JP4818682B2 - Manufacturing method of resin laminate - Google Patents

Description

  The present invention relates to a method for producing a resin laminate having a plate shape and the like excellent in transparency, antistatic properties, and scratch resistance, suitable for applications such as a display front plate.

  Acrylic resins are characterized by good transparency, impact resistance, easy moldability and the like, and are widely used as industrial materials, building materials, and the like. In recent years, it has been used as a front plate for various displays such as CRTs and liquid crystal televisions due to its transparency and impact resistance. However, like other resins, acrylic resin is softer than glass, and scratches due to scratching or the like may easily occur. In addition, since acrylic resin has a high surface resistivity, transparency may be easily reduced due to adhesion of dust due to static electricity.

  As a method for improving the scratch resistance, it is known as a known technique that a polyfunctional monomer such as polyfunctional (meth) acrylate is used to form a crosslinked coating on the surface of a substrate. However, conventional crosslinked coatings often do not exhibit antistatic ability or are insufficient.

  Therefore, a method of imparting antistatic properties in addition to scratch resistance has been proposed. For example, Patent Document 1 and Patent Document 2 disclose a method of laminating a coating film containing a conductive powder containing tin oxide as a main component, but in the case of a coating film containing a conductive powder such as tin oxide. If the film thickness is increased until good scratch resistance is obtained, the conductive powder may be colored or the transparency may be lowered due to surface irregularities. Moreover, since the coating film containing electroconductive powder cannot be formed continuously, there existed a problem that productivity was low.

On the other hand, there is known a method for producing a resin molded body having antistatic properties and having a surface layer excellent in scratch resistance with high productivity. For example, Patent Document 3 discloses a method for producing a resin molded body by film transfer, but transparency is easily impaired, and further improvements are required.
JP-A-60-181177 JP 62-206709 A JP 2003-326538 A

  An object of the present invention is to produce a resin laminate having a surface layer excellent in antistatic property, scratch resistance and transparency with high productivity.

  In the present invention, an antistatic film of a film having at least one surface of an antistatic film containing an antistatic component and a polymer having a weight average molecular weight of 5,000 to 1,000,000 is used as a mold side, and an ultraviolet curable coating (A) is interposed. The first step of attaching the film to the mold, the second step of irradiating the ultraviolet ray through the film and curing the ultraviolet curable coating (A), the ultraviolet curable coating (A) on the mold The third step of peeling the film leaving the cured coating film and the antistatic film laminated on the coating film, the cured coating film of the ultraviolet curable coating (A) and the laminated film on the coating film A fourth step of producing a mold using the mold having an antistatic film, a fifth step of injecting a resin raw material into the mold to perform cast polymerization, and a resin formed by the polymerization after the completion of the polymerization A molded body, an antistatic film, Of the coating and film is a sixth step, the manufacturing method of the resin laminate comprising peeling the sequentially laminated resin laminate from the mold. The antistatic component is preferably composed of conductive fine particles.

  According to the present invention, a surface layer (cured coating) having a superior surface free from defects due to foreign matters and the like, having a sufficient antistatic property and excellent in scratch resistance and transparency since it is a transfer of the mold surface. A resin laminate having a film) can be produced with high productivity.

  The film having an antistatic film on at least one surface in the present invention will be described.

  Examples of the antistatic component used in the present invention include conductive fine particles, a surfactant, and a conductive polymer. From the viewpoint of antistatic performance and transparency, conductive fine particles are preferable.

  Examples of the conductive fine particles include fine particles obtained by doping tin oxide or tin oxide with one or more elements such as antimony, phosphorus, fluorine, zinc, tellurium, bismuth, cadmium, or indium oxide or indium oxide. Fine particles doped with elements such as tin, fluorine, phosphorus, and antimony, and antimony pentoxide fine particles are used. In order to obtain good transparency, the average particle size of the conductive fine particles is preferably 100 nm or less, and more preferably 50 nm or less. Further, it is preferably 1 nm or more in order to obtain stable dispersibility.

  The film used in the present invention preferably has a solvent resistance that transmits ultraviolet rays used for curing described later, does not swell by the ultraviolet curable coating (A), and has a low oxygen permeability. An example of such a film is a biaxially stretched film of polyethylene terephthalate. The thickness of the film is preferably 1 μm or more from the viewpoint of maintaining the film strength, and is preferably 200 μm or less from the viewpoint of handleability and cost.

  The polymer constituting the antistatic film is used as a binder component that supports the antistatic component and can form a film. For example, a synthetic resin such as a polyolefin resin, an acrylic resin, an epoxy resin, a polyimide resin, a phenol resin, or a polyester resin. Is mentioned. From the viewpoint of transparency and transferability to the ultraviolet curable coating (A), an acrylic resin is preferred. This polymer may be a homopolymer composed of one kind of monomer or a copolymer composed of a plurality of monomers.

  The molecular weight of the polymer is preferably a weight average molecular weight of 5,000 to 1,000,000. When the weight average molecular weight is 5000 or more, excessive swelling due to the monomer during the casting polymerization is suppressed, the network structure serving as an electron conduction path can be maintained by contact between the conductive fine particles, and antistatic performance is exhibited. When the weight average molecular weight is 1,000,000 or less, the polymer is swollen by the ultraviolet curable coating (A), and good transferability is obtained. In addition, the adhesion between a cured coating film and an antistatic film, which will be described later, is good even in a high humidity environment.

  A dispersion stabilizer such as a polar monomer, a surfactant, or an amine may be added to the polymer for the purpose of improving the dispersion stability of the conductive fine particles.

  In the present invention, the method for forming the antistatic film on at least one surface of the film is not particularly limited, but it is formed by applying a solution obtained by dissolving and dispersing the polymer and the antistatic component in a solvent and evaporating the solvent. The method is preferred.

  The solvent is used for the purpose of reducing the viscosity of the polymer and the antistatic component by diluting to make the viscosity easy to apply to the film and improving the dispersion stability of the conductive fine particles. Examples of the solvent include methanol, ethanol, 2-propanol, 2-butanol, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, methyl acetate, ethyl acetate, water and the like.

The antistatic film preferably has a thickness of 0.05 μm to 5 μm. In such a range, the appearance is good and the antistatic performance is also good. The surface resistance of the antistatic film is preferably ^{10 10 Ω} / □ or less, more preferably 10 ⁸ Ω / □ or less. When the surface resistance value is in this region, the antistatic performance of the resin laminate is sufficient. The surface resistance value can be adjusted by appropriately selecting the addition amount of the antistatic component. In the case of conductive fine particles, the addition amount is 50 parts by mass or more with respect to 100 parts by mass of the polymer as the binder component. It is preferable. Moreover, it is preferable that it is 90 mass parts or less from a viewpoint of adhesiveness with a base material.

  The method for applying the diluted solution of the polymer and the antistatic component to the film is not particularly limited, and for example, brush coating, bar coating, flow coating, spray coating, knife coating, roll coating, die coating and the like can be applied.

  In the present invention, as the first step, the antistatic film on at least one surface of the film is used as the mold side, and the film is attached to the mold with the ultraviolet curable paint (A) interposed.

  As the ultraviolet curable coating (A), those composed of a compound having at least two (meth) acryloyloxy groups in the molecule and a photoinitiator are preferable.

  Major examples of compounds having at least two (meth) acryloyloxy groups in the molecule include esterified products obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or derivatives thereof, Examples thereof include linear esterified products obtained from a monohydric alcohol, a polyvalent carboxylic acid or anhydride thereof, and (meth) acrylic acid or a derivative thereof.

  Specific examples of the esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate of polyethylene glycol such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) ) Acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.

  A linear esterified product obtained from a polyhydric alcohol, a polycarboxylic acid or anhydride thereof, and (meth) acrylic acid or a derivative thereof. In the linear esterified product, a polyhydric alcohol, polyhydric carboxylic acid or anhydride thereof, and (meth) acrylic acid Preferred combinations of are, for example, malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / penta Erythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (Meth) acrylic acid, adipic acid / trimethylolethane / (meta Acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic Acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid , Sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, Fumaric acid / trimethylol propa / (Meth) acrylic acid, fumaric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (Meth) acrylic acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (Meth) acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid, maleic anhydride / pentaerythritol / (meth) acrylic acid and the like.

  Other examples of UV curable coatings (A) include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethyl. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N per mole of polyisocyanate obtained by trimerization of diisocyanate such as hexamethylene diisocyanate -Methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 1,2,3-propanetriol-1,3-di Urethane (meth) acrylate obtained by reacting 3 mol or more of an acrylic monomer having active hydrogen such as meth) acrylate and 3-acryloyloxy-2-hydroxypropyl (meth) acrylate; tris (2-hydroxyethyl) isocyanuric acid And poly [(meth) acryloyloxyethylene] isocyanurate such as di (meth) acrylate or tri (meth) acrylate; epoxy poly (meth) acrylate; urethane poly (meth) acrylate; Here, “(meth) acryl” means “methacryl” or “acryl”.

  Examples of the photoinitiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α , α-Dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one Carbonyl compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, etc .; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyl Ethoxy phosphine oxide, and the like.

  The addition amount of the photoinitiator is preferably 0.1% by mass or more from the viewpoint of curability by ultraviolet rays among all the components constituting the ultraviolet curable coating (A), and 10 from the viewpoint of maintaining a good color tone of the coating film. The mass% or less is preferable.

  For the ultraviolet curable coating (A), if necessary, a monomer having one functional group in the molecule, a leveling agent, conductive inorganic fine particles, non-conductive inorganic fine particles, an ultraviolet absorber, light Various components such as a stabilizer can be further added. The addition amount is preferably 10% by mass or less.

  In the present invention, examples of the method for attaching the film to the mold in the first step include a method in which the ultraviolet curable coating (A) is applied to the mold or the film and the film is pressure-bonded with a rubber roll. In particular, in order to prevent air entrainment at the time of bonding, it is preferable to apply an excessive amount of the ultraviolet curable coating (A) on the mold and apply the film while squeezing the excessive coating with a rubber roll through the film.

  Regarding the thickness of the ultraviolet curable coating (A) layer, the thickness after curing is preferably 5 μm to 100 μm. When the thickness is 5 μm or more, sufficient surface hardness is exhibited, and when the thickness is 100 μm or less, the coloring inherent to the film does not become a problem and the appearance is improved and the antistatic performance is improved.

  In this invention, after sticking a film to a type | mold at a 1st process, as a 2nd process, an ultraviolet-ray is irradiated through a film and an ultraviolet curable coating material (A) is hardened. An ultraviolet lamp may be used for this ultraviolet irradiation. Examples of the ultraviolet lamp include a high pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp. Curing by ultraviolet irradiation may be performed in one step via a film, for example, precuring via a film (second step), peeling the film (third step), and then further applying ultraviolet rays. Curing may be performed in two stages, such as irradiation and curing.

  In the present invention, after curing in the second step, as a third step, on the coating film (hereinafter referred to as “cured coating film”) on which the ultraviolet curable coating (A) is cured on the mold and on the cured coating film. The film is peeled off leaving the antistatic film laminated on. That is, the antistatic film applied to the film is transferred to the cured coating film on the mold. The cured coating film and the antistatic film laminated on the cured coating film are hereinafter collectively referred to as “laminated film”.

  As a fourth step, a mold is prepared using the mold having a coating film (cured coating film) obtained by curing the ultraviolet curable paint (A) and an antistatic film (laminated film) laminated on the coating film.

  As a member constituting the mold, for example, a stainless steel plate having a mirror surface, a glass plate, a stainless steel plate having irregularities on the surface, a glass plate, or the like can be used. For producing the mold, for example, a hollow shape made of soft polyvinyl chloride, ethylene-vinyl acetate copolymer, polyethylene, ethylene-methyl methacrylate copolymer or the like is sandwiched between two molds as a gasket, It can be performed by a process such as assembling a mold composed of a mold by fixing with a clamp. In addition, as a method of continuous casting polymerization (cast polymerization), two stainless endless belts that run opposite to each other as shown in FIG. 1 are used as a mold, and the resin raw material is cast polymerization between these endless belts. Thus, a method for producing a resin plate is known, and this is the most preferable method in terms of productivity. In this case, by forming, for example, a cured coating film on the stainless steel endless belt surface in advance, a resin laminate having a layer made of the film can be manufactured with high productivity.

  Further, as a fifth step, a resin raw material is injected into the mold and cast polymerization is performed.

  When performing cast polymerization of a resin raw material to be a base material inside the produced mold, various conventionally known raw materials can be used as the resin raw material. For example, in the case of producing an acrylic resin molded article by cast polymerization, as the resin raw material, a monomer of (meth) acrylic acid ester alone, a monomer having this as a main component, or this Examples thereof include a syrup containing a mixture of a monomer and a polymer composed of the monomer. Examples of such acrylic resins include homopolymers of esters of (meth) acrylic acid or copolymers having this as the main monomer component. Examples of (meth) acrylic acid esters include methyl methacrylate. For example, when copolymerizing methyl methacrylate as the main monomer component, other monomer components include acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acid esters; methacrylic acid esters other than methyl methacrylate such as cyclohexyl methacrylate, phenyl methacrylate, and benzyl methacrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene;

  When a partially polymerized product is contained in methyl methacrylate, the polymer may be dissolved in methyl methacrylate, or methyl methacrylate may be partially polymerized. Examples of the initiator for polymerizing the acrylic resin material include commonly used azo initiators and peroxide initiators, and cast polymerization is performed by a known method using these initiators. A release agent, an ultraviolet absorber, a dye and the like can be added to the acrylic resin raw material according to other purposes.

  After the completion of the polymerization, as a sixth step, the resin laminate in which the resin molded body, the antistatic film, and the cured coating film are sequentially laminated is peeled from the mold. The resin laminate thus obtained has a superior surface free from defects due to foreign matters and the like because it is a transfer of the mold surface, and is excellent in scratch resistance and antistatic properties.

  Further, the resin laminate may be provided with another functional thin film such as an antireflection film on the surface as necessary. For example, when an antireflection film is formed, the method is not particularly limited, and examples thereof include a method using a commercially available antireflection coating; a physical vapor deposition method such as a vapor deposition method and a sputtering method; and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Here, the abbreviations of the compounds used in Production Examples, Examples and Comparative Examples are as follows.

“MMA”: methyl methacrylate “BA”: butyl acrylate “MA”: methyl acrylate “AIBN”: 2,2′-azobis (isobutyronitrile)
“N-OM”: n-octyl mercaptan “S100A”: glycerol monostearate (RIKEN Vitamin Co., Ltd.)
(Rikemar S-100A)
“C6DA”: 1,6-hexanediol diacrylate (Osaka Organic)
(Chemical Industry Co., Ltd.)
“TAS”: Succinic acid / trimethylolethane / acrylic acid
1: 2: 4 condensation mixture (Osaka Organic Chemical Industry Co., Ltd.)
(Made by company)
"BEE": Benzoin ethyl ether (manufactured by Seiko Chemical Co., Ltd.)
In addition, evaluation of the physical property in an Example was performed based on the following method.

(A) Surface resistance value Super insulation resistance meter (made by TOA, ULTRA MEGOHMMETER
The surface resistance value (Ω / □) after 1 minute was measured at an applied voltage of 500 V on the laminated film side of the resin laminate under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 50% using MODEL SM-10E). As a sample for measurement, a sample conditioned at 23 ° C. and 50% relative humidity for 1 day was used.

(A) Ash adhesion test The surface having the laminated film of the resin laminate was rubbed 10 times with a dry face cloth, and then the surface having the laminated film was brought close to a cigarette ash on a plane at a certain distance. At that time, ash adhesion was evaluated.

○: Ash does not adhere even when the distance is close to 10 mm.
(Triangle | delta): When approaching from 50 mm to 10 mm, ash adheres on the way.
X: Ash adheres at a distance of 50 mm.

(C) Transferability of antistatic film to ultraviolet curable coating (A) Surface condition of the surface layer of the PET film after the third step (step of peeling the polyethylene terephthalate (hereinafter referred to as “PET”) film) Judging from the result of visual observation.

○: No antistatic film remains on the PET film.
X: The antistatic film remains on the PET film.

(D) Adhesion evaluation after humidity resistance test The sample was allowed to stand in an atmosphere of 65 ° C and 95% relative humidity for 7 days, and then evaluated by a cross-cut test (JIS K5600-5-6).

○: No peeling of the film from the substrate ×: There is peeling of the film from the substrate (e) Total light transmittance and haze In accordance with the measurement method shown in JIS K7136 using Nippon Denshoku HAZE METER NDH2000 The total light transmittance and haze were measured.

(F) Abrasion resistance The haze change (Δhaze) before and after the abrasion test was evaluated. In other words, a circular pad with a diameter of 25.4 mm equipped with # 000 steel wool was placed on the surface of the laminated film side of the sample, and under a load of 9.8 N, a 20 mm distance was scratched 100 times, and before and after scratching. The difference of the haze value after that was calculated | required from the following Formula (1).

[△ haze (%)] = [haze value after abrasion (%)] − [haze value before abrasion (%)]
(1)
(G) Weight average molecular weight Measured by gel permeation chromatography method (hereinafter referred to as “GPC method”). The GPC method was measured by dissolving the polymer in tetrahydrofuran (THF) and using liquid chromatography HLC-8020 manufactured by Tosoh Corporation. The separation columns used were two TSK-Gel GMHXLs in series. The solvent was THF (tetrahydrofuran), the flow rate was 1.0 ml / min, the detector was a differential refractometer, the measurement temperature was 40 ° C., the injection amount was 0.1 ml, and polystyrene resin was used as the standard polymer.

[Production Example 1]
In a polymerization apparatus equipped with a stirrer, a monomer mixture consisting of 58 parts by mass of sodium 2-sulfoethyl methacrylate, 31 parts by mass of aqueous potassium methacrylate (potassium methacrylate content 30% by mass), and 11 parts by mass of methyl methacrylate; 900 parts by mass of deionized water was added and dissolved by stirring. Thereafter, the mixture was heated to 60 ° C. with stirring under a nitrogen atmosphere, and kept at 60 ° C. with stirring for 6 hours to obtain an aqueous anionic polymer compound solution. At this time, after the temperature reached 50 ° C., 0.1 part by mass of ammonium persulfate was added as a polymerization initiator, and 11 parts by mass of methyl methacrylate weighed separately was continuously added to the above reaction system over 75 minutes. It was dripped in. Let the anionic polymer compound aqueous solution obtained by the above-mentioned manufacturing method be (A1).

  In a 20-liter container equipped with a stirrer, a monomer mixture consisting of 90 parts by mass of MMA, 9 parts by mass of BA, and 1 part by mass of MA, 0.1 parts by mass of AIBN as a polymerization initiator, and n-OM0.22 as a chain transfer agent 0.2 part by mass of S100A was added as a part by mass and a release agent, and the mixture was stirred and mixed. Further, in a container having a capacity of 20 liters equipped with another stirrer, 150 parts of deionized water, 0.3 part by weight of the aqueous anionic polymer compound (A1) obtained in Production Example 1 as a dispersion stabilizer, and dispersion stabilization assistant. As an agent, 0.35 part by mass of sodium sulfate was added and stirred and mixed.

  The contents of each of the 20 liter containers were put into a 40 liter polymerization container equipped with a stirrer, and after replacing with nitrogen, the temperature was raised to 80 ° C. After completion of the polymerization exothermic peak, the temperature was maintained at 115 ° C. for 20 minutes, and then cooled to 30 ° C. to complete the polymerization. Then, washing | cleaning dehydration processing and drying were carried out, and the bead-like copolymer (B1) was obtained. The weight average molecular weight of the obtained bead-shaped copolymer (B1) was about 100,000.

[Example 1]
10 parts by mass of the obtained copolymer, 1 part by mass of triethylamine, and 7 parts by mass of antimony-doped tin oxide fine particles (trade name FSS-10M, manufactured by Ishihara Sangyo Co., Ltd.) having an average particle diameter of 20 nm are added to 82 parts by mass of isopropanol. The antistatic paint obtained by dissolving and dispersing was applied to a PET film having a smooth surface with a thickness of 24 μm to a thickness of 1.1 μm using a bar coater. Next, the coating film on this film was dried in a hot air drying oven at 70 ° C. for 5 minutes to obtain a PET film with an antistatic film having an antistatic film having a thickness of 0.2 μm on one side. The surface resistance value was 3 × 10 ⁸ Ω / □.

  Next, an ultraviolet curable coating (A) composed of 50 parts by mass of TAS, 50 parts by mass of C6DA, and 1.5 parts by mass of BEE was applied onto a stainless (SUS304) plate as a mold.

  On the stainless steel plate UV curable coating (A), the PET film with the antistatic film is laminated with the antistatic film surface facing the mold side, and a rubber roll having a JIS hardness of 40 ° is used. Then, the ultraviolet curable paint (A) was pressure-bonded so as not to contain air bubbles while squeezing out an excessive paint so as to have a thickness of 15 μm. The thickness of the ultraviolet curable paint (A) was calculated from the supply amount and the development area of the paint (A). Next, the cured UV light is passed through a position of 20 cm below the fluorescent UV lamp (FL40BL manufactured by Toshiba Corporation) with an output of 40 W through the PET film at a speed of 0.3 m / min. An antistatic film (laminated film) was obtained.

  Thereafter, the PET film was peeled off leaving the laminated film on the mold. All antistatic films were transferred to the cured coating. Next, the surface of the stainless steel plate with the laminated film facing upward is passed through a position 20 cm under a high-pressure mercury lamp with an output of 30 W / cm at a speed of 0.3 m / min, and the coating film is further cured to a film thickness of 13 μm. A laminated film was obtained. In addition, the film thickness of the laminated film was determined by measuring from a differential interference micrograph of a cross section of the obtained product.

  Two stainless steel plates having a laminated film formed in this way were prepared, facing each other so that the laminated film was on the inside, and the periphery was sealed with a gasket made of soft polyvinyl chloride to produce a casting polymerization mold. . In this template, from 100 parts by weight of a mixture of 20 parts by weight of MMA polymer having a weight average molecular weight of 220,000 and 80 parts by weight of MMA monomer, 0.05 part by weight of AIBN, and 0.005 part by weight of sodium salt of dioctylsulfosuccinate The resin raw material to be formed was poured, the distance between the opposing stainless steel plates was adjusted to 2.5 mm, and polymerization was performed in an 80 ° C. water bath for 1 hour and then in a 130 ° C. air furnace for 1 hour. After cooling, the obtained resin plate is peeled off from the stainless steel plate to obtain a laminated film with a thickness of 2 mm having a laminated film on both sides, that is, a cured coating film on the surface and an antistatic film inside. Obtained.

The obtained acrylic resin laminate had a total light transmittance of 92% and a haze of 0.2%, and was excellent in transparency. Furthermore, there was no appearance defect due to foreign matter, and it had a good appearance. The surface resistance value was 8 × 10 ¹³ Ω / □, and as a result of the ash adhesion test, ash did not adhere to the resin plate surface. The haze increment after scratching was 0.0%, and the antistatic property and scratch resistance were excellent.

[Example 2]
First, a PET film with an antistatic film was obtained in the same manner as in Example 1. Next, an ultraviolet curable paint (A) was prepared in the same manner as in Example 1. A belt below the endless belt made of stainless steel (SUS304) with a mirror finish of 1200 mm in width and 1 mm in thickness that travels in the same direction (2.5 m / min) in the same direction relative to this UV curable coating (A). It applied by the method similar to Example 1, and the PET film with an antistatic film was crimped | bonded using the rubber roll. Next, UV curing was performed in the same manner as in Example 1, and the PET film was peeled off to obtain a laminated film composed of an antistatic film and a cured coating film on a stainless steel endless belt. All of the antistatic film on the film surface was transferred to the cured coating film. Next, the coating film was further cured by the same method as in Example 1. FIG. 2 shows a cross-sectional view of an apparatus for performing these steps.

  An endless belt having a laminated film formed on one side as described above and another endless belt are opposed to each other, and a soft polyvinyl chloride gasket that runs at the same speed as both endless belts at both ends of the opposite side A mold was constructed, and the gap between the two endless belts was set in advance to a thickness of 2.5 mm. The same base resin raw material as in Example 1 was poured into this mold at a constant flow rate, polymerized and cured for 30 minutes with a hot water shower at 78 ° C. along with the movement of the belt, and heat treatment at 135 ° C. with a far-infrared heater for 20 minutes. Was cooled to 100 ° C. over 10 minutes, and the resin plate obtained from the endless belt was peeled off to obtain a 2 mm thick acrylic resin laminate having a laminated film, that is, a cured film and an antistatic film on one surface.

The resulting resin plate had a total light transmittance of 92% and a haze of 0.2%, and was excellent in transparency. Furthermore, there was no appearance defect due to foreign matter, and it had a good appearance. The surface resistance value was 8 × 10 ¹³ Ω / □, and as a result of the ash adhesion test, ash did not adhere to the resin plate surface. The haze increment after scratching was 0.0%, and the antistatic property and scratch resistance were excellent.

Table 1 shows the polymerization average molecular weight and evaluation results of the copolymer of this example.

[Examples 3-8, Comparative Examples 1-4]
The amount of n-OM and AIBN added in this production example and the polymerization temperature were changed as shown in Table 2, and bead copolymers (B2, B3, B4, B5, B6, B7) were obtained. An acrylic resin laminate was produced and evaluated in the same manner as in Example 1 except that the type of polymer and the weight average molecular weight were changed as shown in Tables 1 and 3. The results are shown in Tables 1 and 3.

  In Examples 3 to 8, since a polymer having a weight average molecular weight of 5000 to 1000000 was used, the polymer had good performance.

In Comparative Example 1, since the weight average molecular weight of the polymer was less than 5000, excessive swelling due to the monomer during the casting polymerization occurred, the network structure of the conductive fine particles was destroyed, and the antistatic performance was poor. In Comparative Example 2, since the weight average molecular weight of the polymer was larger than 1,000,000, the polymer constituting the antistatic film by the ultraviolet curable coating (A) was insufficiently swelled and the transferability was poor. In Comparative Example 3, since a non-polymerized product having a weight average molecular weight of less than 5000 was used, it became cloudy and the appearance was poor. In Comparative Example 4, since it was used without forming an antistatic layer on the PET film, it became a resin laminate composed only of a cured coating film and did not exhibit antistatic performance.

  According to the present invention, a surface layer (laminated film) having a superior surface free from defects due to foreign matters and the like because it is a transfer of a mold surface and exhibiting sufficient antistatic properties and excellent scratch resistance and transparency. ) Can be produced with high productivity.

  Such excellent resin laminates can be used for nameplates of various electrical equipment, various glazings such as partitions, front plates of various displays such as CRTs, liquid crystal televisions, projection televisions, front plates of information display units such as liquid crystal of information terminals, etc. It can be used suitably.

It is typical sectional drawing which illustrates the belt type continuous cast board | plate apparatus which can be used for the method of this invention. It is typical sectional drawing which illustrates the formation apparatus of the laminated film which can be used for the method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 Endless belt 3, 4, 5, 6 Main pulley 7 Carrier roll 8 First polymerization zone 9 Hot water spray 10 Second polymerization zone 11 Cooling zone 12 Gasket 13 Removal direction of resin laminated body 14 Polymerization raw material injection apparatus 15 Charging PET film with protective film 16 UV curable paint (A)
17 Rubber roll 18 Fluorescent ultraviolet lamp 19 High pressure mercury lamp 20 Multilayer film

Claims (3)

  The antistatic film of a film having at least one surface of an antistatic film containing an antistatic component and a polymer having a weight average molecular weight of 5,000 to 1,000,000 is used as a mold side, and an ultraviolet curable paint (A) is interposed therebetween. A first step of attaching the film to the mold, a second step of irradiating ultraviolet rays through the film to cure the ultraviolet curable coating (A), and a coating in which the ultraviolet curable coating (A) is cured on the mold A third step of removing the film while leaving the film and the antistatic film laminated on the coating film; a coating film cured with the ultraviolet curable coating (A); and an antistatic film laminated on the coating film. A fourth step of producing a mold using the mold having, a fifth step of injecting a resin raw material into the mold to perform cast polymerization, and a resin molded body formed by the polymerization after the completion of the polymerization; Antistatic film, cured coating film and Sixth step, the manufacturing method of the resin laminate comprising peeling the sequentially laminated resin laminate from the mold.   The method for producing a resin laminate according to claim 1, wherein the antistatic component comprises conductive fine particles.   The method for producing a resin laminate according to claim 1 or 2, wherein the resin molded body is an acrylic resin molded body.

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