JPH02291552A - Antistatic layer - Google Patents

Abstract

PURPOSE:To improve transparency and to eliminate haze in spite of a rapid drying by introducing a polyalkylene oxide chain into a water soluble conductive polymer. CONSTITUTION:The water soluble conductive polymer of a plastic film having the antistatic layer consisting of the reaction product of the water soluble conductive polymer and a hardener has the polyalkylene oxide chain. For example, a monomer having the polyalkylene oxide chain is copolymerized with the water soluble conductive polymer. The antistatic layer for the plastic film which is excellent in transparency and is free from the haze in spite of the rapid drying is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antistatic layer for a plastic film, and 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. Nowadays, when high-sensitivity photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed through automatic printers,
In particular, antistatic measures are important.

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 antistatic agents have been used, such as fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, sulfonic acids, Polymers having phosphoric acid groups in their molecules are used.

In particular, fluorine-based surfactants are often used to adjust the charge series, or 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 bottle holes 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 carpoxyl group, a hydrophobic polymer having a carpoxyl group, and a polyfunctional aziridine. According to this method, the antistatic ability can be maintained even after treatment.

However, the transparency of the coating depends largely on the drying speed, so if it is slowly dried it will be transparent, but if it is rapidly dried to increase production efficiency, the transparency will drop to a level that is completely unusable. There was a drawback.

[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 plastic film that has excellent transparency even when quickly dried and has no haze. An object of the present invention is to provide a silver halide photographic light-sensitive material.

[Structure of the invention]

The above object of the present invention is to provide a plastic film having an antistatic layer made of a reaction product of a water-soluble conductive polymer and a curing agent, characterized in that the water-soluble conductive polymer has polyalkylene oxide chains. This is achieved by an antistatic layer.

The details of the present invention will be explained below.

The water-soluble conductive polymer according to claim 1 of the present invention is a polymer 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, and a carpoxyl group. can be mentioned. 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. These groups contain 5 per polymer molecule.
It is preferably at least % by weight.

The polymer has a molecular weight of 3000 to 100000,
Preferably it is 3500-50000.

As a method for introducing a polyalkylene oxide chain into the water-soluble conductive polymer of the present invention, a method by copolymerizing a monomer having a polyalkylene oxide chain is preferred.

As the heptanomer, those represented by the following general formula CM) are preferable.

vinegar. R is a hydrogen atom, an aryl group, a lower alkyl group,
X, and X represents fR2-OfnRs. R2 is -CH. CH2 - CH, CH, - CIItCHxCHzCH2CHtCHCH*1
R represents a hydrogen atom, a lower alkyl group, an alkylsulfonic acid or a salt thereof, an alkylcarboxylic acid group or a salt thereof. n is an integer of 2 or more and 70 or less.

Next, specific examples of these monomers will be given.

General formula (M) Rl Cl{1 gourd C L-X where R is a hydrogen atom, a halogen atom, a lower alkyl group, -CI{. -L- represents X, L is -COO
R1 -CON- or an aryl group having 6 to 12 carbon atoms as shown in Table M-19 M-21 C11, M CI. M l2 CH, C}l. -C Coo{CH2CH,O}re{01zCHCHO]H
OH M-17 M M-26 CH Hereinafter, examples of the water-soluble conductive bolymer P used in the present invention will be given, but the present invention is not limited thereto.

P-1 P-5 P P-6 P P-7 P-10 P 1 P-11 P-9 P-12 M- 8uuo CHtOSOsNa CL u-toooo P-13 P -16 CH. ■ P-14 P-17 P-15 CH, P-18 rt- loooo P-19 In addition, in (1) to (l9) above, x, y, z, and W each represent the mol% of the monomer component. , and M represents an average molecular weight (in this specification, the average molecular weight refers to a number average molecular weight).

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

Next, the hydrophobic polymer particles that may be 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 polymer includes styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives,
It is obtained by polymerizing monomers selected in any combination from halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 mol% or more.

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. Emulsion polymerization is preferable because it allows the production of

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant, and 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.

Margins below... ・、・１・１ ・、；． '／ 2. 9. l0 11. 12. S.O. Na ? O■Na Shil13 CH. So. Na CONHCCH2SO3Na CH. CI, 6. 7. 13. 14. S.O. Na In the present invention, a conductive layer is coated on a transparent support.

Any transparent support for photography can be used, but is preferred. death Kuha, Transmits more than 90% of visible light Yo Made with sea urchin polyethylene tele-7 tallate or cellulose This is Liacete 1.

These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, they may be seasoned with a small amount of dye so as not to substantially inhibit light transmission. good.

The support of the present invention may be coated with an undercoat containing a latex polymer after being subjected to a corona discharge treatment. The energy value of corona discharge treatment is l mW” I
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. Also,
The drying temperature is 60°C, preferably 90°C or higher.

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.

For drying, parallel flow drying, vertical flow drying, etc. may be used in combination with infrared drying, microwave drying, etc., but for production efficiency, the overall heat transfer coefficient is 20 Kcal/m"hr.
It is preferable to dry at a temperature of ℃ or higher.

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 all 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 interior and surface layer of the grain, in which 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 emulsion used in the present invention is, for example, US Pat. No. 2,444,607, US Pat. No. 2,716,062, US 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-tetramethylene-7-hydroxy-S-triazolo (1.5-a) Pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo (1.5-a)
Pyrimidine, 5-methyl-7-hydroxy-S-+-riazolo (1.5-a) Pyrimidine, 5-methyl-7-hydroxy-S-triazolo (1.5-a) Pyrimidine, 7-hydroxy-S -} Riazolone (1.5-a)
Pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazo(1.5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, brovyl gallate, sodium gallate), mercaptans (l-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), penzotriazoles (5-prombenttriazole, 5-methylbenttriazole), benzimidazole 11 (6-
(nitropenzimidazole) 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 hydroquinone or an inhibitor such as penzotriazole can be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the packing 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.

As the developing agent used for developing the silver halide photographic light-sensitive material according to the present invention, T.I. H. The Theory of the Photographic Process by James, 4th edition (
The Theory of Photography
cProcess Fourth Edition) pages 291-334 and Journal of the American Chemical Society (Journal
of the American Chemi
Developers such as those described in Cal Society, 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. 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.

Further, as a preservative, hydroxylamine or a hydrazide compound can be used, and in this case, the amount used is preferably 5 to 500 g, more preferably 2 to 500 g per 1Q of developer solution.
It is 0-200g.

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,
(2), 5-pentanediol and the like, but 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 pn 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 to-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 less, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds to 40°C. 50 seconds often produces good results. 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 processes can be done by hand development such as plate development or frame development, or by roller development,
Mechanical development such as hanger development may be used. ] [Example] The present invention will be specifically described 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 to polyethylene terephthalate treated with subbing, an antistatic liquid having the following composition was applied at 10 mff/di"
The coating was performed 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 of the present invention (A) log/f
f latex (B) 4 g/
Q Hardener (H) Drying air temperature 90°CS Overall heat transfer coefficient 25Kg/mjhr'
Dry for 30 seconds under the parallel flow drying conditions of c.
Heat treatment was performed at 140°C for 90 seconds. Gelatin was coated on this antistatic layer at a concentration of 2.0 g/m'' and a haze test was conducted.As hardeners for gelatin, formalin,
,4-dichloro6-hydroxyS-triazine sodium was used. The results are shown in Table I.

Haze test Turbidity meter Model T-260O manufactured by Tokyo Denshoku Co., Ltd.
The film support was measured using DA and the transmittance was expressed in %.

The results are shown in Table 1.

Table 1 (a) M-5000 Example 2 described in JP-A-55-84658 Particles containing 10-' mol of rhodium per mol of silver were prepared by the controlled double jet method in an acidic atmosphere of pH 3.0. . Particle growth was performed in a system containing 30 mg of penzyladenine per 1% gelatin aqueous solution la. 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.

Then, 60+ng of 6-methyl-4-hydroxy-1.3.38.7-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 layered on a polyethylene terephthalate support (100 μm thick) subbed with poly(vinylidene itaconic acid) latex. It was applied to.

Latex polymer: Styrene-butyl acrylate acrylic acid ternary copolymer 1.0 g/m" Tetraphenylphosphonium chloride 30 mg/m" Savonin 200 mg/m"
Polyethylene glycol 100 n+g/m
"Sodium dodecylbenzenesulfonate 100 m
g/m” Hydroquinone 200 mg/o
“Phenidone 100 mg/m
“Sodium styrene sulfonate-maleic acid polymer (
MW-250,000) 200 mg/m”
Gallic acid butyl ester 500 mg/n+
"30 g/m" 5-methylbenzotriazole 30 mg/m"
2-Mercaptobenzimidazole-5-sulponic acid
30 n+g/m” inert ossein gelatin (isoelectric point 4.9) ■・5
g/m" 1-(p-acetylamidophenyl)-5 mercaptotetrazole 30 a+g/m" 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 300B/a
+” Matting agent: Polymethyl methacrylate (average particle size 3.5μ
m) 100 mg/+”
Lithium nitrate salt 30 mg/m”
Acid-treated gelatin (isoelectric point 7.0) 1.2 g/
m” Colloidal Silica 5o-g/I
12 Sodium styrene sulfonate-maleic acid copolymer 100 mg/m" Mordant dye (packing layer) 30 W/s" in advance on the support opposite to the emulsion layer
After corona discharge with a power of sin, a poly(vinylidene itaconic acid) latex polymer was applied in the presence of a hexamethyleneaziridine hardener, and an antistatic layer of the present invention was applied as in Example-1. Coating was carried out in the same manner, and then a packing layer containing a packing dye having the following composition was coated on this layer. The gelatin layer was hardened with glyoxal and l-oxy-3,5-dichloroS-triazine sodium salt.

(Packing layer) Hydroquinone 100 mg/m
'7 Enidon 30 mg/m
"Latex polymer: Butyl acrylate styrene copolymer 0.5 g/m" Styrene-maleic acid copolymer 100 mg/rn" Citric acid
40 mg/m"penzotriazole 100 mg/m"styrene sulfonic acid soda maleic acid copolymer
200 mg/m” lithium nitrate salt
30 mg/m'packing dye (a)
．． (b). (c) 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 25 gl-phenyl-4.4 dimethyl-3-virazolidone 0.4 g sodium bromide 3 g 5-methylbenzotriazole 0.385 ditroindazole
0.05 g diethylaminopropane-1,2-diol 10 g Potassium sulfite 90 g Sodium 5-sulfosalicylate 75 g Sodium ethylenediaminetetraacetate 2 g Finished to 1Q with water.

pi was set to 11.5 with caustic soda.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5w% aqueous solution) 240
mα Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g Sodium citrate dihydrate
2g acetic acid (90w% aqueous solution) 13.
6m4 (Composition B) Pure water (ion exchange water) 17 mQ sulfuric acid (50W% aqueous solution) 3.0g aluminum sulfate (AQ.O. converted content is 8.1w% aqueous solution) 2
0g When using the fixer, add the above composition B to 500mQ of water.
It was melted in the order of 112 and used. 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.

It was dried for 20 seconds and further heat-treated for 90 seconds. After that, Actual Table 2 This invention l/ Comparison (A) (B) Transmittance (%) (a) (b) 75 Surface specific resistance (s-/co+) 5XIO" 6X10Io 6X1O"6X10" From the results of Table 2 It is clear that the sample according to the present invention has excellent antistatic ability and good transparency.

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

The back surface was processed in the same manner as in Example 1 of the tetrazolium compound, and the same evaluation was conducted. The results are shown in Table 3.

Table 3 (A) (B) Transmittance Invention (4) (1) 90//
(6) (4) 92//
(13) (3) 88 ratio
Comparison (a) (b) 65Table 3
From the results, the sample of the present invention has excellent transmittance.

〔Effect of the invention〕

According to the present invention, it was possible to provide an antistatic layer for a plastic film that has excellent transparency and no haze even after rapid dry storage, and a silver halide photographic material that has excellent antistatic performance.

Example 3

Claims (1)

[Claims] 1. A plastic film comprising an antistatic layer made of a reaction product of a water-soluble conductive polymer and a curing agent, wherein the water-soluble conductive polymer has a polyalkylene oxide chain.