WO2022054693A1

WO2022054693A1 - Multilayer sheet, multilayer film, and decorative molded article in which same is used

Info

Publication number: WO2022054693A1
Application number: PCT/JP2021/032335
Authority: WO
Inventors: 達也金川
Original assignee: 三菱瓦斯化学株式会社; Ｍｇｃフィルシート株式会社
Priority date: 2020-09-08
Filing date: 2021-09-02
Publication date: 2022-03-17
Also published as: CN116096567A; JPWO2022054693A1; TW202224949A

Abstract

According to the present invention, it is possible to provide a multilayer sheet or multilayer film composed of a laminate that has a polycarbonate-based resin layer as a substrate and that moreover has a silicon-dioxide-particle-containing thermoplastic acrylic-based resin layer on one or both outermost surfaces of the substrate, wherein the average particle diameter of the silicon dioxide particles is 0.1-2 μm, and the silicon dioxide particle content is greater than 1 mass% and no greater than 10 mass% relative to the entirety of the thermoplastic acrylic-based resin layer.

Description

Multi-layer sheet and multi-layer film, and decorative molded products using them

The present invention relates to a multilayer sheet and a multilayer film obtained by laminating a thermoplastic acrylic resin layer containing silicon dioxide particles having a specific average particle size in a specific ratio on at least one surface of the polycarbonate resin layer.

Sheets and films based on polycarbonate resin are widely used as structural materials to replace glass because of their excellent lightness, transparency, heat resistance, and impact resistance. Recently, it has been used as a decorative film because it is easy to print and heat-mold. For example, OA / electricity for automobile applications such as heat controller panels, car navigation touch panels, instrument covers, glazing, lamp lenses, housings and display panel front plates of mobile phones and mobile mobile terminals, and shatterproof films for glass members. It is widely used for electronic applications, greenhouse covering materials, arcades, building materials such as roofing materials for daylighting, road materials such as sidewalk wainscots and highway fences, and industrial materials such as name plates. However, its use has been limited due to its insufficient scratch resistance.

On the other hand, in order to improve the scratch resistance of polycarbonate, Patent Document 1 discloses a decorative film in which a thermoplastic acrylic resin layer is laminated on a polycarbonate resin layer. However, since the thermoplastic acrylic resin is laminated by this method, the pencil hardness equivalent to that of the thermoplastic acrylic resin can be obtained, but the scratch resistance (steel) when dust or dust is accumulated on the molded product and wiped off. Wool hardness) could not be sufficiently improved.

In addition, a sheet in which a thermoplastic acrylic resin layer is laminated on a polycarbonate resin layer is placed in an injection molding machine mold, and colloidal silica having a particle size of 10 to 20 nm is placed on the surface of the molded product in which the polycarbonate resin is injected into the mold. Patent Document 2 discloses a laminate that is thermally cured after applying the coating composition contained therein. However, although the scratch resistance is improved by this method, since the coating composition is applied to the molded product having a curved surface after molding, appearance defects such as dust adhesion and coating unevenness are likely to occur, and the productivity is poor.
Further, there is a problem that the haze is increased by applying the coating composition. If the coating composition is applied to the laminated sheet before injection molding, the productivity will be improved, but since the coating composition is poor in thermoplastic and brittle, cracks are likely to occur on the coated surface during the molding process. Has the drawback that it is limited to those with a large curvature.
In Patent Document 2, the average particle size of silica (silicon dioxide) in colloidal silica is preferably 4 to 20 nm, and the silica content is preferably 50 to 200 parts by weight with respect to the organoalkoxysilane which is a component of the coating. As an example thereof, a laminate having a haze of 0.7% or more is exemplified, but the haze value is not at a satisfactory level.

On the other hand, Patent Document 3 discloses a sheet in which a thermoplastic acrylic resin layer containing silicon dioxide particles is laminated on a polycarbonate resin layer, but further improvement in scratch resistance and impact resistance is desired. Was there.

Japanese Patent Application Laid-Open No. 7-156197 Japanese Unexamined Patent Publication No. 2006-35519 Patent No. 6495173

An object of the present invention is to provide a multilayer sheet and a multilayer film which have high transparency and scratch resistance and are easy to print and heat-mold in order to solve the above-mentioned problems of the prior art.

As a result of diligent studies to solve the above problems, the present inventors have laminated a thermoplastic acrylic resin layer containing silicon dioxide particles having a specific average particle size in a specific ratio on the polycarbonate resin layer. As a result, it has been found that it is possible to provide a multilayer sheet and a multilayer film having high transparency and scratch resistance and easy to print and heat-mold.

That is, the present invention uses the following <1> polycarbonate-based resin layer as a base material, and a thermoplastic acrylic resin layer containing silicon dioxide particles is provided on the outermost layer on one side or the outermost layer on both sides of the base material. A multi-layer sheet or multi-layer film made of a laminated body having
The multilayer having an average particle diameter of 0.1 to 2 μm and a content of the silicon dioxide particles of more than 1% by mass and 10% by mass or less with respect to the total amount of the thermoplastic acrylic resin layer. It is a sheet or multilayer film.
<2> The multilayer sheet or film according to <1> above, wherein the total light transmittance is 85% or more and less than 93%, and the haze is 0.01% or more and less than 0.7%.
<3># 0000 steel wool is attached to a 33 mm × 33 mm square pad, and the surface of the thermoplastic acrylic resin layer of the laminate is reciprocated 15 times under a load of 1000 g, and the haze after scratching is 0.01% or more 1.5. % Is the multilayer sheet or film according to <1> or <2> above.
<4> The above-mentioned <1> to <3>, wherein the overall average thickness of the laminated body is 0.03 to 2 mm, and the average thickness of the thermoplastic acrylic resin layer is 1 μm or more and less than 10 μm. It is a multilayer sheet or a multilayer film.
<5> A decorative molded product using the multilayer film or multilayer sheet according to any one of <1> to <4> as the outermost layer.
<6> The method for manufacturing a multilayer film or a multilayer sheet according to any one of <1> to <4> above.
When forming the laminate, the feed block method is used in which the ratio of the laminated width of the feed block to the effective die length (laminated width of the feed block (mm) / effective die length (mm)) is in the range of 0.03 to 0.7. The manufacturing method is characterized by the above.

The multilayer sheet and the multilayer film of the present invention can achieve both high transparency and scratch resistance by using a thermoplastic acrylic resin layer containing silicon dioxide having a specific average particle size in a specific ratio. Further, as compared with a sheet having a hard coat layer having a poor thermoplasticity on the surface, the heat forming property is good, cracks are less likely to occur at the time of forming, and the productivity is also good. Further, by laminating the above-mentioned thermoplastic acrylic resin layer thinly, it is possible to impart good film strength in addition to the above-mentioned characteristics.

Hereinafter, the present invention will be described in detail.
The polycarbonate-based resin constituting the polycarbonate-based resin layer in the present invention is obtained by an interfacial polymerization method using an aromatic dihydroxy compound or a small amount of the polyhydroxy compound and phosgen, or an aromatic dihydroxy compound. A optionally branched thermoplastic polycarbonate polymer obtained by an ester exchange reaction with a carbonic acid diester can be used.
In particular, a carbonic acid ester polymer containing bisphenol A obtained by an interfacial polymerization method as a main raw material is most preferable from the viewpoint of thermal stability and moldability.
The molecular weight of the polycarbonate resin used is preferably 20,000 to 28,000, more preferably 21,000 to 28,000 in terms of viscosity average molecular weight. If the viscosity average molecular weight is less than 20,000, a decrease in impact resistance may be observed. If the viscosity average molecular weight exceeds 28,000, the shapeability may decrease. Other resins and various additives may be added to the polycarbonate-based resin as long as its transparency and antistatic properties can be maintained. Examples of the additives include an ultraviolet absorber, an antioxidant, and an antioxidant. , Flame retardants, mold release agents, antistatic agents, dyes and pigments.
In particular, the thickness of the multilayer sheet and the multilayer film of the present invention is usually 0.03 mm to 2.0 mm, preferably 0.1 mm to 1.0 mm in consideration of moldability. If it is too thin, it will break easily, and if it is too thick, the shapeability will decrease.

The thermoplastic acrylic resin layer in the present invention is mainly composed of a thermoplastic acrylic resin and contains silicon dioxide particles.
(1) Thermoplastic Acrylic Resin The thermoplastic acrylic resin constituting the thermoplastic acrylic resin layer in the present invention is a copolymer of methyl methacrylate and an acrylic acid ester such as methyl acrylate, ethyl acrylate or butyl acrylate. Yes, the copolymerization composition and molecular weight may be appropriately selected depending on the coextrusion conditions. The copolymerization composition ratio is preferably 80 to 99% for methyl methacrylate and 1 to 20% for acrylic acid esters such as methyl, ethyl or butyl acrylate, but is not limited thereto. The molecular weight is preferably, but is not limited to, a weight average molecular weight of 30,000 to 300,000. The higher the load deflection temperature of the thermoplastic acrylic resin, the higher the glass transition temperature, and the roll transfer temperature is close to the roll transfer temperature of the polycarbonate resin, so that a laminate with excellent roll transferability and excellent appearance can be obtained. .. Therefore, the load bending temperature of the thermoplastic acrylic resin is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and further preferably 100 ° C. or higher.

A rubber-like polymer and / or rubber particles may be added to the thermoplastic acrylic resin as long as the transparency and surface hardness are not significantly reduced in order to impart impact resistance. In this case, the Rockwell hardness (M scale) of the added thermoplastic acrylic resin composition is preferably 30 or more. When the lockwell hardness is less than 30, the transparency is lowered, the print performed on the back surface by the haze when used as a housing is deteriorated, and the required surface hardness may not be obtained.

Further, other resins and various additives may be added to the thermoplastic acrylic resin as long as the transparency and the moldability can be maintained, and the additives include, for example, an ultraviolet absorber and an antioxidant. , Color inhibitor, flame retardant, mold release agent, antistatic agent, dye pigment and the like. In order to prevent ultraviolet deterioration of the polycarbonate-based resin layer and the thermoplastic acrylic resin layer in the present invention, it is particularly preferable to add an ultraviolet absorber.

Examples of the ultraviolet absorber that can be used include benzotriazole-based, benzophenone-based, salicylate phenyl ester-based, benzoxazine-based, malonic acid ester-based, triazine-based, and polymer-type ultraviolet absorbers to which they are added as pendants. ..
Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo. Triazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl) -6- (2H-benzotriazole) -2-yl) phenol], 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorbenzophenone, 2,2. -Dihydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like can be exemplified.
Further, examples of the salicylic acid phenyl ester-based ultraviolet absorber include pt-butylphenyl salicylate ester and the like. Examples of the benzoxazine-based ultraviolet absorber include 2,2'-(1,4-phenylene) bis [4H-3,1-benzoxadin-4-one] and the like.

Examples of the malonic acid ester-based ultraviolet absorber include [(4-methoxyphenyl) -methylene] dimethyl malonate and the like.
Examples of triazine-based ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4- Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,6-di (4-biphenyl)- 4- (2-Hydroxy-4- (2-ethylhexyl) oxyphenyl) -1,3,5triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5 -Triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6 (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4) -Butoxyethoxy) -1,3,5-triazine and the like can be mentioned, but the present invention is not limited to these, and generally available ultraviolet absorbers and the like are included.

Polymer-type UV absorbers have a hydroxybenzohenone or hydroxybenzotriazole structure in the molecule, and some of them have a hydrogen atom substituted with an alkyl group. As an example of the polymer type ultraviolet absorber, there is UVA-633L (2-hydroxy-4- (methacryloyloxyethoxy) benzophenone) methyl methacrylate copolymer commercialized by BASF.

Commercially available thermoplastic acrylic resins suitable for the present invention include Kuraray Co., Ltd. Parapet HR-1000L, Arkema ALTUGLAS V020, Mitsubishi Rayon IRG304, and the like.

The average thickness of the thermoplastic acrylic resin layer in the present invention is preferably 1 μm or more and 55 μm or less, more preferably 1 μm or more and 40 μm or less, further preferably 1 μm or more and less than 10 μm, and particularly preferably 1 μm or more and 9 μm or less. By reducing the average thickness of the thermoplastic acrylic resin layer, the transparency and strength of the laminate can be significantly improved. On the other hand, the hardness of the pencil may be lowered, but the pencil is lowered by providing, for example, a thermoplastic acrylic resin layer containing no silicon dioxide between the thermoplastic acrylic resin layer and the polycarbonate resin layer in the present invention. It can also supplement the hardness.

(2) Silicon Dioxide Particles The silicon dioxide particles constituting the thermoplastic acrylic resin layer in the present invention preferably have an average particle diameter of 0.1 to 2 μm, and more preferably 0.2 to 0.6 μm. If the average particle size is small, the scratch resistance effect is not sufficient, and if it is large, the punctate defects of the multilayer sheet and the multilayer film increase. The content of the silicon dioxide particles is more than 1% by mass and 10% by mass or less, preferably more than 1% by mass and 5% by mass or less, and more preferably 1.5 to 3. 0% by mass is optimal. If the content of the silicon dioxide particles is low, sufficient scratch resistance cannot be obtained, and if the content is high, the haze of the multilayer sheet and the multilayer film increases.
The method for producing the silicon dioxide particles is not particularly limited, but the silicon dioxide particles can be produced by a known method such as a VMC method, a wet synthesis method, or a melting method. In particular, the VMC method is preferable in consideration of the uniformity of the particle size of silicon dioxide. The VMC method is a method in which silicon dioxide powder is put into an oxygen stream and oxidized to obtain fine spherical silicon dioxide particles using the heat of reaction.
Commercially available products of silicon dioxide particles include Admafine SO-C1, Admafine SO-C2, Admafine SO-C4, Admafine SO-C5, Admafine SC110G-SQ manufactured by Admatex Co., Ltd., which are appropriately selected. Can be used alone or in combination. In particular, Admafine SC110G-SQ, which suppresses large particles of 10 μm or more contained in the product to 100 ppm or less, is good with extremely few point defects when the laminate is formed by extrusion molding.

The silicon dioxide particles contained in the thermoplastic acrylic resin layer in the present invention can be identified by the following method. It is possible to confirm the presence of silicon dioxide particles by observing the surface or cross section of the molded body using a surface observation device such as TEM and FE-SEM. By these measurements, it is possible to confirm the dispersed state of the particles and the bleed-out state to the surface. At the same time, silicon dioxide particles can be identified by using them in combination with surface elemental analyzers such as EDX, XPS, and EPMA.

Further, the average particle size and content of the silicon dioxide particles contained in the thermoplastic acrylic resin layer in the present invention can be measured by the following method.
As a pretreatment, a test piece and a sample solution can be prepared by the following method. A method of embedding the molded body with epoxy resin, cutting out only the acrylic resin layer from the embedded molded body using a surface cutting device such as an ultramicrotome, and dissolving it in a good solvent (dichloromethane, THF, etc.), or The sample solution can be prepared by any of the methods of punching a certain area of the molded product and dissolving the punched pieces in a good solvent (dichloromethane, THF, etc.).

The content of silicon dioxide particles can be measured by the following method. First, a solution in which Si particles having a known concentration are dispersed is impregnated into a filter paper and dried. X-ray fluorescence measurements are performed at three levels of concentration for use as a calibration curve. Next, the above-mentioned sample solution that has been pretreated and dissolved is dropped onto a filter paper, dried, and the dried filter paper is similarly measured by a fluorescent X-ray measuring device to quantify the Si element. It is possible.
The particle size can be measured by using a particle size measuring device manufactured by using a principle such as laser diffraction or dynamic light scattering for the prepared solution.

As a means for forming the thermoplastic acrylic resin layer on at least one surface of the polycarbonate resin layer, a method of co-extruding the thermoplastic acrylic resin layer and the polycarbonate resin layer, and thermoplasticity on the surface of the extruded polycarbonate. Examples thereof include a method of thermally laminating an acrylic resin film, a method of applying a solution in which silicon dioxide particles are dispersed in a thermoplastic acrylic resin solution onto a polycarbonate substrate, and a method of drying. In particular, the coextrusion method is most preferable because a multilayer film can be obtained in one step, the thickness ratio of each layer has a degree of freedom, and sufficient scratch resistance and high transparency can be achieved at the same time. When the heat laminating method is used, the thermoplastic acrylic resin film is preferably extruded. For example, when a film obtained by injection molding is heat-laminated, sufficient scratch resistance may not be obtained. Further, the multilayer sheet and the multilayer film obtained by applying a solution in which silicon dioxide particles are dispersed in a thermoplastic acrylic resin solution on a polycarbonate base material and drying it can obtain a sufficient scratch resistance effect. Must contain large amounts of silicon dioxide particles, which can result in impaired transparency.

Specific examples of the coextrusion method most suitable for producing the multilayer sheet and the multilayer film of the present invention as described above are described below.
The extruder used for manufacturing is generally composed of a main extruder that extrudes a polycarbonate resin that constitutes a substrate layer and a sub extruder that extrudes a thermoplastic acrylic resin that constitutes a coating layer. Normally, the sub extruder is the main extruder. A smaller one than the extruder is adopted. The temperature condition of the extruder for extruding the polycarbonate resin is usually 230 to 300 ° C, preferably 240 to 290 ° C, and the temperature condition of the extruder for extruding the thermoplastic acrylic resin is usually 200 to 270 ° C, preferably 200 to 270 ° C. It is 220 to 260 ° C.

As a general coextrusion method laminating method, there are a feed block method in which a laminate merged in a feed block is stretched and molded inside a T-die, and each layer is spread in each manifold inside the die and near the lip outlet. There is a multi-manifold method for merging, but in the present invention, the feed block method is preferable.
In the feed block method, the ratio of the laminated width of the feed block to the effective die length is particularly important, and the range of the laminated width (mm) of the feed block / effective die length (mm) = 0.03 to 0.7 is preferable. Further, the range of the laminated width (mm) of the feed block / effective die length (mm) = 0.05 to 0.2 is most preferable. If the laminated width (mm) / effective die length (mm) of the feed block is too large or too small, streak-like defects are likely to appear in the laminated body. The multi-manifold method, in which the laminated width and the effective lip length are the same, is a laminating method that is disadvantageous for forming the laminated body of the present invention with a high appearance because streak-like defects are likely to appear on the film.

The temperature of the die is usually 230 to 340 ° C, preferably 260 to 320 ° C. If the temperature of the die is too high or too low, the scratch resistance effect may not be exhibited. The laminated and sheet-shaped resin is flowed into a molding roll whose surface is mirror-treated or molded to form a laminated body. Cooling is performed while passing through the forming roll to form a laminate. As a cooling method, a film method in which the laminate is pressed at a low pressure between the No. 1 roll and the No. 2 roll and then hung on the No. 3 roll to form the laminate, and the No. 1 roll and the No. 2 roll are used. After sandwiching the laminate with the rolls at high pressure to form a bank (resin pool), further pressurize between the No. 2 roll and the No. 3 roll at high pressure, and laminate from the No. 3 roll with a take-up roll. There is a sheet method (bank method) that peels off the body. Since there is no difference in the transparency and scratch resistance of the laminate regardless of which method is used for cooling, it may be appropriately selected according to the required thickness and physical properties.

When the multilayer sheet and the multilayer film of the present invention are used for transparent applications, the total light transmittance is preferably 85% or more and less than 93%, more preferably 90% or more and less than 93%. Further, the haze of the multilayer sheet and the multilayer film of the present invention is preferably 0.01% or more and less than 0.7%, and more preferably 0.01% or more and less than 0.5%.
The scratch resistance of the multilayer sheet and the multilayer film of the present invention can be evaluated by the steel wool hardness test shown below.
# 0000 steel wool manufactured by Nippon Steel Wool Co., Ltd. was attached to a 33 mm x 33 mm square pad, and this pad was placed on the thermoplastic acrylic resin layer surface of the laminate held on the table, and 15 reciprocations under a load of 1000 g. Scratch. After cleaning this scratched surface with ethanol, the haze is measured. The haze after this scratch resistance test (steel wool hardness test) is preferably 0.01% or more and less than 15%, more preferably 0.01% or more and less than 10%, and most preferably 0.01% or more and less than 1.5%.
When a laminate having a large haze after the steel wool hardness test is used as a decorative film and a decorative sheet, which will be described later, scratches occur in daily use and the appearance of the molded product deteriorates, which is not preferable.

The laminate of the present invention is preferably used as a decorative film and a decorative sheet. Considering transparency and scratch resistance after commercialization, a polycarbonate resin layer having a thermoplastic acrylic resin layer containing silicon dioxide formed on one side thereof is preferably used. As a method of decoration, for example, a method of directly printing various designs on a polycarbonate resin layer surface by continuous gravure printing, silk printing, screen printing, etc., a method of transferring a transfer foil, a method of transferring metal plating by vapor deposition, sputtering, etc. Examples thereof include a method of applying decoration and a method of laminating other decorated resin films such as printing and vapor deposition.

Further, the decorative film and the decorative sheet can be used by laminating a thermoplastic resin sheet for the purpose of protecting the decorative surface. As the resin constituting the thermoplastic resin sheet, for example, a polycarbonate resin, a thermoplastic acrylic resin, an ABS resin, a polyvinyl chloride resin, a polyurethane resin, a polyester resin, a polyolefin resin, or at least two or more of them are kneaded. Examples thereof include the resin composition obtained.

The obtained decorative film or decorative sheet is placed on the side (usually the outside) where the thermoplastic acrylic resin layer containing silicon dioxide is required to have scratch resistance. A decorative molded product can be obtained by laminating it on a molded product. Here, as the resin constituting the thermoplastic resin molded product, for example, a polycarbonate resin, a thermoplastic acrylic resin, an ABS resin, a polyvinyl chloride resin, a polyurethane resin, a polyester resin, a polyolefin resin, or at least two kinds thereof. Examples thereof include a resin composition obtained by kneading the above.

As a method for obtaining a decorative molded product, a known molding method such as an in-mold molding method, an insert molding method, or an injection molding simultaneous bonding method is used. Considering the appearance of the decorative molded product, the in-mold molding method and the insert molding method are particularly suitable as the processing method for the laminate of the present invention.
The in-mold molding method is a method in which a decorative film or a decorative sheet is preformed in an injection molding die by vacuum molding or pressure molding, and then molten resin is injected therein to form an injection-molded product at the same time. This is a method of attaching a decorative film or a decorative sheet to the molded product.
In the insert molding method, a decorative film or a decorative sheet is preformed by vacuum molding or pressure molding, then inserted into an injection molding die, and a molten resin is injected into the injection molded product. At the same time as forming the above, it is a method of attaching a decorative film or a decorative sheet to the molded product.

The decorative molded product of the present invention uses a multilayer film or a multilayer sheet made of a laminated body having excellent scratch resistance as the outermost layer as described above. Therefore, the decorative molded product of the present invention is also excellent in scratch resistance.

Examples of the present invention are shown below, but the present invention is not limited thereto.
The evaluation and measurement methods used in this example are shown below.
(1) Average particle size of silicon dioxide particles contained in the thermoplastic acrylic resin layer of the laminate Measurement was carried out using the particle size distribution measuring device Nanotrack Wave Series EX250 manufactured by Nikkiso Co., Ltd. As a pretreatment, the molded product was punched into a certain area (circle with a diameter of 10 mm), and the punched pieces were dissolved in THF (tetrahydrofuran). The solution was poured into the cell of the measuring device and the average particle size of the silicon dioxide particles was measured.
(2) Content of silicon dioxide particles contained in the thermoplastic acrylic resin layer of the laminate The Si content was quantified using a fluorescent X-ray apparatus.
(3) Measurement of thickness of laminated body The central part of the laminated body was measured 10 times with a micrometer, and the average value was taken as the thickness.
(4) Measurement of layer thickness of laminated body The central part of the laminated body is cut off, the cross section is cut with a microtome, and the layer thickness of the polycarbonate resin layer and the thermoplastic acrylic resin layer is cut using the optical microscope ME600 and DIGITAL SIGHT manufactured by Nikon Co., Ltd. Was measured.
(5) Steel wool hardness test # 0000 steel wool manufactured by Nippon Steel Wool Co., Ltd. was attached to a 33 mm x 33 mm square pad, and this pad was placed on the surface of the sample held on the table and reciprocated 15 times under a load of 1000 g to scratch. did. After washing this sample with ethanol, the total light transmittance and haze were measured.
(6) Total light transmittance measurement The total light transmittance of the laminate was measured according to JIS K 7361-1 using a reflection / transmittance meter HR-100 manufactured by Murakami Color Technology Research Institute Co., Ltd.
(7) Haze measurement The haze of the laminated body was measured according to JIS K 7136 using a reflection / transmittance meter HR-100 manufactured by Murakami Color Technology Research Institute Co., Ltd.
(8) Tensile test (yield stress / fracture nominal strain)
Yield stress and fracture nominal strain were measured according to JIS K 7161 using a stromagraph VE20 manufactured by Toyo Seiki Seisakusho Co., Ltd.
(9) Drilling test (breaking energy)
The film is firmly fixed with a 5K-50 SUS F304 flange, and a bullet-shaped weight whose tip is processed into a hemisphere with a curvature of 3 mmR is dropped in the center of the film. Was calculated.
Breaking energy (J) = weight of broken weight (Kgf) x height of breaking (m) x 9.8 (N / Kgf)
(10) Appearance The obtained laminate was visually observed and compared with a laminate having a good appearance and containing no silicon dioxide particles.

(Example 1)
-Polycarbonate resin layer material Iupiron S-3000R N114 manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used as the polycarbonate resin layer material.
-Preparation of thermoplastic acrylic resin layer material ALTUGLAS V020 (thermoplastic acrylic resin) 95.55% by mass and Admafine SO-C1 (silicon dioxide with average particle diameter 0.20 μm) manufactured by Admatex Co., Ltd. 3. 7% by mass, Rikemar H-100 (slipper) manufactured by RIKEN Vitamin Co., Ltd. 0.14% by mass, Adecastab PEP-36 (heat stabilizer) 0.04% by mass manufactured by ADEKA Co., Ltd., K-NOXBHT manufactured by Kyodo Yakuhin Co., Ltd. ( While supplying 0.07% by mass of heat stabilizer and 0.5% by mass of Tinuvin1600 (ultraviolet absorber) manufactured by BASF with a weight-based quantitative feeder, 240 using a twin-screw extruder TEM-26SS manufactured by Toshiba Machinery Co., Ltd. It was kneaded at ° C and pelletized.
Molding of laminated body As an extruder for the polycarbonate resin layer (A), a single-screw extruder with a screw diameter of 100 mm and L / D = 32 is used, the cylinder temperature is set to 280 ° C., and the feed block is 236 kg / hr. The screw rotation speed was adjusted so that it could be supplied at. As the extruder for the thermoplastic acrylic resin layer (B) containing silicon dioxide particles as the coating layer, a single-screw extruder with a screw diameter of 50 mm and L / D = 32 is used, and the cylinder temperature is 240 ° C. The gear pump rotation speed was adjusted to 10 kg / hr and supplied to the feed block. The screw rotation speed was automatically controlled so that the resin pressure at the inlet of the gear pump was 7.0 MPa. Two types of resins simultaneously supplied in a feed block set at 260 ° C. were laminated with a width of 200 mm, spread in a film shape in a die with an effective lip length of 1650 mm set at 280 ° C., and discharged. The film-like laminate discharged from the die was sandwiched between a No. 1 roll having a diameter of 300 mm and a width of 2000 mm and a No. 2 roll having a diameter of 450 mm and a width of 2000 mm at 0.25 MPa, and then hung on the No. 3 roll to form a film. Each roll temperature was set to No. 1 roll: 60 ° C, No. 2 roll: 120 ° C, No. 3 roll: 140 ° C, and the roll speed was 10.9 m. As the No. 1 roll, a rubber roll with a rubber thickness of 5 mm and a rubber hardness of 80 ° is covered with a mirror-polished metal sleeve, and a SF roll manufactured by Chiba Kikai Kogyo Co., Ltd. is used, which is mirror-polished as a No. 2 roll and a No. 3 roll. A common metal rigid roll was used.

As a result of analyzing the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Example 2)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 96.85% by mass, and Admafine SO-C1 (average particle diameter 0.20 μm) manufactured by Admatex Co., Ltd. was used. A laminate was obtained by the same method as in Example 1 except that 7% by mass was set to 2.4% by mass of Admafine SO-C1 (average particle size 0.31 μm). As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Example 3)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 98.15% by mass, and Admafine SO-C1 (average particle diameter 0.20 μm) manufactured by Admatex Co., Ltd. was used. A laminate was obtained by the same method as in Example 1 except that 7% by mass was set to 1.1% by mass of Admafine SO-C5 (average particle size 1.50 μm). As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Example 4)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 89.25% by mass, and Admafine SO-C1 (average particle diameter 0.20 μm) manufactured by Admatex Co., Ltd. was used. 7% by mass is Admafine SO-C1 (average particle size 0.20 μm) and 10% by mass, the discharge rate of the polycarbonate resin layer (A) for molding the laminate is 241 kg / h, and the thermoplastic acrylic resin layer (1). A laminated body was obtained by the same method as in Example 1 except that the discharge amount of B) was 3.3 kg / h. As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Example 5)
A laminated body was obtained by the same method as in Example 2 except that the discharge amount of the polycarbonate resin layer (A) was 114 kg. As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Example 6)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Arkema was set to 96.847% by mass, and silicone oil KF-96 manufactured by Shinetsu Chemical Industry Co., Ltd. was added in an amount of 0.003% by mass. Obtained a laminated body by the same method as in Example 2. As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation and preparation of the above-mentioned thermoplastic acrylic resin layer material. ..
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Example 7)
The preparation of the polycarbonate-based resin layer material and the thermoplastic acrylic resin layer material was the same as in Example 2.
-Molding of laminate Using a single-screw extruder with a screw diameter of 120 mm and L / D = 32 as an extruder for the polycarbonate resin layer (A), set the cylinder temperature to 280 ° C and 305 kg / g to the feed block. The screw rotation speed was adjusted so that it could be supplied by hr. As the extruder for the thermoplastic acrylic resin layer (B) containing silicon dioxide particles as the coating layer, a single-screw extruder with a screw diameter of 50 mm and L / D = 32 is used, and the cylinder temperature is 240 ° C. The gear pump rotation speed was adjusted to 1.5 kg / hr and supplied to the feed block. The screw rotation speed was automatically controlled so that the resin pressure at the inlet of the gear pump was 4.0 MPa. Two types of resins simultaneously supplied in a feed block set at 260 ° C. were laminated with a width of 200 mm, and spread out in a sheet shape in a die with an effective lip length of 1180 mm set at 260 ° C. and discharged. The sheet-like laminate discharged from the die is sandwiched at 10 MPa using a No. 1 roll having a diameter of 360 mm and a surface length of 1500 mm and a No. 2 roll having a diameter of 360 mm and a surface length of 1500 mm to form a bank (resin pool), and then No. A .2 roll and a No. 3 roll having a diameter of 360 mm and a surface length of 1500 mm were pressed at 10 MPa, and the sheet-like laminate was peeled off from the No. 3 roll with a take-up roll to form a molded product. Each roll temperature is set to No. 1 roll: 130 ℃, No. 2 roll: 140 ℃, No. 3 roll: 180 ℃, and the roll speed is No. 1 roll: 2.93m / min, No. 2 roll: 2.93 m / min, No. 3 roll: 2.95 m / min, take-back roll: 3.26 m / min. The No. 1 roll, No. 2 roll, and No. 3 roll all used mirror-polished general metal rigid body rolls. A rubber roll having a hardness of 60 ° was used as the take-up roll.

(Comparative Example 1)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 98.75% by mass, and Admafine SO-C5 (average particle diameter 1.50 μm) manufactured by Admatex Co., Ltd. 1. A laminate was obtained by the same method as in Example 3 except that 1% by mass was set to 0.5% by mass of Admafine SO-C5 (average particle size 1.50 μm). As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Comparative Example 2)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 87.25% by mass, and Admafine SO-C1 (average particle diameter 0.20 μm) manufactured by Admatex Co., Ltd. 10. A laminate was obtained by the same method as in Example 4 except that 0% by mass was set to 12.0% by mass of Admafine SO-C1 (average particle size 0.20 μm). As a result of the analysis of the obtained laminate, the average particle size and the content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparing the thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Comparative Example 3)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 87.25% by mass, and Admafine SO-C1 (average particle diameter 0.20 μm) manufactured by Admatex Co., Ltd. was used. A laminate was obtained by the same method as in Example 1 except that 7% by mass was set to 12.0% by mass of Admafanano YC100C (average particle size 0.09 μm) manufactured by Admatex Co., Ltd. As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

(Comparative Example 4)
In the preparation of the thermoplastic acrylic resin layer material, ALTUGLAS V020 (thermoplastic acrylic resin) manufactured by Alchema was set to 99.15% by mass, and Admafine SO-C1 (average particle size 0.20 μm) was set to 3.7% by mass. A laminate was obtained by the same method as in Example 1 except that the fine SO-C6 (average particle size 2.10 μm) was 0.1% by mass. As a result of analysis of the obtained laminate, the average particle size and content of silicon dioxide contained in the thermoplastic acrylic resin layer were the same as the values at the time of preparation of the above-mentioned thermoplastic acrylic resin layer material.
Moreover, the thickness and the layer thickness of the central portion of the laminated body were measured. The sum of the thickness measured with a micrometer and the thickness of each layer measured with an optical microscope was the same value. A steel wool test was performed on the surface of the layer (B) of this laminate, and the total light transmittance and haze before and after the test were measured. The evaluation results are shown in Table 1.

From the results of the examples and comparative examples summarized in Table 1, the following became clear. First, in each of Comparative Examples 1 to 4, the content of the silicon dioxide particles is 1% by mass or less or more than 10% by mass, or the average particle diameter of the silicon dioxide particles is less than 0.1 μm or more than 2 μm. ing. According to these comparative examples, it was confirmed that the haze value was greatly increased after the scratch resistance test and the appearance was inferior.
More specifically, in Comparative Example 1 (0.5% by mass) in which the content of the silicon dioxide particles is small, the haze after the steel wool test increases even if the silicon dioxide particles having a large particle size are used, and the resistance is increased. It was confirmed that it was inferior in scratch resistance. In Comparative Example 2 (12% by mass) in which the content of silicon dioxide particles is high, silicon dioxide particles having a small particle size are used, and even if the acrylic resin layer thickness is made as thin as possible, the haze before the steel wool test is high. It was confirmed that the transparency was inferior and punctate defects occurred. Further, it was confirmed that in Comparative Example 3 (0.09 μm) in which the particle size of the silicon dioxide particles was small, the haze after the steel wool test was remarkably high and the scratch resistance effect was not exhibited at all. It was confirmed that in Comparative Example 4 (2.1 μm) in which the particle size of the silicon dioxide particles was large, the haze after the steel wool test was high and the transparency was inferior, and punctate defects were generated.

On the other hand, in Examples 1 to 7 of the present invention, unlike the above-mentioned comparative example, the thermoplastic acrylic resin layer contains an appropriate amount of silicon dioxide particles having an average particle diameter in an appropriate range. There is. As a result, it was confirmed that the increase in the haze value was suppressed even after the scratch resistance test, the sheet (laminated body) had excellent scratch resistance, and the appearance of the sheet and the decorative molded product was good. Was done. It was also confirmed that the scratch resistance was further improved by using the silicon dioxide particles and an appropriate amount of silicone oil in combination.

Claims

A multilayer sheet or film composed of a laminate having a polycarbonate-based resin layer as a base material and having a thermoplastic acrylic resin layer containing silicon dioxide particles on the outermost layer on one side or the outermost layers on both sides of the base material. ,
The multilayer having an average particle diameter of 0.1 to 2 μm and a content of the silicon dioxide particles of more than 1% by mass and 10% by mass or less with respect to the total amount of the thermoplastic acrylic resin layer. Sheet or multilayer film.
The multilayer sheet or film according to claim 1, wherein the total light transmittance is 85% or more and less than 93%, and the haze is 0.01% or more and less than 0.7%.
# 0000 steel wool was attached to a 33 mm x 33 mm square pad, and the surface of the thermoplastic acrylic resin layer of the laminate was reciprocated 15 times under a load of 1000 g, and the haze after scratching was 0.01% or more and less than 1.5%. The multilayer sheet or the multilayer film according to claim 1 or 2.
The multilayer sheet or film according to any one of claims 1 to 3, wherein the overall thickness of the laminated body is 0.03 to 2 mm, and the average thickness of the thermoplastic acrylic resin layer is 1 μm or more and less than 10 μm.
A decorative molded product using the multilayer film or multilayer sheet according to any one of claims 1 to 4 as the outermost layer.