JP2009178957A - Antistatic resin molding and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin molding which does not deteriorate in the surface resistivity and transparency when its surface is cleaned by wiping with a wiping cloth impregnated with an alcohol. <P>SOLUTION: The antistatic resin molding has at least one antistatic layer on a substrate. The main ingredients of the antistatic layer comprise a vinyl chloride-vinyl acetate copolymer and carbon fiber, and the vinyl chloride to vinyl acetate mass ratio of the copolymer is 82/18 to 99/1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antistatic resin molded body and a method for producing the molded body. Specifically, the present invention relates to an antistatic resin molded body in which the antistatic property and transparency are not deteriorated even after the surface of the antistatic resin molded body is rubbed a plurality of times with a cloth or the like.

  Conventionally, transparent applications such as partitions, partitions used in clean rooms, etc. that can be seen through, such as viewing windows of equipment, and that dislike dust, have used a transparent antistatic resin plate that releases static electricity and prevents dust from adhering. I came. For example, Patent Document 1 discloses a transparent antistatic plate in which an antistatic layer is provided on the surface of a plastic substrate. The antistatic layer of the transparent antistatic plate is composed of a conductive powder and a binder resin, and the conductive powder uses a conductive powder in which barium sulfate particles are coated with tin oxide containing antimony oxide. . This transparent antistatic plate exhibits conductivity when the conductive powder comes into contact with each other, and exhibits an antistatic effect.

  However, when the conductive powder is used for the antistatic layer, the antistatic property will not be expressed unless it is added in a larger amount than the shape of the conductive powder. If the bending process is performed, the antistatic layer will crack and the antistatic layer will become white. In addition, there is a problem that the antistatic property is not exhibited unless the antistatic layer having a certain thickness or more is formed. In addition, there is a problem that the conductive powder having antistatic properties is relatively expensive.

  Therefore, an antistatic resin plate in which conductive powder, which is a conductive material that has been used conventionally, is changed to carbon fibers such as carbon nanotubes has been proposed. For example, Patent Document 2 discloses an antistatic transparent resin plate having an antistatic layer made of a transparent thermoplastic resin containing carbon nanotubes on at least one surface of a substrate made of a thermoplastic resin. In addition, the carbon nanotubes of the antistatic resin plate may be separated into the thermoplastic resin of the antistatic layer in a state where the carbon nanotubes are separated one by one or in a state where a plurality of bundles are separated one by one. Distributed and in contact with each other.

  On the other hand, when the surface of the antistatic resin molding is wiped and washed with a wiping cloth containing alcohol such as isopropyl alcohol (IPA), the surface resistivity of the antistatic resin molding is increased. There was a problem of falling. Further, when the wiping and washing are performed, there is a problem that transparency is also deteriorated at the same time.

Therefore, for example, in Patent Document 3, the antistatic resin molding in the case where the wiping and cleaning is performed by the antistatic resin molded body in which the resin layer is laminated on the outer surface of the antistatic layer of the antistatic resin molded body. A technique for preventing an increase in surface resistivity of the body and deterioration of transparency is disclosed.
JP 7-310034 A Japanese Patent Laid-Open No. 2004-230690 JP 2007-130950 A

  However, in the antistatic resin molded body in which the resin layer is laminated on the outer surface of the antistatic layer of the above antistatic resin molded body, the surface resistivity value of the antistatic resin molded body is substantially ineffective. There was a problem that it was enough. Further, when the resin layer is not laminated on the outer surface of the antistatic layer of the antistatic resin molding, there is a problem that the surface resistivity and transparency of the antistatic resin molding are deteriorated.

  In view of the above problems, the first object of the present invention is that the surface resistivity and transparency do not deteriorate when the surface of the antistatic resin molded product is wiped and cleaned with a wiping cloth containing alcohol such as IPA. The object is to provide an antistatic resin molding. The second object of the present invention is to provide a method for producing the antistatic resin molded body.

  Means for solving the first object is an antistatic resin molded article having at least one antistatic layer on a substrate, wherein the main component of the antistatic layer is vinyl chloride-vinyl acetate copolymer. It is composed of a coalescence and carbon fiber, and the mass ratio of vinyl chloride and vinyl acetate constituting the vinyl chloride-vinyl acetate copolymer is in the range of 82/18 to 99/1. It is a functional resin molding.

  Further, the means for solving the second object is characterized in that the antistatic layer is formed by a coating method, and the antistatic resin molded body manufacturing method, and the antistatic layer is formed by a transfer method. A method for producing an antistatic resin molded body, and a method for producing an antistatic resin molded body, wherein the antistatic layer is formed by compounding.

  According to the present invention, since a vinyl chloride-vinyl acetate copolymer having a constant mass ratio is used as the binder resin, the antistatic resin molding is performed with a wiping cloth containing alcohol such as IPA. When the surface of the body is wiped off and washed, it is possible to provide an antistatic resin molded body in which the surface resistivity and transparency are not deteriorated.

  Hereinafter, an antistatic resin molded body (hereinafter referred to as “the molded body”) as an example of an embodiment of the invention will be described. However, the scope of the present invention is not limited to the embodiments described below.

  The molded body is a molded body having a base material and at least one antistatic layer on the base material. Here, “on the substrate” as used in the present invention refers to the case where an antistatic layer is provided directly on the surface of the substrate, and another layer which is a single layer or a multilayer is provided on the surface of the substrate. This means that an antistatic layer is provided on the layer.

In addition, in the present invention, when “X to Y” (X and Y are arbitrary numbers) is described, it is “greater than X and smaller than Y” with the intention of “X to Y” unless otherwise specified. The intention of “preferably” is also included.

Furthermore, in the present invention, “X / Y” means that the mass ratio is X to Y.

The “mainly” and “main component” defined in the present invention mean that the total mass of the carbon fiber and the binder resin is 50% by mass or more of the antistatic layer with respect to the total antistatic layer mass. .

(Molded body)
The molded body is a molded body having a base material and at least one antistatic layer. The molded product as used in the present invention means all shapes, for example, a plate shape, a spherical shape, a rod shape, a triangular pyramid, a triangular prism, a cylinder, a cone, and the like. Further, a shape without a general name can be included in the molded body of the present invention.

(Base material)
As the base material constituting the molded body, a material used as a known base material can be used. For example, a thermoplastic resin or a thermosetting resin. Especially, it is preferable to use a thermoplastic resin as a base material from the point of a shaping | molding process. Examples of the thermoplastic resin used in the molded article include polyolefin (PO) resins or polyolefin elastomers, amorphous polyolefin resins (APO) such as cyclic polyolefin, polystyrene (PS), acrylonitrile-butadiene-styrene copolymer ( ABS), polystyrene resins such as styrene-butadiene-styrene (SBS) or hydrogenated styrene elastomers such as styrene-ethylene-butadiene-styrene (SEBS), polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) ) Resin, polymethyl methacrylate (PMMA), acrylic resin such as copolymerized acrylic, polyester resin (PET-G) copolymerized with cyclohexanedimethanol, amorphous polyethylene phthalate (AP) T) such as polyester resins, polycarbonate (PC) resin, and the like. In addition, although the thermoplastic resin used for a base material can also be used only by 1 type, it is also possible to mix and use 2 or more types.

  Among them, polyvinyl chloride (PVC) resin, polycarbonate (PC) resin, polyester resin copolymerized with cyclohexanedimethanol (PET-G), and amorphous polyethylene phthalate (A-PET), which are excellent in transparency and durability. Acrylic resins such as polyester resins such as polymethyl methacrylate (PMMA) and copolymerized acrylic are preferred.

  In addition, the base material of this molded object can also use the base material containing various additives in consideration of a flame retardance, transparency, thermal stability, etc. Specific examples of the additive include a lubricant, a colorant, a pigment, a flame retardant, an antibacterial agent, an antifungal agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, a plasticizer, and a flow modifier.

  Specific examples of the thermosetting resin include novolak type epoxy resin, sylock type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, water Bisphenol A type epoxy resin, aliphatic type epoxy resin, orthocresol novolak type epoxy resin, phenol novolak type epoxy resin, modified phenol type epoxy resin, alkyl modified triphenolmethane type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, Glycidylamine type epoxy resin, bisphenol A novolak type epoxy resin, brominated phenol novolak type epoxy resin, naphthol type epoxy resin, stilbene type epoxy resin, Polyphenol methane type epoxy resins, alkyl-modified triphenolmethane type epoxy resins, triazine nucleus-containing epoxy resins, etc. or a phenoxy resin. These may be used alone or in combination of two or more.

  The lower limit of the thickness of the base material of the molded body is 1 mm or more, preferably 2 mm or more, more preferably 3 mm or more, and the upper limit is 20 mm or less, preferably 10 mm or less, more preferably 5 mm or less. If the thickness of the base material is 1 mm or more, the thickness of the base material is too thin, and the problem that the strength of the antistatic resin plate is reduced is less likely to occur. Moreover, if the thickness of a base material is 20 mm or less, a visible light can be permeate | transmitted and a favorable haze value will be obtained, without a total light transmittance falling extremely.

(Antistatic layer)
The molded body has at least one antistatic layer on the substrate. By having the antistatic layer, it is possible to reduce static charge on the surface of the molded body and prevent dust and the like from adhering to the surface of the molded body. The antistatic layer of the molded body is mainly composed of a vinyl chloride-vinyl acetate copolymer as a binder resin and carbon fibers as a conductive material. However, you may add another additive in the range which does not inhibit the physical property anticipated for the antistatic layer of this molded object. Examples of other additives include additives such as a dispersant, a plasticizer, a lubricant, a surface modifier, and a stabilizer. As the dispersant, specifically, a polymer dispersant such as an alkyl ammonium salt solution of an acidic polymer, a tertiary amine-modified acrylic copolymer or a polyoxyethylene-polyoxypropylene copolymer, a coupling agent, and the like are used. The

  The antistatic layer of the molded body can be produced by a known production method. For example, the antistatic layer of the molded body is prepared by previously dissolving a binder resin and carbon fiber in a solvent to prepare a conductive paint, and then applying the conductive paint to a base material or a peelable base film (referred to as a transfer film). Manufactured by coating.

(Carbon fiber)
The antistatic layer of the molded body contains carbon fiber as a conductive material. The lower limit of the content of carbon fibers contained in the molded body is 2% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more, and the upper limit is 19% by mass or less, 15% by mass or less. More preferably, it is the range of 12 mass% or less. If the content rate of the carbon fiber in the antistatic layer is 2% by mass or more, the amount of the carbon fiber is sufficient, so that the problem that the carbon fiber is difficult to contact and the antistatic property does not occur does not occur. Furthermore, since a π-electron jumps between the carbon fibers having a certain distance and a tunneling current due to a tunneling effect exhibiting antistatic properties is likely to occur, the surface resistivity is reduced and dust is difficult to adhere. Moreover, if the mass ratio of the carbon fibers in the antistatic layer is 9% by mass or less, visible light is easily transmitted, the total light transmittance is increased, and the haze value is also likely to be decreased. In addition, the mass ratio of the carbon fiber of the present invention is a mass ratio with respect to the total mass ratio of the antistatic layer.

  The preferred average fiber diameter of the carbon fibers used in the molded article has a lower limit of 0.7 nm or more, preferably 10 nm or more, more preferably 20 nm or more, and an upper limit of 80 nm or less, preferably 70 nm or less, more preferably. 60 nm or less is preferable from the viewpoint of transparency and dispersibility. If the average fiber diameter is 0.7 nm or more, the fiber diameter will be too small and will scatter and no sanitary problems will occur. Moreover, if an average fiber diameter is 80 nm or less, the problem that a haze value becomes high does not generate | occur | produce. In addition, this average fiber diameter is the value calculated by making the cross section of a fiber into an equivalent circle diameter. The equivalent circle diameter means the diameter of a circle having the same area as the projected area of the particles.

  The aspect ratio (ratio of fiber diameter to fiber length) of the carbon fibers used in the molded body is 100 or more, preferably 200 or more, more preferably 500 or more. If the aspect ratio is 100 or more, the carbon fibers are easily in contact with each other, and a sufficient conductive path is formed. In consideration of the form of the carbon fiber, the antistatic property can be sufficiently obtained if the aspect ratio of the carbon fiber is 1,000,000 or less.

  Carbon fibers include so-called carbon nanotubes and carbon nanofibers. The carbon nanotube includes a single type in which the tube structure of the carbon is a single tube, a double type in which the tube structure is a double tube, and a multi-type structure in which the tube structure is triple or more. Also, a carbon fiber having a shape such as a nanohorn type in which the mouth of one end of the tube is closed and the end of the other mouth is open, or a cup type in which the opening at one end is larger than the opening at the other end is used. It is also possible to do. Among these, multi-type carbon nanotubes are preferably used from the viewpoints of transparency and conductivity.

(Vinyl chloride-vinyl acetate copolymer)
The antistatic layer of the molded body uses a vinyl chloride-vinyl acetate copolymer having a certain mass ratio as a binder resin. By using a vinyl chloride-vinyl acetate copolymer with a certain mass ratio as the binder resin, the surface of the antistatic resin molded product is wiped and washed with a wiping cloth containing alcohol such as IPA. It is possible to prevent the surface resistivity of the electrically conductive resin molding from increasing and the transparency from deteriorating (improvement of wiping resistance). That is, the glass transition temperature (Tg) can be adjusted by setting the vinyl chloride-vinyl acetate copolymer to a certain mass ratio. And by adjusting the glass transition temperature (Tg) of the vinyl chloride-vinyl acetate copolymer of the binder resin, it becomes possible to bond at a relatively low temperature, so that the antistatic layer adheres firmly to the substrate. And wiping resistance is improved.

  Further, since the antistatic layer of the molded body is composed of a vinyl chloride-vinyl acetate copolymer having a constant glass transition temperature, the problem that the base material of the molded body is warped by heat does not occur, and By firmly adhering the base material of the molded body and the antistatic layer, it is possible to prevent peeling between the base material of the molded body and the antistatic layer even after wiping and washing.

  The mass ratio of vinyl chloride in the vinyl chloride-vinyl acetate copolymer contained in the antistatic layer of the molded body is 82 or more, preferably 85 or more, more preferably 87 or more, and the upper limit is 99 or less, preferably 96 or less, more preferably 95 or less. If the mass ratio of vinyl chloride is 82 or more, the amount of vinyl acetate is appropriate, so that the problem that carbon fibers are difficult to disperse does not occur. On the other hand, when the mass ratio of vinyl chloride is 99 or less, the glass transition temperature of the vinyl chloride-vinyl acetate copolymer is adjusted to an appropriate temperature. Since no environment is required, there is no problem that workability is good and the resin molded body is easily deformed. For example, when the antistatic layer is installed on the base material by the transfer method, if the antistatic layer can be attached to the base material at 150 ° C. or lower, the problem that the base material is warped by heat does not occur.

  The lower limit of the mass ratio of vinyl acetate in the vinyl chloride-vinyl acetate copolymer contained in the antistatic layer of the molded article is 1 or more, preferably 4 or more, more preferably 5 or more, and the upper limit is 18 Hereinafter, it is preferably 15 or less, more preferably 13 or less. If the mass ratio of vinyl acetate in the vinyl chloride-vinyl acetate copolymer is 18 or less, preferably 15 or less, the carbon nanotubes are well dispersed. Further, if the mass ratio of vinyl acetate in the vinyl chloride-vinyl acetate copolymer is 1 or more, the glass transition temperature of the vinyl chloride-vinyl acetate copolymer is adjusted to an appropriate temperature. Since a high-temperature environment is not required when coating, transferring, or compositing, there is no problem that workability is good and the resin molded body is easily deformed.

  The lower limit of the content of the vinyl chloride-vinyl acetate copolymer contained in the conductive paint forming the antistatic layer of the molded body is 0.05% by mass or more, preferably with respect to the total mass of the antistatic layer. Is 0.20 mass% or more, more preferably 0.30 mass% or more, and the upper limit is 2.0 mass% or less, preferably 1.5 mass%, more preferably 1.2 mass%. If the content of the vinyl chloride-vinyl acetate copolymer is 0.05% by mass or more, the amount of the binder resin in the paint is sufficient, and thus the strength of the transparent antistatic layer after the paint is dried is sufficient. It also has good adhesion to the molded body. On the other hand, if the content of the vinyl chloride-vinyl acetate copolymer is 2.0% by mass or less, the amount of the binder resin in the coating is appropriate, and thus conductivity is exhibited.

  The lower limit of the content of the vinyl chloride-vinyl acetate copolymer in the antistatic layer of the molded article is 81% by mass or more, preferably 85% by mass or more, more preferably mass, with respect to the total mass of the antistatic layer. The upper limit is 98% by mass or less, preferably 97% by mass, and more preferably 96% by mass. When the content of the vinyl chloride-vinyl acetate copolymer is 81% by mass or more, the problem that the resin base material and the antistatic layer peel off does not occur.

  The lower limit of the glass transition temperature of the vinyl chloride-vinyl acetate copolymer of the antistatic layer of the molded product is 50 ° C or higher, preferably 55 ° C or higher, more preferably 60 ° C or higher, and the upper limit is 85 ° C. Hereinafter, it is preferably 83 ° C or lower, more preferably 80 ° C or lower. If the glass transition temperature of the vinyl chloride-vinyl acetate copolymer is 50 ° C. or higher, there is no problem of peeling between the base material of the molded body and the antistatic layer even if wiping and washing are performed. Layers can be formed. If the glass transition temperature of the vinyl chloride-vinyl acetate copolymer is 85 ° C. or lower, the antistatic layer can be formed without causing the problem of warping of the molded article substrate.

  Moreover, you may copolymerize the other component which contains a functional group in a side chain to the vinyl chloride-vinyl acetate copolymer used by this molded object as needed. Examples of the functional group include a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, and an amide group.

(transparency)
The molded body is excellent in transparency. The total light transmittance measured in accordance with JISK7105 after the wiping resistance test conducted in accordance with JISL0849 described below is 58% or more, preferably 60% or more, and more preferably 62% or more. Further, the haze value measured according to JISK7105 after the wiping resistance test conducted according to JISL0849 described below is 5% or less, preferably 4% or less, more preferably 3.5% or less. When the total light transmittance is 58% or more and the haze value is 5% or less, when this molded body is used for a clean room partition or a viewing window of a test apparatus, the transparency is good and the visibility is excellent.

  The molded product of the present invention does not deteriorate in transparency even after the wiping resistance test. That is, after the anti-wiping property test shown below, the reduction in the total light transmittance of the molded product is 1.0% or less, preferably 0.5% or less, and more preferably 0.3% or less. That means. If the reduction value of the total light transmittance is 1.0% or less after the wiping resistance test, it is possible to perform wiping cleaning when this molded body is used for a partition or the like, and the visibility of the partition facing surface There is no loss.

  Furthermore, after the wiping resistance test, the increase in haze value of the molded body is 1.0% or less, preferably 0.5% or less, and more preferably 0.3% or less. If the increase value of the total light transmittance is 1.0% or less after the wiping resistance test, it is possible to perform wiping cleaning when the molded body is used for a partition or the like, and the visibility of the partition facing surface There is no loss.

(Antistatic)
The surface resistivity of the molded body measured according to JISK6911 after the wiping resistance test is 10 ¹⁰ Ω / □ or less, preferably 10 ⁹ Ω / □ or less. If the surface resistivity is 10 ¹⁰ Ω / □ or less, an appropriate antistatic property is exhibited, and dust hardly adheres to the antistatic resin plate.

The molded body has a surface resistivity increasing value of 10 ⁴ Ω / □ or less, preferably 10 ³ Ω / □ or less after the wiping resistance test. After the wiping resistance test, if the value of increase in the surface resistivity of the molded product is 10 ⁴ Ω / □ or less, it is possible to perform wiping cleaning when the molded product is used for a partition or the like. .

(solvent)
The lower limit of the mass ratio of the content of the solvent contained in the conductive coating is 97.0% by mass, preferably 98.0% by mass, more preferably, when the mass of the conductive coating is 100%. The upper limit is 99.9% by mass or less, preferably 99.8% by mass or less, and more preferably 99.7% by mass or less. When the content of the solvent is 97.0% by mass or more, since the amount of the solvent is appropriate, the antistatic layer from which the solvent has evaporated after drying the paint does not become thick and the transparency is good. On the other hand, if the content of the solvent is 99.9% by mass or less, the antistatic layer from which the solvent has evaporated after drying the paint does not become thin, and the antistatic layer has good strength and chemical resistance.

  The type of solvent is not particularly limited as long as it is a solvent that dissolves vinyl chloride-vinyl acetate copolymer, but aromatic solvents such as toluene, xylene, trimethylbenzene, tetrahydrofuran, 1,4 dioxane, methyl cellosolve, cellosolve, Ether solvents such as butyl cellosolve, methyl tachery butyl ether, cyclopentyl methyl ether, ketone solvents such as acetone, methyl-ethyl ketone, methyl-isobutyl ketone, diisobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, And ester solvents such as ethylene glycol monoethyl ether acetate. Two or more kinds of the above-mentioned solvents may be mixed and used.

  Among these solvents, it is preferable to use tetrahydrofuran or cyclohexanone, since the solubility of the vinyl chloride-vinyl acetate copolymer is good, the dispersibility of the carbon fiber is good, and it is difficult to remain as a residual solvent. In particular, a solvent comprising a combination of two kinds of tetrahydrofuran having a relatively low boiling point and cyclohexanone having a relatively high boiling point is preferable because the thickness of the antistatic layer after drying the paint is small.

A method for attaching the conductive paint of the present invention to the resin molded body as an antistatic layer to obtain the molded body is not particularly limited, and examples thereof include the following methods.
1. Apply a conductive paint on the transfer film in advance, and after drying, form an antistatic layer on the transfer film. Then, the antistatic layer surface of the transfer film and the resin molded product face each other and are bonded together by heat fusion or the like. A manufacturing method (transfer method) in which an antistatic layer is adhered to a resin molded body and then a transfer film is peeled off.
2. A manufacturing method (coating method) in which a conductive paint is applied directly to a substrate.
3. A conductive paint is applied on a base film (referred to as a “composite film”) that can be bonded to the resin molded body in advance, and after drying, the surface of the composite film without the antistatic layer is thermally bonded to the resin molded body. Manufacturing method (composite method) that uses and primer.

  The conductive paint of the present invention can be applied to a resin molded body, a peelable substrate film, and a substrate film that can be bonded to the resin molded body by spray coating, dip coating, spin coating, knife coating, kissing. It can be applied by other known methods such as coating, gravure coating, die coating, dipping coating, screen printing, ink jet printing, pad printing, other types of printing, or roll coating. Among these, gravure coating, spin coating, and die coating that can perform thin film coating with high accuracy are preferable.

  Various known films can be used as the transfer film. For example, polyester resin, polycarbonate resin, triacetyl cellulose, cellophane, polyamide resin, aromatic polyamide resin, polyimide resin, polyetherimide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polypropylene resin, polyethylene resin, polystyrene resin The surface of these films may be subjected to mold release treatment with silicone, alkyd resin, polyurethane resin, fluorine resin, or the like, if necessary. Of these, a polypropylene film and a polyester film which have been release-treated with an alkyd resin are preferable from the viewpoint of ease of peeling.

  Various known films can be used as the composite film. For example, polyester resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, copolymer resin containing vinyl chloride, triacetyl cellulose, cellophane, polyamide resin, aromatic polyamide resin, polyimide resin, polyetherimide resin, polyphenylene sulfide Examples of such films include resins, polysulfone resins, polyethersulfone resins, polypropylene resins, and polystyrene resins. Among them, polyester resins, polycarbonate resins, acrylic resins, polyvinyl chloride resins, and copolymer resins containing vinyl chloride have moderate rigidity and are easy to handle.

  Furthermore, if the adhesion between the antistatic layer and the resin molded body or the composite film and the resin molded body is not good at the time of transfer, polyacrylic adhesive resin, polyurethane adhesive resin or epoxy adhesive resin, UV curing An adhesive layer such as a resin may be used as appropriate.

Hereinafter, although an example is described, the present invention is not limited to this.
(Evaluation methods)
1. Surface resistivity measurement The surface resistivity of the molded body was measured as follows according to JIS K6911.
(1) Measuring device Hirestar UP MCP-HT450 (Mitsubishi Chemical Corporation)
(2) Measurement method Constant voltage application method (3) Applied voltage 1000V

2. Total Light Transmittance / Haze Value Measurement The total light transmittance / haze value of the molded article was measured as follows according to JIS K7105.
(1) Reflectance and transmittance meter ■ Murakami Color Research Laboratory HR-100

3. Evaluation of wiping resistance The wiping resistance of the molded product was evaluated by the following method.
In accordance with JIS L 0849, 1 cc of isopropyl alcohol (100%) is infiltrated into the nell cloth, and the wiping resistance is evaluated under the following conditions.
(1) Nell cloth: Cotton flannel (100%)
(2) Test load: 250g
(3) Abrasion resistance tester (fastness to friction) RT-200 (manufactured by Daiei Scientific Instruments)
(4) Number of wiping: 500 times (5) After carrying out the wiping test under the above conditions, the transparency, haze, and surface resistance value of the antistatic resin molded body are measured.

4). Evaluation of carbon fiber dispersibility The dispersibility of carbon fibers in the conductive coating used in the molded article was evaluated by the following method.
The carbon fibers in the respective conductive paints used in the production of the molded bodies of Examples and Comparative Examples are dispersed by the bead collision method. Immediately after the dispersion, the paint is placed in a transparent glass container, It was placed and observed for the presence of precipitates, and the dispersibility was evaluated.

Example 1
(Preparation of conductive paint and transfer film)
In THF (tetrahydrofuran) solvent, vinyl chloride-vinyl acetate copolymer (C-150S vinyl acetate content 11% by mass, Shin-Daiichi PVC Co., Ltd.) and carbon fiber (CNT diameter, fiber diameter 10-40 nm, aspect ratio as binder resin The coating composition was prepared so that the solid content concentration was 1.5% by mass of the vinyl chloride-vinyl acetate copolymer and 0.1% by mass of the carbon fiber. 50 cc of glass beads (0.8 mm in diameter) is added to 50 cc of the prepared paint, and PAINT SHAKER (manufactured by Toyo Seiki Seisakusho) is used. Was made. The obtained conductive coating material 1 had good carbon fiber dispersibility.

  The conductive paint 1 is applied to a releasable polyester film (TP-02, manufactured by Panac, release layer alkyd resin, thickness 50 μm, total light transmittance 90.0%, haze 6.5%) and thickness 0 The film was applied using a bar coater to a thickness of 0.1 μm and dried at 100 ° C. for 1 minute to obtain a transfer film provided with an antistatic layer.

(Creation of antistatic resin molding)
The transfer film was made of a vinyl chloride resin substrate having a thickness of 5.0 mm, a total light transmittance of 84.0%, a haze value of 1.8%, and a surface resistivity of 2.2 × 10 ¹⁵ Ω / □ (manufactured by Mitsubishi Plastics, Ltd. Plate) and passed between two rubber rolls at a temperature of 150 ° C. at a pressure of 0.2 MPa and a speed of 0.25 m / min, and then peeled off at the interface between the antistatic layer and the transfer film. The antistatic resin molding of Example 1 was produced. Table 1 shows the evaluation of haze value, total light transmittance, surface resistivity, and wiping resistance of Example 1.

(Example 2)
The conductive paint 1 was coated with a vinyl chloride resin substrate (made by Mitsubishi Plastics Co., Ltd.) having a thickness of 5.0 mm, a total light transmittance of 84.0%, a haze value of 1.8%, and a surface resistivity of 2.2 × 10 ¹⁵ Ω / □. In this example, the coating is applied to one side of the plate with a bar coater so that the thickness is 0.1 μm, dried at 100 ° C. for 1 minute, and further coated and dried in the same manner on the other side. 2 antistatic resin moldings were produced. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Example 2 produced.

(Example 3)
The conductive paint 1 was coated with a vinyl chloride resin sheet (thickness 0.1 mm, total light transmittance 90.0%, haze value 0.9%, surface resistivity 2.2 × 10 ¹⁵ Ω / □, manufactured by Mitsubishi Plastics, Inc. , Vinyl foil C-7902) was applied using a bar coater to a thickness of 0.1 μm to prepare a composite. In addition, as for the drying conditions of a coating composition, temperature is 100 degreeC and time is 1 minute.
The composite was made into a vinyl chloride resin substrate (manufactured by Mitsubishi Plastics, Ltd., having a thickness of 5.0 mm, a total light transmittance of 84.0%, a haze value of 1.8%, and a surface resistivity of 2.2 × 10 ¹⁵ Ω / □ The sheet is placed on both sides of the plate) so that the vinyl chloride sheet faces the vinyl chloride resin substrate, and is hot-pressed at a temperature of 100 ° C., a time of 10 minutes, and a pressure of 1.96 MPa. Produced. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Example 3 produced.

Example 4
A conductive paint 2 is produced in the same manner as in Example 1 except that the binder resin is changed to a vinyl chloride-vinyl acetate copolymer (C-150ML, vinyl acetate content 15 mass%, manufactured by Shin Daiichi Vinyl Co., Ltd.). did. The obtained conductive paint had good carbon fiber dispersibility. Moreover, the transfer film was obtained by the method similar to Example 1, and the antistatic resin molding of Example 4 was obtained. Table 1 shows the evaluation of haze value, total light transmittance, surface resistivity, and wiping resistance of Example 4.

(Example 5)
An antistatic resin molded body of Example 5 was prepared from the conductive paint 2 in the same manner as in Example 2. Table 1 shows the evaluation of the haze value, the total light transmittance, the surface resistivity, and the wiping resistance of the antistatic resin molded article of Example 5 produced.

(Example 6)
An antistatic resin molded body of Example 6 was prepared from the conductive paint 2 in the same manner as in Example 3. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Example 6 produced.

(Example 7)
A conductive paint 3 was produced in the same manner as in Example 1 except that the binder resin was changed to a vinyl chloride-vinyl acetate copolymer (C8J vinyl acetate content 5 mass%, manufactured by Shin Daiichi Vinyl Co., Ltd.). The obtained conductive coating material 3 had good dispersibility of carbon fibers.

(Example 8)
An antistatic resin molded body of Example 8 was prepared from the conductive paint 3 in the same manner as in Example 2. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Example 8 produced.

Example 9
An antistatic resin molded body of Example 9 was prepared from the conductive paint 3 in the same manner as in Example 3. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Example 9 produced.

(Comparative Example 1)
A conductive paint 4 was produced in the same manner as in Example 1 except that the binder resin was changed to a vinyl chloride-vinyl acetate copolymer (vinyl acetate content 20 mass%). The obtained conductive paint 2 was found to have carbon fiber deposits and was not dispersible. Moreover, the transfer film was obtained by the method similar to Example 1, and the antistatic resin molding of the comparative example 1 was obtained. Table 1 shows the evaluation of haze value, total light transmittance, surface resistivity, and wiping resistance of Comparative Example 1.

(Comparative Example 2)
An antistatic resin molded body of Comparative Example 2 was prepared from the conductive paint 4 in the same manner as in Example 2. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Comparative Example 2 produced.

(Comparative Example 3)
An antistatic resin molded body of Comparative Example 3 was prepared from the conductive paint 4 in the same manner as in Example 3. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Comparative Example 3 produced.

(Comparative Example 4)
A conductive paint 5 was produced in the same manner as in Example 1 except that the binder resin was changed to vinyl chloride (S-1008 manufactured by Kaneka Corporation). The obtained conductive paint 5 had good dispersibility of carbon fibers.
(Comparative Example 5)
An antistatic resin molded body of Comparative Example 5 was prepared using the conductive paint 5 in the same manner as in Example 2. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Comparative Example 5 produced.

(Comparative Example 6)
An antistatic resin molded body of Comparative Example 6 was prepared using the conductive paint 5 in the same manner as in Example 3. Table 1 shows the evaluation of the haze value, total light transmittance, surface resistivity, and wiping resistance of the antistatic resin molded article of Comparative Example 6 produced.

  From Table 1, since the antistatic resin laminated body of Examples 1-9 uses the vinyl chloride-vinyl acetate copolymer comprised by the mass ratio of vinyl chloride and vinyl acetate of the predetermined range for binder resin. In addition, even after 500 wiping-proof experiments, good evaluation results were obtained with little decrease in haze value, total light transmittance, and surface transmittance. Further, the CNT dispersibility of the conductive paints prepared in Examples 1 to 3 and Examples 7 to 9 was good because the mass ratio of vinyl chloride in the vinyl chloride-vinyl acetate copolymer was appropriate. . Since the dispersibility of CNTs of the conductive paints produced in Examples 4 to 6 was good within 24 hours, there was no problem in producing the molded article. On the other hand, the antistatic resin laminates of Comparative Examples 1 to 3 were subjected to 500 wiping resistance tests because the binder resin had a large proportion of vinyl acetate in the vinyl chloride-vinyl acetate copolymer. Later, deterioration in haze value, total light transmittance, and surface transmittance was observed. Moreover, since the antistatic resin laminated body of Comparative Examples 4-6 uses the vinyl chloride resin for binder resin, after performing a wiping-off test 500 times, haze value, total light transmittance, surface The resistivity was deteriorated.

  As described above, the electroconductive paint of the present invention and the antistatic molded body obtained by coating, transferring, and combining the electroconductive paint of the present invention on the resin molded body are conductive paints having excellent transparency and antistatic properties. In addition, it is an antistatic molded body, and can be suitably used particularly for applications that dislike dust, such as clean room partitions, carrier boxes used in semiconductor / liquid crystal manufacturing, outer plates of manufacturing apparatuses, and viewing windows of manufacturing apparatuses.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and the antistatic resin molded body and the method of manufacturing the molded body with such changes are also described in the present invention. It should be understood as being included in the technical scope of the invention.

Claims (6)

  An antistatic resin molded article having at least one antistatic layer on a substrate, wherein the main components of the antistatic layer are composed of a vinyl chloride-vinyl acetate copolymer and carbon fiber, An antistatic resin molded product, wherein a mass ratio of vinyl chloride and vinyl acetate constituting the vinyl chloride-vinyl acetate copolymer is in a range of 82/18 to 99/1. The antistatic layer is composed of 81 to 98% by mass of vinyl chloride-vinyl acetate copolymer and 2 to 19% by mass of carbon fiber with respect to the total mass of the antistatic layer. The antistatic resin molded product according to claim 1.   The antistatic resin molded article according to claim 1 or 2, wherein the carbon fiber has an average fiber diameter of 0.7 to 80 nm and an aspect ratio of 100 or more.   The method for producing an antistatic resin molded body according to any one of claims 1 to 3, wherein the antistatic layer is formed by a transfer method.   The method for producing an antistatic resin molded body according to any one of claims 1 to 3, wherein the antistatic layer is formed by a coating method.   The method for producing an antistatic resin molded body according to any one of claims 1 to 3, wherein the antistatic layer is formed by compounding.