JP2007130950A - Antistatic molded resin body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic molded resin body excellent in resistance to wiping with alcohols and capable of approximately retaining initial surface resistivity, optical properties and electric properties if it is wiped with alcohols. <P>SOLUTION: The antistatic molded resin body A1 is constituted by laminating an antistatic layer 3 containing an extrafine conductive fiber 31 on the one side of a synthetic resin main body 1 and further a resin layer 4 on the outer surface of the antistatic layer 3. It is preferable to involve a small amount of a conductive material such as the extrafine conductive fiber 31 in the resin layer 4. Since resistance to wiping with a wiping cloth containing isopropyl alcohol and the like is improved with the resin layer 4, and the extrafine conductive fiber 31 is not wiped off to fall away, the molded body can be excellent in surface resistivity, saturated charge and half-life period. The conductive material contained in the resin layer 4 enables an voltage decay to be instant. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic resin molded article having excellent friction fastness characteristics on the surface of the antistatic resin molded article and excellent charge attenuation characteristics.

  Conventionally, antistatic resin plates that release static electricity and prevent dust adhesion have been used for clean room partitions, carrier boxes used in semiconductor / liquid crystal manufacturing, and outer panels of manufacturing equipment. Yes. Also, in order to ensure the cleanliness of the clean room above a certain level, it is indispensable to remove the adhering dust etc. after construction of the clean room or during regular maintenance in the clean room. The antistatic resin plate is wiped and cleaned with a wiping cloth containing alcohol or the like.

As such an antistatic resin plate, the present applicant has proposed a thermoformable antistatic resin molded article comprising a thermoplastic resin base material and an antistatic resin layer containing conductive long fibers (Patent Document 1). ). Furthermore, an antistatic transparent resin plate was proposed in which an antistatic layer was formed in which carbon nanotubes were separated from each other on a substrate made of a transparent thermoplastic resin and in contact with each other (Patent Document 2).
JP-A-10-226007 JP 2004-2306901 A

In the antistatic resin molded article described in Patent Document 1, since the conductive long fibers contained in the antistatic resin layer are twisted and dispersed in contact with each other, the molded article is subjected to secondary processing. However, it has the advantage that the long fibers that are tortuous are stretched and contact with each other is not cut off, so that secondary processing can be performed. Moreover, since the antistatic transparent resin plate described in Patent Document 2 is separated from each other by the carbon nanotubes contained in the antistatic layer, the dispersibility is good, and even if there are few carbon nanotubes, The contact was maintained and the transparency could be improved.
However, in the antistatic synthetic resin plates described in Patent Documents 1 and 2, since the antistatic layer containing long fibers or carbon nanotubes is on the outermost surface, the surface is inferior in friction fastness characteristics, and isopropyl alcohol When used in applications where the surface of the antistatic layer is wiped and cleaned with alcohols such as (IPA), the long-term fibers or carbon nanotubes fall off and the surface resistivity decreases, and the antistatic performance is satisfactory over a long period of time. The problem of being unable to maintain was inherent.

  The present invention has been made to address the above problems, and has excellent friction fastness characteristics. Even if the surface of the antistatic resin plate is wiped and washed repeatedly with a wiping cloth containing alcohols, etc., the surface resistivity is improved. An object of the present invention is to provide an antistatic resin molded product that can suppress an increase in the resistance and can maintain a practically sufficient antistatic performance.

  In order to solve the above problems, the antistatic resin molded body of the present invention is a resin molded body in which an antistatic layer is laminated on at least one surface of a resin main body, and the antistatic layer includes ultrafine conductive fibers. In addition, a resin layer is laminated on the outer surface of the antistatic layer.

  In this antistatic resin molding, it is preferable that the resin layer contains a conductive material, and in particular, the resin layer contains a conductive material of ultrafine conductive fiber, and the content thereof is that of the antistatic layer. However, it is preferably 0.005 to 5% by mass. Moreover, it is also preferable that the antistatic layer is laminated | stacked on the resin main body through the contact bonding layer.

  Another antistatic resin molded body of the present invention is a resin molded body in which an antistatic layer is laminated on at least one surface of a resin main body, the antistatic layer including ultrafine conductive fibers, and the outer surface side of the antistatic layer. The content of the ultrafine conductive fiber is smaller than that of the inner side of the antistatic layer.

  In this antistatic resin molded product, the content of the ultrafine conductive fibers on the outer surface side of the antistatic layer is preferably 0 to 5% by mass.

  The ultrafine conductive fibers used in the antistatic resin moldings of these inventions are preferably carbon nanotubes.

  Like the antistatic resin molding of the present invention, when the antistatic layer laminated on the resin main body contains ultrafine conductive fibers and the resin layer is laminated on the outer surface of the antistatic layer, The resin layer improves friction fastness characteristics. Even if the surface of the antistatic resin molding is repeatedly wiped and washed with a wiping cloth containing alcohol, etc., the surface resistivity does not increase and the antistatic property is maintained over a long period of time. The performance can be maintained.

  When the resin layer of this antistatic resin molded body contains a conductive material such as ultrafine conductive fibers, in addition to improving the fastness to friction by the resin layer, a conductive path is also formed in the resin layer, Since static electricity charged on the surface flows to the antistatic layer through the conductive path and is discharged at the end, charging attenuation is instantaneously performed. The content of the ultrafine conductive fiber, which is a conductive material contained in the resin layer, is less than that of the antistatic layer, so that the fastness of the antistatic resin molded body surface is maintained, and the ultrafine conductive fiber is Since it is thin and long, the conductive path is surely formed in the resin layer, and charging attenuation is instantaneously performed. In particular, when the content of the ultrafine conductive fiber contained in the resin layer is 0.005 to 5% by mass, the conductive path can be more reliably formed, and the charge decay can be instantaneously performed. Can be sufficiently practical. And when the antistatic layer is laminated | stacked on the resin main body through the contact bonding layer, an antistatic layer does not adhere | attach and laminate | stack on a resin main body, but it can exhibit antistatic performance over a long period of time.

  Further, in another antistatic resin molded body of the present invention, the antistatic layer laminated on the resin main body includes ultrafine conductive fibers, and the content is uniform when the outer surface side is less than the inner side of the antistatic layer. Compared with the antistatic layer containing ultrafine conductive fibers dispersed in the resin, the resin content on the outer surface side increases and the coating strength increases, so that the surface fastness to friction is improved. Therefore, even if the surface is wiped and washed with a wiping cloth containing alcohols, it is suppressed that the surface resistivity becomes high. Furthermore, since the outer surface side of the antistatic layer contains ultrafine conductive fibers, a conduction path leading to the outer surface side and the inner side is ensured, and the antistatic performance is fully exhibited and at the same time charged. Attenuation is also instantaneous. When the content of the ultrafine conductive fiber on the outer surface side is 0 to 5% by mass, the above-mentioned friction fastness characteristics, antistatic performance and charging attenuation characteristics are satisfactorily exhibited, and these functions are provided over a long period of time. It becomes possible to set it as the antistatic resin molding.

  If the ultrafine conductive fibers used in these antistatic resin moldings are carbon nanotubes, the carbon nanotubes are very thin and long, so that contact between the carbon nanotubes can be secured even if the content is further reduced. Can exhibit sufficient antistatic properties. Therefore, since the antistatic layer can be made transparent and the resin layer containing carbon nanotubes can be made transparent, a transparent antistatic resin molded product can be obtained.

  Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to these.

  FIG. 1 is a partially enlarged cross-sectional view of an antistatic resin molded body according to an embodiment of the present invention.

  This embodiment shows a transparent plate-like antistatic resin molding A1, a transparent plate-like resin body 1, an adhesive layer 2 laminated on the surface of one side thereof, an antistatic layer 3, And the resin layer 4. Note that the adhesive layer 2, the antistatic layer 3, and the resin layer 4 may be laminated on both surfaces of the resin body 1.

The resin body 1 is formed by forming a transparent thermoplastic resin or a transparent curable resin that is cured by heat, ultraviolet rays, electron beams, radiation, or the like into a plate shape. Examples of the thermoplastic resin include polyethylene and polypropylene. Olefin resins such as cyclic polyolefin, vinyl resins such as polyvinyl chloride, polymethyl methacrylate, polystyrene, cellulose resins such as nitrocellulose and triacetyl cellulose, polycarbonate, polyethylene terephthalate, polydimethylcyclohexane terephthalate, aromatic polyester, etc. Ester resins, ABS resins, copolymer resins of these resins, mixed resins of these resins, etc. are used, and as curable resins, for example, thermosetting such as epoxy resins, polyimide resins, acrylic resins, etc. Resin and UV curable Such as fat is used. Among these resins, polyvinyl chloride has good chemical resistance and good secondary workability, and uses chemicals such as cleaning liquids, which require various parts, semiconductor manufacturing parts, liquid crystal manufacturing parts, chemical manufacturing It is preferably used as a resin that is processed into a plate-like or irregular shape such as a member.
In the resin main body 1, a plasticizer, a stabilizer, an antioxidant, and the like are appropriately blended with the resin, so that moldability, thermal stability, weather resistance, and the like are enhanced. Although the thickness of this resin main body 1 is suitably changed according to a use, it is normally used by the thickness of about 0.03-10 mm.

  In this embodiment, the resin main body 1 is formed into a transparent plate-like body, but it may be formed into other irregular shapes, or the plate-like body is secondarily molded into an irregular shape such as a container. May be. Moreover, you may mix | blend a filler and a coloring agent and you may make it opaque.

  The adhesive layer 2 is made of a thermoplastic resin having an adhesive function, and a thermoplastic resin that is the same type or compatible with the resin main body 1 described above is preferably used. As a typical adhesive resin, an acrylic resin having excellent adhesiveness and transparency to many resins is used, and if a vinyl chloride resin is used for the resin body 1, other than the acrylic resin Vinyl chloride resins such as vinyl chloride resins and vinyl chloride-vinyl acetate copolymer resins are preferably used. Note that the adhesive layer 2 is not necessarily used, and may be omitted when the antistatic layer 3 is satisfactorily laminated with the resin body 1.

  The thickness of the adhesive layer 2 may be about 0.5 to 300 μm, and if it is thinner than 0.5 μm, the adhesive performance is inferior, and even if it is thicker than 300 μm, the adhesive performance is not improved. When the adhesive layer 2 having such a thickness is formed using an adhesive layer film obtained by forming the adhesive layer 2 into a film, a coating solution obtained by dissolving an adhesive resin in a solution is directly applied to a thickness of about 50 to 300 μm. When formed by coating, the thickness is about 30 to 200 μm. When the adhesive resin is applied to a release film to form a transfer film, the thickness is set to 0.5 to 100 μm, more preferably 0.5 to 30 μm. desirable.

The antistatic layer 3 is a transparent layer composed of the ultrafine conductive fibers 31 and the binder resin 32, and the ultrafine conductive fibers 31 are uniformly dispersed therein. The content of the ultrafine conductive fiber 31 is 2 to 90 mass because it is necessary to give the antistatic resin molded body A1 a surface resistivity of 10 ⁵ to 10 ¹¹ Ω / □ and to exhibit practically sufficient antistatic performance. %, And more preferably 8 to 50% by mass. If it is less than 2% by mass, it will be difficult to impart antistatic performance to the molded product A1, while if it exceeds 90% by mass, no further improvement in antistatic performance will be seen, so material waste. It becomes use. In particular, since the antistatic resin molding A1 has the resin layer 4 laminated on the outer surface of the antistatic layer 3, not the surface resistivity of the antistatic layer 3, but the surface resistance of the antistatic resin molding A1. It is necessary to contain it in consideration of the rate. However, since the surface resistivity is measured by applying a voltage, the surface resistivity of the antistatic layer 3 itself may be 10 ⁵ to 10 ¹¹ Ω / □.

  The thickness of the antistatic layer 3 is preferably 50 to 500 nm. If the thickness is less than 50 nm, the chance of contact between the ultrafine conductive fibers 31 is reduced and the antistatic performance cannot be exhibited. On the other hand, if it is thicker than 500 μm, it is not preferable because the transparency is lowered, and the surface resistivity is too low.

The ultrafine conductive fiber 31 may be contained in the antistatic layer 3 in an amount capable of developing antistatic properties, but in order to obtain a transparent antistatic resin molded body A1, the antistatic layer 3 is also transparent. There is a need. For that purpose, it is preferable to contain the ultrafine conductive fiber 31 as little as possible. In order to provide the surface resistivity with this small content, the ultrafine conductive fibers 31 are separated one by one or a plurality of the fine conductive fibers 31 are gathered. In a state where the bundles are separated one by one, it is preferable to disperse them without agglomeration and bring them into contact with each other. That is, the fine conductive fibers 31 are slightly bent but separated one by one or one bundle, and the binder resin 32 of the antistatic layer 3 is simply crossed without being intricately entangled with each other, that is, without agglomerating. It is preferable to disperse in the interior of the glass and contact at each intersection.
Here, the term “contact” is used as a term meaning both the case where the fine conductive fibers are actually in contact and the case where the fine conductive fibers are close to each other with a small gap that allows conduction. Yes.

  When dispersed in this way, compared to the case where they are agglomerated, the ultrafine conductive fibers 31 are present in a wide range and the chances of contact between the ultrafine conductive fibers 31 are significantly increased. Even if the content is reduced, the antistatic layer 3 exhibits a low resistivity, and can provide satisfactory antistatic properties to the resin molded body A1. Accordingly, the transparency is improved by the amount of the ultrafine conductive fiber 31 and the antistatic layer 3 can be made thinner, so that the transparency can be further improved. Further, when the antistatic resin molded body A1 is bent, the bent portion of the ultrafine conductive fiber 31 extends, the contact point that is in cross contact, or the contact point is shifted when the antistatic resin molding A1 is bent. Is once again in contact with other ultrafine conductive fibers even if the contact state is removed, the contact between the ultrafine conductive fibers 31 is not reduced, and the surface resistivity is not increased.

  Such dispersion does not require the fine conductive fibers 31 to be separated and dispersed completely one by one or one bundle, and there may be small agglomerates that are intertwined in part. The average diameter is preferably 0.5 μm or less.

  As the ultrafine conductive fiber 31, ultrafine carbon fibers such as carbon nanotubes, carbon nanohorns, carbon nanowires, carbon nanofibers, and graphite fibrils, or metal nanotubes such as platinum, gold, silver, nickel, and silicon, and ultrafine lengths such as nanowires. Metal fibers, metal oxide nanotubes such as zinc oxide, and ultrafine metal oxide fibers such as nanowires have a diameter of 0.3 to 100 nm and a length of 0.1 to 20 μm, preferably a length of 0.1. Ultrafine conductive fibers having a size of 1 to 10 μm are preferably used.

  Among these ultrafine conductive fibers 31, carbon nanotubes are most preferably used. This carbon nanotube has a multi-walled carbon nanotube concentrically provided with a plurality of cylindrically closed carbon walls having different diameters around the central axis, and a single cylindrically closed carbon wall around the central axis. There are single-walled carbon nanotubes, both of which are preferably used. Most of the multi-walled carbon nanotubes are dispersed in a state of being separated one by one, but the two- to three-walled carbon nanotubes may be dispersed in a bundle. On the other hand, single-walled carbon nanotubes do not disperse alone, but exist in a bundle of two or more, and the bundles are dispersed in a state of being separated one by one.

  As the binder resin 32 forming the antistatic layer 3, a resin that is the same type or compatible with the adhesive layer 2 is used. Therefore, if the adhesive layer 2 is an acrylic resin, an acrylic resin that can be bonded to the adhesive layer, or a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin (particularly, the proportion of vinyl acetate is 20% by mass or less). Resin) such as a vinyl chloride resin, and a mixed resin of vinyl chloride resin and vinyl acetate resin (particularly, those having a vinyl acetate resin ratio of 20% by mass or less) are preferably used. When these binder resins 32 are used, the bonding strength and adhesion of the antistatic layer 3 to the adhesive layer 2 are improved, and peeling of the antistatic layer 3 can be prevented. Among the binder resins 32 described above, since the vinyl resin is preferably used for the resin body 1 as described above, a vinyl chloride resin which is a resin similar to this is preferably used.

  In order to improve the dispersibility of the ultrafine conductive fibers 31 in the antistatic layer 3, it is desirable to add a dispersant. As such a dispersant, a polymer dispersant such as an alkyl ammonium salt solution of an acidic polymer, a tertiary amine-modified acrylic copolymer, a polyoxyethylene-polyoxypropylene copolymer, a coupling agent, or the like is used. The antistatic layer 3 may be appropriately added with additives such as an ultraviolet absorber, a surface modifier, and a stabilizer to improve weather resistance and other physical properties.

  The resin layer 4 is a layer formed of a synthetic resin on the outer surface of the antistatic layer 3. As this resin, any synthetic resin may be used. However, in order to improve the surface fastness property of the resin molded body A1 and improve the wiping detergency with a wiping cloth containing alcohol on the surface. Resin such as vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride resin such as mixed resin of vinyl chloride resin and vinyl acetate resin, or polyethylene terephthalate, polydimethylcyclohexane terephthalate, aromatic polyester Such ester resins and urethane resins are preferably used. In particular, since the vinyl chloride resin is excellent in chemical resistance, the surface of the resin layer 4 formed with this resin (the surface of the molded body A1) is wiped and cleaned with a wiping cloth containing alcohols such as isopropyl alcohol. Even if the resin layer 4 is exposed to chemicals or exposed to a chemical atmosphere, the vinyl chloride resin layer 4 blocks alcohols and chemicals. It will not reach. In addition, if the resin is a synthetic resin such as a urethane resin, a polyester resin, a copolymer resin thereof, or a mixed resin of these resins, static electricity charged on the surface can be generated without including a conductive material in the resin layer 4. This is preferable because charging can be attenuated in a short time.

  The resin layer 4 has a thickness of 50 to 1000 nm, preferably 100 to 600 nm. If the thickness is less than 50 nm, when the surface is wiped with alcohol, the resin layer 4 is melted, and the ultrafine conductive fibers 31 contained in the antistatic layer 3 are wiped off and fall off, which may increase the surface resistivity. On the other hand, when it becomes thicker than 1000 nm, the low resistance of the antistatic layer 3 is cut off by the resin layer 4 and the antistatic property may not be exhibited.

Although the surface of the antistatic layer 3 is covered with the resin layer 4, the surface resistivity of the molded body A1 is substantially the same as that of the antistatic layer 3. Although the reason is not certain, it is considered that the surface resistivity is measured by applying a voltage so that the applied voltage reaches the internal antistatic layer 3 and the resistivity is measured. Therefore, it is desirable to reduce the thickness of the resin layer 4 within the above range. Furthermore, in order to perform static charge decay in a short time, a polyester resin, a urethane resin, a copolymer resin thereof, and a mixture thereof. A resin layer 4 made of resin or the like is desirable.
The resin that forms the resin layer 4 is appropriately mixed with plasticizers, stabilizers, ultraviolet absorbers, processing aids, and the like that are generally used for molding the resin, so that moldability and thermal stability are appropriately blended. The weather resistance is improved.

The antistatic resin molded body A1 having the above configuration is manufactured, for example, by the following method.
One manufacturing method is to apply an adhesive paint in which a resin having an adhesive function is dissolved in a solvent on the surface of the resin body 1 and dry it to form the adhesive layer 2, and then dissolve the binder resin 32 in the solvent to further reduce the fine conductivity. Applying antistatic coating in which the fibers 31 are uniformly dispersed and drying to form the antistatic layer 3, and finally applying and drying a resin coating in which a synthetic resin is dissolved in a solvent to form the resin layer 4. Thus, the antistatic resin molded body A1 in which the resin main body 1, the adhesive layer 2, the antistatic layer 3, and the resin layer 4 are laminated in this order can be manufactured.

  In another manufacturing method, first, the antistatic coating is applied to the surface of the adhesive layer film made of a synthetic resin having an adhesive function and dried to form the antistatic layer 3, and further, the resin coating is applied and dried. By forming the resin layer 4, an antistatic laminate film is produced. Next, the antistatic laminate film is laminated on the surface of the resin main body 1 by means of thermocompression bonding, extrusion lamination, or the like, whereby the resin main body 1, the adhesive layer 2 (adhesive layer film), the antistatic layer 3 and the resin are laminated. The antistatic resin molding A1 in which the layer 4 is laminated in this order can be manufactured.

  In still another production method, the resin coating is applied to the surface of a release film such as polyethylene terephthalate and dried to form the resin layer 4, and the antistatic coating is applied and dried to form the antistatic layer 3. Further, an antistatic transfer film formed by applying the adhesive paint and drying to form the adhesive layer 2 is prepared. Next, the adhesive layer 2 of the antistatic transfer film is overlapped and thermocompression bonded so as to be on the resin main body 1 side, and the adhesive layer 2, the antistatic layer 3 and the resin layer 4 are transferred, whereby the resin main body 1 The antistatic resin molded body A1 in which the adhesive layer 2, the antistatic layer 3, and the resin layer 4 are laminated in this order can be manufactured.

  The antistatic resin molding A1 manufactured in this way is obtained by laminating the adhesive layer 2, the antistatic layer 3 and the resin layer 4 on the surface of the resin body 1, and the antistatic layer 3 is bonded. The layer 2 does not adhere to the resin body 1 and peel off. Since the antistatic layer 3 is covered with the resin layer 4, the alcohol and chemicals such as isopropyl alcohol are not blocked by the resin layer 4 and do not penetrate into the antistatic layer 3. Can be maintained. Therefore, the alcohol-resistant wiping property of the antistatic resin molding A1 is improved, and even if the surface is repeatedly wiped and cleaned with a wiping cloth containing isopropyl alcohol or the like, it is possible to suppress an increase in surface resistivity. The initial practically sufficient antistatic performance can be maintained.

  Further, since the surface of the antistatic resin molded body A1 is covered with the resin layer 4, it is possible to exhibit the friction fastness of the resin itself, and the surface of the molded body A1 is repeatedly wiped with the wiping cloth or the like. Even after washing, the surface is not affected, the surface state can be maintained, and optical characteristics such as total light transmittance and haze can be maintained.

On the other hand, even if the antistatic layer 3 is covered with the resin layer 4, it contains the ultrafine conductive fibers 31 necessary to develop the antistatic performance of the molded body A1, so the surface resistivity of the molded body A1 is reduced. 10 ⁵ to 10 ¹¹ Ω / □, and adhesion of dust medium can be prevented. Moreover, in a state where the ultrafine conductive fibers 31 contained in the antistatic layer 4 are separated one by one or in a state where a plurality of bundles are bundled and separated one by one, they are dispersed without agglomeration. Therefore, even if the content of the ultrafine conductive fiber 31 is reduced, the antistatic resin molded product A1 can secure the contact between the ultrafine conductive fibers and exhibit sufficient antistatic properties. In addition, the transparency can be improved by the amount of the ultrafine conductive fiber 31 reduced, and the transparent antistatic resin molded body A1 can be obtained.

  FIG. 2 is a cross-sectional view showing a partially enlarged antistatic resin molded body according to another embodiment of the present invention.

This antistatic resin molding A2 includes a transparent plate-shaped resin body 1, an adhesive layer 2 laminated on the surface of one side thereof, an antistatic layer 3, and a resin layer 40 containing conductive material (conductive). Material-containing resin layer 40). Note that the adhesive layer 2, the antistatic layer 3, and the conductive material-containing resin layer 40 may be laminated on both surfaces of the resin body 1.
In the antistatic resin molded body A2, the resin main body 1, the adhesive layer 2, and the antistatic layer 3 are the resin main body 1, the adhesive layer 2, and the antistatic layer 3 of the antistatic resin molded body A1. Since they are the same, the same reference numerals are given and description thereof is omitted.

For the conductive material-containing resin layer 40, the same resin as that used for the resin layer 4 of the above embodiment is used, and this resin is tin oxide, antimony-doped tin oxide, conductive titanium oxide, conductive carbon, carbon nanotube. It is a layer formed by containing a conductive material such as the above-mentioned ultrafine conductive fiber. Among these, the conductive material of ultrafine conductive fibers such as tin oxide, antimony-doped tin oxide, and carbon nanotube can make the conductive material-containing resin layer 40 transparent, so that the transparent antistatic resin molded body A2 is formed. When obtaining, it is preferably used.
Of these conductive materials, antimony-doped tin oxide is contained in an amount of 20 to 70% by mass, and ultrafine conductive fibers such as carbon nanotubes are contained in an amount of 0.005 to 5.0% by mass, more preferably 0.01 to 2% by mass. It is desirable to make it.

Even if such a conductive material is included in the conductive material-containing resin layer 40 with the above content, the surface resistivity of the conductive material-containing resin layer 40 itself is 10 ¹⁶ Ω / □ or more, and has antistatic performance. There is nothing. However, the surface resistivity of the conductive material-containing resin layer surface (the surface of the resin molding A2) is 10 ⁵ to 10 ¹¹ Ω / □ due to the antistatic layer 3 inside the resin molding A2, and the resin molding A2 has the antistatic performance. As described above. In addition, since the conductive material contained in the conductive material-containing resin layer 40 forms a conductive path in the conductive material-containing resin layer 40 through the surface of the resin molded body A2 and the antistatic layer 3, the charged static electricity Can flow to the antistatic layer 3 through the conduction path, conduct to the end of the antistatic layer 3, and discharge at the end to extinguish static electricity, and charge decay is instantaneous (within 1 second). Can be done.

That is, the conductive material contained in the conductive material-containing resin layer 40 is added to form a conduction path inside the layer 40, and it is not necessary to exhibit the antistatic performance. Therefore, as described above, the surface resistivity may be as high as 10 ¹⁶ Ω / □ or higher, and the content can be made smaller than the amount contained in the antistatic layer 3. If the conductive path is a carbon nanotube having a small fiber diameter and a long fiber length, the carbon nanotubes can easily come into contact with each other. Therefore, the conductive path can be formed with a small content, and the friction of the conductive material-containing resin layer 40 can be formed. The fastness characteristic can be exhibited well, and the performance of the resin itself can be exhibited.

  Since the conductive material contained in the conductive material-containing resin layer 40 is small as described above, the conductive material-containing resin layer 40 maintains the properties of the resin and has resistance to alcohols such as a solvent and isopropyl alcohol. Maintains friction fastness characteristics. Therefore, even if the surface of the antistatic resin molding A2 is wiped and cleaned with a wiping cloth containing alcohols or the like, the conductive material-containing resin layer 40 having alcohol wiping resistance on the surface is wiped. Since the ultrafine conductive fiber 31 in the antistatic layer 3 does not fall off, the surface resistivity exhibited by the antistatic layer 3 does not increase.

  Further, since the conductive material-containing resin layer 40 contains little conductive material, there is very little risk of the conductive material falling off. In addition, since the conductive material only needs to form a conductive path, even if a part of the conductive material is dropped, the conductive path can be secured by another conductive material, and charging decay can be instantaneously performed. Can do. In addition, if the resin forming the conductive material-containing resin layer 40 is a vinyl chloride resin, the resin has chemical resistance. However, the surface is hardly affected. And since the chemical | medical agent and chemical | medical agent vapor | steam are interrupted | blocked by the electrically conductive material containing resin layer 40, and it does not osmose | permeate to the internal antistatic layer 3, antistaticity can be maintained.

The antistatic resin molding A2 having the above-described configuration is manufactured, for example, by the following method.
In one manufacturing method, the adhesive coating and the antistatic coating used for the antistatic resin molding A1 are applied to the surface of the resin main body 1 and dried to form the adhesive layer 2 and the antistatic layer 3. The conductive material-containing resin layer 40 is formed by applying and drying a conductive material-containing resin paint obtained by dissolving and dispersing in a solvent a smaller amount of the fine conductive fibers 31 and the resin than the fine conductive fibers 31 contained in the electropaint. Thus, the antistatic resin molded body A2 in which the resin main body 1, the adhesive layer 2, the antistatic layer 3, and the conductive material-containing resin layer 40 are laminated in this order can be manufactured.

  Further, as in the above embodiment, the antistatic layer 3 is formed by the antistatic paint on the surface of the adhesive layer film, and the conductive material-containing resin layer 40 is further formed by the conductive material-containing resin paint. An electric laminate film is produced. Next, the antistatic laminate film is laminated on the surface of the resin main body 1 by means of thermocompression bonding, extrusion lamination, etc., so that the resin main body 1, the adhesive layer 2 (adhesive layer film), the antistatic layer 3, and the conductive material are obtained. The antistatic resin molding A2 in which the containing resin layer 40 is laminated in this order can be manufactured.

  Furthermore, the conductive material-containing resin layer 40 is formed by the conductive material-containing resin paint, the antistatic layer 3 is formed by the antistatic paint, and the adhesive layer 2 is formed by the adhesive paint on the surface of the release film of the embodiment. Thus, an antistatic transfer film is produced. Next, the adhesive layer 2 of the antistatic transfer film is superposed on the surface of the resin body 1 and thermocompression bonded to transfer the adhesive layer 2, the antistatic layer 3, and the conductive material-containing resin layer 40. The antistatic resin molding A2 in which the 1, the adhesive layer 2, the antistatic layer 3, and the conductive material-containing resin layer 40 are laminated in this order can be manufactured.

  FIG. 3 is a cross-sectional view showing a partially enlarged antistatic resin molded body A3 according to still another embodiment of the present invention.

This antistatic resin molded body A3 has a transparent plate-like resin main body 1, the content of the adhesive layer 2 and the ultrafine conductive fiber 31 on the surface of one side thereof, and the gradient concentration is reduced on the outer surface side. The antistatic layer 30 (gradient antistatic layer 30) is laminated and integrated. Note that the adhesive layer 2 and the gradient antistatic layer 30 may be laminated and integrated on both surfaces of the resin body 1.
In the antistatic resin molded body A3, the resin main body 1 and the adhesive layer 2 are the same as the resin main body 1 and the adhesive layer 2 of the above-described embodiment, and thus the same reference numerals are given and description thereof is omitted.

  The inclined antistatic layer 30 is made of the same resin as that used for the antistatic layer 3 of the antistatic resin molding A1, and ultrafine conductive fibers 31 such as carbon nanotubes are formed on the inclined antistatic layer 30. It is contained so as to have the smallest content on the outer surface side (the surface side of the antistatic resin molding A3). That is, the content of the ultrafine conductive fiber 31 on the outer surface side of the gradient antistatic layer 30 is made smaller than that inside. In the gradient antistatic layer 30 shown in FIG. 3, the content gradually increases from the outer surface side toward the inside, but is not limited to this. For example, the content gradually increases. Also good.

The ultrafine conductive fiber included in the gradient antistatic layer 30 is 8 to 90 mass% as a whole, and preferably 10 to 50 mass%, so that the layer 30 can exhibit antistatic performance. Even in such a content, since the ultrafine conductive fibers 31 are dispersed and contained in the gradient antistatic layer 30, the surface resistance of 10 ⁵ to 10 ¹¹ Ω / □ is brought into contact with each other's fibers. Rate, and antistatic performance can be exhibited. Then, even if the content on the outer surface side of the gradient antistatic layer 30 is reduced, a conductive path is formed so that the charged static electricity can flow, so that the charged static electricity is exposed to the outside through the conductive path of the gradient antistatic layer 30. It can be discharged.

It is preferable to contain 0-5 mass% of this on the outer surface side where the content of the ultrafine conductive fiber 31 is small. Even if the content on the outer surface side is 0%, the surface resistivity can be set to 10 ⁵ to 10 ¹¹ Ω / □ similarly to the molded body A1 of the above embodiment, so that the antistatic performance is exhibited. Can do. If the content increases, the surface resistivity decreases, but the alcohol wiping resistance and friction fastness properties deteriorate, so it is preferable to suppress the content to 5% by mass. Further, if a resin such as a polyester resin, a urethane resin, a copolymer resin thereof, or a mixed resin thereof is used as a resin for forming the gradient antistatic layer 30, even if it is 0% by mass, electrostatic charging is performed. Attenuation can be performed in a short time.

  However, the more preferable content on the outer surface side is 0.005 to 5% by mass. When at least 5% by mass is contained in this way, a conductive path necessary for flowing charged static electricity is formed and the electric charge moves, so that the inside of the gradient antistatic layer 30 reaches the inside containing a large amount of the fine conductive fibers 31. It is possible to cause charging to be instantaneously performed by flowing inside and discharging. Therefore, even if it is a vinyl chloride type resin etc., charging attenuation can be performed instantaneously, and it can be set as the gradient antistatic layer 30 with favorable alcohol wiping-proof property and friction fastness characteristic.

  Since the resin and the ultrafine conductive fiber 31 used for the gradient antistatic layer 30 of the antistatic resin molding A3 are the same as those used for the antistatic layer 3, description thereof is omitted.

  Even in such an antistatic resin molded body A3, the content of the ultrafine conductive fiber 31 contained in the inclined antistatic layer 30 is reduced on the outer surface side. Maintains the properties of the resin, has resistance to solvents and alcohols such as isopropyl alcohol, and maintains friction fastness characteristics. Therefore, even if the surface of the antistatic resin molded product A3 is wiped and cleaned with a wiping cloth containing alcohol or the like, the surface resistivity does not increase. And since there is little content of the ultrafine conductive fiber 31 of this outer surface, there is almost no possibility that this ultrafine conductive fiber 31 will fall off, and even if some ultrafine conductive fibers 31 fall off, other ultrafine conductive fibers 31 As a result, a conductive path can be secured and charging attenuation can be instantaneously performed. In addition, if the resin forming the gradient antistatic layer 30 is a vinyl chloride resin, the resin has chemical resistance, so even if it is used for applications where chemicals come in contact or chemical vapors are generated, The surface is hardly attacked.

The antistatic resin molding A3 having the above-described configuration is manufactured, for example, by the following method.
In one manufacturing method, the adhesive coating 2 is formed on the surface of the resin body 1 by applying and drying the adhesive paint. Then, several kinds of conductive fiber-containing resin paints with different contents of the fine conductive fibers 31 are prepared, and the conductive fiber-containing resin paints are successively dried on the surface of the adhesive layer 2 in order from the paint having the highest content. By applying the coating and mixing the interfaces of the paints to form the gradient antistatic layer 30 whose content decreases toward the outer surface side, the resin body 1, the adhesive layer 2, and the ultrafine conductivity on the outer surface side are formed. An antistatic resin molded body A3 in which the gradient antistatic layer 30 having a reduced fiber content is laminated in this order can be manufactured.

  Further, as in the above-described embodiment, the conductive fiber-containing resin paint is not dried on the surface of the antistatic layer 3 in order from the paint having the higher content of the plurality of conductive fiber-containing resin paints on the surface of the adhesive layer film. The antistatic laminate film is produced by forming the gradient antistatic layer 30 whose content decreases toward the outer surface side by continuously applying and mixing the interfaces of the respective paints. Next, this antistatic laminate film is laminated on the surface of the resin main body 1 by means of thermocompression bonding, extrusion lamination, etc., so that the resin main body 1, the adhesive layer 2 (adhesive layer film), and the ultrafine conductive fiber on the outer surface side It is possible to manufacture the antistatic resin molded body A3 in which the gradient antistatic layer 30 in which the content of is reduced is laminated in this order.

  Moreover, it is continuously applied to the surface of the release film of the embodiment before the conductive fiber-containing resin paint is dried on the surface of the release film in order from the paint having a low content of the plurality of conductive fiber-containing resin paints. By forming the gradient antistatic layer 30 with the content decreasing toward the release film side by mixing the interfaces of the respective paints, and subsequently forming the adhesive layer 2 with the adhesive paint, the antistatic transfer Make a film. Next, the adhesive body 2 of the antistatic transfer film is laminated on the resin body 1 so that the adhesive layer 2 is on the resin body 1 side, and is thermocompression-bonded, thereby transferring the adhesive layer 2 and the gradient antistatic layer 30 to the resin body. 1, an antistatic resin molded body A3 in which the adhesive layer 2 and the gradient antistatic layer 3 in which the content of the ultrafine conductive fibers on the outer surface side is reduced can be laminated in this order.

  In each of these manufacturing methods, a plurality of paints having different contents of the conductive fiber-containing resin paint are used, and by mixing their interfaces, the antistatic layer having an antistatic layer whose content gradually increases from the outer surface to the inner side. If the next paint is applied after applying and drying each paint, the ultrafine conductive fibers will not mix at the interface, and the content will be stepwise. An antistatic resin molded body having a varying gradient antistatic layer can be produced.

  Next, more specific examples of the antistatic resin molded body according to the present invention will be described.

[Example 1]
A polymethyl methacrylate film (PMMA film) having a thickness of 100 μm, a total light transmittance of 94%, and a haze of 0.6% was used as the adhesive layer film.

  In addition, a vinyl chloride-vinyl acetate copolymer is dissolved as a binder resin in a solvent (cyclohexanone) to obtain a resin solution, and based on single-walled carbon nanotubes [Document Chemical Physics Letters, 323 (2000), P580-585. And a solution of alkyl ammonium salt of acidic polymer as a dispersing agent, and uniformly mixed and dispersed to obtain 0.3% by mass of single-walled carbon nanotubes. A coating liquid containing 0.1% by mass of the agent and 2.0% by mass of the binder resin (hereinafter referred to as CNT coating liquid A) was prepared.

  Further, the single-walled carbon nanotubes and the dispersant are added to the resin solution of the vinyl chloride-vinyl acetate copolymer resin and mixed and dispersed uniformly. The single-walled carbon nanotubes are 0.02% by mass, and the dispersant is added. A coating liquid (CNT-containing resin coating liquid X) containing 0.01% by mass and 6.0% by mass of the copolymer resin was prepared.

  Then, the antistatic layer is formed by applying and drying the prepared CNT coating liquid A on the surface of the adhesive layer film so that the antistatic coating film has a thickness of 200 nm. Subsequently, the antistatic layer is formed. A CNT-containing resin layer is formed by applying the adjusted CNT-containing resin coating solution X so as to have a thickness of 270 nm on the adhesive film, and the antistatic layer and the CNT-containing resin layer are formed on the adhesive layer film. An electrically conductive laminate film was produced. Then, this antistatic laminate film is placed on the surface of a 5.0 mm thick polycarbonate resin plate (total light transmittance 89.5%, haze 0.2%), and the adhesive layer film is on the polycarbonate resin plate side. Thus, a transparent antistatic resin plate was manufactured by thermocompression bonding.

  Table 1 below shows the results of measuring the surface resistivity, total light transmittance, and haze of this antistatic resin plate. Further, the surface of the antistatic resin plate (surface of the antistatic layer) was repeatedly wiped with a wiping cloth containing isopropyl alcohol, and the surface resistivity and total light transmittance after 100, 200 and 300 times were repeated. The haze was measured, and the results are shown in Table 1 below. Further, the saturation voltage of this antistatic resin plate and the time (half-life) during which this voltage is halved were measured, and the results are shown in Table 1.

  The surface resistivity is a value measured by Hiresta UP manufactured by Dia Instruments Co., Ltd., and the total light transmittance and haze are measured by a direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. according to ASTM D1003. The saturation voltage and the half-life are values measured with a Static Honest Meter H-0110 manufactured by Sicid Electrostatic Co., Ltd. according to JIS L 1094.

[Example 2]
A coating solution (CNT-containing resin coating solution) in which the single-walled carbon nanotubes contained in the CNT-containing resin coating solution are changed to 0.06 mass%, the dispersant is 0.03% by mass, and the copolymer resin is 6.0 mass%. A transparent antistatic resin plate was produced in the same manner as in Example 1 except that Y) was used.

  For this antistatic resin plate, the surface resistivity, total light transmittance, and haze were measured in the same manner as in Example 1 and the operation of wiping with a wiping cloth containing isopropyl alcohol was repeated 100 times, 200 times, and 300 times. Thereafter, the surface resistivity, the total light transmittance, and the haze were measured, and the results are also shown in Table 1 below. Further, the saturation voltage of this antistatic resin plate and the time (half-life) during which this voltage is halved are measured, and the results are also shown in Table 1.

[Example 3]
In the solvent (cyclohexanone), the vinyl chloride-vinyl acetate copolymer is dissolved as a binder resin, and the single-walled carbon nanotubes used in Example 1 and the dispersant used in Example 1 are added and mixed uniformly. In addition to the CNT coating liquid A which was dispersed and prepared in Example 1, the coating liquid (CNT containing 0.6% by mass of the single-walled carbon nanotubes, 0.2% by mass of the dispersant, and 2.0% by mass of the binder resin) Coating solution B) and a coating solution (CNT coating solution C) containing 0.15% by mass of the single-walled carbon nanotube, 0.06% by mass of the dispersant, and 2.0% by mass of the binder resin were prepared. did.

  On the surface of the adhesive layer film used in Example 1, the above-prepared three types of CNT coating liquids, each of the antistatic coatings having a thickness of 100 nm on the film in the order of CNT coating liquids B, A, and C The antistatic layer is formed by coating and drying as described above, whereby the antistatic layer formed of three types of antistatic coating films having different single-walled carbon nanotube contents is formed on the adhesive layer film. An electrically conductive laminate film was produced. The antistatic laminate film is placed on the surface of a 5.0 mm thick polycarbonate resin plate (total light transmittance 89.5%, haze 0.2%), and the adhesive layer film side is the polycarbonate resin plate side. Thus, a transparent antistatic resin plate in which the content of single-walled carbon nanotubes on the outer surface side of the gradient antistatic layer was smaller than that in the interior was manufactured by thermocompression bonding.

  For this antistatic resin plate, the surface resistivity, total light transmittance, and haze were measured in the same manner as in Example 1 and the operation of wiping with a wiping cloth containing isopropyl alcohol was repeated 100 times, 200 times, and 300 times. The subsequent surface resistivity, total light transmittance, and haze were measured, and the results are also shown in Table 1 below. Further, the saturation voltage of this antistatic resin plate and the time (half-life) during which this voltage is halved are measured, and the results are also shown in Table 1.

[Example 4]
A resin coating solution in which a polyester resin was dissolved in a solvent was prepared. Then, on the surface of the adhesive layer film used in Example 1, the antistatic layer was formed by applying and drying the CNT coating liquid A used in Example 1 so that the antistatic coating thickness was 200 nm. Subsequently, the resin coating liquid is applied on the antistatic layer to a thickness of 270 nm to form a resin layer, and the antistatic layer and the resin layer are formed on the adhesive layer film. An adhesive laminate film was produced. Then, this antistatic laminate film is placed on the surface of a 5.0 mm thick polycarbonate resin plate (total light transmittance 89.5%, haze 0.2%), and the adhesive layer film is on the polycarbonate resin plate side. Thus, a transparent antistatic resin plate was manufactured by thermocompression bonding.

  For this antistatic resin plate, the surface resistivity, total light transmittance, and haze were measured in the same manner as in Example 1 and the operation of wiping with a wiping cloth containing isopropyl alcohol was repeated 100 times, 200 times, and 300 times. The subsequent surface resistivity, total light transmittance, and haze were measured, and the results are also shown in Table 1 below. Further, the saturation voltage of this antistatic resin plate and the time (half-life) during which this voltage is halved are measured, and the results are also shown in Table 1.

[Comparative Example 1]
An antistatic laminate film was prepared by simply applying and drying the CNT coating liquid A on the adhesive layer film used in Example 1, and laminating in the same manner as in Example 1, and then adhering the adhesive layer (for the adhesive layer) to the polycarbonate resin plate. A transparent antistatic resin plate in which an antistatic layer was laminated via a film) was produced. The thickness of the antistatic layer was 200 nm. And about this antistatic resin board, while measuring surface resistivity, a total light transmittance, and haze similarly to Example 1, the operation | work wiped off with the wiping cloth containing isopropyl alcohol is performed 100 times, 200 times, 300 times. The surface resistivity, the total light transmittance, and the haze after repeated times were measured, and the results are also shown in Table 1 below. Further, the saturation voltage of this antistatic resin plate and the time (half-life) during which this voltage is halved are measured, and the results are also shown in Table 1.

As can be seen from Table 1, in each of Examples 1, 2, 3 and Comparative Example 1, the initial surface resistivity is substantially the same as 10 ⁶ to 10 ⁷ Ω / □. However, each example maintains substantially the same surface resistivity even when the number of times of wiping with wiping cloth containing isopropyl alcohol is increased, whereas Comparative Example 1 has a rapidly increased surface resistivity. It turns out that it has no antistatic performance. This is presumably because the single-walled carbon nanotubes contained in the surface antistatic layer were wiped off by the wiping cloth and dropped off.
Further, Example 4 in which a resin layer not containing single-walled carbon nanotubes was provided on the surface was higher than the surface resistivity of Examples 1, 2, and 3 in which a resin layer containing single-walled carbon nanotubes was provided. However, it can be seen that it has a surface resistivity of 10 ⁷ Ω / □ and can sufficiently exhibit antistatic performance.

  Further, in the optical characteristics, Examples 1, 2, and 3 and Comparative Example 1 are substantially the same within a range where the initial total light transmittance is 80 to 83% and the haze is 3 to 4.5%. . However, when the number of times of wiping is increased, it can be seen that only the comparative example 1 is deteriorated in total light transmittance and haze. This is probably because the surface of the antistatic layer became rough as a result of wiping off the single-walled carbon nanotubes contained in the antistatic layer on the surface.

  Further, in terms of electrical characteristics, each of Examples 1, 2, and 3 and Comparative Example 1 have an initial saturation band voltage of 10 V or less and a half-life of less than 1 second. However, when the number of wiping operations is increased, each example shows the same value, but in Comparative Example 1, the saturation band voltage increases to 700 V, 3200 V, 3400 V, and the half-life becomes 74 seconds, 120 seconds or more, which is a long time. It can be seen that it is charged over a period of time and hardly attenuates or does not attenuate. With such electrical characteristics of Comparative Example 4, the charged static electricity may cause electrostatic breakdown of the electronic component, which is not preferable as a molded body used for manufacturing semiconductors, liquid crystals, and partitioning.

It is sectional drawing which partially enlarges and shows the antistatic resin molding which concerns on one Embodiment of this invention. It is sectional drawing which partially enlarges and shows the antistatic resin molding which concerns on other embodiment of this invention. It is sectional drawing which partially enlarges and shows the antistatic resin molding which concerns on other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin body 2 Adhesion layer 3 Antistatic layer 30 Inclined antistatic layer 31 Extra fine conductive fiber 32 Binder resin 4 Resin layer 40 Conductive material containing resin layer

Claims (8)

  A resin molded body in which an antistatic layer is laminated on at least one surface of a resin body, the antistatic layer containing ultrafine conductive fibers, and a resin layer laminated on the outer surface of the antistatic layer. Characteristic antistatic resin molded product.   The antistatic resin molded article according to claim 1, wherein the resin layer contains a conductive material.   The antistatic resin molded article according to claim 1, wherein the resin layer contains a conductive material of ultrafine conductive fibers, and the content thereof is smaller than that of the antistatic layer.   The antistatic resin molded article according to claim 2 or 3, wherein the content of the ultrafine conductive fibers contained in the resin layer is 0.005 to 5 mass%.   The antistatic resin molded article according to any one of claims 1 to 4, wherein the antistatic layer is laminated on the resin main body via an adhesive layer.   A resin molded body in which an antistatic layer is laminated on at least one surface of a resin main body, the antistatic layer including ultrafine conductive fibers, and the content of the ultrafine conductive fibers on the outer surface side of the antistatic layer is within the antistatic layer. An antistatic resin molded product characterized by being less than the side.   The antistatic resin molded article according to claim 6, wherein the content of the ultrafine conductive fibers on the outer surface side of the antistatic layer is 0 to 5 mass%.   The antistatic resin molded article according to any one of claims 1 to 7, wherein the ultrafine conductive fiber is a carbon nanotube.

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