JP3416835B2 - Antistatic plastic film material and silver halide photographic material using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film having an antistatic property improved so that it is less affected by changes in humidity, such as a magnetic tape, a floppy disk, a flexible substrate, a base material for a membrane switch, and a printer recording paper. Since it can be used as a film, and a film that does not particularly impair transparency can be provided, it can be used for applications such as OHP films, liquid crystal display devices, touch panels, and stained glass. Further, since its excellent transparency is good without adversely affecting photographic characteristics, it can be used for photographic light-sensitive materials. In particular, in the case of a photographic light-sensitive material, due to its excellent characteristics, it is possible to use not only the silver salt that has been used conventionally but also a field using a light-sensitive material other than a silver salt.

[0002]

2. Description of the Related Art Generally, a plastic film (hereinafter, also simply referred to as a film) has a strong charging property and is often restricted in use except for the purpose of utilizing this physical property.
For example, a silver halide photographic light-sensitive material (hereinafter abbreviated as photographic light-sensitive material) generally uses a plastic film having electrical insulation as a support, and a so-called photographic light-sensitive material layer comprising this support and a photographic light-sensitive material layer. Since it is a composite material, during the manufacturing process of the photographic light-sensitive material and at the time of use,
It tends to be charged during contact friction or peeling with the surface of the same or different material. The electrostatic charge accumulated by charging causes many obstacles. The most serious obstacle is that the photosensitive emulsion layer is exposed to light by discharging the electrostatic charge accumulated before the development process, and when the photographic film is processed for development, it is a dot-shaped spot or so-called static mark. It is the formation of dendritic and feather-like spots. For example, if this phenomenon appears in a medical or industrial X-ray film or the like, it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the very troublesome problems.
Further, these accumulated electrostatic charges may cause a failure such as dust adhering to the film surface or failure in uniform coating on the film surface.

Many failures other than those mentioned above occur due to such charging. For example, it is caused by contact friction between a photographic film and a roller in the manufacturing process, or winding of the photographic film, separation of the support surface from the emulsion surface during the rewinding process, and the like. In the case of finished products, the photographic film is wound and the base surface and emulsion surface are separated when switching is performed, or contact is made between the mechanical part during X-ray film automatic photography or the fluorescent intensifying screen. It is caused by separation etc. It also occurs when it comes into contact with other packaging materials. The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases.
Particularly in recent years, the development of photographic light-sensitive materials and the increased chances of severe handling due to high-speed coating, high-speed photography, high-speed automatic processing, etc. have made it easier to generate static marks.

Further, the adhesion of dusts after the development process has become a big problem in recent years, and improvement for keeping the antistatic property after the development process is required.

The best way to eliminate these static disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be dissipated in a short time before the stored charge is discharged.

Therefore, conventionally, a method of improving the conductivity of a support of a photographic light-sensitive material or various coated surface layers has been considered,
Attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers and the like. For example, JP-A-49-91165 and JP-A-49-121523 disclose examples in which an ionic polymer having a dissociative group in the polymer main chain is applied. Other JP-A-2-9689
And conductive polymers as described in JP-A-2-182491, JP-A-63-55541 and JP-A-63-14.
No. 8254, No. 63-148256, JP-A-1-31
Inventions and the like relating to surfactants such as those described in No. 4191 are known.

However, many of these materials show specificity depending on the type of film support and photographic composition, and give good results for certain film supports and photographic emulsions and other photographic components. , Other different film supports and photographic components not only do nothing to prevent antistatic, but can also adversely affect photographic performance and adhesion between the antistatic layer and the support.

[0008]

As described above, although efforts have been made for many years to overcome the obstacles of plastic films due to static electricity, the relationship between their generation mechanism and materials is still unknown. In particular, in the field of photography, where obstacles have a catastrophic effect on merchandise, coating highly conductive materials has been the best choice.

Therefore, the object of the present invention is to solve the problems such as the adhesion of the antistatic layer, the stability of the coating solution, the workability, etc., which are caused by the large amount of the conductive material added, and it is high even under low humidity. (EN) It is intended to provide a transparent plastic film material having an antistatic property, and particularly to provide a silver halide photographic light-sensitive material using the same.

[0010]

[Means for Solving the Problems]

(1). A film material having at least one conductive layer, wherein the absolute value of impedance of the film material at a frequency of 20 Hz is 4 × 10 ⁵ Ω or more and 1 × 10 ^20.
Ω or less, and at least one layer of the conductive layer comprises a polymer binder and latex particles having a conductive organic polymer on the surface, and the conductive layer contains 10 vol of the conductive organic polymer. % Or more and 50 vol% or less, an antistatic plastic film material.

(2). The latex particles having a conductive organic polymer on the surface are particles obtained by protecting the hydrophobic polymer particles (A) into a protective colloid with a conductive organic polymer (B) which is a hydrophilic polymer compound having an anionic functional group. The plastic film material as described in (1) above.

(3). The weight of the conductive organic polymer (B) is 3 with respect to the weight of the hydrophobic polymer particles (A).
1 to 500%, The plastic film material according to (2).

(4). The plastic film material according to (1), (2) or (3), wherein the film material is a plastic film containing syndiotactic polystyrene as a main component.

(5). A silver halide photographic light-sensitive material comprising the film material described in (1), (2), (3) or (4) as a support.

According to the present invention, it is possible to use a magnetic tape, a floppy disk, a flexible substrate, a base material for a membrane switch, a printer recording paper, etc. in addition to the photographic light-sensitive material, and it is possible to provide a film which does not particularly impair transparency. It can be used for antistatic of various films including applications for OHP films, liquid crystal display devices, touch panels, stained glass and the like. Thus, the present invention is particularly effective for improving the adhesiveness between the antistatic layer and the support, but the effects of the present invention can be applied to other than transparent films.

As is known, the conductivity of a material depends on the cation,
It is expressed by anions or charge carriers existing in the particles such as electrons and holes.

When the main charge carrier is an ion, it becomes a solid electrolyte, and when the charge carrier is an electron, it becomes a semiconductor.

Further, a detailed study was conducted on the conductivity. Generally, if the conductivity of the material increases as shown in the following known formula (1), the absolute value of the impedance Z including the term of resistance will be It is well known that it decreases.

| Z | = [R ² + (1 / ωC) ² ] ^1/2 (1) where Z: impedance R: resistance C: capacitance ω: 2πf f: frequency However, under special conditions It was found that the problem caused by electrification of the film such as dust adhesion is solved when the absolute value of impedance at a frequency of 20 Hz is 4 × 10 ⁵ Ω or more. To prevent static electricity, if the film is coated with an excessive amount of conductive polymer to such an extent that the adhesion between the film support and the antistatic layer is impaired, the conductivity of the film surface is improved and measured using direct current. In addition, the magnitude of the surface resistivity is sufficiently low, and at the same time, the absolute value of the impedance measured by AC is also low. Such a film material does not cause electrostatic damage, but defeats the purpose of the present invention because it significantly impairs adhesion. When the adhesiveness is prioritized and the amount of the conductive polymer added is reduced, the surface resistivity increases and the absolute value of impedance also increases. Although the adhesiveness is improved, the antistatic performance is deteriorated, and problems such as dust adhesion and the like caused by static electricity occur.

As is apparent, if the surface resistivity is reduced,
That is, if the absolute value of impedance is lowered, antistatic performance is improved. Although the antistatic technology up to now has been continuously developed based on such a concept, the present invention does not sacrifice the adhesiveness, and the static electricity is generated by a special combination of the absolute value of the impedance and the composition. Overcoming obstacles.

That is, in order to satisfy the adhesiveness, it is necessary to reduce the addition amount of the conductive polymer, but if the addition amount of the conductive polymer is reduced, the surface resistivity is improved as described above. Becomes difficult. However, the inventors diligently studied the relationship between antistatic performance and impedance, and in a small amount addition region of conductive particles that does not affect adhesiveness,
It has been discovered that even if the absolute value of the impedance is made larger than 4 × 10 ⁵ Ω, the antistatic property can be prevented. Increasing the absolute value of impedance does not need to increase the amount of conductive polymer added, and it becomes possible to control with an organic substance that does not have conductivity but can improve various physical properties of the film, limiting adhesion. It was discovered that it is a new means of achieving antistatic while receiving

As described above, in the addition region in which the amount of the conductive polymer is small to the extent that the adhesiveness is not affected, the absolute value of the impedance at the frequency of 20 Hz is controlled by the organic substance that has the least optical influence, thereby improving the adhesiveness. We believe that it is possible to complete a film that satisfies both antistatic properties, clarify the conditions for the absolute value of the impedance that the film material must satisfy, and clarify the addition amount of the conductive polymer that does not affect the adhesiveness, and the binder in that range. The present invention has been completed by making an effort to clarify the composition.

The present invention will be described in detail below.

In the present invention, for the impedance measurement of the film material, a general impedance measurement device used for measuring the dielectric constant of electronic parts can be used, but preferably an impedance measurement device capable of measurement at a frequency of 1 Hz or higher, It is a device that combines electrodes for film measurement. For example, it is a combination of Precision LCR meters HP4284A and HP16451B manufactured by Yokogawa-Hewlett-Packard (hereinafter YHP). When using another device, it is necessary to correct the electrode portion. In order to achieve the present invention, it is necessary to measure the impedance of the film material correctly, so that a desirable result cannot be obtained when an uncorrectable device is used. An example of obtaining the absolute value of the impedance at 20 Hz with this combination of devices will be described in detail, but the present invention does not limit the measuring method as long as the accurate absolute value of the impedance at the frequency of 20 Hz of the film material can be measured.

Using a precision LCR meter HP4284A connected to HP16451B having two electrodes constituted by parallel planes and a guard electrode, 23 ° C., 20% R
The absolute value of the impedance of the film material is measured by the void method in an H atmosphere. Regarding the measurement of the void method, H
Follow the electrode non-contact method described in the instruction manual of P16451B. The size of the sample is not particularly limited as long as it is larger than the electrode plane, but the diameter of the main electrode is 3.
In the case of 8 cm, the size is 6 cm x 6 cm to 5 cm x
A 5 cm square sample is preferred. If the magnitude of the surface resistivity measured using the direct current of the sample is equal on the front and back sides, either side may be placed on the upper side, but if they are not the same on the front and back sides, the side with the lower surface resistivity is placed on the upper side. Towards
A sample is placed between two electrodes composed of parallel planes, and measurement is performed by the void method while applying an AC voltage.

The measured preferable range is that the absolute value of the impedance at a frequency of 20 Hz measured using an electrode having an area of 11 to 12 cm ² is 4 × 10 ⁵ Ω or more, preferably 8 × 10 ⁵ Ω or more, and more preferably. 1 x 10 ⁶
When the composition is in the range of Ω or more and 10 ²⁰ Ω or less, the film material having both antistatic performance and adhesiveness can be manufactured.

The content of the conductive organic polymer contained in the conductive layer varies depending on the content of the latex particles having the conductive organic polymer on the surface. The content of the layer is 50 per unit volume
Vol% or less, preferably 40 vol% or less, and more preferably 37 vol% or less. The minimum required amount of the conductive polymer is selected from the conditions that the absolute value of impedance falls within the preferable range described above. If this condition is emphasized, the conductive polymer needs to be 1 vol% or more, preferably 5 vol% or more, more preferably 10 vol%.
% Or more is required.

In the present invention, the conductive polymer means a polymer described in "Conductive Polymer" published by Kodansha Scientific (edited by Naoya Ogata).

In the present invention, various kinds of electroconductive organic polymers can be mentioned, and for example, electroconductive organic polymers (B) which are hydrophilic polymer compounds having an anionic functional group are preferable. .

The conductive organic polymer (B) according to the present invention is a hydrophilic polymer compound having an anionic functional group, which is a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt or a carboxyl group. Polymers having at least one conductive group selected from the group are mentioned. The conductive group needs to be 5% by weight or more per polymer molecule. The water-soluble conductive polymer may contain a hydroxyl group, amino group, epoxy group, aziridine group, active methylene group, sulfinic acid group, aldehyde group or vinyl sulfone group.

The molecular weight of the polymer is 1,000 to 500,000, preferably 2,000 to 100,000. Specific examples of the conductive organic polymer (B) according to the present invention are shown below, but the invention is not limited thereto. Not a thing.

[0032]

[Chemical 1]

[0033]

[Chemical 2]

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

In the above P-1 to P-21, the average molecular weight means the number average molecular weight, and is the value measured by GPC in terms of polyethylene glycol.

When the weight average molecular weight of the conductive organic polymer (B) is less than 1000, the hydrophobic polymer particles (A)
This is because the adsorption to the main body becomes insufficient and the dispersion stability may deteriorate when the conductive particle body of the present invention is used in the form of an emulsion or the like. On the contrary, when the weight average molecular weight exceeds 500,000, when the conductive particle body of the present invention is produced by an emulsion polymerization method or the like, the viscosity of the aqueous solvent may be increased, which may hinder the production. Because there is.

Further, the conductive organic polymer (B) of the present invention is particularly preferably a compound having a sulfonic acid group and a carboxyl group, for example, a polymerizable monomer having a sulfonic acid group and a polymerizable monomer having a carboxyl group. It can be produced by copolymerizing with a monomer.

Examples of the polymerizable monomer having a sulfonic acid group include vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamidoethyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, Examples thereof include styrene sulfonic acid and the like and salts thereof. Of these, styrene sulfonic acid and salts thereof are preferably used because of their excellent conductivity.

Examples of the polymerizable monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other monocarboxylic acids or dicarboxylic acids or dicarboxylic acid anhydrides. To be Among these, dicarboxylic acid is preferably used, and maleic acid is particularly preferable, because the formed coating film has higher water resistance.

Further, in the conductive organic polymer (B) of the present invention, other functional groups may be introduced in addition to the sulfonic acid group and the carboxyl group. Therefore, in addition to the above-mentioned polymerizable monomer, for example, a monomer having a copolymerizable vinyl group may be used.

The method of polymerizing the above-mentioned polymerizable monomer is not particularly limited, and conventionally known methods can be applied. Specifically, for example, in water, the polymerizable monomer having a sulfonic acid group and a polymerizable monomer having a carboxyl group, further other polymerizable monomers are dissolved as necessary,
Polymerization can be carried out by adding a polymerization initiator (for example, potassium persulfate) and the like and heating.

Also, it can be manufactured by a method other than the above. That is, a polymerizable monomer having no sulfonic acid group and a polymerizable monomer having a carboxyl group are polymerized to prepare a copolymer, and the copolymer is subjected to a sulfonation treatment to obtain a conductive material. Organic polymer (B) can be obtained. In this case, the sulfonation rate is not specified, but it is 3
0 to 95% is preferable, and 45 to 90% is particularly preferable for dispersion stability.

The polymerizable monomer having no sulfonic acid group is not particularly limited, and examples thereof include styrene and α-methylstyrene.

Then, the monomer is polymerized by the above-mentioned method to prepare a copolymer, and the sulfonation treatment is applied to the copolymer. The method of this sulfonation treatment is not particularly limited, and a conventionally known method can be applied. Specifically, the above copolymer is put into a solvent, and a sulfonation treatment is performed using a sulfonating agent.

As the above solvent, dichloromethane, 1,
Chlorinated hydrocarbons such as 2-dichloroethane, hydrocarbons such as n-hexane and cyclohexane, dioxane and the like are mentioned as good solvents. Among these, it is difficult to react with a sulfonating agent and does not form a salt during neutralization. Dichloroethane etc. can be mentioned as a suitable solvent.

Further, as the sulfonating agent, S
Examples thereof include O ₃ , a complex of Lewis acid and SO _3, and chlorosulfonic acid. The reaction of the sulfonating agent in the above solvent is preferably carried out under low temperature conditions of 30 ° C or lower.

In such a conductive organic polymer (B), the ratio of the sulfonic acid group and the carboxylic acid group is a molar ratio of functional groups, that is, sulfonic acid group / carboxylic acid group = 10/9.
0 to 95/5, preferably sulfonic acid group / carboxylic acid group = 20/80 to 80/20, and particularly preferably sulfonic acid group / carboxylic acid group = 30/70 to 60/40.

Next, the hydrophobic polymer particles (A) in the present invention are produced by polymerizing a monomer having a polymerizable functional group. Examples of such a monomer include vinyl. Examples thereof include monomers, polyfunctional vinyl monomers, and epoxy group-containing monomers, which may be used alone or in combination of two or more.

Examples of the vinyl monomer include aromatic vinyl monomers such as styrene and α-methylstyrene, acrylic acid such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate, or Ester of methacrylic acid, monocarboxylic acid or dicarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, or dicarboxylic acid anhydride, vinyl halide, vinyl chloride, vinylidene chloride, etc. , Vinyl esters such as vinyl acetate, and conjugated dienes such as butadiene and isoprene.

Examples of polyfunctional vinyl monomers include vinylbenzene, trivinylbenzene, diallyl phthalate, allyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and the like.

Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate.

Among these monomers having a polymerizable functional group, it is preferable to use a polyfunctional vinyl monomer because the formed coating film has more excellent water resistance.

In addition to the above-mentioned monomer, a monomer having a vinyl group and another functional group capable of reacting can be mentioned, and it is preferable to use this for the same reason as above. Examples of the reactive functional group other than the vinyl group include functional groups such as an epoxy group, a methylol group, an oxazoline group and an isocyanate group. Specific examples of the monomer having these functional groups and vinyl groups include trimethylolpropane triacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, vinyl oxazoline, 2- Examples include propenyl, 2-oxazoline, m-isopropyl-α, α-dimethylbenzyl isocyanate and the like.

Next, a method for producing latex particles having a conductive organic polymer on the surface of the present invention (hereinafter, also referred to as conductive particles) will be described.

The conductive particles of the present invention are prepared by polymerizing the monomer having a polymerizable functional group in an aqueous solvent containing the conductive organic polymer (B). Specifically, it is carried out by a polymerization method such as an emulsion polymerization method or a dispersion polymerization method.

Water is usually used as the above-mentioned aqueous solvent, but in addition to this, alcohols such as ethanol and propanol, and, if necessary, an organic solvent can also be used.

Conductive organic polymer (B) in the above aqueous solvent
Dissolve. The conductive organic polymer (B) may be neutralized with sodium hydroxide, for example. The conductive organic polymer (B) is blended in an amount of 31 to 500 parts, preferably 100 parts by weight of the monomer having a polymerizable functional group (hereinafter abbreviated as "part"),
100 to 400 parts, particularly preferably 200 to 300 parts. That is, if the proportion is 30 parts or less, the stability of the particles produced tends to be insufficient, the dispersion stability of the particles obtained in the emulsion form tends to deteriorate, and sufficient conductivity cannot be obtained. Further, if it exceeds 500 parts, the film-forming property and the water resistance of the obtained coating film tend to be lowered. Then, by introducing a monomer having a polymerizable functional group into this aqueous solvent and carrying out emulsion polymerization, the conductive particles can be obtained in an emulsion form.

If necessary, the above-mentioned aqueous solvent may be used.
You may mix | blend surfactant for emulsion polymerization, a seed emulsion, and other hydrophilic polymers in the range which does not affect the performance of the electroconductive particle which is a product.

Examples of the surfactant for emulsion polymerization include anionic surfactants such as fatty acid, alkylbenzene sulfonate, higher alcohol sulfate ether salt, and nonionic surfactants such as polyethylene glycol.

Examples of the seed emulsion include acrylic emulsion, acrylic / styrene emulsion and the like, and specific examples include styrene / butyl methacrylate / methacrylic acid and the like.

Examples of the other hydrophilic polymer include polyvinyl alcohol, acrylic resin, polyester resin and the like.

The mixing ratio of the emulsion polymerization surfactant, the seed emulsion, and the hydrophilic polymer is within the range of 0.5 to 500 parts per 100 parts of the monomer having a polymerizable functional group. is there.

Further, in addition to the above-mentioned surfactants and the like, polymerization initiators such as persulfates such as potassium persulfate, inorganic substances such as sodium acetate, and chain transfer agents such as n-dodecyl mercaptan can be added.

When a monomer having a vinyl group and another functional group capable of reacting is used as the monomer having a polymerizable functional group, in a water-based solvent for the purpose of promoting this reaction, You may mix | blend a reaction accelerator. Examples of this reaction accelerator include aqueous ammonia, triethylamine,
Examples thereof include triethanolamine and triethylammonium chloride.

The particle size of the conductive particles of the present invention is usually 0.01 to 2.0 μm, preferably 0.04 to
It is 0.1 μm.

The conductive particles of the present invention may be in the form of a sol or powder in which the aqueous solvent is partially or completely removed, in addition to the emulsion and dispersion described above. When used in the form of a sol or powder, it can be used again as a coating type antistatic agent by dispersing it in an aqueous solvent at the time of use.

The conductive particles of the present invention may be coated from a coating solution without a binder, but it is preferable to use it in combination with another polymer binder.

Examples of the binder for the conductive layer used in the present invention include proteins such as gelatin, derivative gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, diacetyl cellulose and triacetyl cellulose; agar and sodium alginate. , Sugar derivatives such as starch derivatives;
Synthetic hydrophilic colloids such as polyvinyl alcohol, polyacrylic acid copolymers or their derivatives, and partial hydrolysates, vinyl polymers such as polyacrylic acid esters and copolymers thereof, natural products such as rosin and shellac, and the like Derivatives and many other synthetic resins are used. In addition, polyester, acrylic modified polyester,
Vinylidene chloride, polyethyleneimine, polyurethane,
Use of water emulsions such as styrene-butadiene copolymer, polyacrylic acid, polyacrylic acid ester and its derivatives, polyvinyl acetate, vinyl acetate-acrylic acid ester copolymer, polyolefin, olein-vinyl acetate copolymer, etc. You can

Among these, preferably, copolymers of gelatin and its derivatives, cellulose compounds, polyesters, acrylic modified polyesters, polyurethanes, polyacrylic acid and its derivatives are used. Even more preferred are copolymers of gelatin, acrylic modified polyesters, polyacrylic acid esters and their derivatives.

Various organic or inorganic curing agents may be added to the antistatic layer containing the conductive particles of the present invention. These curing agents may be low molecular weight compounds or high molecular weight compounds, and these may be used alone or in combination.

As the low-molecular curing agent, for example, tea
TH THEORY OF THE PHOTOGRAPH PROCESS by TH James (THE THEORY OF THE PHOTOGRAPH)
process), 4th edition, pp. 77-
The low-molecular curing agent described on page 88 is used, among which vinyl sulfonic acid, aziridine group, epoxy group,
Those having a triazine ring are preferable, and especially JP-A-53-53.
The low molecular weight compounds described in Nos. 41221 and 60-225143 are preferable.

The polymer hardening agent is preferably a compound having a molecular weight of 2000 or more and having at least two groups opposite to the hydrophilic colloid such as gelatin in the same molecule and reacting with the hydrophilic colloid such as gelatin. Examples of the group include aldehyde group, epoxy group, active halide (dichlorotriazine, chloromethylstyryl group, chloroethylsulfonyl group, etc.), active vinyl group, active ester group and the like.

As the polymer curing agent used in the present invention, for example, dialdehyde starch, polyacrolein, polymers having an aldehyde group such as acrolein copolymers described in US Pat. No. 3,396,029, US Pat. , 623, 878, which has an epoxy group, Research Disclosure Magazine 17333
(1978) and the like, polymers having a dichlorotriazine group, JP-A-56-66841, polymers having an active ester group, JP-A-56.
-142524, U.S. Pat. No. 4,161,407, JP-A No. 54-65033, Research Disclosure Magazine 16725 (1978), and the like are polymers having an active vinyl group or a group serving as a precursor thereof. It is preferable to use an active vinyl group with a long spacer, particularly as described in JP-A-56-142524.
Alternatively, a group having a precursor group bonded to the polymer main chain is preferable.

The amount of the curing agent used is 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on the binder when the binder is used.

When no binder is used, the amount is 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on the conductive particles of the present invention.

In the present invention, the plastic film used for the film material includes, for example, cellulose nitrate film, cellulose acetate film,
Examples thereof include a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, and laminates thereof.

Of these films, it is also possible to select polymer polymerization conditions and use a highly stereoregular polymer. For example, a plastic film containing syndiotactic polystyrene (SPS) as a main component may be used. The effect of the present invention is more effective in a film that is particularly easily charged, such as an SPS film.

In the present invention, a film containing syndiotactic polystyrene as a main component means that the stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, the main chain formed from carbon-carbon bonds is a side chain. A phenyl group or a substituted phenyl group, which is a chain, has a steric structure alternately located in opposite directions, and the main chain of the main chain is a styrene polymer that is a racemo chain, or a composition containing the same. A styrene homopolymer can be polymerized by the method described in JP-A No. 62-117708, and the polymer is described in JP-A Nos. 1-46912 and 1-178505. It can be obtained by polymerization according to the method described.

The tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ¹³
The tacticity measured by the C-NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. However, the styrene-based polymer having a predominantly syndiotactic structure as referred to in the present invention is usually a racemic diad of 75% or more, preferably 85% or more, or a racemic triad of 60%.
It is suitable that the content is not less than 75%, preferably not less than 75%, or 30% not less than racemic pentad, preferably not less than 50%.

Specific monomers of the polymer constituting the syndiotactic polystyrene composition are styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, A single or a mixture containing vinyl benzoate as a main component. In particular, the copolymer of alkyl styrene and styrene is 50 μm
This is a preferable combination for obtaining a film having a thickness of m or more.

The polystyrene-based resin having a syndiotactic structure of the present invention is disclosed in JP-A-5-320448, 4-1 as a catalyst for polymerization of the above raw material monomers.
(A) described on page 0. (A) a transition metal compound and (b) a compound containing aluminoxane as a main component, or (b). It can be produced by polymerization using a compound containing as a main component a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex.

These plastic film materials are
It can be used as a support for a photographic light-sensitive material. Further, the transparent support is not limited to a colorless and transparent one, but it can be colored and transparent by adding a dye or a pigment.

As the light-sensitive material according to the present invention, an ordinary black-and-white silver halide light-sensitive material (for example, a black-and-white light-sensitive material for photographing, X
-Line black-and-white sensitive material, printing black-and-white sensitive material, etc., ordinary multilayer color light-sensitive materials (eg color reversal film, color negative film, color positive film, etc.), transfer image forming materials (eg used for proof printing of printing) Various light-sensitive materials such as color proof) can be mentioned.

[0087]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

<< Synthesis of Latex Particles Having Conductive Organic Polymer on Surface (Conductive Particles P1 of the Present Invention) >> Stirrer,
700 parts of water was put into a reaction vessel equipped with a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and a sodium salt of a copolymer of styrenesulfonic acid and maleic acid (polymerization molar ratio, styrenesulfonic acid: maleic acid was added thereto. = 3: 1 Mw = 500
0) 100 parts was added with stirring to make an aqueous solution. Then, nitrogen gas was introduced through the above-mentioned nitrogen introducing pipe to make the inside of the reaction vessel under a nitrogen gas atmosphere and eliminate dissolved oxygen in the aqueous solution. Then, the temperature of the aqueous solution was raised to 80 ° C. 90 parts of styrene, 10 parts of butyl acrylate, and 10 parts of potassium persulfate aqueous solution (concentration: 1% by weight) were added to this aqueous solution.
0 part was added dropwise, and a polymerization reaction was carried out at 80 ° C. under a nitrogen gas reflux to obtain the target conductive particles of the present invention.

Example 1 << Preparation of support for silver halide photographic light-sensitive material >> A polyethylene terephthalate film having a thickness of 100 μm after biaxial stretching and heat setting was subjected to corona discharge treatment of 8 W min / m ² on both sides, The undercoating coating solution B-1 described below was applied as a subbing layer B-1 to a dry film thickness of 0.8 μm as described in JP-A-59-19941 and dried at 100 ° C. for 1 minute. On the surface of the polyethylene terephthalate film opposite to the subbing layer B-1, there is disclosed in JP-A-59-77439.
As described in No. 1, the undercoating coating liquid B-2 is added to the undercoating layer B-
2 was applied and dried at 110 ° C. for 1 minute.

[0090] << 1st layer of subbing >>   <Undercoating liquid B-1>       Butyl acrylate 30% by weight, t-butyl acrylate         Rate 20% by weight, styrene 25% by weight and 2-hi         Copolymerization of 25% by weight droxyethyl acrylate         Body latex liquid (solid content 30%) 270g       Compound A 0.6g       Hexamethylene-1,6-bis (ethylene urea) 0.8 g       Make up to 1 liter with water.

<Undercoating liquid B-2> Copolymer latex liquid (solid content 20%) of 40% by weight of butyl acrylate, 20% by weight of styrene and 40% by weight of glycidyl acrylate 80 g P1 (conductivity of the above-mentioned present invention Particles) 60 g Water 860 g << Undercoating second layer >> Furthermore, the undercoating layers B-1 and B-2
Then, a corona discharge of 8 W min / m ² was applied, and the undercoat layer B-3 was coated with the following undercoat coating solution B-3 to a dry film thickness of 0.1 μm, and dried at 100 ° C. for 1 minute.

[0092]   <Undercoating liquid B-3>       Gelatin 10g       Compound A 0.4 g       Compound B 0.1 g       0.1 g of silica particles having an average particle size of 3 μm       Make up to 1 liter with water.

[0093]

[Chemical 7]

<< Preparation of Silver Halide Emulsion >> Silver halide grains containing 10 ⁻⁵ mol of rhodium per 1 mol of silver were prepared by the control double jet method in an acidic atmosphere of pH 3.0. The growth of silver halide grains was carried out by adding 30 mg of benzyladenine per liter of a 1% aqueous gelatin solution.
It carried out by the system containing. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added per mol of silver halide, followed by washing with water and desalting.

Then, 60 m per mol of silver halide
g of 6-methyl-4-hydroxy-1,3,3a, 7-
After adding tetrazaindene, it was sensitized with sulfur. As a stabilizer after sulfur sensitization, 6-methyl-4-hydroxy-
1,3,3a, 7-Tetrazaindene was added.

<< Silver Halide Emulsion Layer >> The silver halide emulsion obtained as described above was prepared by adding the additives in the following amounts, and the undercoat layers B-2 and B-3 were provided. It was applied on the body.

Latex polymer: styrene-butyl acrylate-acrylic acid ternary copolymer 1.0 g / m ² tetraphenylphosphonium chloride 30 mg / m ² saponin 200 mg / m ² polyethylene glycol 100 mg / m ² sodium dodecylbenzenesulfonate 100 mg / m ² hydroquinone 200 mg / m ² phenidone 100 mg / m ² sodium styrenesulfonate-maleic acid copolymer (Mw = 250,000) 200 mg / m ² gallic acid butyl ester 500 mg / m ² tetrazolium compound 30 mg / m ² 5-methylbenzo triazole 30 mg / m ² 2-mercaptobenzimidazole-5-sulfonic acid 30 mg / m ² Inner toe Thane gelatin (isoelectric point ^{4.9) 1.5g / m 2 1- (} p- acetyl amide Fe Le) -5-mercapto Totetorazoru 30 mg / m ² silver amount 2.8 g / ^{m 2}

[0098]

[Chemical 8]

(Emulsion layer protective film) An emulsion layer protective film was prepared and coated in the following amounts.

Fluorinated dioctyl sulfosuccinate 300 mg / m ² matting agent: polymethylmethacrylate (average particle size 3.5 μm) 100 mg / m ² lithium nitrate 30 mg / m ² acid-treated gelatin (isoelectric point 7.0) 1.2 g / m ² colloidal silica 50 mg / m ² sodium styrenesulfonate-maleic acid copolymer 100 mg / m ² mordant 30 mg / m ² dye 30 mg / m ²

[0101]

[Chemical 9]

<< Backing Layer >> A backing layer containing a backing dye having the following composition was adjusted and coated on the support on the side opposite to the emulsion layer so as to have the following coating amounts. The gelatin layer is glyoxal and 1-oxy-3,5-dichloro-
The film was hardened with S-triazine sodium salt and a hydroxy-containing epoxy compound (d).

Hydroquinone 100 mg / m ² Phenidone 30 mg / m ² Latex polymer: butyl acrylate-styrene copolymer 0.5 g / m ² Styrene-maleic acid copolymer 100 mg / m ² Citric acid 40 mg / m ² Benzotriazole 100 mg / M ² Styrene sulfonic acid-maleic acid copolymer 100 mg / m ² Lithium nitrate 30 mg / m ² Backing dye (a) (b) (c) 40,30,30 mg / m ² Ocein gelatin 2.0 g / m ^Two

[0104]

[Chemical 10]

The sample obtained as described above was exposed on the whole surface and developed using the developing solution and fixing solution shown below, and then the surface specific resistance test and the ash adhesion test method were performed. The results are shown in Table 1.

[0106] <Developer formulation>     Hydroquinone 25g     1-phenyl-4,4-dimethyl-3-pyrazolidone 0.4 g     Sodium bromide 3g     5-methylbenzotriazole 0.3 g     5-nitroindazole 0.05g     Diethylaminopropane-1,2-diol 10 g     90g potassium sulfite     Sodium 5-sulfosalicylate 75 g     Ethylenediamine tetrasodium acetate 2g     Make up to 1 liter with water.

The pH was adjusted to 11.5 with caustic soda.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5 w% aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90 w% aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50 w% aqueous solution) 3.0 g Aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1 w%) 20 g Water 500 ml when using the fixing solution In the above composition A, composition B
Were melted in this order and finished to 1 l for use. P of this fixer
H was about 5.6.

(Development processing conditions) (Process) (Temperature) (Time) Development 40 ° C. for 8 seconds Fixing 35 ° C. for 8 seconds Rinse at room temperature 10 seconds (Evaluation of antistatic performance: Ash adhesion test method (dust adhesion resistance)) 23 Rubbing the emulsion side of the developed sample several times with a rubber roller under the conditions of 20 ° C. and 20% RH, bring the ash of the cigarette close to
Whether or not the film adheres was examined according to the following evaluation.

[0110] ◯: No adhesion even when approached to 1 cm ○ △: Adheres when approaching from 1 cm to 4 cm △: Adheres when approaching from 4 cm to 10 cm X: Adhesion is applied even at 10 cm or more There is no problem in practical use if it is ○ △ or more.

(Absolute Impedance Measurement Method) For impedance measurement, a combination of Precision LCR meters HP4284A and HP16451B manufactured by Yokogawa Hewlett-Packard (hereinafter YHP) was used.

The absolute value of the impedance of the film material was measured by the void method in an atmosphere of 23 ° C. and 20% RH.
Regarding the measurement of the void method, HP 16451B instruction manual (part number 16451-97000, print 198)
Electrode non-contact method described in December 1997). Using Electrode-A having a main electrode diameter of 3.8 cm, the sample size was cut into a square of 5.5 cm x 5.5 cm. The dispersed layer of conductive particles was measured upward.

(Haze Test) Samples subjected to undercoating treatment up to the second layer, ie, undercoating coating liquids B-1 and B-2 and samples at the stage where B-3 was applied to the upper layer of each of them were used for Tokyo Denshoku Co., Ltd. The haze was measured by using a company turbidity meter Model T-2600 DA and expressed in%.

Example 2 The sample preparation conditions were the same as in Example 1 except that the undercoating coating solution B-0-3 was used in place of the undercoating coating solution B-2 in Example 1. Then, the same evaluation as in Example 1 was performed.

* Undercoating first layer <Undercoating coating liquid B-0-3> Copolymer latex liquid containing 40% by weight of butyl acrylate, 20% by weight of styrene and 40% by weight of glycidyl acrylate (solid content 20%) 80 g P1 80 g Polyethylene glycol (Molecular weight: 600) 0.1 g Water 820 g Comparative example 1 The sample preparation conditions are as follows: the undercoating coating liquid B-2 in place of the undercoating coating liquid B-2 of Example 1. It was prepared in the same manner as in Example 1 except that 0-1 was used, and the same haze value evaluation as in Example 1 was performed.

[0116]   <Undercoating liquid B-0-1>         Butyl acrylate 40% by weight, styrene 20% by weight           And glycidyl acrylate 40% by weight copolymer LATEC           Liquid (30% solid content) 270g         Make up to 1 liter with water.

Comparative Example 2 The sample preparation conditions were the same as in Example 1 except that the undercoating coating solution B-0-2 was used in place of the undercoating coating solution B-2 in Example 1. Then, the same evaluation as in Example 1 was performed. However, a 30% aqueous solution of a copolymer of styrene sulfonic acid and maleic acid (V-TL manufactured by Kanebo NSC Co., Ltd.) was used as the conductive organic polymer.

[0118]   <Undercoating liquid B-0-2>         Butyl acrylate 40% by weight, styrene 20% by weight           And glycidyl acrylate 40% by weight copolymer LATEC           Liquid (solid content 20%) 40g         V-TL 100g         800 g of water The above results are shown in Table 1.

[0119]

[Table 1]

As is apparent from Table 1, the photographic light-sensitive material of the present invention has good dust resistance and transparency even though the absolute value of impedance is large.

It was possible to provide a plastic film material having excellent transparency and a high antistatic property even under low humidity, and a silver halide photographic light-sensitive material using the same.

[0122]

EFFECTS OF THE INVENTION The present invention solves the problems such as the adhesion of the antistatic layer, the stability of the coating solution, the workability, etc., which are caused by the large amount of the conductive material added, and the high electrostatic charge is achieved even in low humidity. It was possible to provide a transparent plastic film material having a preventive property and a silver halide photographic light-sensitive material using the same.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-6-301152 (JP, A) JP-A-7-248577 (JP, A) JP-A-7-77762 (JP, A) JP-A-3- 243684 (JP, A) JP 2-291551 (JP, A) JP 2-287350 (JP, A) JP 62-288832 (JP, A) JP 62-111251 (JP, A) JP 59-202852 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 7/04-7/18 G03C 1/00-1 / 95

Claims (5)

(57) [Claims] 1. A film material having at least one conductive layer, wherein the absolute value of impedance of the film material at a frequency of 20 Hz is 4 × 10 ⁵ Ω or more and 1 ×.
10 ²⁰ Ω or less, and at least one layer of the conductive layer comprises a polymer binder and latex particles having a conductive organic polymer on the surface, and the conductive layer contains the conductive organic polymer. 10 vol% or more and 50 vol% or less is contained, The antistatic plastic film material characterized by the above-mentioned. 2. A latex colloid having a conductive organic polymer on the surface thereof, wherein the hydrophobic polymer particle (A) is protected by a conductive organic polymer (B) which is a hydrophilic polymer compound having an anionic functional group. The plastic film material according to claim 1, wherein the plastic film material is an emulsified particle. 3. The weight of the conductive organic polymer (B) is
31 to 5 relative to the weight of the hydrophobic polymer particles (A)
It is 00%, The plastic film material of Claim 2 characterized by the above-mentioned. 4. The plastic film material according to claim 1, 2 or 3, wherein the film material is a plastic film containing syndiotactic polystyrene as a main component. 5. A silver halide photographic light-sensitive material comprising the film material according to claim 1, 2, 3 or 4 as a support.