CONDUCTIVE POLYMER DISPERSION; CONDUCTIVE FILM AND METHOD FOR CREATING THEM; AND ANTISTATIC CONTAINE

专利摘要:
There is provided a conductive polymer dispersion including: a conductive composite containing a π-conjugated conductive polymer and a polyanion; a vinyl versatate polymer; and a dispersion medium.
公开号:BE1025965B1
申请号:E2018/5548
申请日:2018-07-31
公开日:2019-08-28
发明作者:Sou Matsubayashi
申请人:Shin-Etsu Polymer Co., Ltd.；
IPC主号:

专利说明:

CONDUCTIVE POLYMER DISPERSION; CONDUCTIVE FILM AND PROCESS
TO CREATE IT; AND ANTISTATIC CONTAINER AND METHOD FOR THE PRODUCTION THEREOF
BACKGROUND This disclosure relates to a conductive
Polymer dispersion containing a π-conjugated conductive polymer, a conductive film and a method for producing the same, and an antistatic container and a method for producing the same.
This application claims priority from Japanese Patent Application No. 2017-153567 filed on Aug. 8, 2017, the contents of which are incorporated by reference in their entirety.
A conductor, which is formed by forming a conductive layer on a
Surface of a plastic base material is used in applications where antistatic properties are required, such as a package or a container for an electronic part and a package or a container for food.
A π-conjugated conductive polymer is sometimes used as a conductive material contained in the conductive layer because the π-conjugated conductive polymer has excellent conductivity and transparency, and also its conductivity is stable without moisture dependency.
For example, as a method for forming the conductive layer containing the π25 conjugated conductive polymer, a method is given in which a conductive polymer dispersion in which a conductive composite containing the π conjugated conductive polymer and a polyanion disperses in water is applied to a base material and then dried (WO 2015/108001 A1).
In general, a plastic base material is hydrophobic and has low hydrophilicity. The conductive layer formed by applying the aqueous conductive polymer dispersion described in WO 2015/108001 A1 to the plastic base material accordingly tends to have a low adhesive property to the base material. If a polyolefin, that itself
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BE2018 / 5548 for plastics has a high hydrophobicity when the base material is used, the conductive layer formed from the aqueous conductive polymer dispersion has a particularly low adhesive property to the base material.
In addition, the conductive layer formed from the aqueous conductive polymer dispersion tends to have low water resistance due to its high hydrophilicity, and therefore the water resistance must be improved.
SUMMARY
It is an object of this disclosure to provide a conductive polymer dispersion that enables easy formation of a conductive layer that is excellent in adhesive property to a plastic base material and in water resistance. Another goal of this
It is a disclosure to provide a conductive film including a conductive layer excellent in adhesive property to a plastic film base material and in water resistance, a method of manufacturing the same, and an antistatic container and a method of manufacturing the same.
[0005] This disclosure includes the following aspects.
[1] A conductive polymer dispersion including: a conductive composite containing a π-conjugated conductive polymer and a polyanion; a vinyl versatate polymer; and a dispersion medium.
[2] Conductive polymer dispersion according to aspect [1], wherein the
Vinyl versatate polymer contains a monomer unit derived from a vinyl versatate and a monomer unit derived from vinyl acetate.
[3] Conductive polymer dispersion according to aspect [1] or [2], wherein the vinyl versatate polymer has a pH value, which is measured according to JIS Z 8802: 2011, of 4 to 9.
[4] Conductive polymer dispersion according to one of the aspects [1] to [3], wherein the dispersion medium contains water.
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BE2018 / 5548 [5] Conductive polymer dispersion according to one of the aspects [1] to [4], the π-conjugated conductive polymer comprising poly (3,4-ethylenedioxythiophene).
[6] Conductive polymer dispersion according to one of the aspects [1] to [5], the polyanion comprising polystyrene sulfonic acid.
[7] Conductive polymer dispersion according to one of the aspects [1] to [6], which also contains a binder component.
[8] Conductive polymer dispersion according to aspect [7], wherein the
Binder component includes a polyester resin.
[9] Conductive polymer dispersion according to aspect [7], wherein the
Binder component includes a glycidyl group-containing acrylic resin.
[10] Conductive film including: a film base material; and a conductive layer which is arranged on a surface of the film base material and is formed from the conductive polymer dispersion according to one of the aspects [1] to [9].
[11] The conductive film according to aspect [10], wherein the film base material contains a polyolefin-based resin.
[12] The conductive film according to aspect [11], wherein the polyolefin-based resin comprises a polypropylene resin.
[13] A method of manufacturing a conductive film, comprising applying the conductive polymer dispersion according to any one of [1] to [9] to at least one surface of a film base material, followed by drying to form a conductive layer.
[14] A method of manufacturing a conductive film according to aspect [13], wherein the film base material contains a polyolefin-based resin.
[15] A method of manufacturing a conductive film according to aspect [14], wherein the polyolefin-based resin includes a polypropylene resin.
[16] A method of manufacturing a conductive film according to any one of [13] to [15], wherein the film base material has a hydrophilic group on a surface thereof.
[17] A method of manufacturing a conductive film according to aspect [16], wherein the film base material is obtained by a surface
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[18] Antistatic container containing a molded product obtained by molding the conductive film according to any one of [10] to 5 [12] into a container shape.
[19] A method of making an antistatic container which includes:
Manufacturing a conductive film by the method of manufacturing a conductive film according to any one of [13] to [17]; and
Form the conductive film into a container shape.
[20] A method of manufacturing an antistatic container according to aspect [19], wherein forming the conductive film comprises subjecting the conductive film to vacuum forming.
According to the conductive polymer dispersion of this disclosure, the conductive layer excellent in the adhesive property to a plastic base material and in water resistance can be easily formed.
The conductive film of this disclosure contains a conductive layer which is excellent in adhesive property to a plastic film base material and in which it is water-resistant.
According to the method of manufacturing a conductive film of this disclosure, the above-mentioned conductive film can be easily manufactured.
The antistatic container of this disclosure includes a conductive layer which is excellent in adhesive property to a plastic film base material and in water resistance.
According to the antistatic container manufacturing method of this disclosure, the above antistatic container can be easily manufactured.
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BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view illustrating an example of a conductive film of this disclosure.
Fig. 2 is a cross-sectional view illustrating a
Example of an antistatic container of this disclosure.
DESCRIPTION OF THE EMBODIMENTS <Conductive Polymer Dispersion>
A conductive polymer dispersion in one aspect of this
Disclosure includes a conductive composite, a vinyl versatate polymer, and a dispersion medium.
(Conductive Composite)
The conductive composite in this aspect contains a π-conjugated conductive polymer and a polyanion with anion groups. The
Polyanion is coordinated to the π-conjugated conductive polymer, and the anion groups of the polyanion are doped into the π-conjugated conductive polymer. This creates the conductive composite with conductivity.
Not all of the anion groups of the polyanion are doped into the conjugated conductive polymer, and the polyanion has an excess anion group. The excess anion group is a hydrophilic group, so that the conductive composite has water dispersibility.
[Π-conjugated conductive polymer]
The π-conjugated conductive polymer can be used without any special
Restriction may be any organic polymer with a backbone formed from a π-conjugated system as long as the effects of this disclosure are obtained. Examples include a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, a polyacetylene-based conductive polymer, a polyphenylene-based conductive polymer, a polyphenylene-vinylene-based conductive polymer, a polyaniline-based conductive polymer, a conductive Polyacene-based polymer, a conductive polythiophene-vinylene-based polymer and copolymers thereof. In terms of stability in the air, a conductive polymer based on polypyrrole, a conductive polymer
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Polythiophene-based and a conductive polyaniline-based polymer are preferred, and a polythiophene-based conductive polymer is more preferable in terms of transparency.
[0012] Examples of the conductive polythiophene-based polymer include polythiophene,
Poly (3-propylthiophene),
Poly (3-heptylthiophen)
Poly (3-methylthiophene),
Poly (3-butylthiophene),
Poly (3-octylthiophene),
Poly (3-ethylthiophene),
Poly (3-hexylthiophene),
Poly (3-decyl thiophene),
Poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene),
Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene),
Poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene),
Poly (3-heptyloxythiophene), decyloxythiophene), octadecyloxythiophene), dimethoxythiophene), dipropoxythiophene), dihexyloxythiophene), dioctyloxythiophene), didodecyloxythiophene),
Poly (3-octyloxythiophen)
Poly (3-
Poly (3-dodecyloxythiophen) Poly (3- Poly (3,4-dihydroxythiophene), Poly (3,4- Poly (3,4-diethoxythiophen) Poly (3,4- Poly (3,4-dibutoxythiophen) Poly (3,4- Poly (3,4-diheptyloxy-thiophene), Poly (3,4- Poly (3,4-didecyloxythiophen) Poly (3,4- Poly (3,4-ethylenedioxythiophene), Poly (3,4-
Poly (3,4-butylenedioxythiophene), poly (3-methyl-4-propylenedioxy-thiophene), methoxythiophene),
Poly (3-methyl-4-ethoxythiophene), poly (3carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene) and poly (3-methyl-4-carboxybutylthiophene).
Examples of the conductive polypyrrole-based polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole),
Poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole) , Poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole),
Poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole),
Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole),
Poly (3-butoxypyrrole), poly (3-hexyloxypyrrole) and poly (3-methyl-4hexyloxypyrrole).
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Examples of the conductive polyaniline-based polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2aniline sulfonic acid) and poly (3-aniline sulfonic acid).
Of the π-conjugated conductive polymers, poly (3.45 ethylenedioxythiophene) is particularly preferred from the viewpoints of conductivity, transparency and heat resistance.
The π-conjugated conductive polymers to be contained in the conductive composite can be used alone or in combination.
[Poly13]
The polyanion is a polymer that has two or more monomer units in the molecule, each with an anion group. The anion groups of the polyanion act as dopants for the π-conjugated conductive polymer to improve the conductivity of the π-conjugated 15 conductive polymer.
The anion groups of the polyanions are each preferably a sulfonic acid group or a carboxy group.
Specific examples of such polyanions include: polymers each having a sulfonic acid group, such as polystyrene sulfonic acid, 20 polyvinyl sulfonic acid, polyallylsulfonic acid, polyacrylic sulfonic acid,
Polymethacrylic sulfonic acid, poly (2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polysulfoethyl methacrylate, poly (4sulfobutyl methacrylate) and polymethacryloxy-benzenesulfonic acid; and polymers each having a carboxy group such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamido-2-methyl propane carboxylic acid), polyisoprene carboxylic acid and polyacrylic acid. The polyanion can be any of these homopolymers or a copolymer of two or more types thereof.
Of these polyanions, in order to further increase the conductivity, a polymer having a sulfonic acid group is preferred, and polystyrene sulfonic acid is more preferred.
The polyanions can be used individually or in combination.
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The weight average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The mass average molecular weight of the polyanion refers to a mass based one
Molecular weight, which is determined on the basis of an elution time versus molecular weight calibration curve, which is obtained in advance from polystyrene standard substances with known molecular weights by measuring an elution time by means of gel permeation chromatography (GPC).
The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more to 1000 parts by mass or less, more preferably in the range of 10 parts by mass or more to 700 parts by mass or less, still more preferably in the range of 100 parts by mass or more to 500 parts by mass or less based on 100 parts by mass of the π-conjugated conductive polymer. When the content ratio of the polyanion is equal to or larger than the lower limit mentioned above, its doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. Meanwhile, if the content of the polyanion is equal to or less than the above upper limit, a sufficient amount of the π-conjugated conductive polymer can be contained, and thus sufficient conductivity can be ensured. (Vinyl versatate polymer)
The vinyl versatate polymer is a homopolymer of a vinyl versatate or a copolymer of the vinyl versatate and another monomer copolymerizable with the vinyl versatate. Herein, the vinyl versatate refers to a vinyl ester represented by the following chemical formula (1). The vinyl ester is a monomer with high hydrophobicity, and a polymer obtained by polymerizing the monomer also has high hydrophobicity.
In the following chemical formula (1), R ¹ and R ² each represent an alkyl group, and at least one of R ¹ or R ² represents an alkyl group having a branched structure. In addition, the sum of the carbon number of R ¹ and the carbon number of R ² preferably 4 or
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Examples of the alkyl group represented by each of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, a 1,1-dimethylbutyl group, a 2methylpentyl group, a 3-methylpentyl group, a 4methylpentyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3-ethylbutyl group and one 1-methyl-l-ethylpropyl.
Of the alkyl groups, the alkyl group with a branched structure is an isopropyl group (1-methylethyl group), a tert-butyl group (1,1-dimethylethyl group), a sec-butyl group (1-methylpropyl group), an isobutyl group (2-methylpropyl group), a tert -Pentyl group (1,1-dimethylpropyl group), an isopentyl group (3-methylbutyl group), a sec-pentyl group (1-methylbutyl group), a 1,1-dimethylbutyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4methylpentyl group, a 1-ethylbutyl group , a 2-ethylbutyl group, a 3-ethylbutyl group or a 1-methyl-1-ethylpropyl group.
The vinyl versatate may be a mixture of compounds each represented by the chemical formula (1), the compounds having a total of 9 or more and 11 or less carbon atoms.
[0016]
o. < n,%
C — C — R (1) />
CH ₂ = CH-OR Examples of the other monomer copolymerizable with the vinyl versatate include vinyl acetate, vinyl alcohol, an (meth) acrylic acid alkyl ester, (meth) acrylic acid, an olefin and
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Of the other monomers, vinyl acetate, vinyl alcohol, a (meth) acrylic acid alkyl ester, (meth) acrylic acid or an olefin are preferred because the copolymerization with the vinyl versatate is easy and the adhesive property of a conductive layer to a plastic base material and the water resistance of the conductive layer are further improved ,
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate and glycidyl ( meth) acrylate.
Examples of the olefin include ethylene, propylene and 1-butene. Specific examples of the copolymer of vinyl versatate and the other monomer copolymerizable with the vinyl versatate include a vinyl versatate-vinyl acetate copolymer, a vinyl acetate (meth) acrylic acid alkyl ester copolymer, a (meth) acrylic acid-alkyl ester copolymer, a (meth) acrylic acid alkyl ester (meth) acrylic acid copolymer vinyl versat ethylene vinyl acetate copolymer.
In addition, the vinyl versatate polymer
Acid group included. Examples of sulfonic acid group, a carboxy group When the vinyl versatate polymer contains acid group and the conductive one
Polymer dispersion contains a glycidyl group-containing acrylic resin
Vinyl versatate vinyl versatate vinyl versatate and further a one
Monomer unit with a die
Acid group include a phosphoric acid group. Monomer unit with and a reaction between the vinyl versatate polymer and the glycidyl group-containing acrylic resin instead, whereby the water resistance and the solvent resistance of the conductive layer are further increased. Does the vinyl versatate polymer contain the
Monomer unit with an acid group and, as described later, the plastic base material is subjected to a hydrophilic treatment, the vinyl versatate is directly on the surface of the plastic base material
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Examples of the monomer having an acid group include (meth) acrylic acid and crotonic acid, and a monomer which is a by-product in the synthesis of the vinyl versatate and which has an acid group.
The vinyl versatate polymer sometimes contains a carboxylic acid such as versatic acid or acetic acid as an impurity. The carboxylic acid number of the vinyl versatate polymer is preferably 5 mgKOH / g to 30 mgKOH / g, more preferably 5 mgKOH / g to 20 mgKOH / g. The carboxylic acid value can be measured in accordance with JIS K 0070.
The content of the vinyl versatate unit in the vinyl versatate polymer is preferably 10 mass% or more and 100 mass% or less, more preferably 20 mass% or more and 90 mass% or less, still more preferably 30 masses -% or more and 70 mass% or less, based on the total mass of the vinyl versat polymer. If the content of the vinyl versatate unit in the vinyl versatate polymer is equal to or larger than the above lower limit, the adhesive properties of the conductive layer to the plastic base material and the water resistance are further improved. In the meantime, the dispersibility in the conductive polymer dispersion can be improved if the content of the vinyl versatate unit in the vinyl versatate polymer is equal to or less than the above upper limit.
[0020] The glass transition temperature of the vinyl versatate polymer is preferably 10 ° C or more and 100 ° C or less, more preferably 20 ° C or more and 80 ° C or less. The glass transition temperature of the vinyl versatate polymer can be measured with a differential scanning calorimeter (DSC).
If the glass transition temperature of the vinyl versatate polymer is equal to or higher than the above lower limit, the water resistance and the solvent resistance of the conductive layer can be further improved. If the glass transition temperature is equal to or less than the above upper limit, the
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Adhesive property of the conductive layer to the plastic base material can be improved sufficiently.
The weight average molecular weight of the vinyl versatate polymer is preferably 1,000 or more and 1,000,000 or less, more preferably 5,000 or more and 500,000 or less, still more preferably 10,000 or more and 100,000 or less. The mass average molecular weight of the vinyl versatate polymer refers to a mass-based molecular weight that is determined on the basis of an elution time versus molecular weight calibration curve that is obtained in advance from polystyrene standard substances with known molecular weights by measuring an elution time by means of gel permeation chromatography (GPC).
If the weight average molecular weight of the vinyl versatate polymer is equal to or larger than the above lower limit, the adhesive property of the conductive layer to the plastic base material can be improved sufficiently. If the weight average molecular weight is equal to or less than the above upper limit, the dispersibility of the vinyl versatate polymer in the conductive polymer dispersion can be improved.
A persulfuric acid salt can be used as a polymerization initiator in the manufacture of the vinyl versatate polymer. In this case, water dispersion of the vinyl versatate polymer sometimes shows acidity due to residual sulfate ions. If the water dispersion is acidic, sulfuric acid is preferably neutralized. If sulfuric acid is neutralized, the dispersibility of the vinyl versatate polymer in the conductive polymer dispersion can be improved. That is, the vinyl versatate polymer is preferably free of sulfuric acid as an impurity.
A pH measured according to JIS Z 8802: 2011 for the vinyl versatate polymer is preferably between 4 and 9, more preferably between 4.5 and 8.5. The pH is measured as described below.
1) Weigh exactly 5 g of a sample in the unit of 0.1 g.
2) 95 ml of distilled water are measured in a 100 ml beaker with a measuring cylinder. A pH meter is placed in the beaker, and
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3) The sample is placed in the beaker with the distilled water adjusted to pH 7.0 to provide a dispersion.
4) The dispersion is stirred with a magnetic stirrer for 5 minutes, then the rotation is stopped and the pH is read 1 minute later.
The sulfuric acid contained in the vinyl versatate polymer can be neutralized by adding an alkaline compound.
The alkaline compound can be an inorganic alkaline compound or an organic alkaline compound.
Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium hydrogen carbonate, potassium hydrogen carbonate and
Ammonium bicarbonate.
Examples of the organic alkaline compound include a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium salt and a nitrogen-containing aromatic cyclic compound.
Examples of the primary amine include aniline, toluidine, benzylamine and ethanolamine.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine and dinaphthylamine.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, triphenylamine, tribenzylamine and trinaphthylamine.
Examples of the quaternary ammonium salt include a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetraphenylammonium salt
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Tetrabenzylammonium salt and a tetranaphthylammonium salt. A hydroxide ion is given as the anion which serves as a counterion for ammonium.
Examples of the nitrogen-containing aromatic cyclic compound include aniline, benzylamine, pyrrole, imidazole, 2methylimidazole, 2-propylimidazole, N-methylimidazole, 1- (2-hydroxyethyl) imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl -2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1Acetylimidazole, 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2Hydroxybenzim - (2-pyridyl) benzimidazole and pyridine.
The alkaline compounds can be used alone or in combination.
[0024] The content of the vinyl versatate polymer in the conductive polymer dispersion is preferably 10 parts by mass or more and 100,000 parts by mass or less, more preferably 50 parts by mass or more and 50,000 parts by mass or less, still more preferably 100 parts by mass or more and 10,000 parts by mass or less to 100 parts by mass of the conductive composite. If the content of the vinyl versatate polymer is equal to or larger than the lower limit mentioned above, the adhesive property of the conductive layer to the plastic base material can be further improved. If the content is equal to or less than the above upper limit, a decrease in conductivity due to a decrease in the content of the conductive composite can be prevented.
[Binder component]
Binder resins such as a polyester resin, an acrylic resin, an epoxy resin, an oxetane resin, a polyurethane resin, a polyimide resin, a melamine resin, a silicone resin and a vinyl acetate resin are given as specific examples of a binder component.
In addition, the binder component can be a monomer or oligomer to form one of the above-mentioned binder resins. The binder resin can be formed by polymerizing the monomer or the oligomer at the time of forming the conductive layer.
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The binder components can be used individually or in combination.
Of the binder components, a polyester resin is preferred because the water resistance of the conductive layer is further increased and its mechanical physical properties become satisfactory.
The polyester resin may have an acid group. The polyester resin having an acid group (hereinafter referred to as polyester resin (1)) is a polyester resin which is a polycondensate of a dicarboxylic acid component and a diglycol component and a
Alkali metal salt of an acid group (e.g. a sulfonic acid group, a carboxy group or a phosphoric acid group). The polyester resin (1) has a large polarity and is therefore very well dispersible in water and can be stably dispersed in water without the use of an emulsifier or stabilizer.
Examples of the dicarboxylic acid component include: aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2.5 dimethyl terephthalic acid, 2,6-naphthalenedicarboxylic acid,
Biphenyldicarboxylic acid and orthophthalic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The dicarboxylic acids can be used alone or in combination.
The dicarboxylic acid component preferably contains a dicarboxylic acid with a sulfonic acid substituent of the alkali metal salt type (-SO3 ^- X ⁺ , where X is an alkali metal ion) in which a sulfonic acid group is neutralized with an alkali metal.
The dicarboxylic acid having an alkali metal salt type sulfonic acid substituent is a compound obtained by converting a
Sulfonic acid group in a dicarboxylic acid with a sulfonic acid group in an alkali metal salt is obtained.
Examples of the dicarboxylic acid having a sulfonic acid group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 42018/5548
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Sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and their derivatives. Examples of the alkali metal include sodium and potassium.
The dicarboxylic acid with a sulfonic acid substituent of the alkali metal salt type is preferably a sodium salt of 5-sulfoisophthalic acid or a derivative thereof.
Among the dicarboxylic acid components, as a dicarboxylic acid component other than the dicarboxylic acid having a sulfonic acid substituent of the alkali metal salt type, an aromatic dicarboxylic acid is preferred, and terephthalic acid or isophthalic acid is more preferable. The aromatic core of the aromatic dicarboxylic acid is highly compatible with a hydrophobic plastic and is also outstandingly resistant to hydrolysis.
The content ratio of the dicarboxylic acid having a sulfonic acid substituent of the alkali metal salt type is preferably 6 mol% or more and 20 mol% or less, more preferably 10 mol% or more and 18 mol% or less of all dicarboxylic acid components. If the content ratio of the dicarboxylic acid with an alkali metal salt type sulfonic acid substituent is equal to or larger than the above lower limit, a decrease in the solvent resistance of the conductive layer can be suppressed. If the content ratio is equal to or less than the above upper limit, the water resistance of the conductive layer is further increased.
Examples of the diglycol component for forming the polyester resin (1) include diethylene glycol, an aliphatic glycol with 2 or more and 8 or less carbon atoms, and an alicyclic glycol with 6 or more and 12 or less carbon atoms. Specific examples of the aliphatic glycol having 2 or more and 8 or less carbon atoms and the alicyclic glycol having 6 or more and 12 or less carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, neopentyl glycol, 1,4-butanediol, 1 , 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,6-hexanediol, pXylylene glycol and triethylene glycol. The diglycol components can be used individually or in combination.
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The diglycol component preferably contains diethylene glycol to further improve water resistance and solvent resistance.
to (1) The number average molecular weight of the polyester resin is preferably 2,000 or more and 30,000 or less, more preferably 2,500 or more and 25,000 or less. The number average molecular weight of the polyester resin (1) refers to a number-based molecular weight determined on the basis of an elution time versus molecular weight calibration curve obtained beforehand from standard polystyrene substances with known molecular weights by measuring an elution time by gel permeation chromatography (GPC).
(1) further increased. Is or less than that
dispersible in water
Polyester resin (1) is (1) the one that is not the one above
200 ° C one
If the number average molecular weight of the polyester resin is equal to or larger than the above lower limit, water resistance of the polyester resin becomes the number average molecular weight becomes the upper limit, the polyester resin (1) is further improved. A method for producing the particularly limited, and an example thereof, is a method in which the dicarboxylic acid component and the diglycol component are subjected to esterification or transesterification reaction at 130 ° C or more and or less, followed by
Polycondensation reaction at 200 ° C or more and 250 ° C or less under a reduced pressure state. As the reaction catalyst for producing the polyester resin (1), for example, acetic acid metal salts such as zinc acetate and manganese acetate, metal oxides such as antimony oxide and germanium oxide, and titanium compounds are used.
The polyester resin (1) obtained can be changed into a water dispersion by adding it to water. The water dispersion of the polyester resin (1) preferably has a polyester solid concentration of 30% by mass or less because a high solid concentration makes uniform dispersion difficult.
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BE2018 / 5548 In addition, the binder component is preferably a glycidyl group-containing acrylic resin from the viewpoint of improving the solvent resistance of the conductive layer and its water resistance.
The water resistance and the solvent resistance are believed to be improved by forming a cross-linked structure in the conductive layer when the glycidyl group-containing acrylic resin is contained as a binder component.
In addition, the use of the glycidyl group-containing acrylic resin as a binder component can further improve the adhesive property of the conductive layer to the plastic base material. Although the reason for this has not yet been clarified, it is believed that the glycidyl group-containing acrylic resin penetrates between the plastic base material and the polyanion contained in the conductive composite, thereby fixing the hydrophilic polyanion on the hydrophobic plastic base material. This presumably improves the adhesive property of the conductive layer formed from the aqueous conductive polymer dispersion to the plastic base material.
Particularly when using a plastic base material whose surface has been treated hydrophilically, the glycidyl group-containing acrylic resin easily reacts with a hydrophilic group (e.g., a hydroxy group or a carboxy group) formed on the surface of the plastic base material. This may further improve the adhesive property of the plastic base material. The glycidyl group-containing acrylic resin is a homopolymer formed only from a glycidyl group-containing radically polymerizable unsaturated monomer unit, or a copolymer with a glycidyl group-containing radically polymerizable unsaturated monomer unit and another radically polymerizable unsaturated monomer unit having the above Monomer is copolymerizable.
The glycidyl group-containing acrylic resins can be used alone or in combination.
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BE2018 / 5548 Examples of the glycidyl group-containing radically polymerizable unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, and glycidyl ether such as allyl glycidyl ether. Of these, glycidyl methacrylate is preferred. The radical-polymerizable unsaturated monomers containing glycidyl groups can be used alone or in combination.
The content ratio of the glycidyl group-containing radically polymerizable unsaturated monomer unit in the glycidyl group-containing acrylic resin is preferably 10 mass% or more and 100 mass% or less, more preferably 20 mass% or more and 100 mass% or less, based on 100 mass% of all monomer units. If the content ratio of the radical polymerizable unsaturated monomer unit containing glycidyl group in the glycidyl group-containing acrylic resin is 10 mass% or more, the water resistance and the solvent resistance of the conductive layer formed from the conductive polymer dispersion can be further improved according to this aspect.
Examples of the other radically polymerizable unsaturated monomer copolymerizable with the glycidyl group-containing radically polymerizable unsaturated monomer include vinyl esters, unsaturated carboxylic acid esters (such as an acrylic acid alkyl ester and a methacrylic acid alkyl ester), unsaturated carboxylic acid amides (such as an acrylic acid amide) a methacrylic acid amide), unsaturated nitriles (such as acrylonitrile), unsaturated carboxylic acids (such as acrylic acid and methacrylic acid) and olefin monomers. The other radically polymerizable unsaturated monomers can be used alone or in combination.
An unsaturated carboxylic acid monomer such as acrylic acid or methacrylic acid is preferably used as the other radically polymerizable unsaturated monomer because the water resistance is further increased.
The content ratio of the unsaturated carboxylic acid monomer unit in the glycidyl group-containing acrylic resin is preferably 5 mass% or more and 20 mass% or less, based on 100 mass%
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BE2018 / 5548 of all monomer units. If the content ratio of the unsaturated carboxylic acid monomer unit in the glycidyl group-containing acrylic resin is equal to or larger than the above lower limit, the water resistance and the solvent resistance of the conductive layer can be further improved. If the content ratio is equal to or less than the above upper limit, deterioration in storage stability by gelation of the liquid over time can be suppressed.
A method for producing the glycidyl group-containing acrylic resin is not particularly limited, and the glycidyl group-containing acrylic resin can be produced by, for example, emulsion polymerization.
In the production of the glycidyl group-containing acrylic resin by the emulsion polymerization, for example, a reaction vessel is filled with ion-exchanged water, a polymerization initiator and a surfactant, and then a dropping vessel is filled with ion-exchanged water and a surfactant, and monomers are added to produce a monomer emulsion, followed by one dropwise addition of the monomer emulsion to the reaction vessel to thereby effect radical emulsion polymerization. A reaction temperature is preferably set to 60 ° C or more and 100 ° C or less, and a reaction time is preferably set to 4 hours or more and 10 hours or less.
As the surfactant to be used for the emulsion polymerization, one or two or more kinds of an anionic surfactant, a nonionic reactive surfactant and a nonionic nonreactive surfactant can be used.
Examples of the polymerization initiator to be used for the emulsion polymerization include commonly used radical polymerization initiators such as potassium persulfate, ammonium persulfate, water-soluble peroxides such as hydrogen peroxide, oil-soluble peroxides such as benzoyl peroxide and t-butyl hydroperoxide, and azo compounds such as azobisisobutyronitrile.
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In the production of the glycidyl group-containing acrylic resin by emulsion polymerization, the glycidyl group-containing acrylic resin is obtained as an emulsion.
[0040] The content of the binder component in the conductive
Polymer dispersion is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 5000 parts by mass or less, still more preferably 100 parts by mass or more and 1000 parts by mass or less, based on 100 parts by mass of the conductive composite. Is the salary of the
Binder component equal to or larger than the lower limit mentioned above, the strength of the conductive layer can be improved. If the content is equal to or less than the above upper limit, a decrease in the conductivity can be prevented by reducing the content of the conductive composite.
(Dispersion medium)
Examples of the dispersion medium to be used in this aspect include water, an organic solvent, and a mixed liquid of water and an organic solvent.
Examples of the organic solvent include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent and an aromatic hydrocarbon-based solvent.
Examples of alcohol-based solvents include methanol,
Ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl ether and ethylene glycol monomethyl ether.
Include examples of the ether-based solvent
Diethyl ether, dimethyl ether, ethylene glycol, propylene glycol and a
Propylene glycol dialkyl.
Examples of the ketone-based solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone and diacetone alcohol.
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Examples of the ester-based solvent include ethyl acetate, propyl acetate and butyl acetate.
Examples of the aromatic hydrocarbon-based solvent include benzene, toluene, xylene, ethylbenzene, 5-propylbenzene and isopropylbenzene.
The organic solvents can be used alone or in combination.
Of the organic solvents, methanol is preferred because the dispersibility of the conductive composite and the vinyl versatate 10 polymer can be further improved.
As described later, the conductive composite is obtained as a water dispersion, and therefore the dispersion medium in the conductive polymer dispersion also preferably contains water. The content ratio of water to the total mass of the entire dispersion medium contained in the conductive polymer dispersion is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90 mass% or more and 100 mass% or less. The dispersion medium can be completely water.
[Conductivity improver]
The conductive polymer dispersion may contain a conductivity enhancer to further improve conductivity.
Here, the π-conjugated conductive polymer, the polyanion, the vinyl versatate polymer and the binder component mentioned above are not considered as conductivity improvers.
The conductivity improver is preferably at least one kind of compound selected from the group consisting of saccharides, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxyl groups, a compound having one or more hydroxyl groups and one or more carboxy groups, a compound with an amide group, a compound with an imide group, a lactam compound and a compound with a glycidyl group.
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The conductive polymer dispersion may contain one or two or more types of conductivity improvers.
The content ratio of the conductivity improver in the conductive polymer dispersion is preferably 1 part by mass or more and 10,000
Parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, still more preferably 100 parts by mass or more and 2500 parts by mass or less based on 100 parts by mass of the conductive composite. The content ratio of the conductivity improver is equal to or greater than the lower one mentioned above
Limit value, the conductivity-improving effect of adding the conductivity improver is sufficiently pronounced. If the content ratio is equal to or less than the above upper limit, a decrease in conductivity due to a decrease in the concentration of the π-conjugated conductive polymer can be prevented.
(Other additive)
The conductive polymer dispersion may contain any other known additive.
As an additive, which is not particularly limited, as long as the effects of this disclosure are obtained, for example, a surfactant, an inorganic conductive agent, a defoamer, a coupling agent, an antioxidant or a UV absorber can be used. The additive is made from a compound other than the π-conjugated conductive polymer, the polyanion, the vinyl versatate polymer, the binder component and the
Conductivity improvers as mentioned above are formed.
Examples of the surfactant include nonionic, anionic and cationic surfactants. Of these, a nonionic surfactant is preferred in terms of storage stability. In addition, a polymer-based surfactant such as polyvinylpyrrolidone can be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ions can each be generated by dissolving a metal salt in water.
Examples of the defoamer include a silicone resin, polydimethylsiloxane and a silicone oil.
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Examples of the coupling agent include silane coupling agents each having an epoxy group, a vinyl group or an amino group.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and saccharides.
Examples of the UV absorber include a benzotriazole-based UV absorber, a benzophenone-based UV absorber, a salicylate-based UV absorber, a cyanoacrylate-based UV absorber, an oxanilide-based UV absorber, a hindered amine-based UV absorber and a UV10 absorber based on benzoate.
If the conductive polymer dispersion contains the additive, its content ratio is determined depending on the type of additive and can e.g. between 0.001 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the 15 conductive composite.
(Process for producing a conductive polymer dispersion)
As a method for producing the conductive polymer dispersion according to this aspect, for example, a method is given in which a monomer for forming the π-conjugated conductive polymer is subjected to chemical oxidative polymerization in an aqueous solution of the polyanion to produce a water dispersion of the conductive composite, and the vinyl versatate polymer is added to the water dispersion. If the binder component, the conductivity improver, other additives and the like are to be contained in the conductive polymer dispersion, it is appropriate to add these components to the water dispersion.
In addition, a commercially available product can be used as a water dispersion of the conductive composite.
The vinyl versatate polymer has a high hydrophobicity and therefore, when added as such, has a low dispersibility in the conductive polymer dispersion. Therefore, the vinyl versatate is preferably converted to an emulsion prior to addition to improve the dispersibility in the conductive polymer dispersion.
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BE2018 / 5548 A known catalyst can be used for chemical oxidative polymerization. For example, a catalyst and an oxidizing agent can be used. Examples of the catalyst include transition metal compounds such as iron chloride, iron sulfate, iron nitrate and copper chloride. Examples of the oxidizing agent include persulfuric acid salts such as ammonium persulfate, sodium persulfate and potassium persulfate. The oxidant can return a reduced catalyst to its original oxidation state.
The content of the conductive composite in the conductive polymer water dispersion is preferably 0.1 mass% or more and 10 mass% or less, more preferably 0.3 mass% or more and 5 mass% or less, still more preferably 0, 5 mass% or more and 4 mass% or less, based on the total mass of the conductive polymer dispersion.
(Action and effect)
The conductive polymer dispersion according to this aspect contains the conductive composite containing the π-conjugated conductive polymer and the polyanion, and therefore a layer formed from the conductive polymer dispersion serves as a conductive layer having conductivity.
So far, a surfactant has sometimes been used to impart conductivity to the surface of a plastic base material.
Especially when the conductivity is imparted to a polyolefin-based resin material with high hydrophobicity, the conductivity has often been imparted with the surfactant. However, the conductivity obtained with the surfactant is highly moisture dependent and the conductivity tends to decrease in an environment with low humidity. In contrast, in this aspect in which the conductivity is expressed by the π-conjugated conductive polymer, the conductivity is not moisture-dependent and a stable conductivity can be demonstrated.
A related conductive polymer dispersion containing a π-conjugated conductive polymer is often an aqueous dispersion due to its manufacturing process and therefore has one
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BE2018 / 5548 low wettability to plastic base material. Accordingly, a conductive layer formed from the conductive polymer dispersion has a low adhesive property to the plastic base material and in particular a particularly low adhesive property to a base material made of a polyolefin-based resin. In addition, the conductive layer formed from the aqueous conductive polymer dispersion has a low water resistance.
However, the conductive polymer dispersion according to this aspect contains the vinyl versatate polymer and is therefore improved in wettability to the plastic base material. This can improve the adhesive property of the conductive layer to be formed to the plastic base material. The conductive layer formed from the conductive polymer dispersion in accordance with this aspect has a high adhesive property even with the particularly hydrophobic polyolefin-based base material. Presumably because the vinyl versatate polymer has an alkyl group with high hydrophobicity and high compatibility with the plastic base material, the wettability compared to the plastic base material, in particular the plastic base material based on polyolefin, is improved in order to improve the adhesive properties of the conductive layer. It is also believed that the vinyl versatate polymer is highly compatible with the conductive composite.
In addition, the vinyl versatate polymer has a high hydrophobicity and can thus improve the water resistance of the conductive layer formed from the conductive polymer dispersion according to this aspect.
According to the conductive polymer dispersion according to this aspect, a conductive layer can easily be formed which is excellent in the adhesive property to the plastic base material and the water resistance.
It is believed that especially when the vinyl versatate polymer has a monomer unit with an acid group and the plastic base material is subjected to a hydrophilic treatment, the anion groups of the polyanion serve as a catalyst so that the vinyl versatate polymer and the plastic base material together
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BE2018 / 5548 can react to connect with each other. When the vinyl versatate polymer and the plastic base material are bonded together, the adhesive property of the conductive layer to the plastic base material and the water resistance of the conductive layer are further improved.
The conductive polymer dispersion according to this aspect is mainly applied to a film base material as described later, but can also be applied to a plastic base material having a different shape than the film base material.
<Conductive film>
1 is a cross-sectional view illustrating an example of a conductive film of this disclosure.
A conductive film 1 according to an aspect of this disclosure includes a film base material 2 and a conductive layer 3, which is arranged on at least one surface of the film base material 2 and is formed from the conductive polymer dispersion.
The conductive film according to this aspect can be used as a packaging material or, as described later, as a molding material for an antistatic container. In the packaging material formed from the conductive film in this aspect, the conductive layer functions as an antistatic layer, e.g. the adherence of dust can be prevented. This can prevent the appearance of a packaged product (e.g. food) from being adversely affected by dust adhering to the packaging material.
[0050] The film base material includes a plastic film base material.
A resin for the film base material for forming the plastic film is, for example, a polyolefin-based resin, an ethylene-vinyl acetate copolymer resin, an ethylene-methyl methacrylate copolymer resin, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, 30 polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polyarylide, polyvinylidene, polyvinylidene, polyvinylidene Styrene-based elastomer, a polyester-based elastomer, polyethersulfone, polyetherimide, polyetheretheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate or cellulose acetate propionate. Examples of the polyolefin-based resin
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BE2018 / 5548 include polyethylene, polypropylene, an ethylene-a-olefin copolymer resin and a propylene-a-olefin copolymer resin.
This aspect is appropriate in the case of using a resin film
Polyolefin base, which has a higher hydrophobicity even for plastic films, in particular a polypropylene film. In this aspect, the adhesive property of the conductive layer can be improved with a particularly hydrophobic film base material.
In addition, the backing material of the film can be undrawn or stretched.
In addition, a hydrophilic group, such as one
Carboxy group or a hydroxyl group are formed on the surface of the film base material by a hydrophilic treatment to be described later.
The average thickness of the film base material is preferably 10 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. If the average thickness of the film base material is equal to or greater than the lower limit mentioned above, the risk of breakage is lower. If the average thickness is equal to or less than the above upper limit value, sufficient flexibility can be ensured as the film 20.
Here, the thickness of an element is a value that is obtained by measuring thicknesses at ten arbitrary locations with a micrometer and averaging the measured values.
[0052] The conductive layer in this aspect contains a conductive one
Composite containing a π-conjugated conductive polymer and a polyanion, and a vinyl versatate polymer.
If the conductive polymer dispersion to be used in the production of the conductive film contains a binder component, the conductive layer contains a binder resin.
The average thickness of the conductive layer is preferably 10 nm or more and 20,000 nm or less, more preferably 20 nm or more and 10,000 nm or less, still more preferably 30 nm or more and 5000 nm or less. If the average thickness of the conductive layer is equal to or greater than the above lower limit, may
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BE2018 / 5548 a sufficiently high conductivity can be achieved. If the average thickness of the conductive layer is equal to or less than the above upper limit, the conductive layer can be easily formed.
The surface resistance of the conductive layer, measured under the condition of an applied voltage of 10 V with a resistance measuring device (Hiresta from Mitsubishi Chemical Analytech Co., Ltd.), is preferably between 5.0x10 ⁵ Ω / π and 5.0x10 ⁹ Ω / π , Ω / π means
Ω / sq.
The conductive film according to this aspect can be made by applying the conductive polymer dispersion to at least one surface of the film base material and then drying to form the conductive layer.
Before applying the conductive polymer dispersion, the film base material is preferably subjected to a hydrophilic treatment, such as
Subjected to corona discharge treatment, plasma treatment or flame treatment to form a hydrophilic group (e.g. a hydroxy group, a carboxy group or a carbonyl group) on the surface of the film base material. The adhesive property of the conductive layer can be further improved by the hydrophilic treatment of the film base material. Of the hydrophilic treatments, the corona discharge treatment is preferred because the surface of the
Film base material can be easily hydrophilized.
As a method of applying the conductive polymer dispersion to the film base material, e.g. be applied: a
Application process using a coater such as a slot coater, a spray coater, an gravure coater, a roller coater, a curtain coater, a spin coater, a bar coater, a reverse coater. , a kiss coater, a fountain
A coater, a rod coater, an air doctor coater, a knife coater, a blade coater, a cast coater, or a screen coater, or an immersion method such as immersion.
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As a method for drying after the application of the conductive polymer dispersions, heat drying, vacuum drying and the like are given. If the conductive polymer dispersion contains at least one of the polyester resin (1) or the glycidyl group-containing acrylic resin, heat drying is preferably carried out from the point of view of promoting the reaction. A general process, such as hot air heating or infrared heating, can be used for heat drying.
Hot air heating depends on what is used
Dispersion medium set an appropriate heating temperature, but generally in the range of 50 ° C or more to 150 ° C or less, preferably from 60 ° C or more to 130 ° C or less, more preferably from 70 ° C or more to 120 ° C or less. In this case the heating temperature is the set temperature of a dryer.
In addition, the drying time is preferably 5 minutes or more from the viewpoint of sufficient removal of the dispersion medium.
<Antistatic container>
Fig. 2 is a cross-sectional view illustrating a
Example of an antistatic container of this disclosure.
An antistatic container 10 according to an aspect of this disclosure includes a molded product of the conductive film 1. The antistatic container according to this aspect has an antistatic property due to the conductive layer containing the conductive composite.
The shape of the antistatic container according to this aspect is not particularly limited and only needs to be such that a space is created which can accommodate an object to be transported or stored. The article to be accommodated in the antistatic container according to this aspect is suitably part with the risk of being broken by static electricity discharge, e.g. an electronic part. An example of the antistatic container for holding the electronic part is a band-shaped or sheet-shaped container with a plurality of recesses formed therein
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Inclusion of electronic parts. Examples of the electronic part are a
IC, an LSI and a capacitor.
The antistatic container is made by molding the conductive film into a container shape. A vacuum molding process, a compression molding process or a press molding process can be used as the molding process, for example. Of these molding methods, a vacuum molding method is preferred from the viewpoint that a recess for receiving an object can be formed easily and inexpensively.
The vacuum forming conditions are adapted to the conditions under which a desired recess can be easily formed. Examples of the vacuum molding conditions are a molding temperature and a degree of vacuum.
The mold temperature is preferably set to more than 110 ° C, more preferably 120 ° C or more and 180 ° C or less. The molding temperature refers to the surface temperature of the conductive film at the time of molding. If the molding temperature is set above 110 ° C, the conductive film can be easily molded. If the mold temperature is set equal to or lower than the above upper limit, thermal degradation of the conductive film at the time of molding can be prevented.
Examples (Preparation Example 1)
206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water. While the solution was stirred at 80 ° C, an oxidizing agent solution of 1.14 g of ammonium persulfate, which was previously dissolved in 10 ml of water, was added dropwise over 20 minutes. The resulting solution was stirred for 12 hours.
To the resulting sodium styrene sulfonate-containing solution, 1000 ml of a sulfuric acid diluted to 10% by mass was added, and about 1000 ml of the solution was removed from the solution containing polystyrene sulfonic acid by ultrafiltration. 2000 ml of ion-exchanged water were added to the remaining liquid and
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BE2018 / 5548 about 2000 ml of the solution was removed by ultrafiltration. The above ultrafiltration operation was repeated three times. Furthermore, about 2000 ml of ion-exchanged water was added to the resulting polystyrene sulfonic acid-containing solution and about 2000 ml of the
Solution removed by ultrafiltration. This ultrafiltration operation was repeated three times.
In the resulting solution, water was removed under reduced pressure to provide polystyrene sulfonic acid as a colorless solid. (Production Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g
Polystyrene sulfonic acid in 2000 ml of ion-exchanged water were mixed together at 20 ° C.
While the mixed solution thus obtained was kept at 20 ° C and stirred, an oxidation catalyst solution of 29.64 g of 15 ammonium persulfate and 8.0 g of iron sulfate in 200 ml of ion-exchanged water was slowly added, and the mixture was subjected to a reaction with stirring for 3 hours ,
2000 ml of ion-exchanged water was added to the resulting reaction liquid, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated three times.
Then, 200 ml of a sulfuric acid diluted to 10 mass% and 2000 ml of ion-exchanged water were added to the resulting solution, and about 2000 ml of the solution was removed by ultrafiltration. To the resultant, 2000 ml of ion-exchanged water 25 was added and about 2000 ml of the solution was removed by ultrafiltration.
This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated five times to obtain a solution of poly (3,4-ethylenedioxythiophene) doped with 1.2% polystyrene sulfonic acid (PEDOT-PSS water dispersion). The PSS content based on the PEDOT-PSS solids content is 75% by mass. (Production Example 3)
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A beaker was filled with 18 parts by mass of ion-exchanged water and 3 parts by mass of an anionic surfactant (manufactured by Sanyo Chemical Industries, Ltd., ELEMINOL RS-3000, active ingredient: 50% by mass). Thereafter, 40 parts by mass of glycidyl methacrylate was added to the beaker with stirring to prepare a monomer emulsion.
Then, a four-necked flask was equipped with a condenser, a monomer dropping funnel, a thermometer and a stirrer with 37.5 parts by mass of ion-exchanged water, 1 part by mass of an anionic surfactant (manufactured by Sanyo Chemical Industries, Ltd., ELEMINOL RS-3000) and 0.5 parts by mass of potassium persulfate filled. Thereafter, while the contents in the flask were being stirred, nitrogen purging was carried out and heating was started. After reaching a liquid temperature of 75 ° C, the monomer emulsion was added dropwise over 4 hours. The liquid temperature was kept in the range of 75 ° C or more to 85 ° C or less after the completion of the dropwise addition to continue the reaction, and was decreased 4 hours after the completion of the dropwise addition. After cooling, additional ion-exchanged water was added to obtain a glycidyl group-containing acrylic resin water dispersion with a non-volatile content of 25% by mass.
(Example 1) g of water and 50 g of a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879, solids concentration: 46% by mass, pH 1.7, glass transition temperature: 0 ° C, weight-average molecular weight -weight: 200,000 or more and 500,000 or less, carboxylic acid value: 15 mgKOH / g, shown in Table 1 as Polysol OLX7879) were added to 25 g of the PEDOT-PSS water dispersion obtained in Production Example 2, and these were mixed together to make a conductive To obtain polymer dispersion.
The resulting conductive polymer dispersion was applied with a No. 4 bar coater to a polypropylene film the surface of which was corona treated, and was dried at 85 ° C for 1 minute to form a conductive layer. A conductive film was thus obtained.
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BE2018 / 5548 [0061] (Example 2)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879 neutralized product, solid concentration: 46% by mass, pH 6.2, neutralizer: ammonia, glass transition temperature: 0 ° C, weight-average molecular weight: 200,000 or more and 500,000 or less, carboxylic acid value: 15 mgKOH / g, shown in Table 1 as Neutralized Polysol OLX-7879) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained. (Example 3)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7878, pH 1.8, glass transition temperature: 60 ° C, mass-average molecular weight: 200,000 or more and 500,000 or less, carboxylic acid value: 15 mgKOH / g,
Solids concentration: 46% by mass, shown in Table 1 as Polysol OLX-7878) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 4)
A conductive polymer dispersion was obtained as in Example 1, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878 neutralized product, pH 5.9, neutralizer: ammonia, glass transition temperature: 60 ° C, weight average molecular weight: 200000 or more and 500000 or less, carboxylic acid value: 15 mgKOH / g, solids concentration: 46 mass%, shown in Table 1 as Neutralized Polysol OLX-7878).
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Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 5)
A conductive polymer dispersion was obtained as in Example 1, except that the amount of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was changed to 5 g and also 45 g of an aqueous polyester solution (Goo Chemical Co., Ltd., PLAS COAT Z-690, solid concentration: 25 mass%) were added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 6)
A conductive polymer dispersion was obtained as in Example 5, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7879 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 7)
A conductive polymer dispersion was obtained as in Example 5, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 8)
A conductive polymer dispersion was obtained as in Example 5, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
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BE2018 / 5548 [Example 68]
A conductive polymer dispersion was obtained in the same manner as in Example 7, except that the aqueous polyester solution (Goo Chemical Co., Ltd., PLAS COAT Z-690, solid concentration: 25 mass%) became an aqueous polyester solution (Goo Chemical Co., Ltd., PLAS COAT RZ-105, solid concentration: 25 mass%) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 10)
A conductive polymer dispersion was obtained in the same manner as in Example 7, except that the aqueous polyester solution (Goo Chemical Co., Ltd., PLAS COAT Z-690, solid concentration: 25 mass%) became a water-dispersed aqueous co Polyester solution (Toyobo Co., Ltd., VYLONAL 1245, solid concentration: 30 mass%) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 11)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that the amount of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was changed to 5 g and further 45 g of a mixed one Liquid of a glycidyl group-containing acrylic resin and a polyester resin (manufactured by Takamatsu Oil & Fat Co, Ltd., PESRESIN A647GEX, water dispersion, solid concentration: 20 mass%) was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 12)
A conductive polymer dispersion was obtained as in Example 11, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7879 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
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BE2018 / 5548 [Example 72]
A conductive polymer dispersion was obtained as in Example 11, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was converted into a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 14)
A conductive polymer dispersion was obtained as in Example 11, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 15)
A conductive polymer dispersion was obtained as in Example 1, except that the amount of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was changed to 5 g and also 45 g of the glycidyl group obtained in Production Example 3 -containing acrylic resin water dispersion was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 16)
A conductive polymer dispersion was obtained as in Example 15, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7879 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 17)
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A conductive polymer dispersion was obtained as in Example 15, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko K.K., Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa
Denko K.K., Polysol OLX-7878) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 18)
A conductive polymer dispersion was obtained as in Example 15, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 19)
A conductive polymer dispersion was obtained as in Example 1, except that the amount of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was changed to 10 g 20 and further 40 g that obtained in Production Example 3 Glycidyl group-containing acrylic resin water dispersion was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 20)
A conductive polymer dispersion was obtained as in Example 19, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7879 neutralized product) was changed.
Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 21)
A conductive polymer dispersion was obtained as in Example 19, except that the vinyl versatate-vinyl acetate copolymer emulsion
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BE2018 / 5548 (manufactured by Showa Denko K.K., Polysol OLX-7879) was changed to a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko K.K., Polysol OLX-7878). Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Example 22)
A conductive polymer dispersion was obtained as in Example 19, except that the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) became a vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK , Polysol OLX-7878 neutralized product) was changed. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Comparative Example 1)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that 50 g of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was not added to 25 g of the PEDOT-PSS water dispersion and the amount of water added was increased to 75 g instead. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Comparative Example 2)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that 50 g of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was not added, and instead 50 g of an aqueous polyester solution (Goo Chemical Co., Ltd., PLAS COAT Z-690) was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Comparative Example 3)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that 50 g of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko K.K., Polysol OLX-7879) was not added, and instead 50 g of an aqueous one
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Polyester solution (Goo Chemical Co., Ltd., PLAS COAT RZ-105) was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Comparative Example 4)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that 50 g of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was not added, and instead 50 g of a water-dispersed aqueous Co-polyester solution (Toyobo Co., Ltd., VYLONAL 1245) was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Comparative Example 5)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that 50 g of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was not added, and instead 50 g of a mixed liquid from a glycidyl group-containing acrylic resin and a polyester resin (manufactured by Takamatsu Oil & Fat Co., Ltd., PESRESIN A647GEX) was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained.
(Comparative Example 6)
A conductive polymer dispersion was obtained in the same manner as in Example 1, except that 50 g of the vinyl versatate-vinyl acetate copolymer emulsion (manufactured by Showa Denko KK, Polysol OLX-7879) was not added, and instead 50 g of that in Preparation Example 3 glycidyl group-containing acrylic resin obtained was added. Using the resulting conductive polymer dispersion, a conductive film as in Example 1 was obtained. <Evaluation> [surface resistance value]
For the conductive layer of the conductive film of each example, under the condition of an applied voltage of 10 V with a
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Resistance measuring device (Hiresta from Mitsubishi Chemical Analytech Co., Ltd.) measured a surface resistance value. The measurement results of the surface resistance values are shown in Tables 1 and 2.
[Adhesion property]
A cellophane tape was stuck on the surface of the conductive layer of the conductive film of each example, and then the cellophane tape was peeled off. The presence or absence of peeling of the conductive layer was visually observed in this case, and its adhesive property was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2.
A: There is no peeling of the conductive layer, and the adhesive property is high.
B: The conductive layer peels off and the adhesive property is poor.
[Water resistance]
The surface of the conductive layer of the conductive film of each example was rubbed back and forth ten times with a nonwoven impregnated with water at a pressure of 100 g / cm ² . In this case, the presence or absence of peeling of the conductive layer was visually observed, and its water resistance was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2.
A: There is no peeling of the conductive layer and the water resistance is high.
B: A variety of defects are caused on the conductive layer, and the water resistance is somewhat poor.
C: The conductive layer peels off and the water resistance is poor.
[Resistance to solvents]
The surface of the conductive layer of the conductive film of each example was rubbed back and forth ten times with a non-woven fabric impregnated with isopropanol at a pressure of 100 g / cm ² . In this case, the presence or absence of peeling of the conductive layer was visually observed and its solvent resistance became
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A: There is no peeling of the conductive layer and the solvent resistance is high.
B: A variety of defects are caused on the conductive layer and the solvent resistance is poor.
C: The conductive layer peels off and the solvent resistance is poor.
Table 1
Solvent resistanceω O O O O O O O O O < < < < < < < < < < < < < resistance to water□ Û □ Û □ Û □ Û < < < < < < < < < < < < < < < < < < < adhesion property< < < < < < < < < < < < < < < < < < < < < < < Surface resistance value(Ω / c)CDOxCD LO Ox O σί LOOxO LO Ox O LO ~ LOOxLO ~ CO Ox σ> cn CDOxOCN CDOxOCN r-OxOCO CD Ox O σί CDOxOCN LO Ox O LO ~ r-OxOCN LOOxOCO COOxOCN COOxOCO COOxCD COOxOCN CO Ox O LO ~ CO OCD_ COOxOCN COOxOCN Œ> Ox O LO ~ Vinyl versatate polymer Quantity (g) | O LO LO LO LO LO LO O LO L_< Polysol OLX-7879 | Neutralized polysol OLX-7879 Polysol OLX-7878 | Neutralized polysol OLX-7878 Polysol OLX-7879 | Neutralized polysol OLX-7879 Polysol OLX-7878 | Neutralized polysol OLX-7878 Polysol OLX-7878 | Polysol OLX-7878 | Polysol OLX-7879 | Neutralized polysol OLX-7879 Polysol OLX-7878 | Neutralized polysol OLX-7878 Polysol OLX-7879 | Neutralized polysol OLX-7879 Polysol OLX-7878 | Neutralized polysol OLX-7878 Polysol OLX-7879 | Neutralized polysol OLX-7879 Polysol OLX-7878 | Neutralized polysol OLX-7878 Polysol OLX-7878 binder component Quantity (g) | O LO LO LO LO LO O '' d ^- LO L_< 1 PLAS COAT Z-690 PLAS COAT RZ-105 | VYLONAL1245 | PESRESIN A-647GEX Preparation example3 PESRESIN A-647GEX exampleNo. - CN COLO CO r ^ - CO &) OCN COLO CO r ^ - CO &) O CN CN CN CN CO CN
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Table 2
Comparative Example No. Binder-component VinylversatatPolymer Surface resistance value (Ωο) adhesion property resistance to water Solvent resistance kind quantity(G) kind quantity(G) 1 - 0 5.0x10 ⁵ B C C 2 PLAS COAT Z-690 2.0x10 ⁶ B C C 3 PLAS COAT RZ-105 0 2.0x10 ⁶ B C C 4 VYLONAL 1245 502.0x10 ⁸ B C C 5 PESRESINA 647GEX 3.0x10 ⁸ B C C 6 Production Example 3 2.0x10 ⁸ B C C
In each of Examples 1 to 22, in which the conductive layer was formed from 5 of the conductive polymer dispersion that the conductive
Composite and the vinyl versatate-vinyl acetate copolymer contains, the surface resistance of the conductive layer was small and the conductivity was high. In addition, in each of the conductive films of Examples 1 to 22, the adhesive property of the conductive layer to the film base material was high and the water resistance of the conductive layer was also high.
Of the examples, each of Examples 11 to 22, in which the conductive layer was formed from the conductive polymer dispersion which further contains the glycidyl group-containing acrylic resin, was also excellent in the solvent resistance of the conductive layer.
In contrast, in each of Comparative Examples 1 to 6, in which the conductive layer was formed from the conductive polymer dispersion containing the conductive composite but not containing the vinyl versatate polymer, both the adhesive properties of the conductive layer 20 to the film base material and the water resistance were conductive layer low. In addition, in each of the conductive films
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Comparative Examples 1 to 6 the solvent resistance of the conductive layer is low.
In each of Comparative Examples 2 to 6, the binder component was contained in the conductive polymer dispersion, but the adhesive property and the water resistance of the conductive layer were poor. It is thereby determined that the addition of the binder component to the conductive composite does not improve the adhesive properties and the water resistance of the conductive layer, but that the addition of the vinyl versatate polymer improves the adhesive properties and the water resistance of the conductive layer.
(Example 23)
The conductive film of Example 13 was vacuum formed with a vacuum molding machine with an upper die and a lower die with a recess. Specific was in one
State in which the upper die and the lower die were opened, the conductive film was placed between the upper die and the lower die, and was heated with a heater of the upper die while the surface temperature of the film was measured.
After the surface temperature of the film reached 150 ° C, the lower die was raised toward the upper die to be pressed against the conductive film. In this state, a vacuum was generated from one side of the lower die and the vacuum state was maintained for 20 seconds. Thereafter, the film was cooled to 40 ° C and the lower die was lowered to remove the molded product.
The molded product has a cylindrical recess with a round opening with a diameter of 100 mm and a depth of 30 mm. In addition, the stretch ratio for vacuum forming was set to 3 times.
The molded product obtained by the vacuum molding was also measured for its surface resistance value and for adhesive property, water resistance and
Solvent resistance of its conductive layer evaluated. The results are shown in Table 1.
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The molded product obtained was at a high level with respect to the following: the conductivity, the adhesive property of the conductive layer to the film base material, and the water resistance and solvent resistance of the conductive layer. The product 5 thus shaped can be suitably used as an antistatic container for holding an electronic component or the like.

权利要求:
Claims (20)
[1]
1. Conductive polymer dispersion comprising:
a conductive composite containing a π-conjugated conductive polymer and a polyanion;
a vinyl versatate polymer; and a dispersion medium.
[2]
2. The conductive polymer dispersion according to claim 1, wherein the vinyl versatate polymer contains a vinyl unit-derived monomer unit and a vinyl unit-derived monomer unit.
[3]
3. A conductive polymer dispersion according to claim 1 or 2, wherein the vinyl versatate polymer has a pH, which is measured according to JIS Z 8802: 2011, of 4 to 9.
[4]
4. Conductive polymer dispersion according to one of claims 1 to 3, wherein the dispersion medium contains water.
[5]
5. A conductive polymer dispersion according to any one of claims 1 to 4, wherein the π-conjugated conductive polymer comprises poly (3,4-ethylenedioxythiophene).
[6]
6. A conductive polymer dispersion according to any one of claims 1 to 5, wherein the polyanion comprises polystyrene sulfonic acid.
[7]
7. A conductive polymer dispersion according to any one of claims 1 to 6, which further comprises a binder component.
[8]
8. The conductive polymer dispersion of claim 7, wherein the binder component comprises a polyester resin.
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[9]
9. The conductive polymer dispersion according to claim 7, wherein the binder component comprises a glycidyl group-containing acrylic resin.
[10]
10. Conductive film that includes:
5 a film base material; and a conductive layer disposed on a surface of the film base material and formed from the conductive polymer dispersion according to any one of claims 1 to 9.
10
[11]
11. The conductive film according to claim 10, wherein the film base material contains a polyolefin-based resin.
[12]
12. The conductive film according to claim 11, wherein the polyolefin-based resin comprises a polypropylene resin.
[13]
13. A method of making a conductive film comprising applying the conductive polymer dispersion of any one of claims 1 to 9 to at least one surface of a film base material, followed by drying to form a conductive layer.
[14]
14. A method for producing a conductive film according to claim
13, wherein the film base material contains a polyolefin-based resin.
[15]
15. A method of manufacturing a conductive film according to claim
25 14, wherein the polyolefin-based resin comprises a polypropylene resin.
[16]
16. A method of manufacturing a conductive film according to any one of claims 13 to 15, wherein the film base material has a hydrophilic group on a surface thereof.
[17]
17. A method of manufacturing a conductive film according to claim
16, wherein the film base material is obtained by subjecting a surface of a film base material to a corona discharge treatment.
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[18]
An antistatic container comprising a molded product obtained by molding the conductive film according to any one of claims 10 to 12 into a container shape.
5
[19]
19. A method of making an antistatic container comprising:
Producing a conductive film by the method for producing a conductive film according to any one of claims 13 to 17; and
Form the conductive film into a container shape.
[20]
20. A method of manufacturing an antistatic container according to claim 19, wherein forming the conductive film comprises subjecting the conductive film to vacuum forming.

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法律状态:
2019-10-14| FG| Patent granted|Effective date: 20190828 |

优先权:

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申请号 | 申请日 | 专利标题

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JP2017153567|2017-08-08|

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JP2017-153567|2017-08-08|

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