, No. 2,058゜626, No. 2.118.41
No. 1, Special Publication No. 43-4133, U.S. Patent No. 3,342,
No. 596, Special Publication No. 47-4417, West German Application Publication 2
．． Compounds described in specifications or publications such as No. 149.789, Japanese Patent Publication No. 39-2825, and Japanese Patent Publication No. 49-13566, preferably, for example, 5,6-trimethylene-7-hydroxyne-5-triazolo (1,5-a
) Pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo(1,5-a) Pyrimidine, 5-methyl-7-hydroxy-5-triazolo(1,5-a)
Pyrimidine, 5-methyl-7-hydroxy-s-triazolo(1,5-a)pyrimidine, 7-hydroxy-s
- triacylon(1,5-a)pyrimidine, 5-methyl-6-bromohydroxy-s-triazolo(1°5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate) ,
Sodium gallate), mercaptans (l-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylhenttriazole), benzimidazoles (6-nidro penzimidazole)
It can be stabilized using 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
The iron content is preferably 9 ppm, more preferably i500 ppm, and the iron content is preferably 0.001-50 ppm, more preferably 0.11-1 Opp. The amount of calcium and iron can be adjusted in this manner 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-
Phenyl-catechol, 3-methoxy-catechol, 4
-Acetyl-pyrogallol, sodium ascorbic acid, etc.

Further, as the HO-(CH-CI), -NH2 type developer, ortho and para aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4 -chloro-6-phenylphenol, N-methyl-p-aminophenyl, and the like.

Furthermore, 82N-(CH=CH), -NH! Examples of mold developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, p -Phenylenediamine, etc.

Examples of the heterocyclic developer include 3-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, and l-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 Society).
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.

Hydroxylamine and hydrazide compounds can also be used as preservatives, and in this case, the amount used depends on the developer IQ.
It is preferably 5 to 500g, more preferably 20 to 500g.
It is 200g.

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,
Among them, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g, per developer IQ. 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, the pH value is 10-1 from the viewpoint of storage stability and photographic properties.
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 seconds. often has positive effects. 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 may be so-called manual development such as plate development or frame development, or mechanical development 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 subbing-treated polyethylene terephthalate, an antistatic liquid having the following composition was applied at 10 m12/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) 6g/1Q Latex of the present invention (B) 4g/Q Hardener (C) Cl-2) 1.5g/1
It was dried at 290° C. for 2 minutes and heat treated at 140” for 0.90 seconds.

A base test was conducted by coating gelatin at a concentration of 2.0 g/m'' on this antistatic layer.Formalin, 2.4-dichloro-6-hydroxy S-) Sodium gin was used.

The results are shown in Table-1.

(1) Haze test Tokyo Denshoku Co., Ltd. Turbidimeter Modil T-2600D
Measure the haze on the film support using A.
1 Example-2 Particles containing 10-' mol of rhodium per mol 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 1% aqueous gelatin solution IQ. After mixing silver and halide, 600 mg of 6-methyl-4-hydroquine-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-itaconic acid) latex. did.

Latex polymer: styrene-butyl acrylate
Acrylic acid tertiary copolymer polymer 1-0g/m2 Tetraphenylphosphonium taloride 30mg/m"Saponin 200mg/m"Polyethylene glycol 100mg/m! Sodium dotecylbenzenesulfonate loOmg/m”
Hydroquinone 200mg/m”
Phenidone 100mg/m”
Sodium styrene sulfonate-maleic acid polymer (Mw=250,000) 200mg
/m” gallic acid butyl ester 500mg
/m"30mg/m" 5-methylbenzotriazole 30n+g/a
+22-mercaptobenzimidazole-5-sulfonic acid 30 mg/m" Inatoossein gelatin (isoelectric point 4.9) 1.5 g/mv 1-(p-acetylamidophenyl)-5-mercaptotetrazole 30 mg/m" Silver amount
2.8 g/m" (emulsion layer protective film) Prepare and apply the following coating amount as an emulsion layer protective film.

Fluorinated dioctyl sulfosuccinate 300mg/m" Matting agent: Polymethyl methacrylate (average particle size 3.5μm) 100mg
/m” lithium nitrate salt 30mg/
m” acid-treated gelatin (isoelectric point 7.0) 1.2
g/m” colloidal silica 50mg
/m” Sodium styrene sulfonate-maleic acid copolymer 100mg/m”
CH3CQ0 (backing layer) 30W/m”min was applied to the support opposite to the emulsion layer in advance.
After corona discharge with the power of A backing layer containing a backing dye having the following composition was then applied onto this layer. The gelatin layer contains glyoxal and l-oxy-
Hardening was done with 3,5-dichloro-S-triazine sodium salt.

(Backing layer) Hydroquinone 100mg/m
“Phenidone 30+ng/
m" latex polymer: Butyl acrylate-styrene-acrylic acid copolymer 0.5g/m" styrene-
Malein M co-II combined 100mg/m” citric acid
40mg/m" benzotriazole loOmg/m" styrene sulfonic acid sorter maleic acid copolymer 200mg/m'
Lithium nitrate salt 30mg/m2
Backing dye (a), (b), (c) Ossein gelatin 2.0g/m” (a
) (b) (C) So, Na The entire surface of the sample obtained as described above was exposed and developed using the developer and fixer shown below, and then a film haze test was conducted.

<Developer formulation> Hydroquinone 25g 1-7enyl-4.4dimethyl-3-pyrazolidone 0.4g Sodium bromide 3g 5-methylbenzotriazole 0.3g 5-nitroindazole 0.05g 5g diethylaminopropane
2-diol 10g potassium sulfite
90g Sodium 5-sulfosalicylate 75g
Sodium ethylenediaminetetraacetate - Finished to 1Q with 2g water.

The pH was adjusted to 11.5 with caustic soda.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5w% aqueous solution) 40mQ Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate 2
Water salt 2g acetic acid (90w% aqueous solution)
13.6mQ (composition) Pure water (ion-exchanged water) 17mQ sulfuric acid (50w% aqueous solution) 3.0g aluminum sulfate (Aff, O, aqueous solution with a converted content of 8.1w%) 20g Water 500IIIQ when using the fixer The above-mentioned compositions were dissolved in the order of composition 1 and finished to 1Q for use.

The pH of this fixer was about 5.6.

Development processing conditions> (Process) (Temperature) (Time) Development
Fixing at 40°C for 8 seconds, washing with water at 35°C for 8 seconds, room temperature lθ seconds evaluation was carried out as follows, and the results are shown in ^-2.

Haze test> Turbidity meter MODEL T-260O manufactured by Tokyo Denshoku Co., Ltd.
The film support was measured using DA and the haze was expressed as a percentage.

Table 2 From the results in Table 2, it can be seen that the samples according to the present invention have a low surface resistivity and are excellent in haze.

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

The addition amount unit of the tetrazolium compound polymer and the compound is expressed in g/m2.

The surface resistivity is Ω/0m.

〔Effect of the invention〕

According to the present invention, it was possible to provide an antistatic layer for a plastic film with excellent transparency and no haze, and a silver halide photographic material whose antistatic performance does not deteriorate even after processing such as development.

Claims (1)

[Claims] In a plastic film support 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 An antistatic layer having at least one group selected from a sulfonic acid sulfate group or a salt thereof, and containing a compound represented by the following general formula [I] as a hardening agent. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [R_1 and R_2 represent alkyl groups with up to 4 carbon atoms,
They may be different from each other. X_1, X_2, X_3,
X_4 represents hydrogen, an alkyl group having up to 3 carbon atoms, or a halogen atom, and may be different from each other. L is a simple bond and represents an alkyl group or alkyleneoxy group having up to 4 carbon atoms. ]