JP2008248038A - Antistatic polyolefinic resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic polyolefinic resin film having an electroconductive coated film formed on a stretched film of a polyolefinic resin. <P>SOLUTION: The electroconductivity of the stretched film of the polyolefinic resin is improved by coating the top surface of the stretched film of the polyolefinic resin with the electroconductive coated film containing a surfactant having a 7-15C alkyl group in the side chain and a sulfonic acid group, polypyrrole and a synthetic resin binder. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antistatic polyolefin-based resin film in which a conductive coating film is formed on a stretched film of a polyolefin-based resin, and more specifically, excellent adhesion that does not require surface pretreatment such as corona treatment. It is related with the stretched film of polyolefin resin in which the electrically conductive coating film which shows the outstanding antistatic effect which shows this and has no humidity dependence was formed.

In general, polyolefin-based films are used in various fields including stationery and industrial applications represented by in-process release films.
It is well known that these polyolefin resin films are easily charged and easily generate static electricity.
As a means for suppressing the generation of static electricity in a polyolefin resin film, a method of expressing antistatic performance by kneading a surfactant into a polyolefin resin film and bleeding out the surfactant to the film surface or polyolefin A method of providing a coating film having an antistatic effect on the surface of a resin film has been employed (for example, JP 2000-154286 A and “Surfactant Handbook”, Engineering Library Co., Ltd., published in August 1968, Showa 43). -See page 275, 9.2 Plastic Antistatic Agents).
However, when a surfactant is kneaded into the polyolefin resin film, there is a problem that the antistatic performance varies depending on the outside air temperature and humidity. When a coating film having an antistatic effect is provided, the polyolefin resin In the stretched film, there was a problem that sufficient adhesion could not be obtained unless the film surface was modified such as corona discharge treatment (for example, “Plastic Materials Course Polypropylene Resin” October 10, 1981). Date 6th edition, 220 pages (ii) Printing (a) Refer to film printing.)
JP 2000-154286 A "Surfactant Handbook" Engineering Books Co., Ltd. Published August 1968, pages 268-275 9.2 Plastic antistatic agent , "Plastic Materials Course, Polypropylene Resin" October 10, 1981, 6th edition, issue 220 pages (ii) Printing (a) Film printing

  The present invention provides a stretched polyolefin resin film that does not require a surface pretreatment such as a corona treatment, has excellent adhesion, and has an excellent antistatic effect without humidity dependence. Is an issue.

  As a result of diligent research to solve the above problems, the present inventor has found that when forming a conductive coating film comprising a surfactant, polypyrrole and a synthetic resin binder on a stretched film of polyolefin resin, a specific surface activity is obtained. By using an agent, the present invention has been found to be a stretched polyolefin resin film in which a conductive coating film having excellent adhesion and antistatic effect is formed without performing surface pretreatment such as corona treatment. Was completed.

That is, the present invention
1. An antistatic polyolefin-based resin film in which a conductive coating film is formed on a stretched film of a polyolefin-based resin, wherein the conductive coating film has an alkyl group having 7 to 15 carbon atoms in a side chain, and An antistatic polyolefin-based resin film comprising a surfactant having a sulfonic acid group, polypyrrole, and a synthetic resin binder;
2. 1. The surfactant is di-2-ethylhexyl sodium sulfosuccinate. Antistatic polyolefin resin film as described,
It is about.

According to the present invention, there is provided a stretched polyolefin resin film that does not require surface pretreatment such as corona treatment, and has an excellent anti-static effect that exhibits excellent adhesion and does not depend on humidity. Is done.
As described above, the antistatic polyolefin-based resin film of the present invention can reduce the surface treatment process such as corona treatment, thereby reducing the manufacturing cost, and thereby a special facility for performing the corona treatment. This makes it possible to produce a stretched film of a polyolefin-based resin on which a conductive coating film is formed that exhibits excellent adhesion without moisture and exhibits an excellent antistatic effect without humidity dependency.

The present invention will be described in more detail.
The antistatic polyolefin resin film of the present invention is an antistatic polyolefin resin film in which a conductive coating film is formed on a stretched film of a polyolefin resin, and the conductive coating film has 7 carbon atoms. Or a surfactant having 15 alkyl groups in the side chain and having a sulfonic acid group, polypyrrole, and a synthetic resin binder.

  The conductive coating film according to the present invention is, for example, an O obtained by mixing and stirring an organic solvent, water, and a surfactant having an alkyl group having 7 to 15 carbon atoms in the side chain and having a sulfonic acid group. / W type emulsion is added with a monomer of pyrrole and / or pyrrole derivative, and the monomer is oxidatively polymerized to form conductive fine particles (that is, the conductive fine particles are alkyl groups having 7 to 15 carbon atoms). In the side chain and composed of a surfactant having a sulfonic acid group and polypyrrole) and is used as a synthetic resin in the conductive fine particles (for example, used as a dispersion finely dispersed in an organic solvent). After forming a conductive paint by adding a binder or the like, it is formed by coating on a stretched film of polyolefin resin.

  Examples of pyrrole and derivatives thereof that can be used in the production of the conductive fine particles include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N- Methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxy Pyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethyl Aminopyrrole, 3-diethylaminopyrrole, 3-diph Arylsulfonylamino pyrrole, 3-methylphenylamino pyrrole, 3-phenyl naphthyl amino pyrrole, and the like. Particularly preferred is pyrrole.

The surfactant having a C 7-15 alkyl group in the side chain and having a sulfonic acid group used in the production of the conductive fine particles has a plurality of hydrophobic ends (for example, a branched structure in the hydrophobic group). And those having a plurality of hydrophobic groups) are preferred. By using such an anionic surfactant having a plurality of hydrophobic ends, stable micelles can be formed.
Among anionic surfactants having a plurality of hydrophobic ends, di-2-ethylhexyl sodium sulfosuccinate (4 hydrophobic ends), di-2-ethyloctyl sodium sulfosuccinate (4 hydrophobic ends) and branched type Alkyl benzene sulfonate (two hydrophobic ends) can be preferably used.

  The amount of the surfactant having an alkyl group having 7 to 15 carbon atoms in the side chain and having a sulfonic acid group in the reaction system is less than 0.2 mol with respect to 1 mol of monomers of pyrrole and / or a pyrrole derivative. Is more preferable, and 0.05 mol to 0.15 mol is more preferable. If the amount is less than 0.05 mol, the yield and the dispersion stability are lowered. On the other hand, if the amount is 0.2 mol or more, the resulting conductive fine particles may have a conductivity humidity dependency.

  In the production of the conductive fine particles, the organic solvent forming the organic phase of the emulsion is preferably hydrophobic. Especially, toluene and xylene which are aromatic organic solvents are preferable from the viewpoint of the stability of the O / W emulsion and the affinity with the pyrrole monomer. Although the polypyrrole can be polymerized with an amphoteric solvent, it becomes difficult to separate the organic phase and the aqueous phase when the produced conductive fine particles are recovered.

  The ratio of the organic phase to the aqueous phase in the emulsion is preferably 75% by volume or more in the aqueous phase. When the water phase is 20% by volume or less, the amount of pyrrole monomer dissolved is reduced and the production efficiency is deteriorated.

  Examples of the oxidizing agent used in the production of the conductive fine particles include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, potassium persulfate, Peroxides such as ammonium sulfate and hydrogen peroxide can be used. These may be used alone or in combination of two or more. Polypyrrole can be polymerized with a Lewis acid such as ferric chloride, but the generated particles may aggregate and the conductive fine particles may not be finely dispersed. Particularly preferred oxidizing agents are persulfates such as ammonium persulfate.

  The amount of the oxidizing agent in the reaction system is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol with respect to 1 mol of pyrrole and / or pyrrole derivative monomer. . If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and collect the conductive fine particles. On the other hand, if the amount is 0.8 mol or more, the conductive fine particles are aggregated to increase the particle size. And transparency of the conductive coating film deteriorates.

The method for producing the conductive fine particles is performed, for example, in the following steps:
(A) a step of preparing an emulsion by mixing and stirring a surfactant having an alkyl group having 7 to 15 carbon atoms in the side chain and having a sulfonic acid group, an organic solvent, and water;
(B) a step of dispersing a monomer of pyrrole and / or a pyrrole derivative in the emulsion, (c) a step of oxidative polymerization of the monomer with an oxidizing agent,
(D) A step of separating the organic phase and collecting the conductive fine particles.

  Each of the above steps can be performed using means known to those skilled in the art. For example, the mixing and stirring performed at the time of preparing the emulsion is not particularly limited. For example, a magnetic stirrer, a stirrer, a homogenizer, or the like can be selected as appropriate. The polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.

  In the above production method, when the oxidative polymerization reaction is stopped, the reaction system is divided into two phases, an organic phase and an aqueous phase. At this time, unreacted monomers, oxidizing agents and salts are dissolved in the aqueous phase. Remains. When the organic phase is separated and recovered here and washed several times with ion-exchanged water, conductive fine particles dispersed in an organic solvent can be obtained.

The conductive fine particles thus obtained (consisting of a surfactant having an alkyl group having 7 to 15 carbon atoms in the side chain and a sulfonic acid group) and polypyrrole are dispersed in the organic solvent. As a liquid, an organic solvent is volatilized to some extent as necessary, for example, using a facility such as an evaporator, and used as a concentrated liquid of the dispersion liquid or as an isolated conductive fine particle as a component of a conductive paint. be able to.
The conductive paint is produced by adding a synthetic resin binder and other components as required to the conductive fine particles (for example, used as a dispersion finely dispersed in an organic solvent).

Examples of the synthetic resin binder include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin,
Examples include phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, urethane resin, melamine resin, acrylic resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and urethane resin, melamine resin, acrylic resin, etc. preferable.

As other components, resins such as dispersion stabilizers, thickeners, and ink binders can be added as required for the purpose of application and application.
In addition, these conductive fine particles can be dried to form powdered conductive fine particles, and the powdered conductive fine particles can also be used as a conductive filler or the like in a synthetic resin molded product or the like.

A conductive thin film can be formed by applying the conductive coating to a stretched film of a polyolefin resin and drying it, whereby the antistatic polyolefin resin film of the present invention can be produced.
The coating method is not particularly limited, and printing or coating can be performed using, for example, a gravure printer, an inkjet printer, dipping, a spin coater, a roll coater, or the like. The obtained conductive thin film exhibits a resistance value of 10 ¹⁰ Ω or less, more particularly 10 ⁸ Ω or less.

In the present invention, a surfactant (having an alkyl group having 7 to 15 carbon atoms in the side chain and having a sulfonic acid group), polypyrrole and a synthetic resin binder in the solid content of the conductive coating film The rate is adjusted to a specific range.
Here, the content of the surfactant (having an alkyl group having 7 to 15 carbon atoms in the side chain and having a sulfonic acid group) is 2 to 65 mass based on the total mass of the solid content of the conductive coating film. %, Preferably 2 to 47% by mass, and the content of polypyrrole is 1 to 30% by mass, preferably 1 to 25% by mass, based on the total mass of the solid content of the conductive coating film. The content of is 30 to 97% by mass, preferably 30 to 96% by mass, based on the total mass of the solid content of the conductive coating film.

  The following examples illustrate the invention in more detail. However, the examples are for illustrating the present invention and are not intended to limit the present invention in any way.

Synthesis Example 1 (Preparation of Solution 1)
A surfactant, 1.5 mmol sodium di-2-ethylhexyl sulfosuccinate (alkyl (C8)), was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsification was maintained at 20 ° C. The resulting emulsion was mixed with pyrrole monomer 21.2.
After adding mmol, the mixture was stirred for 30 minutes, and then 50 mL of a 0.2 M aqueous ammonium persulfate solution (corresponding to 0.4 mol) was added dropwise little by little to react for 4 hours. After completion of the reaction, the organic layer was recovered, washed several times with ion-exchanged water, and dispersed in toluene to obtain a dispersion of black conductive fine particles (average particle size of 50 nm). The polypyrrole content was 0.6%, and the surfactant content was 1.4%. This was designated as Solution 1.

Synthesis Example 2 (Preparation of Solution 2)
Surfactant, alkyl (C7) sodium benzenesulfonate (sodium n-heptylbenzenesulfonate) 1.5 mmol was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsification was maintained at 20 ° C. . To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. After completion of the reaction, the organic layer was recovered, washed several times with ion-exchanged water, and dispersed in toluene to obtain a dispersion of black conductive fine particles (average particle size of 50 nm). The polypyrrole content was 0.6%, and the surfactant content was 1.4%. This was designated as Solution 2.

Synthesis Example 3 (Preparation of Solution 3)
Surfactant, alkyl (C12) sodium benzenesulfonate (sodium n-dodecylbenzenesulfonate) 1.5 mmol was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsified while maintaining at 20 ° C. . To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. After completion of the reaction, the organic layer was recovered, washed several times with ion-exchanged water, and dispersed in toluene to obtain a dispersion of black conductive fine particles (average particle size of 50 nm). The polypyrrole content was 0.6%, and the surfactant content was 1.4%. This was designated as Solution 3.

Synthesis Example 4 (Preparation of Solution 4)
Dissolve 1.5 mmol of sodium alkyl (C15) benzenesulfonate (sodium n-pentadecylbenzenesulfonate) as a surfactant in 50 mL of toluene, and stir until emulsification while adding 100 mL of ion-exchanged water and maintaining at 20 ° C. did. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. After completion of the reaction, the organic layer was recovered, washed several times with ion exchange water, and dispersed in toluene to obtain a dispersion of black conductive fine particles (average particle size 100 nm). The polypyrrole content in the dispersion was 0.6%, and the surfactant content was 1.4%. This was designated as Solution 4.

Synthesis Example 5 (Preparation of Solution 5: Use of a surfactant having no sulfonic acid group)
A surfactant, 1.5 mmol of sorbitan monolaurate (alkyl (C12)), was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsification was maintained at 20 ° C. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. After completion of the reaction, the organic layer was collected, washed several times with ion exchange water, and dispersed in toluene to obtain a dispersion of black conductive fine particles (average particle size 75 nm). The polypyrrole content in the dispersion was 0.6%, and the surfactant content was 1.4%. This was designated as Solution 5.

Synthesis Example 6 (Preparation of Solution 6)
Surfactant, alkyl (C6) sodium benzenesulfonate (sodium n-hexylbenzenesulfonate) 1.5 mmol was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsified while maintaining at 20 ° C. . To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. However, since the conductive fine particles in the dispersion liquid aggregated, they could not be used for the paint. (Solution 6)

Synthesis Example 7 (Preparation of Solution 7)
Surfactant, alkyl (C16) sodium benzenesulfonate (sodium n-hexadecylbenzenesulfonate) 1.5 mmol was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsified while maintaining at 20 ° C. did. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. After completion of the reaction, the organic layer was recovered, washed several times with ion exchange water, and dispersed in toluene to obtain a dispersion of black conductive fine particles (average particle size 100 nm). The polypyrrole content in the dispersion was 0.6%, and the surfactant content was 1.4%. This was designated as Solution 7.

Synthesis Example 8 (Preparation of Solution 8)
Surfactant sodium paratoluenesulfonate (alkyl (C1)) 1.5 mmol was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsification was maintained at 20 ° C. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 0.4 mol) of a 0.2 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. However, since the conductive fine particles in the dispersion liquid aggregated, they could not be used for the paint. (Solution 8)

Example 1
To 100 parts by mass of Solution 1 prepared in Synthesis Example 1, a two-component cured urethane resin, that is,
Vernock DN-980 (polyisocyanate prepolymer: solid content = 75%) 1.25 parts by mass and Vernock D6-439 (alkyd resin: solid content = 80%) 0.76 parts by mass were added to obtain a polypyrrole paint. It was.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 1.55 = 39 5: 16.9: 43.6.

Example 2
To 100 parts by mass of Solution 1 prepared in Synthesis Example 1, a two-component cured urethane resin, that is,
Barnock DN-980 (polyisocyanate prepolymer: solid content = 75%) 38 parts by mass and Barnock D6-439 (alkyd resin: solid content = 80%) 22.6 parts by mass were added to obtain a polypyrrole paint.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 46.6 = 2. .9: 1.2: 95.8.

Example 3
To 100 parts by mass of Solution 1 prepared in Synthesis Example 1, 1.7 parts by mass of melamine resin (Dainippon Ink, Super Becamine J820: solid content = 60%) was added to obtain a polypyrrole-based paint.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 1.0 = 46 .7: 20.0: 33.3.

Example 4
An antistatic film was obtained in the same manner as in Example 3 except that the melamine resin (Dainippon Ink, Super Becamine J820: solid content = 60%) was changed to 13.3 parts by mass.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 8.0 = 14 0.0: 6.0: 80.0.

Example 5
To 100 parts by mass of Solution 1 prepared in Synthesis Example 1, 6.7 parts by mass of an acrylic resin (manufactured by Ohashi Chemical Co., Ltd., Polynal No. 500004 clear: solid content = 32%) was added to obtain a polypyrrole paint.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 2.1 = 34 : 1: 14.6: 51.2.

Example 6
An antistatic film was obtained in the same manner as in Example 5 except that the acrylic resin (manufactured by Ohashi Chemical Co., Ltd., Polynal No. 500004 Clear: solid content = 32%) was changed to 26.7 parts by mass.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 8.5 = 13 .3: 5.7: 81.0.

Example 7
To 100 parts by mass of Solution 2 prepared in Synthesis Example 2, a two-component cured urethane resin, that is,
Vernock DN-980 (polyisocyanate prepolymer: solid content = 75%) 1.8 parts by mass and Vernock D6-439 (alkyd resin: solid content = 80%) 1.2 parts by mass were added to obtain a polypyrrole paint. It was.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
In addition, solid content ratio in a coating film is surfactant (alkyl (C7) sodium benzenesulfonate (sodium n-heptylbenzenesulfonate)): polypyrrole: synthetic resin binder = 1.4: 0.6: 2. 3 = 32.6: 14.0: 53.4.

Example 8
To 100 parts by mass of Solution 2 prepared in Synthesis Example 2, 1.7 parts by mass of melamine resin (Dainippon Ink, Super Becamine J820: solid content = 60%) was added to obtain a polypyrrole-based paint.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (sodium alkyl (C7) benzenesulfonate (sodium n-heptylbenzenesulfonate)): polypyrrole: synthetic resin binder = 1.4: 0.6: 1. 0 = 46.7: 20.0: 33.3.

Example 9
To 100 parts by mass of Solution 2 prepared in Synthesis Example 2, 6.7 parts by mass of an acrylic resin (manufactured by Ohashi Chemical Co., Ltd., Polynal No. 500004 clear: solid content = 32%) was added to obtain a polypyrrole paint.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
In addition, solid content ratio in a coating film is surfactant (alkyl (C7) sodium benzenesulfonate (sodium n-heptylbenzenesulfonate)): polypyrrole: synthetic resin binder = 1.4: 0.6: 2. 1 = 34.1: 14.6: 51.2.

Example 10
To 100 parts by mass of Solution 3 prepared in Synthesis Example 3, a two-component cured urethane resin, that is,
Vernock DN-980 (polyisocyanate prepolymer: solid content = 75%) 1.8 parts by mass and Vernock D6-439 (alkyd resin: solid content = 80%) 1.2 parts by mass were added to obtain a polypyrrole paint. It was.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (sodium alkyl (C12) benzenesulfonate (sodium n-dodecylbenzenesulfonate)): polypyrrole: synthetic resin binder = 1.4: 0.6: 2. 3 = 32.6: 14.0: 53.4.

Example 11
To 100 parts by mass of Solution 4 prepared in Synthesis Example 4, a two-component cured urethane resin, that is,
Vernock DN-980 (polyisocyanate prepolymer: solid content = 75%) 1.8 parts by mass and Vernock D6-439 (alkyd resin: solid content = 80%) 1.2 parts by mass were added to obtain a polypyrrole paint. It was.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
In addition, solid content ratio in a coating film is surfactant (alkyl (C15) sodium benzenesulfonate (sodium n-pentadecylbenzenesulfonate)): polypyrrole: synthetic resin binder = 1.4: 0.6: 2 .3 = 32.6: 14.0: 53.4.

Comparative Example 1
Solution 1 prepared in Synthesis Example 1 was used as a coating as it was (no binder was added).
The above coating is applied to one side of a polypropylene resin stretched film (film thickness 300 μm) on a lattice #
The film was applied by a direct reverse method using a gravure roll having a depth of 150 μm and dried at a speed of 20 m / min and a drying temperature of 120 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (di-2-ethylhexyl sulfosuccinate (alkyl (C8)) sodium): polypyrrole: synthetic resin binder = 1.4: 0.6: 0 = 70: 30 : 0.

Comparative Example 2
To 100 parts by mass of the solution 5 prepared in Synthesis Example 5, a two-component cured urethane resin, that is,
Vernock DN-980 (polyisocyanate prepolymer: solid content = 75%) 1.25 parts by mass and Vernock D6-439 (alkyd resin: solid content = 80%) 0.76 parts by mass were added to obtain a polypyrrole paint. It was.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film was as follows: surfactant (sorbitan monolaurate (alkyl (C12))): polypyrrole: synthetic resin binder = 1.4: 0.6: 1.55 = 39.5: 16 9: 43.6.

Comparative Example 3
An attempt was made to prepare a coating material using the solution 6 prepared in Synthesis Example 6, but the conductive fine particles in the dispersion liquid were agglomerated, so that the coating material could not be obtained.

Comparative Example 4
To 100 parts by mass of the solution 7 prepared in Synthesis Example 7, a two-component cured urethane resin, that is,
When 1.25 parts by weight of Bernock DN-980 (polyisocyanate prepolymer: solid content = 75%) and 0.76 parts by weight of Barnock D6-439 (alkyd resin: solid content = 80%) were added, conductive fine particles were Since it aggregated, it was not able to be set as a coating material.

Comparative Example 5
An attempt was made to prepare a coating material using the solution 8 prepared in Synthesis Example 8, but the conductive fine particles in the dispersion liquid were agglomerated, so that the coating material could not be obtained.

Comparative Example 6
Without using a dispersion of conductive fine particles, 100 parts by mass of toluene, a two-component cured urethane resin,
Barnock DN-980 (polyisocyanate prepolymer: solid content = 75%) 1.8 parts by mass and Barnock D6-439 (alkyd resin: solid content = 80%) 1.2 parts by mass were added to obtain a paint.
The paint obtained as described above is applied to one side of a polypropylene resin stretched film (film thickness: 300 μm) by a direct reverse method using a gravure roll having a grid of # 150 and a depth of 60 μm, a speed of 20 m / min, and a drying temperature of 120. It was dried at 0 ° C. to obtain an antistatic film.
The solid content ratio in the coating film is surfactant: polypyrrole: synthetic resin binder = 0: 0: 2.3 = 0: 0: 100.

Comparative Example 7
A stretched polypropylene film containing 0.5 parts by mass of diethanolamine as a surfactant in 100 parts by mass of a polypropylene resin.

４）磨耗性
ＪＩＳ Ｌ ０８４９「摩擦に対する染色堅ろう度試験方法」に準じて摩擦試験を行い、荷重２００ｇで１００回学振後の綿布への塗料の転写を比較し評価した。評価基準としては○は綿布への着色なし、△は若干の着色あり、×は塗料の完全な転写による着色とし評価を行った。 Test example 1
Polypropylene resin stretched film on which the coating films obtained in Examples 1 to 11 and Comparative Examples 1 to 7 were formed (however, in Comparative Example 3-5, the conductive fine particles were aggregated, so the coating film was formed. In Comparative Example 7, the physical properties of the polypropylene resin were not formed because the surfactant was kneaded into the polypropylene resin.
The results are summarized in Table 2.
Evaluation of physical properties is as follows: 1) surface resistance value (Ω), 2) humidity dependency (20% / 80%), 3) adhesion (classification), and 4) wear resistance of the conductive coating film, Evaluated by criteria.
1) Surface resistance value It measured by the applied voltage of 10V using "High Lester" by Mitsubishi Chemical Corporation under the atmosphere of temperature 25 degreeC and humidity 50%.
2) Dependence on humidity The resistance value change was evaluated at an applied voltage of 10 V using a “High Lester” manufactured by Mitsubishi Chemical Corporation in an atmosphere of an air temperature of 25 ° C., a humidity of 20%, and 80%.
As evaluation criteria, “None” was evaluated as less than one digit relative to the initial resistance value, and “Yes” was evaluated as one digit or more.
3) Adhesion
An adhesion test was performed in accordance with JIS K 5600-5-6 "General test method for paints-Adhesiveness" and evaluated.

4) Abrasion A friction test was conducted in accordance with JIS L 0849 “Test Method for Dye Fastness to Friction”, and the transfer of the paint to the cotton cloth after 100 times of vibration at a load of 200 g was compared and evaluated. As evaluation criteria, ◯ indicates that there is no coloration on the cotton cloth, Δ indicates that there is slight coloration, and × indicates that the color is obtained by complete transfer of the paint.

In Table 2, the surfactant types A to H and the binder types I to K mean the following.
<Surfactant>
A: Sodium di-2-ethylhexyl sulfosuccinate (alkyl (C8)) B: Sodium alkyl (C7) benzenesulfonate (sodium n-heptylbenzenesulfonate)
C: alkyl (C12) sodium benzenesulfonate (sodium n-dodecylbenzenesulfonate)
D: Sodium alkyl (C15) benzenesulfonate (sodium n-pentadecylbenzenesulfonate)
E: Sorbitan monolaurate (alkyl (C12))
F: alkyl (C6) sodium benzenesulfonate (sodium n-hexylbenzenesulfonate)
G: Sodium alkyl (C16) benzenesulfonate (sodium n-hexadecylbenzenesulfonate)
H: Sodium paratoluenesulfonate (alkyl (C1))
<Binder>
I: Two-component cured urethane resin (Bernock DN-980 (polyisocyanate prepolymer: solid content = 75%) and Bernock D6-439 (alkyd resin: solid content = 80%))
J: Melamine resin (Dainippon Ink, Super Becamine J820: Solid content = 60%)
K: Acrylic resin (manufactured by Ohashi Chemical Industry, Polynar No. 500004 Clear: solid content = 32%)
Table 2

As shown in Examples 1 to 11, a conductive coating film obtained by using a surfactant having an alkyl group having 7 to 15 carbon atoms in the side chain and a sulfonic acid group was formed. The stretched polyolefin resin film had a low initial surface resistance, the surface resistance was not dependent on humidity, and was excellent in adhesion and wear.
On the other hand, the stretched film of polyolefin resin not using a binder as in Comparative Example 1 was inferior in wear. In addition, as in Comparative Example 2, the stretched film of polyolefin resin in the case of using a surfactant having no sulfonic acid group was inferior in adhesion. Moreover, when using the surfactant (Comparative Example 3: 6 carbon atoms, Comparative Example 5: 1 carbon atom) having an alkyl group having a carbon atom number smaller than 7 in the side chain as in Comparative Examples 3 and 5 The conductive polymer aggregated at the stage of producing the conductive polymer, and could not be used as a paint. Further, when a surfactant (carbon atom number 16) having an alkyl group having a carbon number greater than 15 in the side chain as in Comparative Example 4 is used, the conductive polymer is produced at the stage of producing the conductive polymer. Although the aggregation of the conductive polymer did not occur, the conductive polymer aggregated at the stage when the binder was added, so that the coating material could not be formed. When the conductive polymer was not used as in Comparative Example 6 and only the binder was applied, it was found that although it was excellent in abrasion, it was inferior in adhesion.
Further, in the conventional antistatic film in which a surfactant was kneaded into stretched polypropylene as in Example 7, the surface resistance value was humidity dependent.

Claims (2)

An antistatic polyolefin-based resin film in which a conductive coating film is formed on a stretched film of a polyolefin-based resin, wherein the conductive coating film has an alkyl group having 7 to 15 carbon atoms in a side chain, and An antistatic polyolefin-based resin film comprising a surfactant having a sulfonic acid group, polypyrrole, and a synthetic resin binder. The antistatic polyolefin resin film according to claim 1, wherein the surfactant is di-2-ethylhexyl sodium sulfosuccinate.