JPH02256051A - Polyester base having antistatic layer - Google Patents

Abstract

PURPOSE:To prevent the deterioration of the antistatic performance of an antistatic layer even after development and to improve the adhesive property to a polyester base by interposing an underlayer of latex contg. styrene as a constituent between the polyester base and the antistatic layer. CONSTITUTION:When a polyester base having an antistatic layer is obtd., an underlayer of latex contg. styrene as a constituent is interposed between the polyester base and the antistatic layer. The latex is represented by formula I (where A is one or more kinds of monomers copolymerizable with styrene, x is 10-95mol%, y is 5-90mol% and the monomers A are alkyl acrylate, alkyl methacrylate, olefin derivs., etc., but include >=20mol% alkyl acrylate, alkyl methacrylate or olefin deriv.). The deterioration of the antistatic performance of the antistatic layer is prevented even after development and the adhesive property to the polyester base is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antistatic layer for plastic films, and particularly to a polyester base for silver halide photographic materials.

[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, 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-55-84658, JP-A-61-
No. 174542 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. Although this method allows antistatic properties to remain after processing, this antistatic layer has poor adhesion to the hydrophilic colloid layer coated on top of this layer, and the film may peel off during development. There was a drawback that it occurred.

Therefore, in the above-mentioned patent examples, the polyester base is flame-treated or coated with latex for undercoating to compensate for the drawbacks.

The latex used in the patent examples is vinyl chloride, which has good adhesion to polyester bases, but poor adhesion to water-soluble conductive polymers.

[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 plastic film that does not deteriorate in antistatic ability even after processing such as development and has excellent adhesive properties. Another object of the present invention is to provide a polyester base for silver halide photographic materials that has excellent antistatic properties.

[Structure of the invention]

The above object of the present invention has been achieved by a polyester base having an antistatic layer, characterized in that a latex subbing layer containing styrene as a constituent is provided between the polyester base and the antistatic layer. The antistatic layer is preferably made of a reaction product of (1) a water-soluble conductive polymer, (2) a hydrophobic latex, and (2) a polyfunctional aziridine.

The details of the present invention will be explained below.

The undercoating latex of the present invention is represented by the following formula (I).

one formula CI) It is preferable that the content is above.

The molecular weight of this latex polymer has little effect on adhesion and may be 10,000 or more.

The amount obtained by general emulsion polymerization is approximately 10,000
It has a molecular weight of more than

A specific example of the latex for undercoating of the present invention is shown below.

l.

In the formula, A represents one or more types of heptamers copolymerizable with styrene.

x: 10-95 mol% y: 5-90 mol% Examples of A include alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. Alkyl acrylate, alkyl methacrylate,
The olefin derivative is at least 20 mol% or more, especially 30 mol%2.

C.I.

The rest below CH.

CH.

5.

H2CQ 7.

The water-soluble conductive polymer of the present invention includes 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, a carboxyl group, and a polyethylene oxide group. Can be mentioned. Among these groups, sulfonic acid group, sulfuric acid ester group, -(: CH.

C1l juice rr-f, CO-CH)-r-17-3O,N
a Quaternary ammonium base is preferred. Conductive groups require at least 5% by weight per polymer molecule. Conductive 03Na The molecular weight of the conductive polymer does not matter, but it is between 3000 and 100.
000 is preferred.

Specific examples of water-soluble conductive polymers used in the present invention will be given below.

03Lj CH.

Mζ10,000 dextran sulfate M-500,000 degree of substitution 3
．． 0 The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are composed of so-called latex which is substantially insoluble in water. This hydrophobic polymer contains monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. Obtained by polymerization. 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 hydrophobic polymer into a latex, one is to perform emulsion polymerization, and the other is to dissolve the solid polymer in a low-boiling point solvent, differentiate it, and then distill 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.
It is preferably 0% by weight or less. A large amount of surfactant causes clouding of the conductive layer.

The average particle size of the polymer particles is Coulter N manufactured by Coulter Co.
Measured using 4.

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.

C11゜ ■ 6.

CH.

0OCH3 COOC,H, -n OOH 13° C00CH5 COOC2H60 0OH 14, 15° In the present invention, a conductive layer is coated on a transparent support. As the transparent support, any photographic support can be used, but polyethylene terephthalate or cellulose triacetate, which is made to transmit 90% or more of visible light, is preferred.

These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, a small 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 l mW to l K
W/a''αin is particularly preferably applied.

It is also preferable to carry out corona discharge treatment again after applying the latex undercoat and before applying the conductive layer.

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 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. 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, e.g.
゜6-trimethylene-7-hydroxyne-S-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-hydroxyl S-triazolo(1,5-a)pyrimidine,
'7-hydroxyne-s-triacylone (1,5-a)
Pyrimidine, 5-methyl-6-promorph-hydroxy-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-methylbenztriazole), benzimidazoles (6-nidropenzimidazole), etc. for stabilization. be able to.

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, the backing layer may contain a developing agent or an inhibitor in order to increase the processing ability of the processing solution.

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

The gelatin used in the present invention can be treated with alkali or acid, but when using ossein gelatin, it is preferable to remove calcium or iron. The preferred content of calcium is 1 to 9.
99 ppm, more preferably 11-500 ppm
The iron content is preferably 0.001-50 pp, more preferably 0.1-1 OPPffi. 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, furohydroquinone, methylhydroquinone, 2
．． 3-dibromohydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4-
Phenyl-catechol, 3-methoxy-catechol, 4
-Acetyl-pyrogallol, sodium ascorbic acid, etc.

In addition, typical examples of HO-(CH-CH), -NH2 type developers include ortho and para aminophenols, such as 4-aminephenol, 2-amino-6-phenylphenol, and 2-amino- Examples include 4-chloro-6-phenylphenol and N-methyl-p-aminophenyl.

Furthermore, H2N (CH= CM), Nth type developer such as 4-amino-2-methyl-N, N-diethylaniline, 2.4-diamino-N, N-diethylaniline, N-(4- amino-3-methylphenyl)-
Examples include morpholine and p-phenylenediamine.

Examples of heterocyclic developers include 3-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc. -pyrazolidones,
Examples include l-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

The Theory of the Photographic Process, 4th Edition, by T. H. James
f Photographic Process Fo
urth Edition), pp. 291-334 and Journal of the American Chemical Society.
Chea+1cal 5ociety) Volume 73, No. 3
, p. 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 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.

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 1Q of developer solution. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material according to the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

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 less, 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 processes include so-called manual development processes such as plate development and frame ring image, roller development,
Hanger development etc.I! Mechanical development may also be used.

〔Example〕

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

Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Example 1 Polyethylene terephthalate treated with corona discharge was coated with latex of the following composition.

Latex for undercoating of the present invention (A) 10cc (3Q% solids) Add water to make a total of 100cc.

It was coated at a thickness of 20 μm and dried at 100° C. for 1 minute. After corona discharge on this undercoat layer, 10-g/am was applied using an antistatic liquid with the following composition and an a-rufit coating van and an air knife at a speed of 33 s/win.
' After drying at 90°C for 2 minutes, apply at 140°C.
Heat treatment was performed for 90 seconds.

Water-soluble conductive polymer (B) 6g/(1 Latex (C) 4g/Q Hardener H1.5g/12 Water was added la A film formation test was conducted on this sample.

(1) Adhesion test <On the emulsion surface of the test sample with a dry film, make shallow scratches in the shape of the base with a razor.
When a cellophane adhesive tape was pressure-bonded thereon and then the tape was rapidly peeled off, the residual rate of the emulsion film relative to the adhesive area of the cellophane tape 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.

(2) Haze test Turbidity meter MODEL T-260OD manufactured by Tokyo Denshoku Co., Ltd.
The film support was measured using A and the haze was expressed as a percentage.

Table-1 (A) (B) (C) Drying (%) Treatment (%) Present invention (3
) (5) (8) 100 100//
(4) (4) // 100 100/
! (6) (4) // too
100// (8) (4) //
100 100// (/1) (5)
(7) 100 100// (//
)(11)(12) 100 100//
(// ) (12) (6) 100
100 comparison (a) (4) (8) 80
75a: Poly(vinylidene chloride methyl acrylate-itaconic acid described in JP-A-55-84658) From the results in Table 1, the sample of the present invention had better film adhesion compared to the comparison, and the film adhesion deteriorated even after treatment. It is clear that it does not.

Example 2 Particles containing to-' mol of rhodium per mol of silver were prepared by the Funtrol 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 14 1% aqueous gelatin solution. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added per mole of silver halide, 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 subjected to latex subbing treatment.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer 1.0g/m"Tetraphenylphosphonium chloride 30mg/a"Saponin 200mg/m"Polyethylene glycol 100mg/+m"Sodium dotecylbenzenesulfonate 100g/-2Hydroquinone 200+mg/2 phenidone 100mg/m'
Sodium styrene sulfonate-maleic acid polymer (M
y-250,000) 200mg/m" gallic acid butyl ester 500ag/m" tetrazolium salt 20+++g/m"5-methylbenzotriazole 30+sg/naw 22-mercaptobenzimidazole-5 sulfonic acid
30-g/m" Inatoossein gelatin (isoelectric point 4.9) 1.5 g/m" 1-(p-acetylamidophenyl)-5 mercaptotetrazole 30 mg/m" Silver amount
2.8 g/m'' tetrazolium compound (emulsion layer protective film) The following amount was prepared and coated as an emulsion layer protective film.

Fluorinated dioctyl sulfosuccinate ester 300a+g
/m” Matting agent: Polymethyl methacrylate (average particle size 3゜5μ
”) 100mg/m”Lithium nitrate salt 30g/m
1 acid-treated gelatin (isoelectric point 7.0) 1.2g
/+a” colloidal silica 50mg
/+*"Sodium styrene sulfonate-maleic acid copolymer 100mg/+*" Mordant CHs CQe Dye sea 3.5-dichloro-5-triazine sodium membrane Shiwo 2.

(Backing layer) Hydroquinone phenidone latex polymer: butyl axtyrene copolymer styrene-maleic acid co-11 units citric acid benzotriazole nitrate lithium salt backing dye ossein gelatin lithium salt hardness 100-g/rs' 30 mg/■8 lylate 0.5g/m'100mg/m'40mg/@' ■0011g/11! 30mg/n' 2.0g/w2 (Backing layer) 30W/s"
After corona discharge with +sin power, the undercoat layer and antistatic layer of the present invention were applied, and then a backing layer containing a backing dye having the following composition was applied on this layer. The gelatin layer was prepared by exposing the entire surface of the sample obtained above with glyoxal and l-oxal, developing it using the developer and fixer shown below, and then conducting haze and film tests.

<Developer formulation> Hydroquinone 25g 1-phenyl-4,4dimethyl-3-virazolidone 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
I made it to IQ with 2g of water.

pl (was adjusted to 11.5 with caustic soda.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5v% aqueous solution) Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90w% aqueous solution)
13.6m4 (composition) Pure water (ion exchange water) 17mff
Sulfuric acid (50w% aqueous solution) 3.0g
Aluminum sulfate (Ai + 20. Converted content is 8.11%
20g of aqueous solution) When using a fixer, the above compositions were dissolved in 500mQ of water in the order of composition A1 and finished to 112 before use. The pi of this fixer was about 5.6.

Development processing conditions> (Process) (IIi degree) (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.

Table-2 (A) (B) (C) Haze (%) Drying (%) Treatment (%)
Present invention (3) (5) (8) 100
95// (4) (4) //
95 90tt (5) /
/tt95
95tt (3) tt tt
100 95// // (
5) (7) 100 95
// // (11) (12)
95 90 // // (12)
(6) 95 90 ratio
comparison (a) (4) (8) 75
From the results shown in Table 2, the samples of the present invention, like Example 1, showed good film adhesion, did not deteriorate even after treatment, and had good haze.

〔Effect of the invention〕

According to the present invention, it was possible to provide a polyester base that does not deteriorate in antistatic ability even after development and is excellent in adhesive properties.

Claims (2)

[Claims] (1) A polyester base having an antistatic layer, characterized in that a latex subbing layer containing styrene as a constituent is provided between the polyester base and the antistatic layer. (2) The antistatic layer is made of [1] water-soluble conductive polymer [2]
] Hydrophobic latex [3] The polyester base according to claim 1, comprising a reaction product of polyfunctional aziridine.