JP2006056034A - Antistatic laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic laminate reduced in the humidity dependence of antistatic properties and capable of being manufactured by a simple process without taking cost and excellent in transparency, the adhesion with a base material and flexibility. <P>SOLUTION: The antistatic laminate 1 has the base material 2 and an antistatic layer 3 containing a soluble conductive polymer component. A soluble polymer component having an anionic group and/or an electron withdrawing group and a conductive polymer component are contained in the soluble conductive polymer component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is an antistatic laminate suitable for packaging materials for packaging confectionery and perishable foods, especially powders such as shavings, savory chili, wheat flour, bread crumbs, etc., and packaging precision electronic components that are sensitive to static electricity. About.

Resin films are widely used as transparent packaging materials through which the contents can be seen through. Since the resin film is an insulator as it is, it is easily charged and may be charged with static electricity due to friction or the like. In addition, the static electricity is difficult to escape to the outside, accumulates in the resin film, and may cause various problems. For example, when a resin film is used as a food packaging material that places importance on hygiene, dust and dirt may be adsorbed during display due to static electricity, and the appearance of the product may be significantly impaired. Further, when the powder is packaged with a resin film, the charged powder is adsorbed or repelled with respect to the resin film at the time of packaging or use, making handling difficult. In addition, when precision electronic components are packaged, there is a risk of destroying the precision electronic components due to static electricity.
In order to solve these problems, conventionally, an antistatic property has been imparted by applying a surfactant to the surface of the resin film or kneading the surface of the resin film (for example, see Non-Patent Document 1).
“Fine Chemicals, Antistatic Agents Recent Market Trends (above)”, issued by CMC, Vol. 16, No. 15, 1987, p. 24-36

 However, the antistatic by applying or kneading a surfactant is very susceptible to humidity because its conduction mechanism is ionic conduction. Specifically, it becomes highly conductive when the humidity is high. When the value was low, the conductivity decreased. Therefore, the conventional antistatic resin film has a low antistatic property in an environment where the humidity is low and static electricity is likely to be generated, and the antistatic property is not exhibited when necessary.

Therefore, a method of imparting antistatic properties by blending a metal or carbon having electronic conduction as a conductive mechanism is conceivable. If metal or carbon is added, the humidity dependency of the antistatic property is reduced, but the metal and carbon are not transparent and the packaging material cannot be made transparent.
In addition, metal oxides such as ITO are transparent and use electronic conduction as a conductive mechanism. Therefore, although they are suitable in that respect, film formation must be performed using a sputtering apparatus or the like. In addition, the process is complicated and the manufacturing cost is high. In addition, the coating film of the inorganic metal oxide has low flexibility, and when it is formed on a thin substrate, the coating film is severely cracked and does not show conductivity, and the substrate is organic. Because of its low adhesion to the film, peeling occurred at the interface between them, and the transparency was likely to be lowered.

In addition, conductive polymers are known as organic materials having electronic conduction as a conductive mechanism. However, conductive polymers generally have insoluble and infusible properties, and can be applied to a substrate after polymerization. It was difficult. If the polymerization is carried out directly on the substrate, an antistatic layer can be formed. However, in this case, not only the process becomes complicated, but also the adhesion between the antistatic layer and the substrate is insufficient.
The present invention provides an antistatic laminate that has low antistatic humidity dependency, can be produced in a simple process without cost, and has excellent transparency, adhesion to a substrate, and flexibility, and production thereof It aims to provide a method.

The antistatic laminate of the present invention has a base material and an antistatic layer containing a soluble conductive polymer component,
The soluble conductive polymer component includes a solubilized polymer component having an anion group and / or an electron withdrawing group in the molecule, and a conductive polymer component.
In the antistatic laminate of the present invention, the antistatic layer preferably further contains a binder resin.
In that case, it is preferable that binder resin is a thermoadhesive resin.
In the antistatic laminate of the present invention, it is preferable that the surface of the substrate is subjected to a hydrophilic treatment, and the soluble conductive polymer component and the binder resin are water-soluble.
In the antistatic laminate of the present invention, it is preferable that the soluble conductive polymer component further contains a dopant.
The antistatic laminate of the present invention preferably has a visible light transmittance of 85% or more and a surface voltage of 0.5 kV or less.
The antistatic laminate of the present invention may have a layer other than the base material and the antistatic layer, and the antistatic layer may not be disposed on the surface layer.
In the antistatic laminate of the present invention, when the solubilized polymer component has an anionic group, the anionic group preferably forms a salt.
The method for producing an antistatic laminate of the present invention is a method for producing an antistatic laminate in which an antistatic resin coating containing a soluble conductive polymer component is applied to a substrate,
The soluble conductive polymer component includes a solubilized polymer component having an anion group and / or an electron withdrawing group in the molecule, and a conductive polymer component.
The packaging material of this invention has the said antistatic laminated body, It is characterized by the above-mentioned.

The antistatic laminate of the present invention has low humidity dependency of antistatic properties, can be produced without cost by a simple process, and is excellent in transparency, adhesion to a substrate, and flexibility. Such an antistatic laminate is suitable as a packaging material for food and precision electronic components.
In the antistatic laminate of the present invention, if the antistatic layer further contains a binder resin, the adhesion to the substrate can be further improved.
At that time, if the binder resin is a thermoadhesive resin, the antistatic layer and the other resin layer can be integrated by thermal bonding.
If the surface of the substrate is hydrophilized and the soluble conductive polymer component and the binder resin are water-soluble, the adhesion between the substrate and the antistatic layer can be increased.
In the antistatic laminate of the present invention, if the soluble conductive polymer component further contains a dopant, the conductivity and heat resistance can be improved.
When the visible light transmittance in the antistatic laminate of the present invention is 85% or more and the surface voltage is 0.5 kV or less, the utility value as a laminate is particularly high.
If the antistatic layer in the antistatic laminate of the present invention is a layer other than the surface layer, it is possible to prevent the antistatic property from being lowered and the antistatic layer from being mixed into food.
When the solubilized polymer component has an anionic group, if the anionic group forms a salt, the adhesion between the antistatic layer and the specific substrate can be further increased.
According to the method for producing an antistatic laminate of the present invention, it can be produced in a simple process without cost, and the antistatic property of the resulting antistatic layer can be reduced in humidity dependence, Adhesion and flexibility can be increased.
The packaging material of the present invention has low humidity dependency of antistatic properties, and is excellent in transparency, adhesion to a substrate, and flexibility.

An embodiment of the antistatic laminate of the present invention and a method for producing the same will be described.
FIG. 1 shows an antistatic laminate of this embodiment. This antistatic laminate 1 is a laminate comprising a substrate 2 and an antistatic layer 3 containing a soluble conductive polymer component.

(Base material)
The substrate 2 is a resin film, for example, a low density polyethylene film, a high density polyethylene film, an ethylene-propylene copolymer film, a polypropylene film, an ethylene-vinyl acetate copolymer film, an ethylene-methyl methacrylate copolymer. Film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polyethylene naphthalate (PEN) film, 6-nylon film, 6,6-nylon film, polymethyl methacrylate film, polystyrene film, styrene-acrylonitrile-butadiene Copolymer film, polyacrylonitrile film, cellulose triacetate (TAC) film, polyvinyl chloride film, polyvinylidene chloride film, poly Vinylidene film, polytetrafluoroethylene film formation, polyvinyl alcohol film, ethylene - vinyl alcohol copolymer film, polycarbonate film, polysulfone film, polyether sulfone film, polyether ether ketone film, and polyphenylene oxide film.

Since the surface of these base materials is usually lipophilic and has a low affinity with a soluble conductive polymer component dissolved in an aqueous solvent, it is difficult to form an antistatic layer. For this reason, the surface of the substrate is preferably subjected to a hydrophilic treatment. Examples of the hydrophilic treatment include corona treatment, plasma treatment, anchor coat treatment, and the like.
Furthermore, when the base material surface is hydrophilized, it is preferable that a soluble conductive polymer component and a binder resin described later are water-soluble. If the substrate surface is hydrophilized and the soluble conductive polymer component and the binder resin are water-soluble, the affinity between the soluble conductive polymer component dissolved in the aqueous solvent and the binder resin and the substrate surface is high. This makes it easier to form the antistatic layer.

 The thickness of the substrate 2 is preferably 5 to 100 μm. If the thickness of the substrate 2 is less than 5 μm, the strength of the antistatic laminate may be insufficient, and if it exceeds 100 μm, the flexibility tends to decrease.

(Antistatic layer)
[Soluble conductive polymer component]
The soluble conductive polymer component constituting the antistatic layer 3 includes a solubilized polymer component having an anion group and / or an electron withdrawing group in the molecule and a conductive polymer component.

[Conductive polymer component]
The conductive polymer component includes a (co) heavy composed of substituted or unsubstituted polyaniline, substituted or unsubstituted polypyrrole, substituted or unsubstituted polythiophene, and one or more monomer units selected from these. Coalescence is mentioned. Specific examples of the monomer unit include aniline, o-sulfonic acid aniline, m-sulfonic acid aniline, o-methylaniline, pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-methoxy-4-acetylpyrrole, Examples include thiophene, 3-methylthiophene, 3-methoxythiophene, 3,4-dimethoxythiophene, ethylenedioxythiophene, isothianaphthene, and thianopyrazine.

Among the conductive polymer components composed of the monomer units, a (co) polymer comprising one or more selected from pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, and 3-methoxythiophene. More preferable in terms of resistance value, cost, and reactivity. Furthermore, alkyl-substituted compounds such as poly N-methylpyrrole and poly-3-methylthiophene are particularly preferable because of the effect of improving solvent solubility. Among the alkyl groups of the alkyl-substituted compound, a methyl group is preferable because a decrease in conductivity can be suppressed.
A polymer of 3-methoxythiophene, 3,4-dimethoxythiophene, ethylenedioxythiophene, and isothianaphthene is more preferable because of excellent transparency when an antistatic layer is formed.

[Solubilized polymer component]
The solubilized polymer component has an anionic group such as a sulfonic acid group and a carboxylic acid group and / or an electron withdrawing group such as a cyano group and a nitro group in the molecule. Specific examples of the solubilized polymer component include those having an anion group such as polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methyl. Examples include propane sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid and the like.
Further, as those having an electron-withdrawing group, polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadiene-styrene resin, a resin obtained by cyanoethylating a hydroxyl group or amino group-containing resin, for example, , Cyanoethyl cellulose resin, polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, nitrocellulose and the like.

The solubilized polymer component may be a copolymer. As the copolymer, for example, a copolymer containing one or more units each having an anionic group and a unit having an electron-withdrawing group, a copolymer containing units having different anionic groups, and different Examples thereof include a copolymer containing a unit having an electron-withdrawing group.
Furthermore, other vinyl compounds may be copolymerized with the solubilized polymer component. Examples of other vinyl compounds include styrene, butadiene, acrylic acid, methacrylic acid, hydroxyacrylic acid, hydroxymethacrylic acid, acrylic acid ester, methacrylic acid ester, and p-vinyltoluene. If such a polymerizable vinyl compound is copolymerized, it is possible to improve the solvent solubility and the adhesion to the substrate, or to control the compatibility with the binder resin.

The anionic group and electron-withdrawing group of the solubilized polymer component have high polarity, so that the adhesion to the substrate can be increased, but the solubilized polymer component has a molecular structure such as polyacrylsulfonic acid or polymethacrylsulfonic acid. Those having an ester group include: ethylene-methyl methacrylate copolymer film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polyethylene naphthalate (PEN) film, 6-nylon film, 6,6-nylon It is preferable in terms of particularly excellent adhesion to a film, a polymethyl methacrylate film or the like.
In addition, a solubilized polymer component obtained by copolymerizing other vinyl compounds such as butadiene and acrylic acid ester is preferable in terms of increasing the flexibility of the coating film and contributing to improvement in adhesion.

  Furthermore, it is also preferable that the anionic group of the solubilized polymer component forms a salt, or a monomer having a hydroxyl group such as hydroxyacrylic acid or hydroxymethacrylic acid is copolymerized at the terminal. When an anionic group is converted into a salt or a monomer having a hydroxyl group is copolymerized, an ethylene-vinyl acetate copolymer film, a cellulose triacetate (TAC) film, a polyvinyl alcohol film, an ethylene-vinyl alcohol copolymer are used. Adhesiveness with a polymer film and a substrate whose surface is treated with silica or alumina is improved.

 The solubilized polymer component may contain a synthetic rubber for improving impact resistance, an anti-aging agent, an antioxidant, and an ultraviolet absorber for improving environmental resistance. However, since the amine compound as an antioxidant may inhibit the action of the oxidizing agent used when polymerizing the conductive polymer, a phenolic antioxidant may be used or mixed after polymerization. Countermeasures are necessary.

  The ratio of the solubilized polymer component to the conductive polymer component in the soluble conductive polymer component is preferably such that the mass ratio of the solubilized polymer component to the conductive polymer component is between 5:95 and 99: 1. . If the ratio of the conductive polymer component is less than 1, sufficient antistatic properties may not be obtained, and if it exceeds 95, the solvent solubility tends to be insufficient.

[Dopant]
The soluble conductive polymer component preferably contains a dopant in order to improve its conductivity and heat resistance. Usually, halogen compounds, Lewis acids, proton acids, etc. are used as dopants, for example, organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, fullerene hydroxides, fullerenes of carboxylic acids, Examples thereof include sulfonated fullerenes.

Examples of organic acids include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane disulfonic acid, Anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, pyrene sulfonic acid and the like can be mentioned. These metal salts can also be used.
Examples of the organic cyano compound include dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

[Binder resin]
The antistatic layer may contain a binder resin. When a binder resin is contained in the antistatic layer, compatibility with the solubilized polymer component, flexibility, and adhesion to the base material are further increased. Preferred binder resins include, for example, polyester, polyurethane, polyamide, polyamideimide, polyimide, polyacryl, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and water-soluble by adding a sulfonic acid group or a carboxylic acid group in the molecule. Water-soluble polyester, water-soluble polyurethane, various ionomers and the like. Further, when the surface of the base material is subjected to a hydrophilic treatment, an antistatic layer is more easily formed, and therefore, a water-soluble binder resin is preferable.
Furthermore, as the binder resin, in addition to the solid resin, a liquid resin that is chain-extended or cross-linked by heat energy or light energy can be used.

The binder resin may be a heat adhesive resin. If the binder resin is a heat-adhesive resin, when a resin layer other than the substrate is provided on one side or both sides of the antistatic layer, thermal bonding can be performed without providing a separate adhesive layer. In addition, when a thermal adhesive layer is separately provided, the adhesive strength is increased.
The heat-adhesive resin refers to a resin that exhibits adhesiveness on the surface when heated to the glass transition point or higher, and becomes stronger when cooled.

 The blending amount of the binder resin varies greatly depending on the required surface resistance value, but the mass ratio of (solubilized polymer component + conductive polymer component): binder resin is 0.001: 99.999 to 95: 5. preferable. When the mass ratio of the binder resin exceeds 99.99, the antistatic property may not be sufficiently exhibited, and when it is less than 5, the adhesion with the substrate may be insufficient.

 The thickness of the antistatic layer 3 is preferably 0.01 to 100 μm, although it depends on the amount of the binder resin and the type of the conductive polymer component. If the thickness of the antistatic layer 3 is less than 0.01 μm, the antistatic property may be insufficient, and if it exceeds 100 μm, it is too thick and uneconomical.

[Production method]
In order to obtain an antistatic laminate, first, a solubilized polymer component is dissolved in a solvent, and a precursor monomer of a conductive polymer and a dopant as necessary are added to this and mixed sufficiently with stirring. Polymerization is allowed to proceed by dropping an oxidant into the body solution. The soluble conductive polymer component is obtained by removing and purifying the oxidant, residual monomer and by-products from the solubilized polymer component and conductive polymer component complex thus obtained. The dopant may be added after purification.
Here, as an oxidizing agent for polymerizing the precursor monomer of the conductive polymer, for example, metal halide compounds such as ferric chloride, boron trifluoride, and aluminum chloride, peroxides such as hydrogen peroxide and benzoyl peroxide are used. Products, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, ozone, oxygen and the like.

 Next, the soluble conductive polymer component obtained as described above is dissolved in a solvent to obtain an antistatic resin coating. Alternatively, a binder resin may be further added, and sufficiently mixed and stirred to obtain an antistatic resin paint. When the binder resin is liquid, it can be added as it is, but when the binder resin is solid or when mixing is difficult even with liquid, it is preferable to dissolve the binder resin in a solvent before mixing. In addition, the soluble conductive polymer component may be easily mixed if dissolved in a solvent in advance.

 Solvents that dissolve the soluble conductive polymer component include, for example, water, methanol, ethanol, acetonitrile, benzonitrile, propylene carbonate, N-methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl. General-purpose solvents such as ketone and toluene can be mentioned, and these can be used alone or in combination.

 In the antistatic resin coating obtained as described above, when the solubilized polymer component has an anionic group, it may exhibit strong acidity and have low handleability. In such a case, it is preferable to convert the anionic group into a salt. Specifically, it is preferable to add a metal compound having sodium, potassium, iron, copper, or the like that forms a salt with carboxylic acid or sulfonic acid, an ammonium compound, an amine compound, or the like to convert it into an anion salt. When the anionic group forms a salt, the pH of the antistatic resin coating can be arbitrarily adjusted in the range of acidity of about pH 1 to alkalinity of about pH 13, but in particular, it can be adjusted to pH 6-8 (neutral). The effect on the inclusions due to acid and alkali is reduced, and the handleability can be improved.

 Then, the antistatic resin coating is applied to the substrate by a known method such as dipping, comma coating, spray coating, etc., and the solvent is dried or the coating is solidified by heat or ultraviolet light, and then applied onto the substrate. An antistatic layer is formed to obtain the antistatic laminate 1 shown in FIG.

At that time, the light transmittance, haze, and surface resistance can be adjusted by the coating thickness of the antistatic layer, but the visible light transmittance (JIS Z 8701) excluding the base material when the thickness of the antistatic layer is 0.1 μm. ) Is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. Further, the haze (JIS K 6714) when the thickness of the antistatic layer is 0.1 μm is preferably 5% or less, more preferably 2% or less, and particularly preferably 1% or less. .
Furthermore, it is preferable that the surface resistance value (JIS K 6911) is 1 × 10 ⁴ to 1 × 10 ¹¹ Ω.

In particular, since the antistatic laminate has a higher utility value as a packaging material, it preferably has a low visible voltage with a high visible light transmittance, and specifically has a visible light transmittance of 85%. Thus, the surface voltage is preferably 0.5 kV or less, more preferably the visible light transmittance is 95% or more and the surface voltage is 0.2 kV.
Here, the surface voltage is a value measured by the friction voltage measurement method described in JIS L 1094.

The antistatic laminate described above has a base material and an antistatic layer, and since the antistatic layer contains a specific soluble conductive polymer component, it has antistatic properties. In addition, since the conductive polymer in the antistatic layer is electronically conductive, the humidity dependency of the antistatic property is small. In addition, since the antistatic layer does not contain metal or carbon, it is excellent in transparency and flexibility, and is excellent in adhesion to the substrate. Furthermore, since the antistatic layer can be formed by applying a soluble conductive polymer component that is solubilized in a solvent onto a substrate, it can be produced in a simple process without cost.
And since the packaging material of this invention has the said antistatic laminated body and has said property, it is suitable as a packaging material of a foodstuff or a precision electronic component. The shape of the packaging material is appropriately selected depending on the shape of the article to be packaged, and may be a sheet shape, a bag shape, or other shapes.

Note that the present invention is not limited to the above-described embodiments. The antistatic laminate of the above-described exemplary embodiment was composed of the base material 2 and the antistatic layer 3, but in addition to these two layers, for example, as shown in FIG. It is also possible to laminate the surface layer 5 on the antistatic layer 3 (antistatic laminate 1a). In this case, if the surface layer 5 is printed, the design of the antistatic laminate can be improved.
Here, as the adhesive forming the adhesive layer 4, known ones such as low density polyethylene having a low melting point, ethylene-vinyl acetate copolymer resin, and polyurethane, polyester, polyamide, polypropylene, etc. as hot melt adhesives are used. used.
Moreover, as the surface layer 5, various films similar to the base material 2 described above can be used.

In addition, as shown in FIG. 3, a gas barrier layer 6 formed between the base material 2 and the antistatic layer 3 (antistatic laminate 1 b) may be used. If the gas barrier layer 6 is formed, the food or the like can be prevented from deteriorating when the antistatic laminate is packaged with the food or the like.
Examples of the gas barrier layer include known layers such as a resin layer made of an ethylene-vinyl alcohol copolymer, vinylidene chloride resin, polyacrylonitrile, polyvinyl alcohol, amide resin, polyester, and the like, and an inorganic layer such as silica and alumina.

  Like the antistatic laminate shown in FIGS. 2 and 3, when the antistatic layer 3 is not disposed on the surface layer, it is preferable in that the antistatic layer 3 is rubbed off and prevented from being mixed into food. . On the other hand, when the antistatic layer 3 is a surface layer, the antistatic property may be lowered when it is rubbed off and the antistatic layer may be mixed into food.

Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
(1) Synthesis of solubilized polymer component Acrylonitrile 50 g, butadiene 5 g, and methylacrylic acid 5 g were dissolved in 500 ml of toluene, 1.5 g of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was stirred at 50 ° C. for 5 hours. Polymerized. The solubilized polymer component produced by the polymerization was washed with methanol.
(2) Preparation of antistatic resin coating material 10 g of the solubilized polymer component obtained in (1) was dissolved in 90 g of acetonitrile, and 50 g of pyrrole and 20 g of sodium octadecylnaphthalenesulfonate were added thereto, and the temperature was kept at -20 ° C. While cooling, a monomer solution was prepared by stirring for 1 hour. To this monomer solution, an oxidant solution in which 250 g of ferric chloride was dissolved in 1250 ml of acetonitrile was dropped over 2 hours while maintaining at −20 ° C., and stirring was further continued for 12 hours to polymerize pyrrole.
After completion of the polymerization, 2000 ml of methanol was added to the solution containing the pyrrole polymer, the precipitate was filtered, washed with methanol and pure water until the filtrate became transparent, dissolved in dimethylacetamide (DMAc) and concentrated. 1% by mass of an antistatic resin paint was obtained.
(3) Production of antistatic laminate The antistatic resin coating was applied onto a PET film as a base material with a coating thickness of 0.1 µm and dried to obtain an antistatic laminate.

  The surface resistance value (temperature: 10 ° C., humidity: 15% RH), visible light transmittance, haze, and surface voltage of this antistatic laminate were measured. The results are shown in Table 1.

(Example 2)
(1) Synthesis of solubilized polymer component 50 g of acrylonitrile and 10 g of styrene were dissolved in 500 ml of toluene, 1.5 g of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was polymerized at 50 ° C. for 5 hours. The solubilized polymer component produced by the polymerization was washed with methanol.
(2) Preparation of antistatic resin coating material A conductive polymer component was synthesized in a solubilized polymer component in the same manner as in Example 1, and a solution of a soluble conductive polymer component having a concentration of 5% by mass (soluble conductivity) Polymer solution) was obtained. To this soluble conductive polymer solution, 1000 parts by mass of polyester (Eneltel UE3600 manufactured by Unitika) as a binder resin was mixed with 100 parts by mass of the solid content of the solution, and stirred to obtain an antistatic resin paint.
(3) Production of antistatic laminate The antistatic laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
(1) Synthesis of solubilized polymer component 50 g of sodium styrenesulfonate was dissolved in 500 ml of water, 0.15 g of ammonium persulfate was added as a polymerization initiator, and polymerized at 70 ° C. for 5 hours. After completion of the polymerization, 30 g of a 30% sulfuric acid aqueous solution was added, and 15000 ml of water was further added, followed by concentration to 300 ml by ultrafiltration. Water was removed from this with a drier to obtain a solubilized polymer component.
(2) Preparation of antistatic resin coating material 10 g of the solubilized polymer component obtained in (1) was dissolved in 90 g of acetonitrile, and 50 g of pyrrole and 20 g of sodium octadecylnaphthalenesulfonate were added thereto, and the temperature was kept at -20 ° C. While cooling, a monomer solution was prepared by stirring for 1 hour. To this monomer solution, an oxidant solution in which 250 g of ferric chloride was dissolved in 1250 ml of acetonitrile was dropped over 2 hours while maintaining at −5 ° C., and stirring was further continued for 12 hours to polymerize pyrrole.
After the polymerization is completed, the solution containing the pyrrole polymer is ultrafiltered to remove the oxidant residue, unreacted monomers and oligomer components, and a soluble conductive polymer solution having a concentration of 5% by mass (soluble conductive polymer). Solution).
To this soluble conductive polymer solution, 1000 parts by mass of a water-soluble polyester resin (Z565 manufactured by Kyoyo Chemical) as a binder resin was mixed with 100 parts by mass of the solid content of the solution, and stirred to obtain an antistatic resin coating. .
(3) Production of antistatic laminate The antistatic laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
(1) Preparation of antistatic resin coating 10 g of the solubilized polymer component obtained in (1) of Example 3 was dissolved in 90 g of water, and 50 g of 3,4-ethylenedioxythiophene was added thereto. While cooling to 5 ° C., the mixture was stirred for 1 hour to prepare a monomer solution. To this monomer solution, an oxidant solution in which 250 g of iron p-toluenesulfonate was dissolved in 1250 ml of water was dropped over 2 hours while maintaining at −5 ° C., and stirring was further continued for 12 hours to 3,4-ethylene. Dioxythiophene was polymerized.
After completion of the polymerization, the solution containing 3,4-ethylenedioxythiophene polymer is ultrafiltered to remove the oxidant residue, unreacted monomers and oligomer components, and a soluble conductive polymer component having a concentration of 1% by mass. Solution (soluble conductive polymer solution) was obtained.
To this soluble conductive polymer solution, 1000 parts by mass of a water-soluble polyester resin as a binder resin was mixed with 100 parts by mass of the solid content of the solution, and stirred to obtain an antistatic resin paint.
(2) Production of antistatic laminate An antistatic laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
(1) Preparation of antistatic resin coating 10 g of the solubilized polymer component obtained in (2) of Example 2 was dissolved in 90 g of acetonitrile, 50 g of 3-methoxythiophene and 20 g of sodium octadecylnaphthalene sulfonate were added, While cooling to 5 ° C., the mixture was stirred for 1 hour to prepare a monomer solution. To this monomer solution, an oxidant solution in which 250 g of ferric chloride was dissolved in 1250 ml of water was dropped over 2 hours while maintaining at −5 ° C., and stirring was further continued for 12 hours to polymerize 3-methoxythiophene. .
After completion of the polymerization, the solution containing the 3-methoxythiophene polymer is ultrafiltered to remove the oxidant residue, unreacted monomer and oligomer components, and a solution of a soluble conductive polymer component having a concentration of 3% by mass (soluble A conductive polymer solution) was obtained.
To this soluble conductive polymer solution, 1000 parts by mass of polyester as a binder resin was mixed with 100 parts by mass of the solid content of the solution, and stirred to obtain an antistatic resin paint.
(2) Production of antistatic laminate An antistatic laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
(1) Preparation of antistatic resin coating 10 g of the solubilized polymer component obtained in (1) of Example 3 was dissolved in 90 g of water, and 50 g of 3,4-ethylenedioxythiophene was added thereto. While cooling to 5 ° C., the mixture was stirred for 1 hour to prepare a monomer solution. To this monomer solution, an oxidant solution in which 250 g of iron p-toluenesulfonate was dissolved in 1250 ml of water was dropped over 2 hours while maintaining at −5 ° C., and stirring was further continued for 12 hours to 3,4-ethylene. Dioxythiophene was polymerized.
After completion of the polymerization, the solution containing 3,4-ethylenedioxythiophene polymer is ultrafiltered to remove oxidant residues, unreacted monomers and oligomer components, and then 1% by mass of sodium hydroxide solution is dropped. Then, the solution was adjusted to pH 7 to obtain a solution of a soluble conductive polymer component (soluble conductive polymer solution).
To this soluble conductive polymer solution, 1000 parts by mass of a water-soluble polyester resin as a binder resin was mixed with 100 parts by mass of the solid content of the solution, and stirred to obtain an antistatic resin paint.
(2) Manufacture of antistatic laminate The antistatic resin paint of (1) is applied on a PET film deposited on silica on the surface as a gas barrier layer with a coating thickness of 10 μm, dried, and an antistatic layer is provided to prevent antistatic A conductive laminate was obtained. And the surface resistance value, haze, and surface withstand voltage were measured. The results are shown in Table 1.

(Example 7)
An antistatic laminate produced in Example 6 and a polypropylene film provided with a silica vapor deposition layer on the surface were prepared, and the antistatic layer of the antistatic laminate and the silica vapor deposition layer of the polypropylene film were face to face. The laminate was heat laminated in the state to obtain a new antistatic laminate. When the surface resistance value, haze, and surface withstand voltage of this antistatic laminate were measured, they were 85%, 2%, and 0.3 kV, respectively.

(Example 8)
Two sheets of the antistatic laminate produced in Example 6 cut into a 40 cm square were prepared, and the antistatic layers were stacked face to face, and in that state, the edges on three sides were heat sealed. A packaging bag was obtained. When the surface withstand voltage of the inner surface and outer surface of this bag was measured, it was 0.1 kV and 0.3 kV, respectively. From the opening portion of the bag, 100 g of a 3 mm square piece of paper was filled while being dropped from a distance of 10 cm above the opening portion. As a result, adhesion to the inner surface of the bag and repulsion did not occur, and the bag was satisfactorily filled.

  The antistatic laminates of Examples 1 to 5 satisfying claim 1 of the present application had a low surface resistance value and had sufficient antistatic properties, but were excellent in transparency.

It is sectional drawing which shows one embodiment of the antistatic laminated body which concerns on this invention. It is sectional drawing which shows the other embodiment example of the antistatic laminated body which concerns on this invention. It is sectional drawing which shows the other embodiment example of the antistatic laminated body which concerns on this invention.

Explanation of symbols

1, 1a, 1b Antistatic laminate 2 Base material 3 Antistatic layer

Claims (10)

A base and an antistatic layer containing a soluble conductive polymer component;
The antistatic laminate, wherein the soluble conductive polymer component includes a solubilized polymer component having an anion group and / or an electron withdrawing group in the molecule, and a conductive polymer component.   The antistatic laminate according to claim 1, wherein the antistatic layer further contains a binder resin.   The antistatic laminate according to claim 2, wherein the binder resin is a thermoadhesive resin.   The antistatic laminate according to claim 2 or 3, wherein the surface of the substrate is hydrophilized and the soluble conductive polymer component and the binder resin are water-soluble.   The antistatic laminate according to any one of claims 1 to 4, wherein the soluble conductive polymer component further contains a dopant.   The antistatic laminate according to any one of claims 1 to 5, wherein the visible light transmittance is 85% or more and the surface voltage is 0.5 kV or less.   It has layers other than a base material and an antistatic layer, and the antistatic layer is not arrange | positioned at the surface layer, The antistatic laminated body in any one of Claims 1-6 characterized by the above-mentioned.   The antistatic laminate according to any one of claims 1 to 7, wherein when the solubilized polymer component has an anionic group, the anionic group forms a salt. A method for producing an antistatic laminate in which an antistatic resin coating containing a soluble conductive polymer component is applied to a substrate,
A method for producing an antistatic laminate, wherein the soluble conductive polymer component comprises a solubilized polymer component having an anion group and / or an electron withdrawing group in the molecule, and a conductive polymer component . A packaging material comprising the antistatic laminate according to claim 1.

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