WO2018181471A1 - Laminate - Google Patents

Laminate Download PDF

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Publication number
WO2018181471A1
WO2018181471A1 PCT/JP2018/012751 JP2018012751W WO2018181471A1 WO 2018181471 A1 WO2018181471 A1 WO 2018181471A1 JP 2018012751 W JP2018012751 W JP 2018012751W WO 2018181471 A1 WO2018181471 A1 WO 2018181471A1
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WO
WIPO (PCT)
Prior art keywords
methacrylic resin
weight
silica
less
laminate
Prior art date
Application number
PCT/JP2018/012751
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French (fr)
Japanese (ja)
Inventor
将一 隅田
和広 山▲崎▼
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2018181471A1 publication Critical patent/WO2018181471A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/20—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by refractors, transparent cover plates, light guides or filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
    • F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters

Definitions

  • the present invention relates to a laminate containing a methacrylic resin layer containing a methacrylic resin and silica particles, and a thermoplastic resin layer.
  • Methacrylic resin is light in weight and has excellent transparency and weather resistance, so it has been attracting attention as a glass replacement for vehicles such as tail lamp covers and head lamp covers, and glazing.
  • the impact resistance is not sufficient compared with glass, in order to improve the impact resistance, a laminate having two or more layers having different compositions has been developed (for example, Patent Document 1).
  • Glass substitutes for vehicles are required to be transparent.
  • the lamp cover for a vehicle is required not only to be transparent, but also to be difficult to be scratched when rubbed with gravel that jumps during traveling (sometimes referred to as “scratch resistance” in this specification).
  • the laminate described in Patent Document 1 is excellent in transparency, it is not satisfactory in terms of scratch resistance.
  • An object of the present invention is to provide a laminate having high transparency and excellent scratch resistance.
  • the present invention includes the embodiments described in [1] to [4] below.
  • Methacrylic resin containing 99.75% by weight or more and less than 99.995% by weight of methacrylic resin and 0.005% by weight or more and 0.25% by weight or less of silica particles having an average primary particle diameter of 0.2 to 2 ⁇ m.
  • the laminated body which contains a resin layer and the thermoplastic resin layer whose content of the said silica particle is 0.005 weight% or less, and the haze measured according to JISK7136 is 5.5% or less.
  • the “laminated body” has at least two layers having different compositions from each other.
  • the “vehicle lamp cover” is a cover provided for the purpose of protecting the light source of the vehicle lamp and improving the illuminance of the light source.
  • the “vehicle lamp” is attached to a vehicle such as an automobile or a motorcycle.
  • a headlamp, a tail lamp, a brake lamp, a direction indicator lamp, a fog lamp, a vehicle width lamp, and a reverse lamp are applicable.
  • the “methacrylic resin layer” is a layer containing a methacrylic resin
  • the “methacrylic resin” is a polymer having a structural unit derived from a monomer having a methacrylic group.
  • “Silica particles” are substantially spherical substances having SiO 2 , and “average primary particle diameter” is an average value of primary particle diameters measured by a laser diffraction particle size distribution analyzer.
  • the “thermoplastic resin layer” is a layer containing a thermoplastic resin as a main component, and the “thermoplastic resin” is a resin having a property of softening when heated and solidifying when cooled.
  • the laminate of the present invention includes a methacrylic resin layer and a thermoplastic resin layer.
  • the methacrylic resin layer contains 99.75% by weight or more and 99.995% by weight or less of methacrylic resin, and 0.005% by weight or more and 0.25% by weight or less of silica particles having an average primary particle diameter of 0.2 ⁇ m or more and 2 ⁇ m or less. It is a layer to do.
  • a methacrylic resin is a polymer having a structural unit derived from a monomer having a methacrylic group.
  • Examples of the methacrylic resin are derived from a methacrylic homopolymer containing only a structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms.
  • the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is a compound represented by CH 2 ⁇ CH (CH 3 ) COOR (R is an alkyl group having 1 to 4 carbon atoms).
  • a vinyl monomer copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms is copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms and has a vinyl group. It is a monomer.
  • alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, and methacrylic acid. Examples thereof include sec-butyl and isobutyl methacrylate, and methyl methacrylate is preferred.
  • the alkyl methacrylates exemplified above may be used alone or in combination of two or more.
  • Examples of vinyl monomers copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms include cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and methacrylic acid.
  • Methacrylic acid esters such as hydroxypropyl and monoglycerol methacrylate (excluding alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms); methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid Acrylic acid esters such as 2-ethylhexyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itacic anhydride Unsaturated carboxylic acids such as acids or their anhydrides; nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, dimethylaminoethyl methacrylate; allyl glycidyl ether, glycidyl acrylate, methacrylic acid And epoxy group-containing mono
  • a vinyl monomer copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms and, if necessary, a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms. May be polymerized by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.
  • the silica particles used in the present invention are substantially spherical substances having SiO 2 .
  • the silica particles may include not only a substantially spherical shape but also a rectangular parallelepiped shape or a pulverized shape having a plurality of corners.
  • the silica particles are preferably spherical.
  • Examples of the spherical silica particles include Admafine (registered trademark) manufactured by Admatechs Co., Ltd., Sunsphere (registered trademark) manufactured by AGC S-Tech Co., Ltd., Sciqas series manufactured by Sakai Chemical Industry Co., Ltd., and Denka Co., Ltd. Examples include the SFP series.
  • silica particles particles treated with a silane coupling agent such as amino silane, epoxy silane, methacryl silane, acrylic silane, vinyl silane, phenyl silane, mercapto silane, etc. may be used, but in terms of scratch resistance, It is preferable to use silica particles that are not surface-treated with the silane coupling agent.
  • surface-treated refers to a state in which a hydroxyl group present on the surface of silica particles is dehydrated and condensed with a hydroxyl group generated by hydrolysis of an alkoxy group of a silane coupling agent.
  • the average primary particle size of the silica particles used in the present invention is 0.2 ⁇ m or more and 2 ⁇ m or less, preferably 0.3 ⁇ m or more and 1.8 ⁇ m or less, more preferably 0.3 ⁇ m or more and 1.6 ⁇ m or less. 3 ⁇ m or more and 1.5 ⁇ m or less is more preferable, 0.3 ⁇ m or more and 1.2 ⁇ m or less is more preferable, and 0.3 ⁇ m or more and 0.8 ⁇ m or less is particularly preferable.
  • the methacrylic resin layer may contain two or more types of silica particles having different particle sizes.
  • the average primary particle diameter can be measured with, for example, a laser diffraction particle size distribution measuring apparatus. By making the average primary particle diameter of the silica particles in the above range, a laminate excellent in both scratch resistance and transparency can be provided.
  • the particle size (diameter) of the silica particles is 0.2 ⁇ m or more and 2 ⁇ m or less, preferably 0.3 ⁇ m or more and 1.8 ⁇ m or less, and 0.4 ⁇ m or more and 1.5 ⁇ m or less. Is more preferable.
  • the major axis of the silica particles is preferably 0.2 ⁇ m or more and 2 ⁇ m or less, more preferably more than 0.4 ⁇ m and 2 ⁇ m or less.
  • the major axis is the length of the longest part of the linear distance of the particles. The long diameter and the particle diameter can be measured by reading from the observation image of the particles with a scanning electron microscope.
  • the content of the methacrylic resin contained in the methacrylic resin layer of the present invention is 99.75% by weight or more and less than 99.995% by weight, and the silica particle content exceeds 0.005% by weight and is 0.25% by weight or less. It is. However, the total of the content of methacrylic resin and the content of silica particles is 100% by weight.
  • the content of silica particles preferably satisfies the following formula (1), and the content of methacrylic resin is preferably (100-y) wt%.
  • x represents the numerical value of the average primary particle diameter of the silica particles represented by the unit “ ⁇ m”
  • y represents the total amount of the methacrylic resin and the silica particles 100.
  • the numerical value of the content of the silica particles expressed with the unit "wt%" with respect to wt% is shown.
  • the content of the silica particles is preferably an amount satisfying the following formula (2) and the following formula (3).
  • 0.005 ⁇ y ⁇ ⁇ 0.253x + 0.206 Formula (2) In the formula, x and y are the same as those in the formula (1). However, x is 0.2 ⁇ x ⁇ 0.5.) 0.005 ⁇ y ⁇ ⁇ 0.045x + 0.1027 Formula (3) (Wherein x and y are the same as in formula (1), where x is 0.5 ⁇ x ⁇ 2)
  • the content of silica particles is more preferably an amount satisfying the following formula (4) and the following formula (5).
  • 0.005 ⁇ y ⁇ ⁇ 0.287x + 0.213 Formula (4) (In the formula, x and y are the same as those in the formula (1). However, x is 0.2 ⁇ x ⁇ 0.5.) 0.005 ⁇ y ⁇ ⁇ 0.041x + 0.090 Formula (5) (Wherein x and y are the same as in formula (1), where x is 0.5 ⁇ x ⁇ 2)
  • the content of the silica particles may be an amount satisfying the following formula (6) and the following formula (7).
  • 0.01 ⁇ y ⁇ 0.036x + 0.073 Formula (6) (X and y in the formula are the same as in the above formula (1), provided that x is 0.5 ⁇ x ⁇ 2.)
  • Formula (7) (X and y in the formula are the same as in the above formula (1), provided that x is 0.2 ⁇ x ⁇ 0.5.)
  • the content of the silica particles is an amount satisfying the following formula (8) and the following formula (9).
  • 0.01 ⁇ y ⁇ 0.036x + 0.073 Formula (8) (X and y in the formula (8) are the same as those in the above formula (1). However, x is 0.5 ⁇ x ⁇ 2.)
  • Formula (9) (X and y in Formula (9) are the same as those in Formula (1) above, provided that x is 0.2 ⁇ x ⁇ 0.5.)
  • the content of the silica particles can be determined by measuring the amount of Si using ICP (Inductively Coupled Plasma) emission spectroscopy and converting it to the amount of SiO 2 .
  • ICP Inductively Coupled Plasma
  • the thermoplastic resin layer contains a thermoplastic resin.
  • the thermoplastic resin layer may contain components other than the thermoplastic resin, and for example, may contain silica particles.
  • the content of silica particles is 0.005% by weight or less (provided that the total content of the thermoplastic resin and the silica particles is 100% by weight).
  • the laminated body of this invention may contain the 2 or more types of thermoplastic resin layer.
  • the thermoplastic resin is a resin having a haze measured in accordance with JIS K7136 of 2% or less when formed into a molded product having a thickness of 3 mm.
  • methacrylic resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin and the like can be mentioned.
  • methacrylic resin or polycarbonate resin is preferable, and methacrylic resin is more preferable.
  • methacrylic resin examples are the same as those exemplified as the methacrylic resin contained in the methacrylic resin layer.
  • the methacrylic resin contained in the thermoplastic resin layer may be the same as or different from the methacrylic resin contained in the methacrylic resin layer.
  • Polycarbonate resin is a resin containing structural units derived from dihydroxy compounds.
  • Polycarbonate resin for example, obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method; polymerizing a carbonate prepolymer by a solid phase transesterification method or the like And those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
  • dihydric phenol examples include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5-dibromo ) Phenyl ⁇ propane, 2,2-bis ⁇ (3-isopropyl-4-hydroxy) phenyl ⁇ propane, 2,2-bis ⁇ (4 -Hydroxy-3-phenyl) phenyl ⁇ propane, 2,2-bis (4-hydroxyphenyl)
  • carbonylating agent examples include carbonyl halides (such as phosgene), carbonate esters (such as diphenyl carbonate), and haloformates (such as dihaloformates of dihydric phenols). These may be used alone or in combination of two or more.
  • a methacrylic resin composition containing methacrylic resin and silica particles is injected into the same mold in a state where a thermoplastic resin is injection-molded into a mold of a molding machine.
  • a two-color molding method for molding or a methacrylic resin layer containing a methacrylic resin composition containing a pre-injection-molded methacrylic resin and silica particles is pasted into a mold, and the inside of the mold to which the methacrylic resin layer is pasted
  • an insert molding method in which a thermoplastic resin is injection molded may be used.
  • the temperature of the cylinder at the time of injection molding is preferably 230 ° C or higher, and preferably 290 ° C or lower.
  • a solution mixing method in which silica particles are added and mixed in a solution in which a methacrylic resin is dissolved in a solvent, and the silica particles are dispersed in the solution; a methacrylic resin and silica particles are converted into a single screw extruder, a twin screw extruder, Examples include a melt kneading method using an apparatus such as a mixing roll; a cast polymerization method in which silica particles are dispersed in a monomer that is a raw material of a methacrylic resin, a polymerization method, a suspension polymerization method, or an emulsion polymerization method.
  • the mixing temperature is preferably 100 ° C. or less, and when applying the melt-kneading method, the kneading temperature is preferably 200 ° C. or more and 300 ° C. or less, and when the cast polymerization method is applied, The polymerization temperature is preferably 150 ° C. or lower, and when the suspension polymerization method or the emulsion polymerization method is applied, the polymerization temperature is preferably 100 ° C. or lower.
  • a melt kneading method is preferable because the amount of silica particles added can be easily adjusted.
  • the amount of methacrylic resin added during the production of the methacrylic resin composition is 99.75 wt% or more and less than 99.995 wt%, and the amount of silica particles added is more than 0.005 wt% and 0.25 wt% or less. It is. However, the total of the addition amount of the methacrylic resin and the addition amount of the silica particles is 100% by weight.
  • the amount of silica particles added is preferably an amount that satisfies the above formula (1), more preferably an amount that satisfies the above formula (2) and the above formula (3), and the above formula (4). It is more preferable that the amount satisfies the above formula (5).
  • the amount of methacrylic resin added is preferably (100-y)% by weight.
  • the methacrylic resin layer or the thermoplastic resin layer may contain an ultraviolet absorber, a slip agent, an antioxidant, a release agent, an antistatic agent, and the like as necessary.
  • examples of the UV absorber include benzophenone UV absorbers, cyanoacrylate UV absorbers, benzotriazole UV absorbers, malonic ester UV absorbers, oxalanilide UV absorbers, and slip agents.
  • examples include silicone oils and polysiloxane compounds.
  • antioxidants include phenolic antioxidants, sulfur antioxidants, and phosphorus antioxidants.
  • mold release agents include higher fatty acids.
  • Examples include esters, higher aliphatic alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, fatty acid derivatives, and the like.
  • Antistatic agents include conductive inorganic particles, tertiary amines, quaternary ammonium salts, and cationic systems. Examples include acrylic ester derivatives and cationic vinyl ether derivatives.
  • the component is added during the production of the methacrylic resin composition, mixed with the methacrylic resin and the silica particles, and a methacrylic resin composition containing the component is added. It is preferable to manufacture.
  • the thermoplastic resin layer contains a component other than the thermoplastic resin, the thermoplastic resin and the component other than the thermoplastic resin are mixed in advance to manufacture the thermoplastic resin composition before the laminate is manufactured. Is preferred.
  • the haze of the methacrylic resin layer measured according to JIS K7136 is preferably 5.5% or less, more preferably 3.5% or less, still more preferably 2.5% or less, and even more preferably 2 0.0% or less, particularly preferably 1.5% or less.
  • the haze of the methacrylic resin layer is 5.5% or less, scattering of light from the vehicle lamp can be suppressed, and therefore, it can be applied to a vehicle lamp cover.
  • the haze of the thermoplastic resin layer measured according to JIS K7136 is preferably 2% or less, preferably 1.5% or less, and more preferably 1.0% or less.
  • the haze of the thermoplastic resin layer is 2.0% or less, scattering of light from the vehicle lamp can be suppressed, and therefore, it can be applied to a vehicle lamp cover.
  • the thickness of the laminate is preferably 0.5 mm or more and 8 mm or less, more preferably 1 mm or more and 6 mm or less, and further preferably 2 mm or more and 5 mm or less.
  • the thickness of the methacrylic resin layer in the laminate is preferably 0.5 mm or more and 8 mm or less, more preferably 1 mm or more and 6 mm or less, and further preferably 1 mm or more and 2.5 mm or less.
  • the laminate of the present invention is superior in both scratch resistance and transparency as compared with a single thermoplastic resin layer or a single methacrylic resin layer.
  • the haze of the laminate measured according to JIS K7136 is 5.5% or less, preferably 3.5% or less, more preferably 3% or less, and even more preferably 2.5% or less. More preferably, it is 2.0% or less, More preferably, it is 1.5% or less. In particular, when the haze of the laminate is 5.5% or less, scattering of light from the vehicle lamp can be suppressed, and therefore, it can be applied to a vehicle lamp cover.
  • the laminate of the present invention is excellent in scratch resistance.
  • the scratch resistance is, for example, FMVSS (Federal Motor Vehicle Safety Standard) No.
  • a wear test using steel wool is performed according to No. 108, and the haze difference ( ⁇ haze) of the laminate before and after the test is evaluated.
  • the wear test is performed on the surface of the laminate on the side of the methacrylic resin layer. It can be said that the smaller the ⁇ haze, the more excellent the scratch resistance of the laminate of the present invention.
  • the ⁇ haze of the laminate of the present invention is preferably less than 15%, more preferably 13% or less, and even more preferably 10% or less.
  • the haze of the laminate before and after the test is measured according to JIS K7136.
  • the laminate of the present invention can be applied to vehicle windows, vehicle front grilles, vehicle pillars, and vehicle lamp covers.
  • the vehicle lamp cover of the present invention includes the above laminate.
  • Examples of the vehicle lamp cover include a headlamp, tail lamp, brake lamp, direction indicator lamp, fog lamp, vehicle width lamp, and reverse lamp cover.
  • the laminate of the present invention can be suitably used as a headlamp cover, ie, a headlamp cover, which is frequently rubbed with gravel and is required to have better scratch resistance.
  • the surface of the obtained methacrylic resin layer or the surface on the methacrylic resin layer side of the laminate was subjected to an abrasion test using steel wool. Specifically, using # 0000 steel wool, the surface of the methacrylic resin layer or laminate was rubbed 11 times at a load of 14 kPa at a speed of 15 cm / sec. According to JIS K7136, the haze of the methacrylic resin layer or laminate before and after the wear test was measured, and the change in haze before and after the test ( ⁇ haze (unit:%)) was calculated. When the ⁇ haze is less than 15%, the scratch resistance is excellent.
  • Silica 1 Admafine (registered trademark) S0-C1 (true spherical shape, average primary particle size: 0.3 ⁇ m) manufactured by Admatechs Co., Ltd.
  • Silica 2 Admafine Co., Ltd.
  • Admafine (registered trademark) S0-C2 spherical, average primary particle size: 0.5 ⁇ m
  • Silica 3 Admafine Co., Ltd.
  • Admafine (registered trademark) S0-C5 spherical, average primary particle size: 1.6 ⁇ m
  • Silica 4 Sunsphere (registered trademark) NP-30 (true spherical shape, average primary particle size: 4.0 ⁇ m) manufactured by AGC S-Itech Co., Ltd.
  • Silica 5 manufactured by Admatechs Co., Ltd.
  • Admanano (registered trademark) YC100C-SM2 (spherical, average primary particle size: 0.1 ⁇ m)
  • Silica 6 Toshiyama Co., Ltd. Sun Seal SS07 (spherical, average primary particle size: 0.8 ⁇ m)
  • the reaction liquid (partial polymer) coming out of the polymerization reactor After preheating the reaction liquid (partial polymer) coming out of the polymerization reactor, it is supplied to a devolatilizing extruder, and unreacted monomer components are vaporized and recovered, and a pellet-like methacrylic resin A is obtained. It was.
  • the monomer unit derived from methyl methacrylate is 97.5% by weight
  • the content of the monomer unit derived from methyl acrylate is 2.5% by weight
  • MFR was 2 g / 10 min.
  • silica-containing methacrylic resin B After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 1, using a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm, the following kneading conditions was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin B.
  • a single screw extruder VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • silica-containing methacrylic resin B2 After mixing 99.0% by weight of methacrylic resin A and 1.0% by weight of silica 1, a single screw extruder having a screw diameter of 40 mm (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) was used and the following kneading conditions were used. Was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin B2.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • silica-containing methacrylic resin C After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 2, a single screw extruder having a screw diameter of 40 mm (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) was used and the following kneading conditions were used. Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin C.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • silica-containing methacrylic resin C2 After mixing 99.0% by weight of methacrylic resin A and 1.0% by weight of silica 2, using a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm, the following kneading conditions was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin C.
  • a single screw extruder VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • silica-containing methacrylic resin D After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 3, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used, and the following kneading conditions: Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin D.
  • VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • Extruder temperature The eight heaters from the raw material inlet to the outlet were set to 200 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 240 ° C., and 250 ° C. from the raw material inlet side, respectively.
  • Rotation speed 200rpm
  • Feeding speed of raw material 12kg / hour
  • Extruder temperature The eight heaters from the raw material inlet to the outlet were set to 200 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 240 ° C., and 250 ° C. from the raw material inlet side, respectively.
  • Rotation speed 200rpm
  • Feeding speed of raw material 12kg / hour
  • Example 1 After mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used and the following kneading conditions were used. The mixture was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-shaped methacrylic resin composition.
  • a single screw extruder VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • the obtained methacrylic resin layer was attached to a 150 mm ⁇ 90 mm ⁇ 3 mm thick mold, and the methacrylic resin A was 150 mm ⁇ 90 mm under the following molding conditions using an injection molding machine (FANUC Corporation 150D).
  • a laminated body including a 1 mm-thick methacrylic resin layer and a layer containing 2 mm-thick methacrylic resin A was obtained by molding into a flat plate shape of 3 mm thickness.
  • the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
  • Screw temperature The five heaters from the raw material inlet to the outlet were respectively set at 220 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
  • Injection speed 30 mm / sec
  • the obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
  • Example 2 Example in which 50% by weight of methacrylic resin A and 50% by weight of silica-containing methacrylic resin B were mixed instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 3 Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin C was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 4 Example except that 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B were mixed, but 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin C were mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 5 Example in which 90% by weight of methacrylic resin A and 10% by weight of silica-containing methacrylic resin D were mixed instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 6 Instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A, 10% by weight of silica-containing methacrylic resin B, and 5% by weight of silica-containing methacrylic resin C. % was obtained in the same manner as in Example 1 except that% was mixed and evaluated.
  • Example 7 Instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 80% by weight of methacrylic resin A, 10% by weight of silica-containing methacrylic resin B, and 10% by weight of silica-containing methacrylic resin C % was obtained in the same manner as in Example 1 except that% was mixed and evaluated.
  • Example 8 After mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used and the following kneading conditions were used. The mixture was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-shaped methacrylic resin composition.
  • VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • the obtained molded body was affixed to a 150 mm ⁇ 90 mm ⁇ 3 mm thick mold, and methacrylic resin A was 150 mm under the following molding conditions using an injection molding machine (EC130SXII-4A manufactured by Toshiba Machine Co., Ltd.).
  • the laminate was formed into a flat plate shape of ⁇ 90 mm ⁇ 3 mm thickness and composed of a 1 mm thick layer containing the methacrylic resin composition and a 2 mm thick layer containing the methacrylic resin A.
  • the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
  • Screw temperature The five heaters from the raw material inlet to the outlet were respectively set to 60 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
  • Injection speed 90 mm / second Maximum injection pressure: 200 MPa Holding pressure: 80 MPa Mold temperature: 60 °C Cooling timer: 45 seconds
  • the obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
  • Example 9 Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 95% by weight of methacrylic resin A and 5% by weight of silica-containing methacrylic resin C was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 10 Example in which 95% by weight of methacrylic resin A and 5% by weight of silica-containing methacrylic resin C2 were mixed instead of mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2. In the same manner as in Example 8, a laminate was obtained and evaluated.
  • Example 11 Except for mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2, Example except that 92% by weight of methacrylic resin A and 8% by weight of silica-containing methacrylic resin C2 were mixed. In the same manner as in Example 8, a laminate was obtained and evaluated.
  • Example 12 Example except that 50% by weight of methacrylic resin A and 50% by weight of silica-containing methacrylic resin C were mixed instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 13 Example except that 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2 were mixed instead of 88% by weight of methacrylic resin A and 12% by weight of silica-containing methacrylic resin C2. In the same manner as in Example 8, a laminate was obtained and evaluated.
  • Example 14 After mixing 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin G, it was melted under the following kneading conditions using a Nippon Steel Works twin screw extruder (model: TEX30SS-30AW-2V). By kneading and extruding into a strand, cooling with water and cutting with a strand cutter, a pellet-shaped methacrylic resin composition was obtained.
  • a Nippon Steel Works twin screw extruder model: TEX30SS-30AW-2V
  • Extruder temperature The eight heaters from the raw material inlet to the outlet were set to 200 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 240 ° C., and 250 ° C. from the raw material inlet side, respectively.
  • Rotation speed 200rpm
  • Feeding speed of raw material 12kg / hour
  • the obtained molded body was affixed to a 150 mm ⁇ 90 mm ⁇ 3 mm thick mold, and methacrylic resin A was 150 mm under the following molding conditions using an injection molding machine (EC130SXII-4A manufactured by Toshiba Machine Co., Ltd.).
  • the laminate was formed into a flat plate shape of ⁇ 90 mm ⁇ 3 mm thickness and composed of a 1 mm thick layer containing the methacrylic resin composition and a 2 mm thick layer containing the methacrylic resin A.
  • the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
  • Screw temperature The five heaters from the raw material inlet to the outlet were respectively set to 60 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
  • Injection speed 90 mm / second Maximum injection pressure: 200 MPa Holding pressure: 80 MPa Mold temperature: 60 °C Cooling timer: 45 seconds
  • the obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
  • Example 15 Example in which, instead of mixing 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin G, 94% by weight of methacrylic resin A and 6% by weight of silica-containing methacrylic resin G was used. In the same manner as in Example 14, a laminate was obtained and evaluated.
  • Example 16 Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin D was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 17 Example in which 90% by weight of methacrylic resin A and 10% by weight of silica-containing methacrylic resin D2 were mixed instead of mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2. In the same manner as in Example 8, a laminate was obtained and evaluated.
  • Example 18 Example in which, instead of mixing 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin G, 90% by weight of methacrylic resin A and 10% by weight of silica-containing methacrylic resin G was used. In the same manner as in Example 14, a laminate was obtained and evaluated.
  • Example 19 ⁇ Injection molding> The silica-containing methacrylic resin B 100% by weight was molded into a flat plate shape of 150 mm ⁇ 90 mm ⁇ 1 mm thickness under the following molding conditions using an injection molding machine (FANUC Corporation 150D) to obtain a methacrylic resin layer.
  • Screw temperature The five heaters from the raw material inlet to the outlet were set to 220 ° C., 240 ° C., 260 ° C., 260 ° C., and 260 ° C. from the raw material inlet side, respectively.
  • Injection speed 100 mm / second Maximum injection pressure: 1800 kg / cm 2 Holding pressure: 800 kg / cm 2 Mold temperature: 60 °C
  • the obtained methacrylic resin layer was attached to a 150 mm ⁇ 90 mm ⁇ 3 mm thick mold, and the methacrylic resin A was 150 mm ⁇ 90 mm under the following molding conditions using an injection molding machine (FANUC Corporation 150D).
  • a laminated body including a 1 mm-thick methacrylic resin layer and a layer containing 2 mm-thick methacrylic resin A was obtained by molding into a flat plate shape of 3 mm thickness.
  • the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
  • Screw temperature The five heaters from the raw material inlet to the outlet were respectively set at 220 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
  • Injection speed 30 mm / sec
  • the obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
  • Example 1 A laminate was obtained and evaluated in the same manner as in Example 15 except that a molded product having a thickness of 1 mm was obtained using 100% by weight of methacrylic resin A instead of 100% by weight of silica-containing methacrylic resin B.
  • Extruder temperature The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
  • Rotation speed 75rpm
  • the obtained methacrylic resin layer was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for each evaluation.
  • Example 5 Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin E was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 6 Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin F was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
  • Example 7 Example except that 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2 were mixed, but 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin C2 were mixed. In the same manner as in Example 8, a laminate was obtained and evaluated.
  • Example 8 A laminate was obtained in the same manner as in Example 1 except that 100% by weight of silica-containing methacrylic resin BC was used instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B. And evaluated.
  • Tables 1 and 2 show the compositions of the methacrylic resin layers and the evaluation results of the methacrylic resin layers or laminates in Examples 1 to 19 and Comparative Examples 1 to 8, respectively.

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Abstract

The present invention provides a laminate which comprises a methacrylic resin layer that contains 99.75% by weight or more but less than 99.995% by weight of a methacrylic resin and more than 0.005% by weight but 0.25% by weight or less of silica particles that have an average primary particle diameter of from 0.2 μm to 2 μm (inclusive) and a thermoplastic resin layer that contains the silica particles in an amount of 0.005% by weight or less, and which has a haze as determined in accordance with JIS K7136 of 5.5% or less.

Description

積層体Laminated body
　本発明は、メタクリル樹脂とシリカ粒子とを含有するメタクリル樹脂層と、熱可塑性樹脂層とを含有する積層体に関する。 The present invention relates to a laminate containing a methacrylic resin layer containing a methacrylic resin and silica particles, and a thermoplastic resin layer.
　メタクリル樹脂は軽量であり、透明性や耐候性に優れるため、テールランプカバーやヘッドランプカバー等の車両用ランプカバーやグレージング等、車両用のガラス代替品として注目されている。しかし、ガラスに比べると耐衝撃性が十分でないことから、耐衝撃性を向上させるため、組成が異なる層を二つ以上有する積層体が開発されている（例えば特許文献１）。 Methacrylic resin is light in weight and has excellent transparency and weather resistance, so it has been attracting attention as a glass replacement for vehicles such as tail lamp covers and head lamp covers, and glazing. However, since the impact resistance is not sufficient compared with glass, in order to improve the impact resistance, a laminate having two or more layers having different compositions has been developed (for example, Patent Document 1).
特開２００１－８１２６８号公報JP 2001-81268 A
　車両用のガラス代替品は、透明性が求められる。また、特に車両用ランプカバーは、透明性だけでなく、走行中に跳ね上がる砂利等で擦れた際に傷付き難いこと（本明細書では「耐擦傷性」ということがある）が求められる。
　しかしながら、特許文献１に記載の積層体は、透明性に優れるものの、耐擦傷性の点で満足できるものではなかった。
　本発明の目的は、透明性が高く、さらに耐擦傷性に優れる積層体を提供することにある。 Glass substitutes for vehicles are required to be transparent. In particular, the lamp cover for a vehicle is required not only to be transparent, but also to be difficult to be scratched when rubbed with gravel that jumps during traveling (sometimes referred to as “scratch resistance” in this specification).
However, although the laminate described in Patent Document 1 is excellent in transparency, it is not satisfactory in terms of scratch resistance.
An object of the present invention is to provide a laminate having high transparency and excellent scratch resistance.
　本発明者らは、前記課題を解決するべく鋭意検討を行った結果、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
　すなわち、本発明は、以下の［１］～［４］に記載の態様を含む。
［１］メタクリル樹脂９９．７５重量％以上９９．９９５重量％未満と、平均一次粒子径０．２μｍ以上２μｍ以下のシリカ粒子０．００５重量％を超え０．２５重量％以下とを含有するメタクリル樹脂層と、前記シリカ粒子の含有量が０．００５重量％以下である熱可塑性樹脂層とを含有し、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズが５．５％以下である、積層体。
［２］ＪＩＳ　Ｋ７１３６に従って測定されるヘイズが３％以下である、［１］に記載の積層体。
［３］前記メタクリル樹脂層の厚さが、０．５ｍｍ以上８ｍｍ以下である、前記［１］または［２］に記載の積層体。
［４］前記［１］～［３］のいずれかに記載の積層体を含む車両用ランプカバー。 That is, the present invention includes the embodiments described in [1] to [4] below.
[1] Methacrylic resin containing 99.75% by weight or more and less than 99.995% by weight of methacrylic resin and 0.005% by weight or more and 0.25% by weight or less of silica particles having an average primary particle diameter of 0.2 to 2 μm. The laminated body which contains a resin layer and the thermoplastic resin layer whose content of the said silica particle is 0.005 weight% or less, and the haze measured according to JISK7136 is 5.5% or less.
[2] The laminate according to [1], wherein the haze measured according to JIS K7136 is 3% or less.
[3] The laminate according to [1] or [2], wherein the methacrylic resin layer has a thickness of 0.5 mm or more and 8 mm or less.
[4] A vehicle lamp cover including the laminated body according to any one of [1] to [3].
　本発明によれば、透明性が高く、さらに耐擦傷性に優れる積層体を提供することができる。 According to the present invention, it is possible to provide a laminate having high transparency and excellent scratch resistance.
　本明細書において、「積層体」とは、互いに組成が異なる層を少なくとも２つ以上有するものである。また、「車両用ランプカバー」とは、車両用ランプの光源の保護および光源の照度向上の目的で備えられるカバーであり、「車両用ランプ」とは、自動車やオートバイ等の車両に装着された照明用、識別用もしくは標識用のランプであり、例えば、前照灯、尾灯、制動灯、方向指示灯、霧灯、車幅灯、後退灯などが該当する。「メタクリル樹脂層」とは、メタクリル樹脂を含有する層であり、「メタクリル樹脂」とは、メタクリル基を有するモノマーに由来する構成単位を有する重合体である。
　「シリカ粒子」とは、ＳｉＯ２を有する略球状の物質であり、「平均一次粒子径」とは、レーザー回折式粒度分布測定装置で測定される一次粒子径の平均値である。「熱可塑性樹脂層」とは、熱可塑性樹脂を主成分として含有する層であり、「熱可塑性樹脂」とは、加熱すると軟化し、冷却すると固化する性質を有する樹脂である。 In this specification, the “laminated body” has at least two layers having different compositions from each other. The “vehicle lamp cover” is a cover provided for the purpose of protecting the light source of the vehicle lamp and improving the illuminance of the light source. The “vehicle lamp” is attached to a vehicle such as an automobile or a motorcycle. For example, a headlamp, a tail lamp, a brake lamp, a direction indicator lamp, a fog lamp, a vehicle width lamp, and a reverse lamp are applicable. The “methacrylic resin layer” is a layer containing a methacrylic resin, and the “methacrylic resin” is a polymer having a structural unit derived from a monomer having a methacrylic group.
“Silica particles” are substantially spherical substances having SiO 2 , and “average primary particle diameter” is an average value of primary particle diameters measured by a laser diffraction particle size distribution analyzer. The “thermoplastic resin layer” is a layer containing a thermoplastic resin as a main component, and the “thermoplastic resin” is a resin having a property of softening when heated and solidifying when cooled.
　本発明の積層体は、メタクリル樹脂層と、熱可塑性樹脂層とを含む。
　メタクリル樹脂層は、メタクリル樹脂９９．７５重量％以上９９．９９５重量％以下と、平均一次粒子径０．２μｍ以上２μｍ以下のシリカ粒子０．００５重量％を超え０．２５重量％以下とを含有する層である。 The laminate of the present invention includes a methacrylic resin layer and a thermoplastic resin layer.
The methacrylic resin layer contains 99.75% by weight or more and 99.995% by weight or less of methacrylic resin, and 0.005% by weight or more and 0.25% by weight or less of silica particles having an average primary particle diameter of 0.2 μm or more and 2 μm or less. It is a layer to do.
　メタクリル樹脂は、メタクリル基を有するモノマーに由来する構成単位を有する重合体である。
　メタクリル樹脂としては、例えば、炭素数１～４のアルキル基を有するメタクリル酸アルキルに由来する構成単位のみを含むメタクリル単独重合体や、炭素数１～４のアルキル基を有するメタクリル酸アルキルに由来する構成単位を、８０重量％以上１００重量％未満と、炭素数１～４のアルキル基を有するメタクリル酸エステルに由来する構成単位と共重合可能な他のビニル単量体に由来する構成単位を、０重量％を超えて２０重量％以下とを有するメタクリル共重合体等が挙げられる。炭素数１～４のアルキル基を有するメタクリル酸アルキルとは、ＣＨ２＝ＣＨ（ＣＨ３）ＣＯＯＲ（Ｒは炭素数１～４のアルキル基）で表される化合物である。炭素数１～４のアルキル基を有するメタクリル酸エステルと共重合可能なビニル単量体とは、炭素数１～４のアルキル基を有するメタクリル酸エステルと共重合可能であり、且つビニル基を有する単量体である。 A methacrylic resin is a polymer having a structural unit derived from a monomer having a methacrylic group.
Examples of the methacrylic resin are derived from a methacrylic homopolymer containing only a structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms. A structural unit derived from another vinyl monomer copolymerizable with a structural unit derived from a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms and 80 wt% or more and less than 100 wt%, And a methacrylic copolymer having more than 0% by weight and not more than 20% by weight. The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is a compound represented by CH 2 ═CH (CH 3 ) COOR (R is an alkyl group having 1 to 4 carbon atoms). A vinyl monomer copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms is copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms and has a vinyl group. It is a monomer.
　炭素数１～４のアルキル基を有するメタクリル酸アルキルとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｔｅｒｔ－ブチル、メタクリル酸ｓｅｃ－ブチル、メタクリル酸イソブチルなどが挙げられ、メタクリル酸メチルが好ましい。上記例示のメタクリル酸アルキルは、単独で使用してもよく、２種以上を混合して使用してもよい。 Examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, and methacrylic acid. Examples thereof include sec-butyl and isobutyl methacrylate, and methyl methacrylate is preferred. The alkyl methacrylates exemplified above may be used alone or in combination of two or more.
　炭素数１～４のアルキル基を有するメタクリル酸エステルと共重合可能なビニル単量体としては、例えば、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸２－エチルヘキシル、メタクリル酸２－ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸モノグリセロールなどのメタクリル酸エステル（但し、炭素数１～４のアルキル基を有するメタクリル酸アルキルを除く）；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸２－エチルヘキシル、アクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシプロピル、アクリル酸モノグリセロール等のアクリル酸エステル；アクリル酸、メタクリル酸、マレイン酸、イタコン酸、無水マレイン酸、無水イタコン酸などの不飽和カルボン酸またはこれらの酸無水物；アクリルアミド、メタクリルアミド、アクリロニトリル、メタクリロニトリル、ジアセトンアクリルアミド、メタクリル酸ジメチルアミノエチル等の窒素含有モノマー；アリルグリシジルエーテル、アクリル酸グリシジル、メタクリル酸グリシジルなどのエポキシ基含有単量体；スチレン、α－メチルスチレンなどのスチレン系単量体が挙げられる。 Examples of vinyl monomers copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms include cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and methacrylic acid. Methacrylic acid esters such as hydroxypropyl and monoglycerol methacrylate (excluding alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms); methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid Acrylic acid esters such as 2-ethylhexyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itacic anhydride Unsaturated carboxylic acids such as acids or their anhydrides; nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, dimethylaminoethyl methacrylate; allyl glycidyl ether, glycidyl acrylate, methacrylic acid And epoxy group-containing monomers such as glycidyl; and styrene monomers such as styrene and α-methylstyrene.
　メタクリル樹脂の製造方法としては、炭素数１～４のアルキル基を有するメタクリル酸エステルと、必要に応じて、炭素数１～４のアルキル基を有するメタクリル酸エステルと共重合可能なビニル単量体とを、塊状重合、溶液重合、懸濁重合、乳化重合等の方法で重合する方法が挙げられる。 As a method for producing a methacrylic resin, a vinyl monomer copolymerizable with a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms and, if necessary, a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms. May be polymerized by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.
　本発明に用いられるシリカ粒子としては、ＳｉＯ２を有する略球状の物質である。シリカ粒子には、略球状だけでなく、直方体状や、複数の角を有した粉砕状などの形状のものが含まれていてもよい。シリカ粒子は、真球状であることが好ましい。真球状のシリカ粒子としては、例えば、株式会社アドマテックス製のアドマファイン（登録商標）、ＡＧＣエスアイテック株式会社製のサンスフェア（登録商標）、堺化学工業株式会社製のＳｃｉｑａｓシリーズ、デンカ株式会社製のＳＦＰシリーズ等が挙げられる。シリカ粒子としては、アミノシラン、エポキシシラン、メタクリルシラン、アクリルシラン、ビニルシラン、フェニルシラン、メルカプトシラン等のシランカップリング剤で表面処理された粒子を使用してもよいが、耐擦傷性の点で、該シランカップリング剤で表面処理されていないシリカ粒子を使用することが好ましい。ここで、「表面処理されている」とは、シリカ粒子の表面に存在する水酸基が、シランカップリング剤が有するアルコキシ基が加水分解されて生成する水酸基と脱水縮合した状態を指す。 The silica particles used in the present invention are substantially spherical substances having SiO 2 . The silica particles may include not only a substantially spherical shape but also a rectangular parallelepiped shape or a pulverized shape having a plurality of corners. The silica particles are preferably spherical. Examples of the spherical silica particles include Admafine (registered trademark) manufactured by Admatechs Co., Ltd., Sunsphere (registered trademark) manufactured by AGC S-Tech Co., Ltd., Sciqas series manufactured by Sakai Chemical Industry Co., Ltd., and Denka Co., Ltd. Examples include the SFP series. As the silica particles, particles treated with a silane coupling agent such as amino silane, epoxy silane, methacryl silane, acrylic silane, vinyl silane, phenyl silane, mercapto silane, etc. may be used, but in terms of scratch resistance, It is preferable to use silica particles that are not surface-treated with the silane coupling agent. Here, “surface-treated” refers to a state in which a hydroxyl group present on the surface of silica particles is dehydrated and condensed with a hydroxyl group generated by hydrolysis of an alkoxy group of a silane coupling agent.
　本発明に用いるシリカ粒子の平均一次粒子径は、０．２μｍ以上２μｍ以下であり、０．３μｍ以上１．８μｍ以下であることが好ましく、０．３μｍ以上１．６μｍ以下がより好ましく、０．３μｍ以上１．５μｍ以下がさらに好ましく、０．３μｍ以上１．２μｍ以下がさらに好ましく、０．３μｍ以上０．８μｍ以下が特に好ましい。メタクリル樹脂層は、粒径が異なる２種以上のシリカ粒子を含んでいてもよい。平均一次粒子径は、例えば、レーザー回折式粒度分布測定装置で測定することができる。シリカ粒子の平均一次粒子径を上記の範囲にすることで、耐擦傷性と透明性との両方に優れる積層体を与え得る。 The average primary particle size of the silica particles used in the present invention is 0.2 μm or more and 2 μm or less, preferably 0.3 μm or more and 1.8 μm or less, more preferably 0.3 μm or more and 1.6 μm or less. 3 μm or more and 1.5 μm or less is more preferable, 0.3 μm or more and 1.2 μm or less is more preferable, and 0.3 μm or more and 0.8 μm or less is particularly preferable. The methacrylic resin layer may contain two or more types of silica particles having different particle sizes. The average primary particle diameter can be measured with, for example, a laser diffraction particle size distribution measuring apparatus. By making the average primary particle diameter of the silica particles in the above range, a laminate excellent in both scratch resistance and transparency can be provided.
　シリカ粒子が真球状である場合、シリカ粒子の粒径（直径）は、０．２μｍ以上２μｍ以下であり、０．３μｍ以上１．８μｍ以下であることが好ましく、０．４μｍ以上１．５μｍ以下がさらに好ましい。シリカ粒子が真球状でない場合、シリカ粒子の長径は、０．２μｍ以上２μｍ以下であることが好ましく、０．４μｍを超えて２μｍ以下であることがより好ましい。長径とは、粒子の直線距離で最も長い部分の長さである。長径および粒径は、走査電子顕微鏡による粒子の観測画像から読み取ることによって測定することができる。シリカ粒子の長径または粒径を上記の範囲にすることで、耐擦傷性と透明性との両方に優れる積層体を与え得る。 When the silica particles are spherical, the particle size (diameter) of the silica particles is 0.2 μm or more and 2 μm or less, preferably 0.3 μm or more and 1.8 μm or less, and 0.4 μm or more and 1.5 μm or less. Is more preferable. When the silica particles are not spherical, the major axis of the silica particles is preferably 0.2 μm or more and 2 μm or less, more preferably more than 0.4 μm and 2 μm or less. The major axis is the length of the longest part of the linear distance of the particles. The long diameter and the particle diameter can be measured by reading from the observation image of the particles with a scanning electron microscope. By making the major axis or particle size of the silica particles in the above range, a laminate excellent in both scratch resistance and transparency can be provided.
　本発明のメタクリル樹脂層に含まれるメタクリル樹脂の含有量は、９９．７５重量％以上９９．９９５重量％未満であり、シリカ粒子の含有量が０．００５重量％を超え０．２５重量％以下である。ただし、メタクリル樹脂の含有量とシリカ粒子の含有量の合計を１００重量％とする。メタクリル樹脂の含有量とシリカ粒子の含有量を上記の範囲にすることで、耐擦傷性と透明性との両方に優れる積層体を与え得る。
　シリカ粒子の含有量は、下記式（１）を満足することが好ましく、メタクリル樹脂の含有量は（１００－ｙ）重量％であることが好ましい。
　０．０１≦ｙ≦－０．０７ｘ＋０．１７　　式（１）
（上記式（１）において、ｘは、単位「μｍ」を付して表された前記シリカ粒子の平均一次粒子径の数値を表し、ｙは、前記メタクリル樹脂と前記シリカ粒子との合計量１００重量％に対する、単位「重量％」を付して表された前記シリカ粒子の含有量の数値を表す。）
　シリカ粒子の含有量を上記式（１）の範囲にすることで、特に車両用ランプカバーに求められる耐擦傷性と透明性を有する積層体を与え得る。 The content of the methacrylic resin contained in the methacrylic resin layer of the present invention is 99.75% by weight or more and less than 99.995% by weight, and the silica particle content exceeds 0.005% by weight and is 0.25% by weight or less. It is. However, the total of the content of methacrylic resin and the content of silica particles is 100% by weight. By setting the content of the methacrylic resin and the content of the silica particles in the above ranges, a laminate excellent in both scratch resistance and transparency can be provided.
The content of silica particles preferably satisfies the following formula (1), and the content of methacrylic resin is preferably (100-y) wt%.
0.01 ≦ y ≦ −0.07x + 0.17 Formula (1)
(In the above formula (1), x represents the numerical value of the average primary particle diameter of the silica particles represented by the unit “μm”, and y represents the total amount of the methacrylic resin and the silica particles 100. (The numerical value of the content of the silica particles expressed with the unit "wt%" with respect to wt% is shown.)
By setting the content of silica particles in the range of the above formula (1), a laminate having scratch resistance and transparency particularly required for a vehicle lamp cover can be provided.
　シリカ粒子の含有量としては、好ましくは、下記式（２）および下記式（３）を満足する量である。
　０．００５＜ｙ≦－０．２５３ｘ＋０．２０６　　　式（２）
（式中、ｘおよびｙは、式（１）と同様である。ただし、ｘは、０．２≦ｘ＜０．５である。）
　０．００５＜ｙ≦－０．０４５ｘ＋０．１０２７　　　式（３）
（式中、ｘおよびｙは、式（１）と同様である。ただし、ｘは、０．５≦ｘ≦２である。） The content of the silica particles is preferably an amount satisfying the following formula (2) and the following formula (3).
0.005 <y ≦ −0.253x + 0.206 Formula (2)
(In the formula, x and y are the same as those in the formula (1). However, x is 0.2 ≦ x <0.5.)
0.005 <y ≦ −0.045x + 0.1027 Formula (3)
(Wherein x and y are the same as in formula (1), where x is 0.5 ≦ x ≦ 2)
シリカの粒子の含有量として、より好ましくは、下記式（４）および下記式（５）を満足する量である。
　０．００５＜ｙ≦－０．２８７ｘ＋０．２１３　　　式（４）
（式中、ｘおよびｙは、式（１）と同様である。ただし、ｘは、０．２≦ｘ＜０．５である。）
　０．００５＜ｙ≦―０．０４１ｘ＋０．０９０　　　式（５）
（式中、ｘおよびｙは、式（１）と同様である。ただし、ｘは、０．５≦ｘ≦２である。） The content of silica particles is more preferably an amount satisfying the following formula (4) and the following formula (5).
0.005 <y ≦ −0.287x + 0.213 Formula (4)
(In the formula, x and y are the same as those in the formula (1). However, x is 0.2 ≦ x <0.5.)
0.005 <y ≦ −0.041x + 0.090 Formula (5)
(Wherein x and y are the same as in formula (1), where x is 0.5 ≦ x ≦ 2)
　シリカ粒子の含有量として、下記式（６）および下記式（７）を満足する量であってもよい。
　０．０１≦ｙ＜－０．０３６ｘ＋０．０７３　　式（６）
（式中のｘおよびｙは、上記式（１）と同様である。ただし、ｘは、０．５＜ｘ≦２である。）
　０．０１≦ｙ＜－０．３２ｘ＋０．２２　　　式（７）
（式中のｘおよびｙは、上記式（１）と同様である。ただし、ｘは、０．２≦ｘ≦０．５である。） The content of the silica particles may be an amount satisfying the following formula (6) and the following formula (7).
0.01 ≦ y <−0.036x + 0.073 Formula (6)
(X and y in the formula are the same as in the above formula (1), provided that x is 0.5 <x ≦ 2.)
0.01 ≦ y <−0.32x + 0.22 Formula (7)
(X and y in the formula are the same as in the above formula (1), provided that x is 0.2 ≦ x ≦ 0.5.)
　シリカ粒子の含有量として、下記式（８）および下記式（９）を満足する量である。
　０．０１≦ｙ＜－０．０３６ｘ＋０．０７３　　式（８）
（式（８）中のｘおよびｙは、上記式（１）と同様である。ただし、ｘは、０．５≦ｘ≦２である。）
　０．０１≦ｙ＜－０．３２ｘ＋０．２２　　　式（９）
（式（９）中のｘおよびｙは、上記式（１）と同様である。ただし、ｘは、０．２≦ｘ＜０．５である。） The content of the silica particles is an amount satisfying the following formula (8) and the following formula (9).
0.01 ≦ y <−0.036x + 0.073 Formula (8)
(X and y in the formula (8) are the same as those in the above formula (1). However, x is 0.5 ≦ x ≦ 2.)
0.01 ≦ y <−0.32x + 0.22 Formula (9)
(X and y in Formula (9) are the same as those in Formula (1) above, provided that x is 0.2 ≦ x <0.5.)
　シリカ粒子の含有量を上記式で示される範囲、例えば式（２）および上記式（３）の範囲、特に式（４）および上記式（５）の範囲にすることで、シリカ粒子の含有量が上記範囲でないものよりも、耐擦傷性と透明性との両方により優れる積層体を与え得る。シリカ粒子の含有量は、ＩＣＰ（Inductively Coupled Plasma）発光分光分析法を用いてＳｉ量を測定し、ＳｉＯ２量に換算することで、求めることができる。 By setting the content of the silica particles to the range represented by the above formula, for example, the range of the formula (2) and the above formula (3), particularly the range of the formula (4) and the above formula (5), However, it is possible to provide a laminate that is more excellent in both scratch resistance and transparency than those not in the above range. The content of silica particles can be determined by measuring the amount of Si using ICP (Inductively Coupled Plasma) emission spectroscopy and converting it to the amount of SiO 2 .
　熱可塑性樹脂層は、熱可塑性樹脂を含有する。熱可塑性樹脂層には、熱可塑性樹脂以外の成分を含んでいてもよく、例えば、シリカ粒子を含んでいてもよい。熱可塑性樹脂層がシリカ粒子を含む場合、シリカ粒子の含有量は０．００５重量％以下である（ただし、熱可塑性樹脂の含有量とシリカ粒子の含有量の合計を１００重量％とする。）。また、本発明の積層体は、２種以上の熱可塑性樹脂層を含んでいてもよい。 The thermoplastic resin layer contains a thermoplastic resin. The thermoplastic resin layer may contain components other than the thermoplastic resin, and for example, may contain silica particles. When the thermoplastic resin layer includes silica particles, the content of silica particles is 0.005% by weight or less (provided that the total content of the thermoplastic resin and the silica particles is 100% by weight). . Moreover, the laminated body of this invention may contain the 2 or more types of thermoplastic resin layer.
　熱可塑性樹脂としては、厚さ３ｍｍの成形体にしたときに、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズが２％以下の樹脂であり、例えば、メタクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ポリアミド樹脂、ポリアリレ－ト樹脂、ポリメタクリルイミド樹脂等が挙げられる。その中でもメタクリル樹脂、又はポリカーボネート樹脂が好ましく、メタクリル樹脂がさらに好ましい。 The thermoplastic resin is a resin having a haze measured in accordance with JIS K7136 of 2% or less when formed into a molded product having a thickness of 3 mm. For example, methacrylic resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin and the like can be mentioned. Among them, methacrylic resin or polycarbonate resin is preferable, and methacrylic resin is more preferable.
　メタクリル樹脂の例示は、メタクリル樹脂層に含まれるメタクリル樹脂として例示したものと同様である。熱可塑性樹脂層に含まれるメタクリル樹脂は、メタクリル樹脂層に含まれるメタクリル樹脂と同じであっても異なっていてもよい。 Examples of the methacrylic resin are the same as those exemplified as the methacrylic resin contained in the methacrylic resin layer. The methacrylic resin contained in the thermoplastic resin layer may be the same as or different from the methacrylic resin contained in the methacrylic resin layer.
　ポリカーボネート樹脂とは、ジヒドロキシ化合物に由来する構成単位を含む樹脂である。ポリカーボネート樹脂としては、例えば、二価フェノールとカルボニル化剤とを界面重縮合法や溶融エステル交換法などで反応させることにより得られたもの；カーボネートプレポリマーを固相エステル交換法などで重合させることにより得られたもの；環状カーボネート化合物を開環重合法で重合させることにより得られたものなどが挙げられる。 Polycarbonate resin is a resin containing structural units derived from dihydroxy compounds. Polycarbonate resin, for example, obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method; polymerizing a carbonate prepolymer by a solid phase transesterification method or the like And those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
　二価フェノールとしては、例えば、ハイドロキノン、レゾルシノール、４，４'－ジヒドロキシジフェニル、ビス（４－ヒドロキシフェニル）メタン、ビス｛（４－ヒドロキシ－３，５－ジメチル）フェニル｝メタン、１，１－ビス（４－ヒドロキシフェニル）エタン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、２，２－ビス（４－ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）、２，２－ビス｛（４－ヒドロキシ－３－メチル）フェニル｝プロパン、２，２－ビス｛（４－ヒドロキシ－３，５－ジメチル）フェニル｝プロパン、２，２－ビス｛（４－ヒドロキシ－３，５－ジブロモ）フェニル｝プロパン、２，２－ビス｛（３－イソプロピル－４－ヒドロキシ）フェニル｝プロパン、２，２－ビス｛（４－ヒドロキシ－３－フェニル）フェニル｝プロパン、２，２－ビス（４－ヒドロキシフェニル）ブタン、２，２－ビス（４－ヒドロキシフェニル）－３－メチルブタン、２，２－ビス（４－ヒドロキシフェニル）－３，３－ジメチルブタン、２，４－ビス（４－ヒドロキシフェニル）－２－メチルブタン、２，２－ビス（４－ヒドロキシフェニル）ペンタン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、１，１－ビス（４－ヒドロキシフェニル）－４－イソプロピルシクロヘキサン、１，１－ビス（４－ヒドロキシフェニル）－３，３，５－トリメチルシクロヘキサン、９，９－ビス（４－ヒドロキシフェニル）フルオレン、９，９－ビス｛（４－ヒドロキシ－３－メチル）フェニル｝フルオレン、α，α’－ビス（４－ヒドロキシフェニル）－ｏ－ジイソプロピルベンゼン、α，α’－ビス（４－ヒドロキシフェニル）－ｍ－ジイソプロピルベンゼン、α，α’－ビス（４－ヒドロキシフェニル）－ｐ－ジイソプロピルベンゼン、１，３－ビス（４－ヒドロキシフェニル）－５，７－ジメチルアダマンタン、４，４'－ジヒドロキシジフェニルスルホン、４，４'－ジヒドロキシジフェニルスルホキシド、４，４'－ジヒドロキシジフェニルスルフィド、４，４'－ジヒドロキシジフェニルケトン、４，４'－ジヒドロキシジフェニルエーテル、及び４，４'－ジヒドロキシジフェニルエステルなどが挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis { (4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo ) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4 -Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) ) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl)- 4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy 3-methyl) phenyl} fluorene, α, α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, and 4,4′-dihydroxydiphenyl ester. These may be used alone or in combination of two or more.
　カルボニル化剤としては、例えばカルボニルハライド（ホスゲンなど）、カーボネートエステル（ジフェニルカーボネートなど）、及びハロホルメート（二価フェノールのジハロホルメートなど）が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 Examples of the carbonylating agent include carbonyl halides (such as phosgene), carbonate esters (such as diphenyl carbonate), and haloformates (such as dihaloformates of dihydric phenols). These may be used alone or in combination of two or more.
　本発明の積層体の製造方法としては、例えば、熱可塑性樹脂を成形機の金型内に射出成形した状態で、メタクリル樹脂とシリカ粒子とを含有するメタクリル樹脂組成物を同じ金型内に射出成形する二色成形法や、あらかじめ射出成形したメタクリル樹脂とシリカ粒子とを含有するメタクリル樹脂組成物を含むメタクリル樹脂層を金型内に貼り付け、該メタクリル樹脂層が貼り付けられた金型内に、熱可塑性樹脂を射出成形するインサート成形法等が挙げられる。射出成形時のシリンダーの温度として、好ましくは２３０℃以上であり、好ましくは２９０℃以下である。 As a method for producing the laminate of the present invention, for example, a methacrylic resin composition containing methacrylic resin and silica particles is injected into the same mold in a state where a thermoplastic resin is injection-molded into a mold of a molding machine. A two-color molding method for molding or a methacrylic resin layer containing a methacrylic resin composition containing a pre-injection-molded methacrylic resin and silica particles is pasted into a mold, and the inside of the mold to which the methacrylic resin layer is pasted In addition, an insert molding method in which a thermoplastic resin is injection molded may be used. The temperature of the cylinder at the time of injection molding is preferably 230 ° C or higher, and preferably 290 ° C or lower.
　上記メタクリル樹脂組成物の製造方法としては、公知の技術を適宜適用することができる。例えば、メタクリル樹脂を溶媒に溶解させた溶液に、シリカ粒子を添加して混合し、溶液にシリカ粒子を分散させる溶液混合法；メタクリル樹脂とシリカ粒子を、単軸押出機、二軸押出機、ミキシングロール等の装置を用いて溶融混練する方法；メタクリル樹脂の原料である単量体にシリカ粒子を分散させて重合するキャスト重合法、懸濁重合法、又は乳化重合法などが挙げられる。溶液混合法を適用する場合、混合時の温度は１００℃以下が好ましく、溶融混練する方法を適用する場合、混練時の温度は２００℃以上３００℃以下が好ましく、キャスト重合法を適用する場合、重合温度は１５０℃以下が好ましく、懸濁重合法又は乳化重合法を適用する場合、重合温度は１００℃以下が好ましい。上記メタクリル樹脂組成物の製造方法としては、シリカ粒子の添加量を調節し易い点から、溶融混練する方法が好ましい。 As the method for producing the methacrylic resin composition, known techniques can be applied as appropriate. For example, a solution mixing method in which silica particles are added and mixed in a solution in which a methacrylic resin is dissolved in a solvent, and the silica particles are dispersed in the solution; a methacrylic resin and silica particles are converted into a single screw extruder, a twin screw extruder, Examples include a melt kneading method using an apparatus such as a mixing roll; a cast polymerization method in which silica particles are dispersed in a monomer that is a raw material of a methacrylic resin, a polymerization method, a suspension polymerization method, or an emulsion polymerization method. When applying the solution mixing method, the mixing temperature is preferably 100 ° C. or less, and when applying the melt-kneading method, the kneading temperature is preferably 200 ° C. or more and 300 ° C. or less, and when the cast polymerization method is applied, The polymerization temperature is preferably 150 ° C. or lower, and when the suspension polymerization method or the emulsion polymerization method is applied, the polymerization temperature is preferably 100 ° C. or lower. As a method for producing the methacrylic resin composition, a melt kneading method is preferable because the amount of silica particles added can be easily adjusted.
　メタクリル樹脂組成物の製造時のメタクリル樹脂の添加量は、９９．７５重量％以上９９．９９５重量％未満であり、シリカ粒子の添加量は、０．００５重量％を超え０．２５重量％以下である。ただし、メタクリル樹脂の添加量とシリカ粒子の添加量の合計を１００重量％とする。メタクリル樹脂の添加量とシリカ粒子の添加量を上記の範囲にすることで、耐擦傷性と透明性との両方に優れる積層体を与え得る。 The amount of methacrylic resin added during the production of the methacrylic resin composition is 99.75 wt% or more and less than 99.995 wt%, and the amount of silica particles added is more than 0.005 wt% and 0.25 wt% or less. It is. However, the total of the addition amount of the methacrylic resin and the addition amount of the silica particles is 100% by weight. By setting the addition amount of the methacrylic resin and the addition amount of the silica particles in the above range, a laminate excellent in both scratch resistance and transparency can be provided.
　シリカ粒子の添加量としては、上記式（１）を満足する量であることが好ましく、上記式（２）および上記式（３）を満足する量であることがより好ましく、上記式（４）および上記式（５）を満足する量であることがさらに好ましい。メタクリル樹脂の添加量としては、（１００－ｙ）重量％であることが好ましい。シリカ粒子およびメタクリル樹脂の添加量を上記（１）の範囲、または、上記式（２）および上記式（３）の範囲にすることで、特に車両用ランプカバーに求められる耐擦傷性と透明性を有する積層体を与え得る。 The amount of silica particles added is preferably an amount that satisfies the above formula (1), more preferably an amount that satisfies the above formula (2) and the above formula (3), and the above formula (4). It is more preferable that the amount satisfies the above formula (5). The amount of methacrylic resin added is preferably (100-y)% by weight. By making the addition amount of silica particles and methacrylic resin in the range of (1) above, or in the range of the above formula (2) and the above formula (3), scratch resistance and transparency particularly required for a vehicle lamp cover. Can be provided.
　メタクリル樹脂層または熱可塑性樹脂層は、必要に応じて、紫外線吸収剤、滑り剤、酸化防止剤、離型剤、帯電防止剤等を含有していてもよい。例えば、紫外線吸収剤としては、ベンゾフェノン系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、マロン酸エステル系紫外線吸収剤、オキサルアニリド系紫外線吸収剤等が挙げられ、滑り剤としては、シリコーンオイルやポリシロキサン系化合物等が挙げられ、酸化防止剤としてはフェノール系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤等が挙げられ、離型剤としては、高級脂肪酸エステル、高級脂肪族アルコール、高級脂肪酸、高級脂肪酸アミド、高級脂肪酸金属塩、脂肪酸誘導体等が挙げられ、帯電防止剤としては、導電性無機粒子、第３級アミン、第４級アンモニウム塩、カチオン系アクリル酸エステル誘導体、カチオン系ビニルエーテル誘導体等が挙げられる。 The methacrylic resin layer or the thermoplastic resin layer may contain an ultraviolet absorber, a slip agent, an antioxidant, a release agent, an antistatic agent, and the like as necessary. For example, examples of the UV absorber include benzophenone UV absorbers, cyanoacrylate UV absorbers, benzotriazole UV absorbers, malonic ester UV absorbers, oxalanilide UV absorbers, and slip agents. Examples include silicone oils and polysiloxane compounds. Examples of antioxidants include phenolic antioxidants, sulfur antioxidants, and phosphorus antioxidants. Examples of mold release agents include higher fatty acids. Examples include esters, higher aliphatic alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, fatty acid derivatives, and the like. Antistatic agents include conductive inorganic particles, tertiary amines, quaternary ammonium salts, and cationic systems. Examples include acrylic ester derivatives and cationic vinyl ether derivatives.
　メタクリル樹脂層が、メタクリル樹脂とシリカ粒子以外の成分を含む場合、メタクリル樹脂組成物の製造時に、該成分を添加し、メタクリル樹脂およびシリカ粒子と共に混合させ、該成分を含有するメタクリル樹脂組成物を製造することが好ましい。
　熱可塑性樹脂層が、熱可塑性樹脂以外の成分を含む場合、積層体を製造する前に、熱可塑性樹脂と熱可塑性樹脂以外の成分とを予め混合されて、熱可塑性樹脂組成物を製造することが好ましい。 When the methacrylic resin layer contains a component other than the methacrylic resin and the silica particles, the component is added during the production of the methacrylic resin composition, mixed with the methacrylic resin and the silica particles, and a methacrylic resin composition containing the component is added. It is preferable to manufacture.
When the thermoplastic resin layer contains a component other than the thermoplastic resin, the thermoplastic resin and the component other than the thermoplastic resin are mixed in advance to manufacture the thermoplastic resin composition before the laminate is manufactured. Is preferred.
　ＪＩＳ　Ｋ７１３６に従って測定されるメタクリル樹脂層のヘイズは、好ましくは５．５％以下であり、より好ましくは３．５％以下であり、さらに好ましくは２．５％以下であり、さらにいっそう好ましくは２．０％以下であり、特に好ましくは１．５％以下である。特にメタクリル樹脂層のヘイズが５．５％以下であると、車両用ランプからの光の散乱を抑えることができるため、車両用ランプカバーに適用することができる。 The haze of the methacrylic resin layer measured according to JIS K7136 is preferably 5.5% or less, more preferably 3.5% or less, still more preferably 2.5% or less, and even more preferably 2 0.0% or less, particularly preferably 1.5% or less. In particular, if the haze of the methacrylic resin layer is 5.5% or less, scattering of light from the vehicle lamp can be suppressed, and therefore, it can be applied to a vehicle lamp cover.
　ＪＩＳ　Ｋ７１３６に従って測定される熱可塑性樹脂層のヘイズは、好ましくは２％以下であり、好ましくは１．５％以下であり、さらに好ましくは１．０％以下である。熱可塑性樹脂層のヘイズが２．０％以下であると、車両用ランプからの光の散乱を抑えることができるため、車両用ランプカバーに適用することができる。 The haze of the thermoplastic resin layer measured according to JIS K7136 is preferably 2% or less, preferably 1.5% or less, and more preferably 1.0% or less. When the haze of the thermoplastic resin layer is 2.0% or less, scattering of light from the vehicle lamp can be suppressed, and therefore, it can be applied to a vehicle lamp cover.
　積層体の厚みとして、好ましくは０．５ｍｍ以上８ｍｍ以下であり、より好ましくは、１ｍｍ以上６ｍｍ以下であり、さらに好ましくは、２ｍｍ以上５ｍｍ以下である。 The thickness of the laminate is preferably 0.5 mm or more and 8 mm or less, more preferably 1 mm or more and 6 mm or less, and further preferably 2 mm or more and 5 mm or less.
　積層体中のメタクリル樹脂層の厚みとして、好ましくは０．５ｍｍ以上８ｍｍ以下であり、より好ましくは、１ｍｍ以上６ｍｍ以下であり、さらに好ましくは、１ｍｍ以上２．５ｍｍ以下である。積層体中のメタクリル樹脂層の厚みを上記の範囲にすることで、透明性に優れる積層体を与え得る。 The thickness of the methacrylic resin layer in the laminate is preferably 0.5 mm or more and 8 mm or less, more preferably 1 mm or more and 6 mm or less, and further preferably 1 mm or more and 2.5 mm or less. By setting the thickness of the methacrylic resin layer in the laminate within the above range, a laminate having excellent transparency can be provided.
　本発明の積層体は、熱可塑性樹脂層単体またはメタクリル樹脂層単体よりも、耐擦傷性と透明性との両方に優れる。 The laminate of the present invention is superior in both scratch resistance and transparency as compared with a single thermoplastic resin layer or a single methacrylic resin layer.
　ＪＩＳ　Ｋ７１３６に従って測定される積層体のヘイズは、５．５％以下であり、好ましくは３．５％以下であり、より好ましくは３％以下であり、さらに好ましくは２．５％以下であり、さらに好ましくは２．０％以下であり、さらにいっそう好ましくは１．５％以下である。特に積層体のヘイズが５．５％以下であると、車両用ランプからの光の散乱を抑えることができるため、車両用ランプカバーに適用することができる。 The haze of the laminate measured according to JIS K7136 is 5.5% or less, preferably 3.5% or less, more preferably 3% or less, and even more preferably 2.5% or less. More preferably, it is 2.0% or less, More preferably, it is 1.5% or less. In particular, when the haze of the laminate is 5.5% or less, scattering of light from the vehicle lamp can be suppressed, and therefore, it can be applied to a vehicle lamp cover.
　本発明の積層体は耐擦傷性に優れる。耐擦傷性は、例えば、ＦＭＶＳＳ（Ｆｅｄｅｒａｌ Ｍｏｔｏｒ Ｖｅｈｉｃｌｅ Ｓａｆｅｔｙ Ｓｔａｎｄａｒｄ） Nｏ．１０８に従ってスチールウールによる摩耗試験を行い、試験前後の積層体のヘイズの差（Δヘイズ）で評価される。該摩耗試験は、積層体のメタクリル樹脂層側の面に対して実施する。かかるΔヘイズが小さいほど、本発明の積層体は耐擦傷性に優れるといえる。本発明の積層体のΔヘイズとして、好ましくは１５％未満であり、より好ましくは１３％以下であり、さらに好ましくは１０％以下である。試験前後の積層体のヘイズは、ＪＩＳ　Ｋ７１３６に従って測定される。 The laminate of the present invention is excellent in scratch resistance. The scratch resistance is, for example, FMVSS (Federal Motor Vehicle Safety Standard) No. A wear test using steel wool is performed according to No. 108, and the haze difference (Δ haze) of the laminate before and after the test is evaluated. The wear test is performed on the surface of the laminate on the side of the methacrylic resin layer. It can be said that the smaller the Δhaze, the more excellent the scratch resistance of the laminate of the present invention. The Δhaze of the laminate of the present invention is preferably less than 15%, more preferably 13% or less, and even more preferably 10% or less. The haze of the laminate before and after the test is measured according to JIS K7136.
　本発明の積層体は、車両用窓、車両用フロントグリル、車両用ピラー、車両用ランプカバーに適用することができる。 The laminate of the present invention can be applied to vehicle windows, vehicle front grilles, vehicle pillars, and vehicle lamp covers.
　本発明の車両用ランプカバーは、上記積層体を含むものである。車両用ランプカバーとしては、前照灯、尾灯、制動灯、方向指示灯、霧灯、車幅灯、後退灯のカバー等が挙げられる。本発明の積層体は、砂利等で擦れる頻度が高く、より優れた耐擦傷性が求められる前照灯のカバー、すなわちヘッドランプカバーとして、好適に用いることができる。 The vehicle lamp cover of the present invention includes the above laminate. Examples of the vehicle lamp cover include a headlamp, tail lamp, brake lamp, direction indicator lamp, fog lamp, vehicle width lamp, and reverse lamp cover. The laminate of the present invention can be suitably used as a headlamp cover, ie, a headlamp cover, which is frequently rubbed with gravel and is required to have better scratch resistance.
　以下、実施例により本発明を説明するが、これらの実施例に特に限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not particularly limited to these examples.
（透明性）
　ＪＩＳ　Ｋ７１３６に従い、得られたメタクリル樹脂層または積層体のヘイズを測定した（単位：％）。ヘイズが５．５％以下であると、透明性に優れる。ヘイズが２．５％以下であると、車両用ランプカバーとして好適に用いることができる。 (transparency)
According to JIS K7136, the haze of the obtained methacrylic resin layer or laminate was measured (unit:%). When the haze is 5.5% or less, the transparency is excellent. When the haze is 2.5% or less, it can be suitably used as a vehicle lamp cover.
（耐擦傷性）
　得られたメタクリル樹脂層の表面または積層体のメタクリル樹脂層側の表面に対して、スチールウールによる摩耗試験を行った。具体的には、＃００００のスチールウールを用いて、メタクリル樹脂層または積層体の表面を、荷重１４ｋＰａで１５ｃｍ／秒の速度で１１往復擦った。ＪＩＳ　Ｋ７１３６に従って、摩耗試験前後のメタクリル樹脂層または積層体のヘイズを測定し、試験前後のヘイズの変化（Δヘイズ（単位：％））を算出した。Δヘイズが１５％未満であると、耐擦傷性に優れる。 (Abrasion resistance)
The surface of the obtained methacrylic resin layer or the surface on the methacrylic resin layer side of the laminate was subjected to an abrasion test using steel wool. Specifically, using # 0000 steel wool, the surface of the methacrylic resin layer or laminate was rubbed 11 times at a load of 14 kPa at a speed of 15 cm / sec. According to JIS K7136, the haze of the methacrylic resin layer or laminate before and after the wear test was measured, and the change in haze before and after the test (Δhaze (unit:%)) was calculated. When the Δhaze is less than 15%, the scratch resistance is excellent.
（使用した主な材料）
シリカ１：株式会社アドマテックス製　アドマファイン（登録商標）Ｓ０－Ｃ１（真球状、平均一次粒子径：０．３μｍ）
シリカ２：株式会社アドマテックス製　アドマファイン（登録商標）Ｓ０－Ｃ２（真球状、平均一次粒子径：０．５μｍ）
シリカ３：株式会社アドマテックス製　アドマファイン（登録商標）Ｓ０－Ｃ５（真球状、平均一次粒子径：１．６μｍ）
シリカ４：ＡＧＣエスアイテック株式会社製　サンスフェア（登録商標）ＮＰ－３０（真球状、平均一次粒子径：４．０μｍ）
シリカ５：株式会社アドマテックス製　アドマナノ（登録商標）ＹＣ１００Ｃ－ＳＭ２（真球状、平均一次粒子径：０．１μｍ）
シリカ６：株式会社トクヤマ製　サンシールＳＳ０７（真球状、平均一次粒子径：０．８μｍ） (Main materials used)
Silica 1: Admafine (registered trademark) S0-C1 (true spherical shape, average primary particle size: 0.3 μm) manufactured by Admatechs Co., Ltd.
Silica 2: Admafine Co., Ltd. Admafine (registered trademark) S0-C2 (spherical, average primary particle size: 0.5 μm)
Silica 3: Admafine Co., Ltd. Admafine (registered trademark) S0-C5 (spherical, average primary particle size: 1.6 μm)
Silica 4: Sunsphere (registered trademark) NP-30 (true spherical shape, average primary particle size: 4.0 μm) manufactured by AGC S-Itech Co., Ltd.
Silica 5: manufactured by Admatechs Co., Ltd. Admanano (registered trademark) YC100C-SM2 (spherical, average primary particle size: 0.1 μm)
Silica 6: Toshiyama Co., Ltd. Sun Seal SS07 (spherical, average primary particle size: 0.8 μm)
＜メタクリル樹脂Ａの製造＞
　攪拌器を備えた重合反応器に、メタクリル酸メチル９７．５重量部及びアクリル酸メチル２．５重量部の混合物と、１，１－ジ（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサン０．０１６重量部と、ｎ－オクチルメルカプタン０．１６重量部とを、それぞれ連続的に供給し、２５５℃、平均滞留時間４３分で重合反応を行った。次いで、重合反応器から出る反応液（部分重合体）を予熱した後、脱揮押出機に供給し、未反応の単量体成分を気化して回収するとともに、ペレット状のメタクリル樹脂Ａを得た。得られたメタクリル樹脂Ａの、メタクリル酸メチルに由来する単量体単位が９７．５重量％であり、アクリル酸メチルに由来する単量体単位の含有量が２．５重量％であり、ＭＦＲは２ｇ／１０分であった。 <Production of methacrylic resin A>
In a polymerization reactor equipped with a stirrer, a mixture of 97.5 parts by weight of methyl methacrylate and 2.5 parts by weight of methyl acrylate, 0.016 parts by weight of 1,1-di (tert-butylperoxy) cyclohexane, , N-octyl mercaptan (0.16 parts by weight) was continuously fed to carry out the polymerization reaction at 255 ° C. and an average residence time of 43 minutes. Next, after preheating the reaction liquid (partial polymer) coming out of the polymerization reactor, it is supplied to a devolatilizing extruder, and unreacted monomer components are vaporized and recovered, and a pellet-like methacrylic resin A is obtained. It was. In the obtained methacrylic resin A, the monomer unit derived from methyl methacrylate is 97.5% by weight, the content of the monomer unit derived from methyl acrylate is 2.5% by weight, and MFR Was 2 g / 10 min.
＜シリカ含有メタクリル樹脂Ｂの製造＞
　メタクリル樹脂Ａを９９．８重量％とシリカ１を０．２重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｂを得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Production of silica-containing methacrylic resin B>
After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 1, using a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm, the following kneading conditions Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin B.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｂ２の製造＞
　メタクリル樹脂Ａを９９．０重量％とシリカ１を１．０重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｂ２を得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Production of silica-containing methacrylic resin B2>
After mixing 99.0% by weight of methacrylic resin A and 1.0% by weight of silica 1, a single screw extruder having a screw diameter of 40 mm (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) was used and the following kneading conditions were used. Was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin B2.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｃの製造＞
　メタクリル樹脂Ａを９９．８重量％とシリカ２を０．２重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｃを得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Production of silica-containing methacrylic resin C>
After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 2, a single screw extruder having a screw diameter of 40 mm (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) was used and the following kneading conditions were used. Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin C.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｃ２の製造＞
　メタクリル樹脂Ａを９９．０重量％とシリカ２を１．０重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｃを得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Production of silica-containing methacrylic resin C2>
After mixing 99.0% by weight of methacrylic resin A and 1.0% by weight of silica 2, using a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm, the following kneading conditions Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin C.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｄの製造＞
　メタクリル樹脂Ａを９９．８重量％とシリカ３を０．２重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｄを得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Production of silica-containing methacrylic resin D>
After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 3, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used, and the following kneading conditions: Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin D.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｄ２の製造＞
　メタクリル樹脂Ａを９９．５重量％とシリカ３を０．５重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｄ２を得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Production of silica-containing methacrylic resin D2>
After mixing 99.5% by weight of methacrylic resin A and 0.5% by weight of silica 3, using a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm, the following kneading conditions Was melt-kneaded and extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-like silica-containing methacrylic resin D2.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｅの製造＞
　メタクリル樹脂Ａを９９．８重量％とシリカ４を０．２重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のシリカ含有メタクリル樹脂Ｅを得た。
（混練条件）
押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ <Manufacture of silica-containing methacrylic resin E>
After mixing 99.8% by weight of methacrylic resin A and 0.2% by weight of silica 4, using a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm, the following kneading conditions Was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain pellet-shaped silica-containing methacrylic resin E.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜シリカ含有メタクリル樹脂Ｆの製造＞
　メタクリル樹脂Ａを９９．０重量％とシリカ５を１．０重量％とを混合した後、日本製鋼所製二軸押出機（型式：ＴＥＸ３０ＳＳ－３０ＡＷ－２Ｖ）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のメタクリル樹脂組成物Ｆを得た。
（混練条件）
押出機温度：原料投入口から出口までの８つのヒーターについて、原料投入口側から、それぞれ２００℃、２００℃、２１０℃、２２０℃、２３０℃、２４０℃、２４０℃、２５０℃に設定した。
回転数：２００ｒｐｍ
原料の投入速度：１２ｋｇ／時 <Manufacture of silica-containing methacrylic resin F>
After mixing 99.0% by weight of methacrylic resin A and 1.0% by weight of silica 5, using a twin screw extruder (model: TEX30SS-30AW-2V) manufactured by Nippon Steel, under the following kneading conditions: Melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-shaped methacrylic resin composition F.
(Kneading conditions)
Extruder temperature: The eight heaters from the raw material inlet to the outlet were set to 200 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 240 ° C., and 250 ° C. from the raw material inlet side, respectively.
Rotation speed: 200rpm
Feeding speed of raw material: 12kg / hour
＜シリカ含有メタクリル樹脂Ｇの製造＞
　メタクリル樹脂Ａを９９．０質量％とシリカ６を１．０質量％とを混合した後、日本製鋼所製二軸押出機（型式：ＴＥＸ３０ＳＳ－３０ＡＷ－２Ｖ）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のメタクリル樹脂Ｇを得た。
（混練条件）
　押出機温度：原料投入口から出口までの８つのヒーターについて、原料投入口側から、それぞれ２００℃、２００℃、２１０℃、２２０℃、２３０℃、２４０℃、２４０℃、２５０℃に設定した。
回転数：２００ｒｐｍ
原料の投入速度：１２ｋｇ／時 <Manufacture of silica-containing methacrylic resin G>
After mixing 99.0% by mass of methacrylic resin A and 1.0% by mass of silica 6, a twin screw extruder manufactured by Nippon Steel Works (model: TEX30SS-30AW-2V) was used under the following kneading conditions. Melt-kneading, extruding into a strand shape, cooling with water and cutting with a strand cutter gave a pellet-shaped methacrylic resin G.
(Kneading conditions)
Extruder temperature: The eight heaters from the raw material inlet to the outlet were set to 200 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 240 ° C., and 250 ° C. from the raw material inlet side, respectively.
Rotation speed: 200rpm
Feeding speed of raw material: 12kg / hour
［実施例１］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のメタクリル樹脂組成物を得た。
（混練条件）
　押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ [Example 1]
After mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used and the following kneading conditions were used. The mixture was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-shaped methacrylic resin composition.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜射出成形＞
　得られたペレット状のメタクリル樹脂組成物を、射出成形機（ファナック株式会社製１５０Ｄ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×１ｍｍ厚の平板形状に成形し、メタクリル樹脂層を得た。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２２０℃、２４０℃、２６０℃、２６０℃、２６０℃に設定した。
射出速度：１００ｍｍ／秒
最大射出圧力：１８００ｋｇ／ｃｍ２
保圧：８００ｋｇ／ｃｍ２
金型温度：６０℃ <Injection molding>
The pellet-shaped methacrylic resin composition obtained was molded into a flat plate shape of 150 mm × 90 mm × 1 mm thickness under the following molding conditions using an injection molding machine (FANUC Corporation 150D) to obtain a methacrylic resin layer. .
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were set to 220 ° C., 240 ° C., 260 ° C., 260 ° C., and 260 ° C. from the raw material inlet side, respectively.
Injection speed: 100 mm / second Maximum injection pressure: 1800 kg / cm 2
Holding pressure: 800 kg / cm 2
Mold temperature: 60 ℃
　次いで、得られたメタクリル樹脂層を、１５０ｍｍ×９０ｍｍ×３ｍｍ厚の金型に貼り付け、メタクリル樹脂Ａを、射出成形機（ファナック株式会社製１５０Ｄ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×３ｍｍ厚の平板形状に成形し、１ｍｍ厚のメタクリル樹脂層と、２ｍｍ厚のメタクリル樹脂Ａを含む層とを含む積層体を得た。ここで、メタクリル樹脂Ａを含む２ｍｍ厚の層単体の、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズは、０．３％であった。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２２０℃、２３０℃、２４０℃、２５０℃、２５０℃に設定した。
射出速度：３０ｍｍ／秒
最大射出圧力：１８００ｋｇ／ｃｍ２
保圧：８００ｋｇ／ｃｍ２
金型温度：６０℃ Next, the obtained methacrylic resin layer was attached to a 150 mm × 90 mm × 3 mm thick mold, and the methacrylic resin A was 150 mm × 90 mm under the following molding conditions using an injection molding machine (FANUC Corporation 150D). A laminated body including a 1 mm-thick methacrylic resin layer and a layer containing 2 mm-thick methacrylic resin A was obtained by molding into a flat plate shape of 3 mm thickness. Here, the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were respectively set at 220 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
Injection speed: 30 mm / sec Maximum Injection pressure: 1800 kg / cm 2
Holding pressure: 800 kg / cm 2
Mold temperature: 60 ℃
　得られた積層体を８０℃のオーブン内で１６時間静置し、その後６時間かけて４０℃まで徐冷して評価を行った。 The obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
［実施例２］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを５０重量％とシリカ含有メタクリル樹脂Ｂを５０重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 2]
Example in which 50% by weight of methacrylic resin A and 50% by weight of silica-containing methacrylic resin B were mixed instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例３］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを８５重量％とシリカ含有メタクリル樹脂Ｃを１５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 3]
Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin C was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例４］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｃを３０重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 4]
Example except that 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B were mixed, but 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin C were mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例５］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを９０重量％とシリカ含有メタクリル樹脂Ｄを１０重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 5]
Example in which 90% by weight of methacrylic resin A and 10% by weight of silica-containing methacrylic resin D were mixed instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例６］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを８５重量％とシリカ含有メタクリル樹脂Ｂを１０重量％とシリカ含有メタクリル樹脂Ｃを５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 6]
Instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A, 10% by weight of silica-containing methacrylic resin B, and 5% by weight of silica-containing methacrylic resin C. % Was obtained in the same manner as in Example 1 except that% was mixed and evaluated.
［実施例７］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを８０重量％とシリカ含有メタクリル樹脂Ｂを１０重量％とシリカ含有メタクリル樹脂Ｃを１０重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 7]
Instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 80% by weight of methacrylic resin A, 10% by weight of silica-containing methacrylic resin B, and 10% by weight of silica-containing methacrylic resin C % Was obtained in the same manner as in Example 1 except that% was mixed and evaluated.
［実施例８］
　メタクリル樹脂Ａを８６重量％とシリカ含有メタクリル樹脂Ｂ２を１４重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のメタクリル樹脂組成物を得た。
（混練条件）
　押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ [Example 8]
After mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used and the following kneading conditions were used. The mixture was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-shaped methacrylic resin composition.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜射出成形＞
　得られたペレット状のメタクリル樹脂組成物を、射出成形機（東芝機械株式会社製ＥＣ１３０ＳＸII－４Ａ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×１ｍｍ厚の平板形状に成形し、成形体を得た。
（成形条件）
　スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ６０℃、２３０℃、２４０℃、２５０℃、２５０℃に設定した。
射出速度：９０ｍｍ／秒
最大射出圧力：２００ＭＰａ
保圧：８０ＭＰａ
金型温度：６０℃
冷却タイマー：４５秒 <Injection molding>
Using the injection molding machine (EC130SXII-4A manufactured by Toshiba Machine Co., Ltd.), the resulting pellet-like methacrylic resin composition was molded into a plate shape of 150 mm × 90 mm × 1 mm thickness under the following molding conditions, Obtained.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were respectively set to 60 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
Injection speed: 90 mm / second Maximum injection pressure: 200 MPa
Holding pressure: 80 MPa
Mold temperature: 60 ℃
Cooling timer: 45 seconds
　次いで、得られた成形体を、１５０ｍｍ×９０ｍｍ×３ｍｍ厚の金型に貼り付け、メタクリル樹脂Ａを、射出成形機（東芝機械株式会社製ＥＣ１３０ＳＸII－４Ａ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×３ｍｍ厚の平板形状に成形し、メタクリル樹脂組成物を含む１ｍｍ厚の層と、メタクリル樹脂Ａを含む２ｍｍ厚の層からなる積層体を得た。ここで、メタクリル樹脂Ａを含む２ｍｍ厚の層単体の、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズは、０．３％であった。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ６０℃、２３０℃、２４０℃、２５０℃、２５０℃に設定した。
射出速度：９０ｍｍ／秒
最大射出圧力：２００ＭＰａ
保圧：８０ＭＰａ
金型温度：６０℃
冷却タイマー：４５秒 Next, the obtained molded body was affixed to a 150 mm × 90 mm × 3 mm thick mold, and methacrylic resin A was 150 mm under the following molding conditions using an injection molding machine (EC130SXII-4A manufactured by Toshiba Machine Co., Ltd.). The laminate was formed into a flat plate shape of × 90 mm × 3 mm thickness and composed of a 1 mm thick layer containing the methacrylic resin composition and a 2 mm thick layer containing the methacrylic resin A. Here, the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were respectively set to 60 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
Injection speed: 90 mm / second Maximum injection pressure: 200 MPa
Holding pressure: 80 MPa
Mold temperature: 60 ℃
Cooling timer: 45 seconds
　得られた積層体を８０℃のオーブン内で１６時間静置し、その後６時間かけて４０℃まで徐冷して評価を行った。 The obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
［実施例９］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを９５重量％とシリカ含有メタクリル樹脂Ｃを５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 9]
Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 95% by weight of methacrylic resin A and 5% by weight of silica-containing methacrylic resin C was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例１０］
　メタクリル樹脂Ａを８６重量％とシリカ含有メタクリル樹脂Ｂ２を１４重量％とを混合する代わりに、メタクリル樹脂Ａを９５重量％とシリカ含有メタクリル樹脂Ｃ２を５重量％とを混合した以外は、実施例８と同様にして積層体を得て、評価を行った。 [Example 10]
Example in which 95% by weight of methacrylic resin A and 5% by weight of silica-containing methacrylic resin C2 were mixed instead of mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2. In the same manner as in Example 8, a laminate was obtained and evaluated.
［実施例１１］
　メタクリル樹脂Ａを８６重量％とシリカ含有メタクリル樹脂Ｂ２を１４重量％とを混合する代わりに、メタクリル樹脂Ａを９２重量％とシリカ含有メタクリル樹脂Ｃ２を８重量％とを混合した以外は、実施例８と同様にして積層体を得て、評価を行った。 [Example 11]
Except for mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2, Example except that 92% by weight of methacrylic resin A and 8% by weight of silica-containing methacrylic resin C2 were mixed. In the same manner as in Example 8, a laminate was obtained and evaluated.
［実施例１２］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを５０重量％とシリカ含有メタクリル樹脂Ｃを５０重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 12]
Example except that 50% by weight of methacrylic resin A and 50% by weight of silica-containing methacrylic resin C were mixed instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例１３］
　メタクリル樹脂Ａを８６重量％とシリカ含有メタクリル樹脂Ｂ２を１４重量％とを混合する代わりに、メタクリル樹脂Ａを８８重量％とシリカ含有メタクリル樹脂Ｃ２を１２重量％とを混合した以外は、実施例８と同様にして積層体を得て、評価を行った。 [Example 13]
Example except that 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2 were mixed instead of 88% by weight of methacrylic resin A and 12% by weight of silica-containing methacrylic resin C2. In the same manner as in Example 8, a laminate was obtained and evaluated.
［実施例１４］
　メタクリル樹脂Ａを９７重量％とシリカ含有メタクリル樹脂Ｇを３重量％とを混合した後、日本製鋼所製二軸押出機（型式：ＴＥＸ３０ＳＳ－３０ＡＷ－２Ｖ）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のメタクリル樹脂組成物を得た。
（混練条件）
押出機温度：原料投入口から出口までの８つのヒーターについて、原料投入口側から、それぞれ２００℃、２００℃、２１０℃、２２０℃、２３０℃、２４０℃、２４０℃、２５０℃に設定した。
回転数：２００ｒｐｍ
原料の投入速度：１２ｋｇ／時 [Example 14]
After mixing 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin G, it was melted under the following kneading conditions using a Nippon Steel Works twin screw extruder (model: TEX30SS-30AW-2V). By kneading and extruding into a strand, cooling with water and cutting with a strand cutter, a pellet-shaped methacrylic resin composition was obtained.
(Kneading conditions)
Extruder temperature: The eight heaters from the raw material inlet to the outlet were set to 200 ° C., 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 240 ° C., and 250 ° C. from the raw material inlet side, respectively.
Rotation speed: 200rpm
Feeding speed of raw material: 12kg / hour
＜射出成形＞
　得られたペレット状のメタクリル樹脂組成物を、射出成形機（東芝機械株式会社製ＥＣ１３０ＳＸII－４Ａ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×１ｍｍ厚の平板形状に成形し、成形体を得た。
（成形条件）
　スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ６０℃、２３０℃、２４０℃、２５０℃、２５０℃に設定した。
射出速度：９０ｍｍ／秒
最大射出圧力：２００ＭＰａ
保圧：８０ＭＰａ
金型温度：６０℃
冷却タイマー：４５秒 <Injection molding>
Using the injection molding machine (EC130SXII-4A manufactured by Toshiba Machine Co., Ltd.), the resulting pellet-like methacrylic resin composition was molded into a plate shape of 150 mm × 90 mm × 1 mm thickness under the following molding conditions, Obtained.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were respectively set to 60 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
Injection speed: 90 mm / second Maximum injection pressure: 200 MPa
Holding pressure: 80 MPa
Mold temperature: 60 ℃
Cooling timer: 45 seconds
　次いで、得られた成形体を、１５０ｍｍ×９０ｍｍ×３ｍｍ厚の金型に貼り付け、メタクリル樹脂Ａを、射出成形機（東芝機械株式会社製ＥＣ１３０ＳＸII－４Ａ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×３ｍｍ厚の平板形状に成形し、メタクリル樹脂組成物を含む１ｍｍ厚の層と、メタクリル樹脂Ａを含む２ｍｍ厚の層からなる積層体を得た。ここで、メタクリル樹脂Ａを含む２ｍｍ厚の層単体の、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズは、０．３％であった。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ６０℃、２３０℃、２４０℃、２５０℃、２５０℃に設定した。
射出速度：９０ｍｍ／秒
最大射出圧力：２００ＭＰａ
保圧：８０ＭＰａ
金型温度：６０℃
冷却タイマー：４５秒 Next, the obtained molded body was affixed to a 150 mm × 90 mm × 3 mm thick mold, and methacrylic resin A was 150 mm under the following molding conditions using an injection molding machine (EC130SXII-4A manufactured by Toshiba Machine Co., Ltd.). The laminate was formed into a flat plate shape of × 90 mm × 3 mm thickness and composed of a 1 mm thick layer containing the methacrylic resin composition and a 2 mm thick layer containing the methacrylic resin A. Here, the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were respectively set to 60 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
Injection speed: 90 mm / second Maximum injection pressure: 200 MPa
Holding pressure: 80 MPa
Mold temperature: 60 ℃
Cooling timer: 45 seconds
　得られた積層体を８０℃のオーブン内で１６時間静置し、その後６時間かけて４０℃まで徐冷して評価を行った。 The obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
［実施例１５］
　メタクリル樹脂Ａを９７重量％とシリカ含有メタクリル樹脂Ｇを３重量％とを混合する代わりに、メタクリル樹脂Ａを９４重量％とシリカ含有メタクリル樹脂Ｇを６重量％とを混合した以外は、実施例１４と同様にして積層体を得て、評価を行った。 [Example 15]
Example in which, instead of mixing 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin G, 94% by weight of methacrylic resin A and 6% by weight of silica-containing methacrylic resin G was used. In the same manner as in Example 14, a laminate was obtained and evaluated.
［実施例１６］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを８５重量％とシリカ含有メタクリル樹脂Ｄを１５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Example 16]
Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin D was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
［実施例１７］
　メタクリル樹脂Ａを８６重量％とシリカ含有メタクリル樹脂Ｂ２を１４重量％とを混合する代わりに、メタクリル樹脂Ａを９０重量％とシリカ含有メタクリル樹脂Ｄ２を１０重量％とを混合した以外は、実施例８と同様にして積層体を得て、評価を行った。 [Example 17]
Example in which 90% by weight of methacrylic resin A and 10% by weight of silica-containing methacrylic resin D2 were mixed instead of mixing 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2. In the same manner as in Example 8, a laminate was obtained and evaluated.
［実施例１８］
　メタクリル樹脂Ａを９７重量％とシリカ含有メタクリル樹脂Ｇを３重量％とを混合する代わりに、メタクリル樹脂Ａを９０重量％とシリカ含有メタクリル樹脂Ｇを１０重量％とを混合した以外は、実施例１４と同様にして積層体を得て、評価を行った。 [Example 18]
Example in which, instead of mixing 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin G, 90% by weight of methacrylic resin A and 10% by weight of silica-containing methacrylic resin G was used. In the same manner as in Example 14, a laminate was obtained and evaluated.
［実施例１９］
＜射出成形＞
　シリカ含有メタクリル樹脂Ｂ１００重量％を、射出成形機（ファナック株式会社製１５０Ｄ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×１ｍｍ厚の平板形状に成形し、メタクリル樹脂層を得た。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２２０℃、２４０℃、２６０℃、２６０℃、２６０℃に設定した。
射出速度：１００ｍｍ／秒
最大射出圧力：１８００ｋｇ／ｃｍ２
保圧：８００ｋｇ／ｃｍ２
金型温度：６０℃ [Example 19]
<Injection molding>
The silica-containing methacrylic resin B 100% by weight was molded into a flat plate shape of 150 mm × 90 mm × 1 mm thickness under the following molding conditions using an injection molding machine (FANUC Corporation 150D) to obtain a methacrylic resin layer.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were set to 220 ° C., 240 ° C., 260 ° C., 260 ° C., and 260 ° C. from the raw material inlet side, respectively.
Injection speed: 100 mm / second Maximum injection pressure: 1800 kg / cm 2
Holding pressure: 800 kg / cm 2
Mold temperature: 60 ℃
　次いで、得られたメタクリル樹脂層を、１５０ｍｍ×９０ｍｍ×３ｍｍ厚の金型に貼り付け、メタクリル樹脂Ａを、射出成形機（ファナック株式会社製１５０Ｄ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×３ｍｍ厚の平板形状に成形し、１ｍｍ厚のメタクリル樹脂層と、２ｍｍ厚のメタクリル樹脂Ａを含む層とを含む積層体を得た。ここで、メタクリル樹脂Ａを含む２ｍｍ厚の層単体の、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズは、０．３％であった。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２２０℃、２３０℃、２４０℃、２５０℃、２５０℃に設定した。
射出速度：３０ｍｍ／秒
最大射出圧力：１８００ｋｇ／ｃｍ２
保圧：８００ｋｇ／ｃｍ２
金型温度：６０℃ Next, the obtained methacrylic resin layer was attached to a 150 mm × 90 mm × 3 mm thick mold, and the methacrylic resin A was 150 mm × 90 mm under the following molding conditions using an injection molding machine (FANUC Corporation 150D). A laminated body including a 1 mm-thick methacrylic resin layer and a layer containing 2 mm-thick methacrylic resin A was obtained by molding into a flat plate shape of 3 mm thickness. Here, the haze measured according to JIS K7136 of the 2 mm-thick single layer containing the methacrylic resin A was 0.3%.
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were respectively set at 220 ° C., 230 ° C., 240 ° C., 250 ° C., and 250 ° C. from the raw material inlet side.
Injection speed: 30 mm / sec Maximum Injection pressure: 1800 kg / cm 2
Holding pressure: 800 kg / cm 2
Mold temperature: 60 ℃
　得られた積層体を８０℃のオーブン内で１６時間静置し、その後６時間かけて４０℃まで徐冷して評価を行った。 The obtained laminate was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for evaluation.
［比較例１］
　シリカ含有メタクリル樹脂Ｂ１００重量％の代わりに、メタクリル樹脂Ａ１００重量％を用いて１ｍｍ厚の成形体を得た以外は、実施例１５と同様にして積層体を得て、評価を行った。 [Comparative Example 1]
A laminate was obtained and evaluated in the same manner as in Example 15 except that a molded product having a thickness of 1 mm was obtained using 100% by weight of methacrylic resin A instead of 100% by weight of silica-containing methacrylic resin B.
［比較例２］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを９７．５重量％とシリカ含有メタクリル樹脂Ｃを２．５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Comparative Example 2]
Instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, except that 97.5% by weight of methacrylic resin A and 2.5% by weight of silica-containing methacrylic resin C were mixed. Were obtained in the same manner as in Example 1 and evaluated.
［比較例３］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを９７．５重量％とシリカ含有メタクリル樹脂Ｄを２．５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Comparative Example 3]
Instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, except that 97.5% by weight of methacrylic resin A and 2.5% by weight of silica-containing methacrylic resin D were mixed. Were obtained in the same manner as in Example 1 and evaluated.
［比較例４］
　メタクリル樹脂Ａを８５重量％とシリカ含有メタクリル樹脂Ｅを１５重量％とを混合した後、スクリュー径４０ｍｍの単軸押出機（田辺プラスチックス機械株式会社製ＶＳ４０）を使用し、以下の混練条件で溶融混練してストランド状に押出し、水冷してストランドカッターでカッティングすることにより、ペレット状のメタクリル樹脂組成物を得た。
（混練条件）
　押出機温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２００℃、２３０℃、２４０℃、２４０℃、２４０℃に設定した。
回転数：７５ｒｐｍ [Comparative Example 4]
After mixing 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin E, a single screw extruder (VS40 manufactured by Tanabe Plastics Machinery Co., Ltd.) with a screw diameter of 40 mm was used and the following kneading conditions were used. The mixture was melt-kneaded, extruded into a strand, cooled with water, and cut with a strand cutter to obtain a pellet-shaped methacrylic resin composition.
(Kneading conditions)
Extruder temperature: The five heaters from the raw material inlet to the outlet were set to 200 ° C., 230 ° C., 240 ° C., 240 ° C., and 240 ° C. from the raw material inlet side, respectively.
Rotation speed: 75rpm
＜射出成形＞
　得られたペレット状のメタクリル樹脂組成物を、射出成形機（ファナック株式会社製１５０Ｄ）を用いて、以下の成形条件で１５０ｍｍ×９０ｍｍ×３ｍｍ厚の平板形状に成形し、メタクリル樹脂層を得た。
（成形条件）
スクリュー温度：原料投入口から出口までの５つのヒーターについて、原料投入口側から、それぞれ２２０℃、２４０℃、２６０℃、２６０℃、２６０℃に設定した。
射出速度：３０ｍｍ／秒
最大射出圧力：１８００ｋｇ／ｃｍ２
保圧：８００ｋｇ／ｃｍ２
金型温度：６０℃ <Injection molding>
The obtained pellet-shaped methacrylic resin composition was molded into a flat plate shape of 150 mm × 90 mm × 3 mm thickness under the following molding conditions using an injection molding machine (150D manufactured by FANUC CORPORATION) to obtain a methacrylic resin layer. .
(Molding condition)
Screw temperature: The five heaters from the raw material inlet to the outlet were set to 220 ° C., 240 ° C., 260 ° C., 260 ° C., and 260 ° C. from the raw material inlet side, respectively.
Injection speed: 30 mm / sec Maximum Injection pressure: 1800 kg / cm 2
Holding pressure: 800 kg / cm 2
Mold temperature: 60 ℃
　得られたメタクリル樹脂層を８０℃のオーブン内で１６時間静置し、その後６時間かけて４０℃まで徐冷して各評価を行った。 The obtained methacrylic resin layer was allowed to stand in an oven at 80 ° C. for 16 hours, and then gradually cooled to 40 ° C. over 6 hours for each evaluation.
［比較例５］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを８５重量％とシリカ含有メタクリル樹脂Ｅを１５重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Comparative Example 5]
Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin E was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
［比較例６］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、メタクリル樹脂Ａを９７重量％とシリカ含有メタクリル樹脂Ｆを３重量％とを混合した以外は、実施例１と同様にして積層体を得て、評価を行った。 [Comparative Example 6]
Example in which, instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B, 97% by weight of methacrylic resin A and 3% by weight of silica-containing methacrylic resin F was mixed. A laminate was obtained in the same manner as in Example 1 and evaluated.
［比較例７］
　メタクリル樹脂Ａを８６重量％とシリカ含有メタクリル樹脂Ｂ２を１４重量％とを混合する代わりに、メタクリル樹脂Ａを８５重量％とシリカ含有メタクリル樹脂Ｃ２を１５重量％とを混合した以外は、実施例８と同様にして積層体を得て、評価を行った。 [Comparative Example 7]
Example except that 86% by weight of methacrylic resin A and 14% by weight of silica-containing methacrylic resin B2 were mixed, but 85% by weight of methacrylic resin A and 15% by weight of silica-containing methacrylic resin C2 were mixed. In the same manner as in Example 8, a laminate was obtained and evaluated.
［比較例８］
　メタクリル樹脂Ａを７０重量％とシリカ含有メタクリル樹脂Ｂを３０重量％とを混合する代わりに、シリカ含有メタクリル樹脂ＢＣを１００重量％を用いた以外は、実施例１と同様にして積層体を得て、評価を行った。 [Comparative Example 8]
A laminate was obtained in the same manner as in Example 1 except that 100% by weight of silica-containing methacrylic resin BC was used instead of mixing 70% by weight of methacrylic resin A and 30% by weight of silica-containing methacrylic resin B. And evaluated.
　実施例１～１９および比較例１～８におけるメタクリル樹脂層の組成と、メタクリル樹脂層または積層体の評価結果を、それぞれ表１および表２に示す。 Tables 1 and 2 show the compositions of the methacrylic resin layers and the evaluation results of the methacrylic resin layers or laminates in Examples 1 to 19 and Comparative Examples 1 to 8, respectively.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (4)

  1. 　メタクリル樹脂９９．７５重量％以上９９．９９５重量％未満と、平均一次粒子径０．２μｍ以上２μｍ以下のシリカ粒子０．００５重量％を超え０．２５重量％以下とを含有するメタクリル樹脂層と、前記シリカ粒子の含有量が０．００５重量％以下である熱可塑性樹脂層とを含有し、ＪＩＳ　Ｋ７１３６に従って測定されるヘイズが５．５％以下である、積層体。 A methacrylic resin layer containing 99.75% by weight or more and less than 99.995% by weight of methacrylic resin, and 0.005% by weight or more and 0.25% by weight or less of silica particles having an average primary particle diameter of 0.2 μm or more and 2 μm or less; A laminate comprising a thermoplastic resin layer having a silica particle content of 0.005% by weight or less, and having a haze of 5.5% or less measured according to JIS K7136.
  2. 　ＪＩＳ　Ｋ７１３６に従って測定されるヘイズが３％以下である、請求項１に記載の積層体。 The laminate according to claim 1, wherein the haze measured according to JIS K7136 is 3% or less.
  3. 　前記メタクリル樹脂層の厚さが、０．５ｍｍ以上８ｍｍ以下である、請求項１または２に記載の積層体。 The laminate according to claim 1 or 2, wherein the methacrylic resin layer has a thickness of 0.5 mm or more and 8 mm or less.
  4. 　請求項１～３のいずれか一項に記載の積層体を含む車両用ランプカバー。 A lamp cover for a vehicle comprising the laminate according to any one of claims 1 to 3.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH023432A (en) * 1988-06-17 1990-01-09 Kohjin Co Ltd Easily bondable film
JP2003201114A (en) * 2001-10-31 2003-07-15 Univ Nihon Modified silica composition, transparent resin composition, thermoplastic resin laminated body using these, automobile parts and method for manufacturing these
JP2009026646A (en) * 2007-07-20 2009-02-05 Stanley Electric Co Ltd Vehicular lamp
JP2013052676A (en) * 2011-08-08 2013-03-21 Toray Ind Inc Optical laminate film
JP2013155245A (en) * 2012-01-27 2013-08-15 Tamura Seisakusho Co Ltd Ultraviolet-curable transparent resin composition
WO2015053328A1 (en) * 2013-10-11 2015-04-16 三菱瓦斯化学株式会社 Scratch-resistant polycarbonate resin laminate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH023432A (en) * 1988-06-17 1990-01-09 Kohjin Co Ltd Easily bondable film
JP2003201114A (en) * 2001-10-31 2003-07-15 Univ Nihon Modified silica composition, transparent resin composition, thermoplastic resin laminated body using these, automobile parts and method for manufacturing these
JP2009026646A (en) * 2007-07-20 2009-02-05 Stanley Electric Co Ltd Vehicular lamp
JP2013052676A (en) * 2011-08-08 2013-03-21 Toray Ind Inc Optical laminate film
JP2013155245A (en) * 2012-01-27 2013-08-15 Tamura Seisakusho Co Ltd Ultraviolet-curable transparent resin composition
WO2015053328A1 (en) * 2013-10-11 2015-04-16 三菱瓦斯化学株式会社 Scratch-resistant polycarbonate resin laminate

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