WO2017094282A1 - 透明樹脂積層体 - Google Patents

透明樹脂積層体 Download PDF

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Publication number
WO2017094282A1
WO2017094282A1 PCT/JP2016/069856 JP2016069856W WO2017094282A1 WO 2017094282 A1 WO2017094282 A1 WO 2017094282A1 JP 2016069856 W JP2016069856 W JP 2016069856W WO 2017094282 A1 WO2017094282 A1 WO 2017094282A1
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Prior art keywords
resin
mass
thermoplastic resin
acrylic
hardness
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PCT/JP2016/069856
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English (en)
French (fr)
Japanese (ja)
Inventor
正樹 平林
Original Assignee
三菱瓦斯化学株式会社
Ｍｇｃフィルシート株式会社
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Application filed by 三菱瓦斯化学株式会社, Ｍｇｃフィルシート株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN201680068388.6A priority Critical patent/CN108290404A/zh
Priority to KR1020187017949A priority patent/KR20180088681A/ko
Priority to JP2017553644A priority patent/JP6787925B2/ja
Publication of WO2017094282A1 publication Critical patent/WO2017094282A1/ja

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    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

Definitions

  • the present invention is used for transparent base materials and protective materials, and has a polycarbonate resin layer and a thermoplastic resin layer containing a specific copolymer and a specific acrylic resin, and has excellent surface hardness and high temperature and high temperature.
  • the present invention relates to a resin laminate having excellent warpage and deformation resistance even when exposed to moisture.
  • Acrylic resin is excellent in surface hardness, transparency, scratch resistance and weather resistance.
  • polycarbonate resin is excellent in impact resistance and the like. Therefore, a laminate having an acrylic resin layer and a polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance, impact resistance, and the like, and is used for automobile parts, home appliances, electronic devices, and portable information terminals. Used for display windows.
  • a laminate having an acrylic resin layer and a polycarbonate resin layer has a problem of warping when used outdoors or in a car under high temperature and high humidity.
  • Patent Document 1 Japanese Patent Laid-Open No. 2014-198454
  • Patent Document 2 International Publication No. 2015/133530
  • a vinyl aromatic monomer unit a methacrylic acid ester monomer unit
  • a laminate comprising a copolymer comprising a cyclic acid anhydride monomer unit, a layer composed of a resin composition obtained by polymer alloying an acrylic resin, and a layer composed of a polycarbonate resin
  • Such a laminate suppresses warpage under high temperature and high humidity of 85 ° C. and 85%, but has a lower surface hardness than an acrylic resin used for polymer alloy, and as a resin laminate used as a substitute for glass in recent years, the surface hardness is low. There may have been insufficient.
  • the present invention provides a resin laminate that can be used as a transparent base material and a transparent protective material, has shape stability that can prevent warpage even in a high-temperature and high-humidity environment, and is excellent in surface hardness. With the goal.
  • thermoplastic resin (B) laminated a thermoplastic resin (B) on at least one surface of a polycarbonate-based resin (A) sheet mainly composed of a polycarbonate resin,
  • This thermoplastic resin (B) has an aromatic vinyl monomer unit of 50 to 80% by mass, an unsaturated dicarboxylic acid anhydride monomer unit of 10 to 25% by mass, and an acrylic compound monomer unit of 5 to 24% by mass.
  • thermoplastic resin (B) A resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate resin (A) sheet mainly composed of a polycarbonate resin
  • the thermoplastic resin (B) It contains 50 to 80% by weight of aromatic vinyl monomer units, 10 to 25% by weight of unsaturated dicarboxylic acid anhydride monomer units, 5 to 24% by weight of acrylic compound monomer units
  • the copolymer (b1) contains a copolymer (b1) in which the mass% of the saturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the acrylic compound monomer It is a resin laminated body characterized by including the acrylic resin (b2) which contains a unit as a main component.
  • the copolymer (b1) is 55 to 90 parts by mass based on 100 parts by mass in total of the contents of the copolymer (b1) and the acrylic resin (b2) in the thermoplastic resin (B).
  • the resin (b2) is 45 to 10 parts by mass, and the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains 80% by mass or more of the acrylic compound monomer unit [1] It is a resin laminated body as described in above.
  • the copolymer (b1) is 10 to 40 parts by mass based on the total content of the copolymer (b1) and the acrylic resin (b2) in the thermoplastic resin (B) being 100 to 40 parts by mass.
  • the resin (b2) is 90 to 60 parts by mass, and the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains an acrylic compound monomer unit of less than 80% by mass [1] It is a resin laminated body as described in above. [4] The resin laminate according to any one of [1] to [3], wherein the thermoplastic resin (B) is a polymer alloy of the copolymer (b1) and the acrylic resin (b2).
  • the HIT hardness ⁇ thermoplastic resin ⁇ Is a resin divided by HIT hardness ⁇ acrylic resin ⁇ (HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ ) of 1.01 or more. It is a laminate.
  • thermoplastic resin (B) layer has a thickness of 10 to 250 ⁇ m and the total thickness of the resin laminate is in the range of 0.05 to 3.0 mm. It is a resin laminated body of a crab.
  • thermoplastic resin (B) layer contains an ultraviolet absorber.
  • thermoplastic resin (B) layer contains an ultraviolet absorber.
  • A) layer contains an ultraviolet absorber.
  • One or more of the anti-fingerprint treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment and antifouling treatment are applied to one or both surfaces of the resin laminate.
  • a transparent substrate material comprising the resin laminate according to any one of [1] to [16].
  • a transparent protective material comprising the resin laminate according to any one of [1] to [17].
  • a touch panel front protective plate including the resin laminate according to any one of [1] to [18].
  • a front plate for an OA device or a portable electronic device comprising the resin laminate according to any one of [1] to [16].
  • thermoplastic resin (B) contains 50 to 80% by weight of aromatic vinyl monomer units, 10 to 30% by weight of unsaturated dicarboxylic anhydride monomer units, 5 to 25% by weight of acrylic compound monomer units, and
  • the copolymer (b1) contains a copolymer (b1) in which the mass% of the saturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the acrylic compound monomer It is a resin laminated body characterized by including the acrylic resin (b2) which contains a unit as a main component.
  • a resin laminate having shape stability such as warpage prevention in a high-temperature and high-humidity environment, and a surface hardness equal to or greater than that of a single acrylic resin
  • the resin laminate is a transparent substrate material.
  • a transparent protective material such as notebook PCs, desktop PC liquid crystal monitors, liquid crystal televisions, etc. It can be suitably used as a front plate for protecting the device.
  • the present invention relates to a resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate-based resin sheet (A) containing a polycarbonate resin as a main component, and this thermoplastic resin (B ) Comprises 50-80% by weight of aromatic vinyl monomer units, 10-25% by weight of unsaturated dicarboxylic acid anhydride monomer units, and 5-24% by weight of acrylic compound monomer units,
  • the copolymer (b1) in which the mass% of the unsaturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the copolymer (b1) and the acrylic compound
  • the present invention relates to a resin laminate comprising an acrylic resin (b2) containing a monomer unit as a main component.
  • the polycarbonate resin (A) used in the present invention is a polycarbonate resin (A) mainly composed of a polycarbonate resin.
  • “having a polycarbonate resin as a main component” means that the content of the polycarbonate resin exceeds 50 mass%.
  • the polycarbonate-based resin (A) preferably contains 75% by mass or more of polycarbonate resin, more preferably 90% by mass or more of polycarbonate resin, and further preferably substantially consists of polycarbonate resin. .
  • the polycarbonate resin (A) contains a carbonate ester bond in the molecular main chain.
  • — [O—R—OCO] — unit (wherein R includes an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure)
  • a polycarbonate containing a structural unit of the following formula [1] By using such a polycarbonate, a resin laminate excellent in impact resistance can be obtained.
  • an aromatic polycarbonate resin for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000 commercially available from Mitsubishi Engineering Plastics Co., Ltd.
  • the polycarbonate resin (A) can be synthesized using a monohydric phenol represented by the following formula [2] as a terminal stopper. preferable.
  • R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
  • R 2 to R 5 each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent.
  • the monohydric phenol of the general formula [2] is more preferably a monohydric phenol represented by the following formula [3].
  • R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
  • the carbon number of R 1 is more preferably within a specific numerical range. Specifically, 22 is more preferable as the upper limit value of the carbon number of R 1 , and 18 is particularly preferable. Moreover, 12 is more preferable as the lower limit of the carbon number of R 1 .
  • terminal terminators represented by general formula [2] or general formula [3]
  • parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.
  • R 1 is a monohydric phenol (termination terminator) having an alkyl group having 16 carbon atoms, glass transition temperature, melt fluidity, moldability, draw-down resistance, monovalent during the production of polycarbonate resin
  • the solvent solubility of phenol is excellent, and it is particularly preferable as a terminal terminator used in the polycarbonate resin used in the present invention.
  • the polyester resin only needs to contain terephthalic acid as a main component as the dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid.
  • a polyester resin obtained by polycondensation of a glycol component containing 20 to 40 (molar ratio, total 100) of 1,4-cyclohexanedimethanol with respect to ethylene glycol 80 to 60 (molar ratio) as a main component So-called “PETG” is preferred.
  • the polycarbonate resin (A) may contain a polyester carbonate resin having an ester bond and a carbonate bond in the polymer skeleton.
  • the weight average molecular weight of the polycarbonate resin (A) affects the impact resistance and molding conditions of the resin laminate. That is, when the weight average molecular weight is too small, the impact resistance of the resin laminate is lowered, which is not preferable. When the weight average molecular weight is too high, an excessive heat source may be required when laminating the resin layer containing the polycarbonate resin (A), which is not preferable. Further, since a high temperature is required depending on the molding method, the polycarbonate resin (A) is exposed to a high temperature, which may adversely affect its thermal stability.
  • the weight-average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.
  • the weight average molecular weight of the polycarbonate resin (A) can be measured based on the description in paragraphs 0061 to 0064 of JP-A-2007-179018. Details of the measurement method are shown below.
  • the relationship between the elution time and the molecular weight of the polycarbonate (PC) is obtained by a universal calibration method to obtain a calibration curve. Then, the PC elution curve (chromatogram) is measured under the same conditions as in the calibration curve, and each average molecular weight is determined from the elution time (molecular weight) and the peak area (number of molecules) of the elution time.
  • the weight average molecular weight is expressed as follows. Moreover, the following formula was used for the conversion formula.
  • MPC 0.47822MPS 1.01470 MPC represents the molecular weight of PC, and MPS represents the molecular weight of PS.
  • the production method of the polycarbonate-based resin (A) used in the present invention can be appropriately selected depending on the monomers used, such as a known phosgene method (interfacial polymerization method) and transesterification method (melting method).
  • thermoplastic resin (B) used in the present invention contains a copolymer (b1) described later, or an acrylic resin (b2) containing the copolymer (b1) and an acrylic compound monomer unit as main components. ). Each component will be described below.
  • the copolymer (b1) contained in the thermoplastic resin (B) according to the present invention contains 50 to 80% by mass of an aromatic vinyl monomer unit, preferably 50 to 75% by mass, more preferably 50 to 70% by mass.
  • the unsaturated dicarboxylic acid anhydride monomer unit is 10 to 30% by mass, preferably 10 to 25% by mass, more preferably 15 to 25% by mass, and the acrylic compound monomer unit is 5 to 25% by mass, preferably Is a copolymer comprising 5 to 24% by weight, more preferably 8 to 21% by weight, and the unsaturated dicarboxylic acid anhydride monomer unit is more than the acrylic compound monomer unit. b1).
  • the aromatic vinyl monomer is not particularly limited, and any known aromatic vinyl monomer can be used. From the viewpoint of availability, styrene, ⁇ -methylstyrene, o-methylstyrene. M-methylstyrene, p-methylstyrene, t-butylstyrene and the like. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these aromatic vinyl monomers may be mixed.
  • Examples of the unsaturated dicarboxylic acid anhydride monomer include maleic acid, itaconic acid, citraconic acid, aconitic acid and other acid anhydrides, and maleic anhydride is preferred from the viewpoint of compatibility with acrylic resins. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
  • acrylic compound monomer includes acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid and (meth) acrylic acid ester.
  • (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. It is done.
  • methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with the acrylic resin. Two or more of these acrylic compound monomers may be mixed.
  • the weight average molecular weight (Mw) of the copolymer (b1) is preferably 50,000 to 300,000, and more preferably 100,000 to 200,000. When the weight average molecular weight is 50,000 to 300,000, the compatibility with the acrylic resin (b2) is good.
  • a weight average molecular weight (Mw), a number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) can be measured using the gel permeation chromatography which used THF and chloroform as a solvent.
  • the thermoplastic resin (B) used in the present invention preferably contains an acrylic resin (b2) containing an acrylic compound monomer unit as a main component in addition to the copolymer (b1).
  • “comprising an acrylic compound monomer unit as a main component” means that the content of the acrylic compound monomer unit exceeds 50 mass%.
  • the acrylic resin (b2) preferably contains 60% by mass or more of acrylic compound monomer units, and more preferably contains 75% by mass or more of acrylic compound monomer units.
  • the acrylic resin (b2) may be a homopolymer substantially consisting of an acrylic compound monomer unit or a copolymer containing other monomer units.
  • acrylic compound monomer used in the present invention examples include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, and methacrylic acid.
  • examples include (meth) acrylic acid ester monomer units such as ethyl, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable.
  • the acrylic resin (b2) may be a polymer obtained by homopolymerizing these monomer units, but may also be a copolymer containing two or more types of monomer units.
  • the acrylic resin (b2) may be a copolymer containing a monomer other than the acrylic compound monomer as long as the acrylic compound monomer is the main component.
  • the monomer other than the acrylic compound monomer is not particularly limited, but an unsaturated dicarboxylic acid anhydride monomer such as an acid anhydride such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, Aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide N-substituted maleimides such as N-arylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimi
  • Examples include a polymer.
  • Examples of the copolymer containing such a monomer include 16% by mass of an aromatic vinyl monomer unit, 8% by mass of an unsaturated dicarboxylic acid anhydride monomer unit, and an acrylic compound monomer unit. Copolymer containing 76% by mass, copolymer containing 4% by mass of aromatic vinyl monomer units, 15% by mass of N-substituted maleimide monomer units, and 81% by mass of acrylic compound monomer units. Coalescence etc. can be used.
  • the weight-average molecular weight of the acrylic resin (b2) containing an acrylic compound monomer unit as a main component is easy to mix (disperse) with the copolymer (b1), and the heat of these polymer alloys. It is determined by the ease of production of the plastic resin (B) layer. That is, if the weight average molecular weight of the acrylic resin (b2) containing the acrylic compound monomer unit as a main component is too large, the difference in melt viscosity between the acrylic resin (b2) and the copolymer (b1) becomes too large.
  • the mixing (dispersing) of the polymer becomes worse, and the transparency of the polymer-alloyed thermoplastic resin (B) layer may be deteriorated, or a problem that stable melt-kneading cannot be continued may occur.
  • the weight average molecular weight of the acrylic resin (b2) containing the acrylic compound monomer unit as a main component is too small, the strength of the polymer-alloyed thermoplastic resin (B) layer is lowered. There is a possibility that a problem such as a decrease in impact resistance of the steel may occur.
  • the weight average molecular weight of the acrylic resin (b2) containing an acrylic compound monomer unit as a main component is preferably in the range of 50,000 to 700,000, and more preferably in the range of 60,000 to 550,000. More preferably, it is in the range of 70,000 to 500,000.
  • the copolymer (b1) On the basis of the total content of the copolymer (b1) and the acrylic resin (b2) being 100 parts by mass, the copolymer (b1) is 5 to 100 parts by mass and the acrylic resin (b2) is 95 to 0 parts by mass. Part. More preferably, the acrylic resin (b2) is 90 to 0 parts by mass with respect to 10 to 100 parts by mass, and still more preferably the acrylic resin (b2) with respect to 10 to 95 parts by mass of the copolymer (b1). ) Is 90 to 5 parts by mass. When the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains less than 80% by mass of an acrylic compound monomer unit, the copolymer (b1) is acrylic with respect to 10 to 40 parts by mass.
  • the resin (b2) is 90 to 60 parts by mass. Further, when the acrylic resin (b2) containing the acrylic compound monomer unit as a main component contains 80% by mass or more of the acrylic compound monomer unit, the copolymer (b1) is 55 to 90 parts by mass. The acrylic resin (b2) is more preferably 45 to 10 parts by mass. By making it within this weight ratio, thermoplasticity having a surface hardness equal to or higher than that of the acrylic resin (b2) alone and having shape stability such as warpage prevention in a high temperature and high humidity environment while maintaining transparency. Resin (B).
  • the thermoplastic resin (B) is preferably a polymer alloy of a copolymer (b1) and an acrylic resin (b2).
  • the polymer alloy refers to a composite material obtained by mixing two or more kinds of polymers. Such a polymer alloy can be obtained by mechanical mixing, melt mixing, or solution mixing of polymers.
  • the content of the copolymer (b1) and the acrylic resin (b2) is such that the copolymer (b1) is 5 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass in total. Yes, the acrylic resin (b2) is more than 0 parts by mass and 95 parts by mass or less.
  • the copolymer (b1) is 10 parts by mass or more and less than 100 parts by mass, and the acrylic resin (b2) is more than 0 part by mass and 90 parts by mass or less. More preferably, the acrylic resin (b2) is 90 to 5 parts by mass with respect to the copolymer (b1) of 10 to 95 parts by mass.
  • the copolymer (b1) is acrylic with respect to 10 to 40 parts by mass. More preferably, the resin (b2) is 90 to 60 parts by mass.
  • the acrylic resin (b2) containing the acrylic compound monomer unit as a main component contains 80% by mass or more of the acrylic compound monomer unit
  • the copolymer (b1) is 55 to 90 parts by mass.
  • the acrylic resin (b2) is more preferably 45 to 10 parts by mass.
  • the hardness of the thermoplastic resin (B) can be evaluated by indentation hardness and pencil hardness.
  • the indentation hardness of the thermoplastic resin (B) is HIT hardness ⁇ thermoplastic resin ⁇
  • the indentation hardness of the acrylic resin (b2) is HIT hardness ⁇ acrylic resin ⁇
  • the HIT hardness ⁇ thermoplastic resin ⁇ is HIT hardness.
  • the value divided by ⁇ acrylic resin ⁇ (HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ ) is preferably 1.01 or more, and more preferably 1.04 or more.
  • the pencil hardness of the thermoplastic resin (B) is preferably equal to or higher than the pencil hardness of the acrylic resin (b1) alone.
  • the method for producing the synthetic resin laminate of the present invention is not particularly limited.
  • a method of laminating (A) and bonding them together with an adhesive a method of co-extrusion molding of a thermoplastic resin (B) layer and a polycarbonate-based resin (A) layer, a thermoplastic resin formed in advance
  • a method of in-mold molding and integrating the polycarbonate resin (A) using the (B) layer but from the viewpoint of production cost and productivity, a method of co-extrusion molding is preferable. .
  • the production method of the thermoplastic resin (B) is not particularly limited, and necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then a Banbury mixer, A known method such as melt kneading by a machine such as a roll, a brabender, a single screw extruder, a twin screw extruder, or a pressure kneader can be applied.
  • a mixer such as a tumbler, a Henschel mixer, or a super mixer
  • a Banbury mixer A known method such as melt kneading by a machine such as a roll, a brabender, a single screw extruder, a twin screw extruder, or a pressure kneader can be applied.
  • the thickness of the thermoplastic resin (B) layer affects the surface hardness and impact resistance of the resin laminate. That is, when the thickness of the thermoplastic resin (B) layer is too thin, the surface hardness is lowered, which is not preferable. If the thickness of the thermoplastic resin (B) layer is too large, the impact resistance deteriorates, which is not preferable.
  • the thickness of the thermoplastic resin (B) layer is preferably 10 to 250 ⁇ m, more preferably 30 to 200 ⁇ m. More preferably, it is 60 to 150 ⁇ m.
  • the total thickness of the resin laminate (sheet), the thickness of the thermoplastic resin (B) layer, and the composition of the thermoplastic resin (B) layer are warped in a high temperature and high humidity environment of the resin laminate. Affect. In other words, if the overall thickness is too thin, the warpage in a high-temperature and high-humidity environment increases. Further, if the thickness of the thermoplastic resin (B) layer is too thin, warpage in a high-temperature and high-humidity environment is reduced, but the hardness is reduced.
  • the weight ratio of the copolymer (b1) and the acrylic resin (b2) of the thermoplastic resin (B) layer matched to the total thickness of each and the thickness of the thermoplastic resin (B) layer is set. Need to find out.
  • the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is preferably 0.05 to 3.0 mm, more preferably 0.1 to 2.0 mm, still more preferably 0.00. 12 to 1.5 mm.
  • the total light transmittance is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more.
  • the upper limit of the total light transmittance is preferably 95%.
  • the haze of the resin laminate (sheet) is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less.
  • the lower limit of Haze is preferably 0.1%.
  • the polycarbonate-based resin (A) that forms the base layer and / or the thermoplastic resin (B) that forms the surface layer can contain components other than the main components described above.
  • a polycarbonate resin (A) and / or a thermoplastic resin (B) can be used by mixing an ultraviolet absorber. If the content of the UV absorber is too high, depending on the molding method, excessive UV absorber may be scattered due to the high temperature applied, which may cause problems because it contaminates the molding environment. Accordingly, the content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and still more preferably 0 to 1% by mass.
  • Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy -4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc.
  • Benzophenone UV absorber 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3 -T-Butyl-5-methylphenyl) benzotriazo , Benzotriazole ultraviolet absorbers such as (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, phenyl salicylate, 2,4-di-t-butyl Benzoate UV absorbers such as phenyl-3,5-di-t-butyl-4-hydroxybenzoate, and hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxy
  • the polycarbonate resin (A) for forming the base material layer and / or the thermoplastic resin (B) for forming the surface layer may be used by mixing various additives in addition to the ultraviolet absorber.
  • additives include antioxidants and anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers, Examples thereof include reinforcing materials such as inorganic fillers.
  • the method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
  • the surface of the thermoplastic resin (B) layer or the surface of the polycarbonate resin (A) layer may be subjected to a hard coat treatment.
  • the hard coat layer is formed by a hard coat process using a hard coat paint that is cured using thermal energy and / or light energy.
  • the hard coat paint that is cured using thermal energy include polyorganosiloxane-based and cross-linked acrylic-based thermosetting resin compositions.
  • a hard coat paint that is cured using light energy for example, a photocurable resin in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers. Examples thereof include a composition.
  • Examples of the hard coat paint to be cured using light energy applied on the surface of the thermoplastic resin (B) layer or the surface of the polycarbonate resin (A) layer in the present invention include 1,9-nonanediol diacrylate.
  • the photopolymerization initiator is contained in 100 parts by mass of a resin composition comprising 40 to 80% by mass of a compound comprising a polyfunctional polyester (meth) acrylate oligomer and / or a polyfunctional epoxy (meth) acrylate oligomer having two or more functions. Examples thereof include a photocurable resin composition to which 10 parts by mass is added.
  • the method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and blurring. .
  • pretreatment of the coated surface may be performed before the hard coat.
  • treatment include known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition. Can be mentioned.
  • thermoplastic resin (B) layer, the polycarbonate resin (A) layer, and the hard coat materials in the present invention for example, the thermoplastic resin (B) and the polycarbonate resin (A) are filtered and purified by filtering. It is preferable. By producing or laminating through a filter, it is possible to obtain a synthetic resin laminate having few appearance defects such as foreign matters and defects. There is no restriction
  • the filter to be used is not particularly limited, and known filters can be used, and are appropriately selected depending on the use temperature, viscosity, and filtration accuracy of each material.
  • the filter medium is not particularly limited, but polypropylene, cotton, polyester, viscose rayon or glass fiber nonwoven fabric or roving yarn roll, phenol resin impregnated cellulose, metal fiber nonwoven fabric sintered body, metal powder sintered body, breaker plate, Alternatively, any combination of these can be used. In view of heat resistance, durability, and pressure resistance, a type in which a metal fiber nonwoven fabric is sintered is preferable.
  • the filtration accuracy for the polycarbonate resin (A) is 50 ⁇ m or less, preferably 30 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the filtration accuracy of the hard coat agent is 20 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less because it is applied to the outermost layer of the resin laminate.
  • thermoplastic resin (B) and the polycarbonate resin (A) it is preferable to use, for example, a polymer filter used for thermoplastic resin melt filtration.
  • the polymer filter is classified into a leaf disk filter, a candle filter, a pack disk filter, a cylindrical filter and the like depending on its structure, and a leaf disk filter having a large effective filtration area is particularly suitable.
  • the resin laminate of the present invention can be subjected to one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one side or both sides.
  • the methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.
  • HIT hardness ⁇ Indentation hardness (HIT hardness)> Using an ultra-micro hardness meter HM2000 (manufactured by Fischer Instruments Co., Ltd.), it was pressed against the thermoplastic resin (B) layer under a pressing pressure of 3 mN, and the HIT hardness (N / mm 2 ) was measured. As a comparison object, the indentation hardness was similarly measured for a layer (Comparative Example 5 or Comparative Example 8 described later) formed of the acrylic resin (b2) alone. Then, the indentation hardness of the thermoplastic resin (B) was HIT hardness ⁇ thermoplastic resin ⁇ , and the indentation hardness of the acrylic resin (b2) was HIT hardness ⁇ acrylic resin ⁇ .
  • thermoplastic resin (B) layer is a layer containing the copolymer (b1) and the acrylic resin (b2)
  • the indentation hardness of the acrylic resin (B2-1 or B2-2) used is used. And evaluated. Further, when the thermoplastic resin (B) layer was composed only of the copolymer (b1), it was evaluated using the indentation hardness of the acrylic resin (B2-1).
  • X (fail) Outside the above range
  • ⁇ Pencil scratch hardness test> In accordance with JIS K 5600-5-4, a layer formed of a thermoplastic resin (B) layer or an acrylic resin (b2) alone at an angle of 45 degrees with respect to the surface and a load of 750 g (Comparative Example 5 or Comparative Example 8 described later) ) The hardness was gradually increased on the surface and the pencil was pressed, and the hardness of the hardest pencil that did not cause scars was evaluated as the pencil hardness. The pencil hardness is indicated by 2B, B, HB, F, H, 2H, 3H, and 4H in order of rank.
  • the pencil hardness of the surface of the thermoplastic resin (B) is equal to or higher than the pencil hardness of the surface of the acrylic resin (b2) alone” means that the pencil hardness of the surface of the thermoplastic resin (B) is the surface of the acrylic resin (b2) alone. It means that it is the same rank as pencil hardness or higher than that. For example, when the pencil hardness of the surface of the acrylic resin (b2) is 2H, the pencil hardness of the surface of the thermoplastic resin (B) is 2H or 3H or more.
  • ⁇ (Pass) The pencil hardness on the surface of the thermoplastic resin (B) is equal to or higher than the pencil hardness on the surface of the acrylic resin (b2)
  • ⁇ (Fail) Other than the above range
  • test piece of the resin laminate was cut into a 10 cm ⁇ 6 cm square.
  • the test piece was set in a two-point support type holder, placed in an environmental testing machine set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more, and after adjusting the state, the warpage was measured. The value at this time was taken as the value of the amount of warp before processing.
  • the test piece was set in a holder, put into an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85%, and kept in that state for 120 hours. Further, the holder was moved into an environmental testing machine set to a temperature of 23 ° C.
  • Total light transmittance measurement> The total light transmittance of the resin laminate was measured according to JIS K7361-1, using a reflection / transmittance meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.), and the total light transmittance test was performed according to the following criteria. A pass / fail decision was made. ⁇ (Pass): Total light transmittance of the resin laminate ⁇ 75% X (fail): Outside the above range
  • Examples of the polycarbonate resin (A), the copolymer (b1), and the acrylic resin (b2) include the following materials, but are not limited thereto.
  • A-1 Polycarbonate resin: Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • b1-1 Copolymer: KX-406 manufactured by Denka Co., Ltd.
  • b1-2 Copolymer: KX-407 manufactured by Denka Co., Ltd.
  • b1-3 Copolymer: KX-422 manufactured by DENKA CORPORATION
  • b1-4 Copolymer: KX-435 manufactured by Denka Co., Ltd.
  • b1-5 Copolymer: R100 manufactured by DENKA CORPORATION b1-6: Copolymer: R200 manufactured by DENKA CORPORATION b2-1: Acrylic resin: Methyl methacrylate resin manufactured by Kuraray Co., Ltd.
  • Production Example 4 [Production of Resin (B14) Pellets] Phosphoric additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2 mass%) were added to 100 parts by mass of KX-406 (b1-1) as copolymer (b1), and mixed and pelleted in the same manner as in Production Example 1. Made. The pellets could be manufactured stably.
  • Production Example 5 [Production of Resin (B15) Pellets] A total of 100 parts by mass of 25 parts by mass of KX-406 (b1-1) as copolymer (b1) and 75 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 7 [Production of Resin (B17) Pellets] A total of 100 parts by mass of 50 parts by mass of KX-406 (b1-1) as the copolymer (b1) and 50 parts by mass of Delpet 980N (b2-3) as the methyl methacrylate resin as the acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 8 [Production of resin (B18) pellets] A total of 100 parts by mass of 60 parts by mass of KX-406 (b1-1) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 10 [Production of Resin (B20) Pellets] For a total of 100 parts by mass of 40 parts by mass of KX-406 (b1-1) as copolymer (b1) and 60 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 12 [Production of resin (B22) pellets] For a total of 100 parts by mass of 60 parts by mass of KX-406 (b1-1) as the copolymer (b1) and 40 parts by mass of PLEXIGLAS hw55 (b2-4) as the methyl methacrylate resin as the acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 14 [Production of Resin (B24) Pellets] 100 parts by mass in total of 50 parts by mass of KX-407 (b1-2) as copolymer (b1) and 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 15 [Production of resin (B25) pellets] 100 parts by mass in total of 75 parts by mass of KX-407 (b1-2) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1.
  • the pellets could be manufactured stably.
  • Production Example 16 [Production of resin (B26) pellets] To 100 parts by mass of KX-407 (b1-2) as copolymer (b1), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed in the same manner as in Production Example 1. Pelletization was performed. The pellets could be manufactured stably.
  • Production Example 18 [Production of resin (B28) pellets] 100 parts by mass in total of 50 parts by mass of KX-422 (b1-3) as copolymer (b1) and 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1.
  • the pellets could be manufactured stably.
  • Production Example 19 [Production of resin (B29) pellets] 100 parts by mass in total of 55 parts by mass of KX-422 (b1-3) as copolymer (b1) and 45 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1.
  • the pellets could be manufactured stably.
  • Production Example 20 [Production of resin (B30) pellets] 100 parts by mass in total of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1.
  • the pellets could be manufactured stably.
  • Production Example 21 [Production of Resin (B31) Pellets] 100 parts by mass in total of 65 parts by mass of KX-422 (b1-3) as copolymer (b1) and 35 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 22 [Production of resin (B32) pellets] 100 parts by mass in total of 75 parts by mass of KX-422 (b1-3) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2)
  • the phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1.
  • the pellets could be manufactured stably.
  • Production Example 23 [Production of resin (B33) pellet] Phosphorous additive PEP36 500 ppm and stearic acid monoglyceride 0.2% to 100 parts by mass of KX-422 (b1-3) as copolymer (b1), mixed and pelletized in the same manner as in Production Example 1. Went. The pellets could be manufactured stably.
  • Production Example 24 [Production of Resin (B34) Pellets] Phosphorus based on a total of 100 parts by mass of 50 parts by mass of KX-422 (b1-3) as copolymer (b1) and 50 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 25 [Production of resin (B35) pellets] Phosphorus based on a total of 100 parts by mass of 55 parts by mass of KX-422 (b1-3) as copolymer (b1) and 45 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 26 [Production of resin (B36) pellets] Phosphorus based on a total of 100 parts by mass of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 27 [Production of resin (B37) pellets] Phosphorus based on a total of 100 parts by mass of 55 parts by mass of KX-422 (b1-3) as copolymer (b1) and 45 parts by mass of Delpet 980N (b2-3) being acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 28 [Production of resin (B38) pellets] For a total of 100 parts by mass of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 29 [Production of resin (B39) pellets] Phosphorus-based addition to 100 parts by mass in total of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of PLEXIGLAS hw55 (b2-4) as acrylic resin (b2) Agent PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 32 [Production of Resin (B42) Pellets] 30 parts by mass of KX-435 (b1-4) as copolymer (b1) and 70 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 33 [Production of Resin (B43) Pellets] 40 parts by mass of KX-435 (b1-4) as copolymer (b1) and 60 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 34 [Production of Resin (B44) Pellets] A total of 100 parts by mass of 50 parts by mass of KX-435 (b1-4) as copolymer (b1) and 50 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 35 [Production of resin (B45) pellet] A total of 100 parts by mass of 60 parts by mass of KX-435 (b1-4) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 36 [Production of Resin (B46) Pellets] For a total of 100 parts by mass of 15 parts by mass of KX-435 (b1-4) as copolymer (b1) and 85 parts by mass of Plexiglas hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 37 [Production of Resin (B47) Pellets] For a total of 100 parts by mass of 25 parts by mass of KX-435 (b1-4) as copolymer (b1) and 75 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 38 [Production of resin (B48) pellets] For a total of 100 parts by mass of 30 parts by mass of KX-435 (b1-4) as copolymer (b1) and 70 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 39 [Production of resin (B49) pellets] For a total of 100 parts by mass of 40 parts by mass of KX-435 (b1-4) as copolymer (b1) and 60 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Production Example 40 [Production of Resin (B50) Pellets] For a total of 100 parts by mass of 50 parts by mass of KX-435 (b1-4) as copolymer (b1) and 50 parts by mass of Plexiglas hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.
  • Comparative Production Example 18 [Production of Resin (D28) Pellets] To 100 parts by mass of Delpet PM120N (b2-2), which is an acrylic resin (b2), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride are added and mixed in the same manner as in Production Example 1, pellets Made. The pellets could be manufactured stably.
  • Comparative Production Example 19 [Production of Resin (D29) Pellets] To 100 parts by mass of Delpet 980N (b2-3), which is an acrylic resin (b2), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride are added and mixed in the same manner as in Production Example 1 and pellets Made. The pellets could be manufactured stably.
  • Example 1 Each extruder in a multi-layer extruder having a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T die connected to the feed block
  • the resin laminate was molded using a multi-layer extrusion apparatus having connected multi-manifold dies.
  • the resin (B11) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.1 kg / h.
  • Polycarbonate resin (A-1) (manufactured by Mitsubishi Engineering Plastics, product name: Iupilon E-2000, weight average molecular weight: 34,000) was continuously introduced into a single screw extruder with a shaft diameter of 65 mm, and the cylinder Extrusion was performed at a temperature of 280 ° C. and a discharge rate of 30.0 kg / h.
  • the feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the temperature was set to 270 ° C. and (B11) and (A-1) were introduced and laminated.
  • thermoplastic resin (B11) layer ⁇ thermoplastic resin ⁇ 275 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.022, which was passed, and the pencil scratch hardness test
  • the result is 2H
  • the warp change amount in a high temperature and high humidity environment is 472 ⁇ m
  • the total light transmittance is 91.3%
  • the haze is 0.2%
  • pass 0.2%. It was a pass in the judgment.
  • Example 2 A laminate (E12) of (B12) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B12) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E12) was 1000 ⁇ m, and the thickness of the layer made of B12 was 60 ⁇ m near the center.
  • thermoplastic resin (B12) layer ⁇ thermoplastic resin ⁇ 280 N / mm 2
  • the result is 2H
  • the warp change amount under high temperature and high humidity environment is 34 ⁇ m
  • the total light transmittance is 91.2%
  • the haze is 0.2%
  • the pass 0.2%. It was a pass in the judgment.
  • Example 3 A laminate (E13) of (B13) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B13) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E13) was 1000 ⁇ m, and the thickness of the layer made of B13 was 60 ⁇ m near the center.
  • Example 4 A laminate (E14) of (B14) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B14) was used instead of the resin (B11).
  • the overall thickness of the obtained laminate (E14) was 1000 ⁇ m, and the thickness of the layer made of B14 was 60 ⁇ m near the center.
  • thermoplastic resin (B14) layer ⁇ thermoplastic resin ⁇ 276 N / mm 2
  • Example 5 A laminate (E15) of (B15) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B15) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E15) was 1000 ⁇ m, and the thickness of the layer made of B15 was 60 ⁇ m near the center.
  • Example 6 A laminate (E16) of (B16) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B16) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E16) was 1000 ⁇ m, and the thickness of the layer made of B16 was 60 ⁇ m near the center.
  • Example 7 A laminate (E17) of (B17) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B17) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E17) was 1000 ⁇ m, and the thickness of the layer composed of B17 was 60 ⁇ m near the center.
  • Example 8 A laminate (E18) of (B18) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B18) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E18) was 1000 ⁇ m, and the thickness of the layer made of B18 was 60 ⁇ m near the center.
  • Example 9 A laminate (E19) of (B19) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B19) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E19) was 1000 ⁇ m, and the thickness of the layer made of B19 was 60 ⁇ m near the center.
  • the result is 2H
  • the warp change amount in a high temperature and high humidity environment is 183 ⁇ m
  • the total light transmittance is 91.0%
  • the haze is 0.1%
  • the pass 0.1%. It was a pass in the judgment.
  • Example 10 A laminate (E20) of (B20) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B20) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E20) was 1000 ⁇ m, and the thickness of the layer made of B20 was 60 ⁇ m near the center.
  • thermoplastic resin (B20) layer ⁇ thermoplastic resin ⁇ 280 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.049
  • passed and the pencil scratch hardness test
  • the result is 2H
  • the warp change amount under high temperature and high humidity environment is 397 ⁇ m
  • the total light transmittance is 91.0%
  • the haze 0.1%
  • the pass 0.1%. It was a pass in the judgment.
  • Example 11 A laminate (E21) of (B21) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B21) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E21) was 1000 ⁇ m, and the thickness of the layer made of B21 was 60 ⁇ m near the center.
  • Example 12 A laminate (E22) of (B22) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B22) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E22) was 1000 ⁇ m, and the thickness of the layer made of B22 was 60 ⁇ m near the center.
  • Example 13 A laminate (E23) of (B23) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B23) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E23) was 1000 ⁇ m, and the thickness of the layer made of B23 was 60 ⁇ m near the center.
  • thermoplastic resin (B23) layer ⁇ thermoplastic resin ⁇ 275 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.022, which was passed, and the pencil scratch hardness test
  • the result is 2H
  • the warp change amount in the high temperature and high humidity environment is 649 ⁇ m
  • the total light transmittance is 91.4%
  • the haze is 0.1%
  • the pass 0.1%. It was a pass in the judgment.
  • Example 14 A laminate (E24) of (B24) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B24) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E24) was 1000 ⁇ m, and the thickness of the layer made of B16 was 60 ⁇ m near the center.
  • Example 15 A laminate (E25) of (B25) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B25) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E25) was 1000 ⁇ m, and the thickness of the layer made of B25 was 60 ⁇ m near the center.
  • Example 16 A laminate (E26) of (B26) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B26) was used instead of the resin (B11).
  • the overall thickness of the obtained laminate (E26) was 1000 ⁇ m, and the thickness of the layer made of B26 was 60 ⁇ m near the center.
  • Example 17 A laminate (E27) of (B27) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B27) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E27) was 1000 ⁇ m, and the thickness of the layer made of B27 was 60 ⁇ m near the center.
  • thermoplastic resin (B27) layer ⁇ thermoplastic resin ⁇ 275 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.022, which was passed, and the pencil scratch hardness test
  • the result is 2H
  • the warp change amount in a high temperature and high humidity environment is 524 ⁇ m
  • the total light transmittance is 91.3%
  • the haze 0.1%
  • the pass It was a pass in the judgment.
  • Example 18 A laminate (E28) of (B28) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B28) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E28) was 1000 ⁇ m, and the thickness of the layer made of B28 was 60 ⁇ m near the center.
  • Example 19 A laminate (E29) of (B29) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B29) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E29) was 1000 ⁇ m, and the thickness of the layer composed of B29 was 60 ⁇ m near the center.
  • thermoplastic resin (B21) layer ⁇ thermoplastic resin ⁇ 287 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.067
  • the pencil scratch hardness test The result is 3H
  • the warp change amount in a high temperature and high humidity environment is 104 ⁇ m
  • the total light transmittance is 91.1%
  • the haze 0.2%
  • the pass 0.2%. It was a pass in the judgment.
  • Example 20 A laminate (E30) of (B30) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B30) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E30) was 1000 ⁇ m, and the thickness of the layer made of B30 was 60 ⁇ m near the center.
  • thermoplastic resin (B30) layer ⁇ thermoplastic resin ⁇ 289 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.004
  • pencil scratch hardness test The result is 3H
  • the warp change amount in the high temperature and high humidity environment is 29 ⁇ m
  • the total light transmittance is 91.0%
  • the haze 0.2%
  • the pass 0.2%. It was a pass in the judgment.
  • Example 21 A laminate (E31) of (B31) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B31) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E31) was 1000 ⁇ m, and the thickness of the layer made of B31 was 60 ⁇ m near the center.
  • Example 22 A laminate (E32) of (B32) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B32) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E32) was 1000 ⁇ m, and the thickness of the layer made of B32 was 60 ⁇ m near the center.
  • Example 23 A laminate (E33) of (B33) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B33) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E33) was 1000 ⁇ m, and the thickness of the layer made of B33 was 60 ⁇ m near the center.
  • Example 24 A laminate (E34) of (B34) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B34) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E34) was 1000 ⁇ m, and the thickness of the layer made of B34 was 60 ⁇ m near the center.
  • the result is acceptable at 3H, the amount of warpage change under a high temperature and high humidity environment is acceptable at 151 ⁇ m, the total light transmittance is acceptable at 91.1%, and the haze is acceptable at 0.2%. It was a pass in the judgment.
  • Example 25 A laminate (E35) of (B35) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B35) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E35) was 1000 ⁇ m, and the thickness of the layer made of B35 was 60 ⁇ m near the center.
  • Example 26 A laminate (E36) of (B36) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B36) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E36) was 1000 ⁇ m, and the thickness of the layer made of B36 was 60 ⁇ m near the center.
  • thermoplastic resin (B36) layer ⁇ thermoplastic resin ⁇ 291 N / mm 2
  • the result is acceptable at 3H
  • the amount of warpage change under a high temperature and high humidity environment is acceptable at 7 ⁇ m
  • the total light transmittance is acceptable at 91.0%
  • the haze is acceptable at 0.2%. It was a pass in the judgment.
  • Example 27 A laminate (E37) of (B37) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B37) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E37) was 1000 ⁇ m, and the thickness of the layer made of B37 was 60 ⁇ m near the center.
  • the result is 2H, the warp change amount in a high temperature and high humidity environment is 529 ⁇ m, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.
  • Example 28 A laminate (E38) of (B38) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B38) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E38) was 1000 ⁇ m, and the thickness of the layer made of B38 was 60 ⁇ m near the center.
  • thermoplastic resin (B38) layer ⁇ thermoplastic resin ⁇ 284 N / mm 2
  • the result is 2H
  • the warp change amount in a high temperature and high humidity environment is 605 ⁇ m
  • the total light transmittance is 91.2%
  • the haze 0.2%
  • the pass It was a pass in the judgment.
  • Example 29 A laminate (E39) of (B39) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B39) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E39) was 1000 ⁇ m, and the thickness of the layer made of B39 was 60 ⁇ m near the center.
  • Example 30 A laminate (E40) of (B40) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B40) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E40) was 1000 ⁇ m, and the thickness of the layer made of B40 was 60 ⁇ m near the center.
  • Example 31 A laminate (E41) of (B41) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B41) was used instead of the resin (B11).
  • the overall thickness of the obtained laminate (E41) was 1000 ⁇ m, and the thickness of the layer made of B41 was 60 ⁇ m near the center.
  • Example 32 A laminate (E42) of (B42) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B42) was used instead of the resin (B11).
  • the overall thickness of the obtained laminate (E42) was 1000 ⁇ m, and the thickness of the layer made of B42 was 60 ⁇ m near the center.
  • Example 33 A laminate (E43) of (B43) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B43) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E43) was 1000 ⁇ m, and the thickness of the layer made of B43 was 60 ⁇ m near the center.
  • Example 34 A laminate (E44) of (B44) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B44) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E44) was 1000 ⁇ m, and the thickness of the layer made of B44 was 60 ⁇ m near the center.
  • Example 35 A laminate (E45) of (B45) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B45) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E45) was 1000 ⁇ m, and the thickness of the layer made of B45 was 60 ⁇ m near the center.
  • thermoplastic resin (B45) layer ⁇ thermoplastic resin ⁇ 277 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.041
  • pencil scratch hardness test The result is 2H
  • the warp change amount in a high temperature and high humidity environment is 508 ⁇ m
  • the total light transmittance is 91.0%
  • the haze 0.2%
  • the pass is 0.2%. It was a pass in the judgment.
  • Example 36 A laminate (E46) of (B46) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B46) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E46) was 1000 ⁇ m, and the thickness of the layer made of B46 was 60 ⁇ m near the center.
  • Example 37 A laminate (E47) of (B47) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B47) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E47) was 1000 ⁇ m, and the thickness of the layer composed of B47 was 60 ⁇ m near the center.
  • the result is 2H, the warp change amount in a high temperature and high humidity environment is 106 ⁇ m, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is It was a pass in the judgment.
  • Example 38 A laminate (E48) of (B48) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B48) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E48) was 1000 ⁇ m, and the thickness of the layer composed of B48 was 60 ⁇ m near the center.
  • thermoplastic resin (B48) layer ⁇ thermoplastic resin ⁇ 273 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.022, which was passed, and the pencil scratch hardness test
  • the result is 2H
  • the warp change under high temperature and high humidity environment is 175 ⁇ m
  • the total light transmittance is 91.2%
  • the haze 0.2%
  • the pass It was a pass in the judgment.
  • Example 39 A laminate (E49) of (B49) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B49) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E49) was 1000 ⁇ m, and the thickness of the layer made of B49 was 60 ⁇ m near the center.
  • Example 40 A laminate (E50) of (B50) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B50) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (E50) was 1000 ⁇ m, and the thickness of the layer composed of B50 was 60 ⁇ m near the center.
  • Example 41 A laminate (E51) of (B51) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B51) was used instead of the resin (B11).
  • the overall thickness of the obtained laminate (E51) was 1000 ⁇ m, and the thickness of the layer made of B51 was 60 ⁇ m near the center.
  • the result is 2H, the warp change amount in a high temperature and high humidity environment is 534 ⁇ m, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.
  • Comparative Example 1 A laminate (F11) of (D11) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D11) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F11) was 1000 ⁇ m, and the thickness of the layer made of D11 was 60 ⁇ m near the center.
  • the result of the test is F, the warp change amount in a high temperature and high humidity environment is 359 ⁇ m, the total light transmittance is 91.2%, and the haze is 0.2%. It was rejected by the comprehensive judgment.
  • Comparative Example 2 A laminate (F12) of (D12) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D12) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F12) was 1000 ⁇ m, and the thickness of the layer composed of D12 was 60 ⁇ m near the center.
  • thermoplastic resin (D12) layer ⁇ thermoplastic resin ⁇ 253 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 0.941
  • pencil scratch hardness test The result of F is rejected with F, the amount of warpage change under a high temperature and high humidity environment is 121 ⁇ m, the total light transmittance is 91.1%, and the haze is 0.2%. It was rejected by the comprehensive judgment.
  • Comparative Example 3 A laminate (F13) of (D13) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D13) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F13) was 1000 ⁇ m, and the thickness of the layer made of D13 was 60 ⁇ m near the center.
  • Comparative Example 4 A laminate (F14) of (D14) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D14) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F14) was 1000 ⁇ m, and the thickness of the layer composed of D14 was 60 ⁇ m near the center.
  • the result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 65 ⁇ m, it is passed, the total light transmittance is passed with 91.0%, and the haze is passed with 0.1%. It was rejected by the comprehensive judgment.
  • Comparative Example 5 A laminate (F15) of (D15) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D15) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F15) was 1000 ⁇ m, and the thickness of the layer made of D15 was 60 ⁇ m near the center.
  • Comparative Example 6 A laminate (F16) of (D16) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D16) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F16) was 1000 ⁇ m, and the thickness of the layer made of D16 was 60 ⁇ m near the center.
  • thermoplastic resin (D16) layer ⁇ thermoplastic resin ⁇ 261 N / mm 2
  • Comparative Example 7 A laminate (F17) of (D17) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D17) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F17) was 1000 ⁇ m, and the thickness of the layer composed of D17 was 60 ⁇ m near the center.
  • Comparative Example 8 A laminate (F18) of (D18) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D18) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F18) was 1000 ⁇ m, and the thickness of the layer composed of D18 was 60 ⁇ m near the center.
  • Comparative Example 9 A laminate (F19) of (D19) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D19) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F19) was 1000 ⁇ m, and the thickness of the layer composed of D19 was 60 ⁇ m near the center.
  • thermoplastic resin (D19) layer ⁇ thermoplastic resin ⁇ 265 N / mm 2
  • Comparative Example 10 A laminate (F20) of (D20) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D20) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F20) was 1000 ⁇ m, and the thickness of the layer composed of D20 was 60 ⁇ m near the center.
  • Comparative Example 11 A laminate (F21) of (D21) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D21) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F21) was 1000 ⁇ m, and the thickness of the layer composed of D21 was 60 ⁇ m near the center.
  • Comparative Example 12 A laminate (F22) of (D22) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D22) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F22) was 1000 ⁇ m, and the thickness of the layer made of D22 was 60 ⁇ m near the center.
  • Comparative Example 13 A laminate (F23) of (D23) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D23) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F23) was 1000 ⁇ m, and the thickness of the layer composed of D23 was 60 ⁇ m near the center.
  • Comparative Example 14 A laminate (F24) of (D24) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D24) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F24) was 1000 ⁇ m, and the thickness of the layer composed of D24 was 60 ⁇ m near the center.
  • Comparative Example 15 A laminate (F25) of (D25) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D25) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F25) was 1000 ⁇ m, and the thickness of the layer composed of D25 was 60 ⁇ m near the center.
  • the result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 24 ⁇ m, the total light transmittance is passed with 91.2%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.
  • Comparative Example 16 A laminate (F26) of (D26) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D26) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F26) was 1000 ⁇ m, and the thickness of the layer composed of D26 was 60 ⁇ m near the center.
  • the result of is rejected with H, the amount of warp change under high temperature and high humidity environment is 422 ⁇ m, passed, the total light transmittance is passed with 91.2%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.
  • Comparative Example 17 A laminate (F27) of (D27) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D27) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F27) was 1000 ⁇ m, and the thickness of the layer composed of D27 was 60 ⁇ m near the center.
  • thermoplastic resin (D27) layer ⁇ thermoplastic resin ⁇ 269 N / mm 2
  • HIT hardness ⁇ thermoplastic resin ⁇ / HIT hardness ⁇ acrylic resin ⁇ 1.000 was rejected, and the pencil scratch hardness test
  • the result of is acceptable at 2H, the amount of warpage change under high-temperature and high-humidity environment is 952 ⁇ m, is rejected, the total light transmittance is 91.6%, and the haze is 0.1%. It was rejected by the comprehensive judgment.
  • Comparative Example 18 A laminate (F28) of (D28) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D28) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F28) was 1000 ⁇ m, and the thickness of the layer composed of D28 was 60 ⁇ m near the center.
  • thermoplastic resin (D28) layer ⁇ thermoplastic resin ⁇ 274 N / mm 2
  • the result of 2 is acceptable at 2H
  • the amount of warpage change under high temperature and high humidity environment is 552 ⁇ m
  • the total light transmittance is acceptable at 91.3%
  • the haze is acceptable at 0.2%, It was rejected by the comprehensive judgment.
  • Comparative Example 19 A laminate (F29) of (D29) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D29) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F29) was 1000 ⁇ m, and the thickness of the layer composed of D29 was 60 ⁇ m near the center.
  • thermoplastic resin (D29) layer ⁇ thermoplastic resin ⁇ 266 N / mm 2
  • Comparative Example 20 A laminate (F30) of (D30) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D30) was used instead of the resin (B11).
  • the total thickness of the obtained laminate (F30) was 1000 ⁇ m, and the thickness of the layer made of D30 was 60 ⁇ m near the center.
  • thermoplastic resin (D30) layer ⁇ thermoplastic resin ⁇ 267 N / mm 2
  • the result of 2 is acceptable at 2H, the warpage change amount in a high temperature and high humidity environment is 356 ⁇ m, the total light transmittance is 91.2%, and the haze is 0.3%. It was rejected by the comprehensive judgment.
  • thermoplastic resin is laminated on a polycarbonate resin layer, and an aromatic vinyl monomer unit, an unsaturated dicarboxylic anhydride monomer unit, and a thermoplastic resin are laminated on the thermoplastic resin.
  • unit for a thermoplastic resin has not been able to suppress the curvature variation in a high temperature, high humidity environment.
  • the laminates (Examples 1 to 41) containing a copolymer in which the mass% of the unsaturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit are acrylic resin alone.
  • the HIT hardness ⁇ thermoplastic resin ⁇ is higher than that of the laminates (Comparative Examples 17 to 20) using No. 1 as the thermoplastic resin, and the amount of change in warpage in a high temperature and high humidity environment is also suppressed.
  • the laminate according to the present invention can improve the surface hardness while suppressing the amount of warpage change in the high temperature and high humidity environment of the conventional laminate of acrylic resin and polycarbonate.
  • the resin laminate according to the present invention that improves the surface hardness and suppresses the amount of warpage change under a high-temperature and high-humidity environment is suitable as a transparent base material or a transparent protective material as a substitute for glass.
  • it can be suitably used as a touch panel front protective plate, a front plate for OA devices or portable electronic devices.

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PCT/JP2016/069856 2015-12-01 2016-07-05 透明樹脂積層体 WO2017094282A1 (ja)

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