WO2021215435A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2021215435A1
WO2021215435A1 PCT/JP2021/016022 JP2021016022W WO2021215435A1 WO 2021215435 A1 WO2021215435 A1 WO 2021215435A1 JP 2021016022 W JP2021016022 W JP 2021016022W WO 2021215435 A1 WO2021215435 A1 WO 2021215435A1
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WIPO (PCT)
Prior art keywords
resin composition
mass
unit
laminate
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/016022
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English (en)
French (fr)
Japanese (ja)
Inventor
祐作 野本
誠史 戒能
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to CN202180029432.3A priority Critical patent/CN115427227B/zh
Priority to JP2022517053A priority patent/JP7645876B2/ja
Priority to EP21792869.6A priority patent/EP4140738A4/en
Publication of WO2021215435A1 publication Critical patent/WO2021215435A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • 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
    • B32B27/30—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
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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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2607/00—Walls, panels

Definitions

  • the present invention relates to a laminate including a layer made of a resin composition containing an acrylic copolymer and a layer made of a resin composition containing polycarbonate.
  • Methacrylic resin has excellent transparency, scratch resistance, weather resistance, etc.
  • polycarbonate is excellent in impact resistance and the like.
  • the laminate having a layer containing methacrylic resin and a layer containing polycarbonate is excellent in transparency, scratch resistance, weather resistance, impact resistance, etc., and is excellent in house walls, furniture, home appliances, electronic devices, display devices, etc. It is used for surface members such as.
  • Patent Document 1 is selected from a methyl methacrylate unit, a methacrylic acid unit, an acrylic acid unit, a maleic anhydride unit, an N-substituted or unsubstituted mailemid unit, a glutaric anhydride structural unit, and a glutaric anhydride structural unit.
  • Patent Document 2 describes a layer made of a methacrylic resin containing a structural unit derived from a methacrylic acid ester having an alicyclic hydrocarbon group and having a glass transition temperature of 120 to 180 ° C., and a layer made of polycarbonate.
  • the laminate provided is disclosed.
  • Patent Document 3 describes a layer made of a vinyl copolymer resin having a (meth) acrylic acid ester structural unit and an aliphatic vinyl structural unit in which 70% or more of aromatic double bonds derived from an aromatic vinyl monomer are hydrogenated.
  • Patent Document 4 discloses a laminate including a layer made of a resin composition containing a methacrylic resin and a SMA resin (a copolymer resin made of styrene and maleic anhydride) and a layer made of polycarbonate. ..
  • the laminates obtained by these methods have a problem that the surface hardness and weather resistance are lowered by containing the structural unit having a ring skeleton.
  • the composition ratio of the structural unit having a ring skeleton it is possible to suppress a decrease in surface hardness and weather resistance, but the glass transition temperature of the obtained resin composition becomes insufficient.
  • the present invention has been made in view of the above problems.
  • the purpose is that in a laminate having a layer made of a resin composition containing an acrylic copolymer and a layer containing polycarbonate, warpage is less likely to occur under high temperature and high humidity, and surface hardness and chemical resistance are improved. It is to provide an excellent laminate.
  • the resin composition (I) contains 1 to 49% by mass of a multilayer copolymer elastomer (B-1) having a methacrylic acid ester unit and an acrylic acid ester unit.
  • the resin composition (I) is a block copolymer elastomer (B-2) 1 to 49 composed of a polymer block (b1) having a methacrylic acid ester unit and a polymer block (b2) having an acrylic acid ester unit.
  • the laminate of the present invention is less likely to warp under high temperature and high humidity, and has good surface hardness and weather resistance.
  • the resin composition (I) contains an acrylic copolymer (A).
  • the resin composition (I) contains an acrylic copolymer (A) and optionally an elastomer (B) and / or a methacrylic resin (C).
  • the elastomer (B) include a multilayer copolymer elastomer (B-1) and a block copolymer elastomer (B-2).
  • the content of the acrylic copolymer (A) in the resin composition (I) is 51% by mass or more, preferably 65% by mass or more, more preferably 80% by mass or more, and 90% by mass. % Or more is more preferable, and it may be composed of only the acrylic copolymer (A).
  • the acrylic copolymer (A) contains a methyl methacrylate unit, an ⁇ -methylstyrene unit, and a structural unit (R).
  • the proportion of methyl methacrylate units is 30 to 87% by mass, preferably 40 to 85% by mass, and more preferably 50 to 80% by mass with respect to the total structural units. %.
  • the proportion of ⁇ -methylstyrene units is 7 to 30% by mass, preferably 8 to 27% by mass, more preferably 11 to 25, based on the total structural units. It is mass%.
  • the ratio of ⁇ -methylstyrene units is less than this range, the saturated water absorption rate of the obtained acrylic copolymer becomes high.
  • an acrylic copolymer having an ⁇ -methylstyrene unit ratio of more than 30% by mass has low polymerizability and lower productivity.
  • the structural unit (R) is a structural unit having at least one ring structure selected from the group consisting of a glutaric anhydride unit and an N-substituted or unsubstituted glutarimide unit in the main chain.
  • the glutaric anhydride unit is a unit having a 2,6-dioxodihydropyrandiyl structure.
  • Examples of the unit having a 2,6-dioxodihydropyrandiyl structure include a structural unit represented by the formula (QII).
  • R 3 is an independent hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and both R 3 are methyl groups.
  • the unit having a 2,6-dioxodihydropyrandiyl structure is derived from the methods described in JP-A-2007-197703, JP-A-2010-96919, etc., for example, two adjacent (meth) acrylic acids. It can be contained in an acrylic copolymer by intramolecular cyclization of structural units, intramolecular cyclization of structural units derived from (meth) acrylic acid and structural units derived from methyl (meth) acrylate, and the like. .. JP-A-2007-197703 and JP-A-2010-96919 are incorporated herein by reference in their entirety.
  • N-substituted or unsubstituted glutarimide unit is a unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure.
  • Examples of the unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure include a structural unit represented by the formula (QI).
  • R 1 each independently represents a hydrogen atom or a methyl group, two R 1 is preferably a both methyl groups.
  • R 2 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an organic group having a cycloalkyl group or a C 6-15 containing an aromatic ring, having 3 to 12 carbon atoms, preferably a hydrogen atom, a methyl radical, n -Butyl group, cyclohexyl group or benzyl group, more preferably methyl group, n-butyl group or cyclohexyl group.
  • the structural unit represented by the formula (QI) may be produced, for example, by the reaction of the corresponding acid anhydride (Q IIa) and the imidizing agent represented by R 2 NH 2 as shown in the scheme (i). Often, it may be produced by an intramolecular cyclization reaction of a copolymer having a partial structure of the formula (QIII). It is preferable to heat the structural unit represented by the formula (QIII) in order to convert it into the structural unit represented by the formula (QI) by an intramolecular cyclization reaction.
  • Scheme (i) In the equation, R 1 and R 2 are as defined above.)
  • the N-substituted or unsubstituted glutarimide unit is a method described in WO2005 / 10838A1, JP-A-2010-254742, JP-A-2008-273140, JP-A-2008-274187, and the like, specifically, adjacent to each other.
  • Structural units or glutaric anhydride units derived from two matching methyl methacrylates, such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-hexylamine, etc.
  • Arophilic hydrocarbon group-containing amines such as aliphatic hydrocarbon group-containing amines, aniline, toluidine, and trichloroaniline
  • alicyclic hydrocarbon group-containing amines such as cyclohexylamine, urea, 1,3-dimethylurea, 1,3 -It can be obtained by reacting an imidizing agent such as diethylurea and 1,3-dipropylurea.
  • an imidizing agent such as diethylurea and 1,3-dipropylurea.
  • ammonia, methylamine, n-butylamine, cyclohexylamine and benzylamine are preferable, and methylamine, n-butylamine and cyclohexylamine groups are more preferable, and methylamine is still more preferable.
  • a part of the methyl methacrylate unit may be hydrolyzed to a carboxyl group, and it is preferable that the carboxyl group is returned to the original methyl methacrylate unit by the reaction with dimethyl carbonate.
  • WO2005 / 10838A1 Japanese Patent Application Laid-Open No. 2010-254742, Japanese Patent Application Laid-Open No. 2008-273140, and Japanese Patent Application Laid-Open No. 2008-274187 are incorporated herein by reference in their entirety.
  • the ratio of the structural unit (R) is 6 to 40% by mass, preferably 7 to 38% by mass, and more preferably 8 to 35 with respect to the total structural units. It is mass%.
  • the ratio of the structural unit (R) and methyl methacrylate By changing the ratio of the structural unit (R) and methyl methacrylate, the orientation birefringence of the acrylic copolymer can be changed. Further, as the content of the structural unit (R) increases, the heat resistance of the acrylic copolymer is improved, but the flexibility is lowered, and the compatibility with other copolymers and the molding processability are lowered. It becomes a tendency.
  • the acrylic copolymer (A) according to the present invention may contain a structural unit (O) other than the methyl methacrylate unit, the ⁇ -methylstyrene unit and the (R).
  • a structural unit (O) a vinyl-based monomer having only one polymerizable carbon-carbon double bond in one molecule such as (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid, and styrene.
  • -A structural unit derived from substituted maleimide can be mentioned, with styrene being preferred.
  • the ratio of having the structural unit (O) is preferably 2% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 10% by mass or less with respect to all the structural units.
  • the ratio of the methyl methacrylate unit, the ⁇ -methylstyrene unit, the structural unit (R), and the structural unit (O) can be measured by 1 H-NMR, 13 C-NMR, or the like.
  • the acrylic copolymer (A) according to the present invention has a weight average molecular weight (Mw) of preferably 40,000 to 200,000, more preferably 50,000 to 1,800,000, and even more preferably 55,000 to 1,600,000.
  • Mw weight average molecular weight
  • Mw is 40,000 or more
  • the strength and toughness of the molded product of the present invention are improved.
  • Mw is 200,000 or less, the fluidity is improved and the molding processability is improved.
  • the weight average molecular weight (Mw) is a value calculated by converting a chromatogram measured by gel permeation chromatography into the molecular weight of standard polystyrene.
  • the acrylic copolymer (A) according to the present invention has an acid value of preferably 0.01 to 0.30 mmol / g, more preferably 0.05 to 0.28 mmol / g.
  • the acid value is a value proportional to the content of the carboxylic acid unit and the carboxylic acid anhydride unit in the acrylic copolymer.
  • the acid value can be calculated, for example, by the method described in JP-A-2005-23272. When the acid value is within the above range, the balance between heat resistance, mechanical properties, and molding processability is excellent.
  • the acrylic copolymer (A) according to the present invention has a glass transition temperature of preferably 130 ° C., more preferably 131 ° C., still more preferably 132 ° C. as a lower limit, and the upper limit is not particularly limited, but is preferable. Is 160 ° C.
  • the "glass transition temperature (Tg)" is measured according to JIS K7121. Specifically, the DSC curve is measured under the condition that the temperature is raised to 230 ° C., then cooled to room temperature, and then the temperature is raised from room temperature to 230 ° C. at 10 ° C./min. The intermediate point obtained from the DSC curve measured at the time of the second temperature rise is obtained as the "glass transition temperature (Tg)".
  • the saturated water absorption rate of the acrylic copolymer (A) according to the present invention can be measured under the following conditions.
  • the acrylic copolymer is press-molded into a sheet having a thickness of 1.0 mm.
  • a 50 mm ⁇ 50 mm test piece is cut out from the central portion of the obtained press-molded sheet, and dried in a dryer at 80 ° C. for 16 hours or more.
  • the weight is measured to 0.1 mg, and the weight is defined as the initial weight Wo.
  • the saturated water absorption rate can be calculated from the formula (2).
  • the saturated water absorption rate is preferably 2.5% or less, more preferably 2.1% or less, still more preferably 2.0% or less.
  • the 1% thermogravimetric reduction temperature of the acrylic copolymer (A) according to the present invention under a nitrogen atmosphere is preferably 265 ° C. or higher, more preferably 270 ° C. or higher.
  • the 1% thermogravimetric reduction temperature can be measured using a thermogravimetric analyzer (TGA).
  • TGA thermogravimetric analyzer
  • the 1% thermogravimetric weight loss temperature can be determined as a temperature at which the weight loss is 1% with respect to the charged weight.
  • the acrylic copolymer (A) according to the present invention is obtained by a method including a ring structure forming reaction of a copolymer of methyl methacrylate and ⁇ -methylstyrene (hereinafter, may be referred to as a precursor polymer). be able to. That is, the method for producing the acrylic copolymer (A) is a monomer containing 70 to 93% by mass of methyl methacrylate, 30 to 7% by mass of ⁇ -methylstyrene, and 0 to 10% by mass of a copolymerizable monomer.
  • Each step can be carried out by a known technique, including a step of causing the obtained precursor polymer to undergo a ring structure forming reaction.
  • the copolymerizable monomer can form a structural unit (O).
  • the laminate of the present invention preferably contains a multilayer copolymer elastomer (B-1) having a methacrylic acid ester unit and an acrylic acid ester unit in the layer made of the resin composition (I).
  • the content of the multilayer copolymer elastomer (B-1) in the resin composition (I) is preferably 1 to 49% by mass, more preferably 5 to 45% by mass, and 10 to 40% by mass. It is more preferable that the range is.
  • the brittleness of the laminate of the present invention is improved when the content of the multilayer copolymer elastomer (B-1) is in the range of 1 to 49% by mass.
  • multilayer copolymer elastomer examples include those composed of an outermost layer made of a thermoplastic polymer (B-1-III) and an inner layer made of a crosslinked polymer in contact with and covered with the outermost layer.
  • the multi-layer copolymer elastomer is, for example, a two-layer polymer elastomer in which the core (inner layer) is a crosslinked rubber polymer (B-1-II) and the outer shell (outermost layer) is a thermoplastic polymer (B-1-III).
  • Core (inner layer) is crosslinked polymer (B-1-I) -Inner shell (inner layer) is crosslinked rubber polymer (B-1-II) -Outer shell (outermost layer) is thermoplastic polymer (B-1) -III) 3-layer polymer elastomer
  • core (inner layer) is crosslinked rubber polymer (B-1-II) -first inner shell (inner layer) is crosslinked polymer (B-1-I) -second inner shell
  • Examples thereof include a four-layer polymer elastomer in which the (inner layer) is a crosslinked rubber polymer (B-1-II) and the outer shell (outermost layer) is a thermoplastic polymer (B-1-III).
  • the polymer contained in each layer so that the difference in refractive index between adjacent layers is preferably less than 0.005, more preferably less than 0.004, and even more preferably less than 0.003. It is preferable to select.
  • the mass ratio of the inner layer to the outermost layer in the multilayer copolymer elastomer is preferably 60/40 to 95/5, more preferably 70/30 to 90/10.
  • the ratio of the layer containing the crosslinked rubber polymer (B-1-II) is preferably 20 to 70% by mass, more preferably 30 to 50% by mass.
  • the multi-layer copolymer elastomer has an average particle size of preferably 0.05 to 3 ⁇ m, more preferably 0.1 to 2 ⁇ m, and even more preferably 0.2 to 1 ⁇ m.
  • an average particle size within such a range, particularly an average particle size of 0.2 to 1 ⁇ m, is used, toughness can be exhibited with a small amount of compounding, and therefore rigidity and surface hardness can be exhibited. Does not spoil.
  • the average particle size in the present specification is an average value in a volume-based particle size distribution measured by a light scattered light method.
  • thermoplastic polymer (B-1-III) is a polymer composed of a methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms and, if necessary, a monofunctional monomer unit other than the methacrylic acid alkyl ester. Is.
  • the thermoplastic polymer (B-1-III) preferably does not contain a polyfunctional monomer unit.
  • the amount of the methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms constituting the thermoplastic polymer (B-1-III) is based on the mass of the thermoplastic polymer (B-1-III). It is preferably 80 to 100% by mass, more preferably 85 to 95% by mass.
  • methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter, may be referred to as methacrylic acid C 1-8 alkyl ester), for example, methyl methacrylate is preferable.
  • the amount of monofunctional monomer units other than the methacrylic acid C 1-8 alkyl ester constituting the thermoplastic polymer (B-1-III) is based on the mass of the thermoplastic polymer (B-1-III). , It is preferably 0 to 20% by mass, and more preferably 5 to 15% by mass.
  • Monofunctional monomers other than C 1-8 alkyl methacrylic acid include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate; aromatics such as styrene. Vinyl compounds can be mentioned.
  • the outermost layer may be a single layer composed of one type of thermoplastic polymer (B-1-III), or a multi-layer composed of two or more types of thermoplastic polymer (B-1-III). May be good.
  • the amount of the thermoplastic polymer (B-1-III) is preferably 40 to 75% by mass, more preferably 45 to 68% by mass, still more preferably, based on the amount of the multilayer copolymer elastomer (B-1). Is 50 to 60% by mass.
  • the inner layer of the crosslinked elastic body is an intermediate layer (inner shell) made of a crosslinked rubber polymer (B-1-II) and a crosslinked polymer (B-1-I). It is composed of and has an inner layer (core) covered in contact with the intermediate layer.
  • the inner layer and the intermediate layer form a core and a shell.
  • the crosslinked polymer (B-1-I) is composed of a methyl methacrylate unit, a monofunctional monomer unit other than methyl methacrylate, and a polyfunctional monomer unit.
  • the amount of the methyl methacrylate unit constituting the crosslinked polymer (B-1-I) is preferably 40 to 98.5% by mass, more preferably 40 to 98.5% by mass, based on the mass of the crosslinked polymer (B-1-I). It is 45 to 95% by mass.
  • the amount of the monofunctional monomer unit other than methyl methacrylate constituting the crosslinked polymer (B-1-I) is 1 to 59.5 mass with respect to the mass of the crosslinked polymer (B-1-I). %, Preferably 4.7 to 54.7% by mass.
  • the monofunctional monomer other than methyl methacrylate include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate; and aromatic vinyl compounds such as styrene. Can be done.
  • the amount of the polyfunctional monomer unit constituting the crosslinked polymer (B-1-I) is preferably 0.05 to 0.5% by mass with respect to the mass of the crosslinked polymer (B-1-I). , More preferably 0.1 to 0.3% by mass.
  • the polyfunctional monomer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl. Isocyanurate and the like can be mentioned.
  • the amount of the crosslinked polymer (B-1-I) is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, still more preferably 10 to 30% by mass, based on the amount of the multilayer copolymer elastomer. Is.
  • the crosslinked rubber polymer (B-1-II) is composed of an acrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms and / or a conjugated diene unit, and a polyfunctional monomer unit.
  • the amount of the acrylic acid alkyl ester unit and / or the conjugated diene unit having an alkyl group having 1 to 8 carbon atoms constituting the crosslinked rubber polymer (B-1-II) is determined by the crosslinked rubber polymer (B-1-II). It is preferably 98.3 to 99% by mass, more preferably 98.4 to 98.8% by mass, based on the mass of.
  • acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate.
  • conjugated diene examples include 1,3-butadiene, isoprene and the like.
  • the crosslinked rubber polymer (B-1-II) containing 1,3-butadiene as a monomer is, for example, a 1,3-butadiene homopolymer or a copolymer composed of 50% by weight or more of 1,3-butadiene units.
  • Polymers can be mentioned.
  • the copolymer include, for example, a butadiene-aromatic vinyl compound copolymer such as a butadiene-styrene copolymer, a butadiene-vinyltoluene copolymer, etc., and further, a 1,3-butadiene unit of 50 weights by weight.
  • ternary copolymers composed of% or more. These can usually be easily produced by known emulsion polymerization.
  • the amount of the polyfunctional monomer unit constituting the crosslinked rubber polymer (B-1-II) is preferably 1 to 1.7% by mass with respect to the mass of the crosslinked rubber polymer (B-1-II). , More preferably 1.2 to 1.6% by mass, still more preferably 1.3 to 1.5% by mass.
  • Examples of the polyfunctional monomer include those exemplified above.
  • the polyfunctional monomer in the crosslinked polymer (B-1-I) is relative to the mass (F) of the polyfunctional monomer unit in the crosslinked rubber polymer (B-1-II).
  • the ratio (G / F) of the mass (G) of the polymer unit is preferably 0.01 to 0.25, more preferably 0.05 to 0.2.
  • the glass transition temperature of the crosslinked rubber polymer (B-1-II) is preferably lower than the glass transition temperature of the crosslinked polymer (B-1-I).
  • the amount of the crosslinked rubber polymer (B-1-II) is preferably 20 to 55% by mass, more preferably 25 to 45% by mass, still more preferably, based on the amount of the multilayer copolymer elastomer (B-1). Is 30 to 40% by mass.
  • the average diameter (d) of the crosslinked elastic layer is preferably 60 to 110 nm, more preferably 65 to 105 nm, and further preferably 70 to 100 nm.
  • the average diameter d (nm) of the layer of the crosslinked elastic body can be measured as follows. Using a hydraulic press molding machine, the resin composition (I) containing the multilayer copolymer elastomer is molded into a mold size of 50 mm ⁇ 120 mm, a press temperature of 250 ° C., a preheating time of 3 minutes, a press pressure of 50 kg / cm 2 , and a press time of 30.
  • the obtained flat plate is cut at ⁇ 100 ° C. in a direction parallel to the long side to obtain a slice having a thickness of 40 nm, and the slice is dyed with ruthenium.
  • the dyed flakes are observed with a scanning transmission electron microscope (JSM7600F manufactured by JEOL Ltd.) at an acceleration voltage of 25 kV and a photograph is taken.
  • the multilayer copolymer elastomer is not particularly limited depending on the production method thereof. For example, emulsion polymerization and the like can be mentioned.
  • the monomer (B-1-i) for forming the crosslinked polymer (B-1-I) is emulsified and polymerized to contain the crosslinked polymer (B-1-I).
  • a monomer (B-1-ii) for forming a crosslinked rubber polymer (B-1-II) is added to the latex to be used to seed the monomer (B-1-ii).
  • Emulsion polymerization is a known method used to obtain a latex containing a polymer. Seed emulsion polymerization is a method in which a monomer polymerization reaction is carried out on the surface of seed particles. Seed emulsion polymerization is preferably used to obtain core-shell structural polymer particles.
  • the laminate of the present invention includes a block composed of a polymer block (b1) mainly having a methacrylic acid ester unit and a polymer block (b2) having an acrylic acid ester unit in a layer made of the resin composition (I). It preferably contains a polymer elastomer (B-2).
  • the content of the block copolymer elastomer (B-2) in the resin composition (I) is preferably 1 to 49% by mass, more preferably 5 to 45% by mass, and 10 to 40% by mass. It is more preferable that the range is.
  • the brittleness of the laminate of the present invention is improved when the content of the block copolymer elastomer (B-2) is in the range of 1 to 49% by mass.
  • the block copolymer elastomer (B-2) is preferably composed of a polymer block (b1) having a methacrylic acid ester unit and a polymer block (b2) having an acrylic acid ester unit.
  • the block copolymer elastomer (B-2) may have only one polymer block (b1) in one molecule, or may have a plurality of block copolymer elastomers (B-2). Further, the block copolymer elastomer (B-2) may have only one polymer block (b2) in one molecule, or may have a plurality of block copolymer elastomers (B-2).
  • the amount of the methacrylic acid ester unit contained in the polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more. ..
  • the methacrylic acid ester for example, methyl methacrylate is preferable.
  • the methacrylic acid ester can be used alone or in combination of two or more in the polymer block (b1).
  • the amount of the polymer block (b1) contained in the block copolymer elastomer (B-2) includes transparency, flexibility, bending resistance, impact resistance, flexibility, molding processability, surface smoothness, and the like. From the viewpoint, it is preferably 40% by mass or more and 90% by mass or less, and more preferably 45% by mass or more and 80% by mass or less.
  • the glass transition temperature of the polymer block (b2) is preferably 20 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
  • the amount of the acrylic acid ester unit contained in the polymer block (b2) is preferably 90% by mass or more.
  • the acrylic acid ester include n-butyl acrylate and benzyl acrylate. These acrylic acid esters can be used alone or in combination of two or more for the polymer block (b2).
  • the polymer block (b2) may contain a monomer unit other than the acrylic acid ester as long as it does not interfere with the object and effect of the present invention.
  • the polymer block (b2) is preferably composed of an acrylic acid alkyl ester unit and a (meth) acrylic acid aromatic ester unit from the viewpoint of transparency and the like.
  • the mass ratio of the acrylic acid alkyl ester unit / (meth) acrylic acid aromatic ester is preferably 50/50 to 90/10, more preferably 60/40 to 80/20.
  • the bond form between the polymer block (b1) and the polymer block (b2) contained in the block copolymer elastomer (B-2) is not particularly limited.
  • one end of the polymer block (b1) connected to one end of the polymer block (b2) (b1-b2 diblock copolymer); a polymer at both ends of the polymer block (b2).
  • a block (b1) in which one end is connected (b1-b2-b1 triblock copolymer) is preferable.
  • the block copolymer elastomer (B-2) has a weight average molecular weight of preferably 52,000 or more and 400,000 or less, and more preferably 60,000 or more and 300,000 or less.
  • the ratio of the weight average molecular weight to the number average molecular weight of the block copolymer elastomer is preferably 1.01 or more and 2.00 or less, and more preferably 1.05 or more and 1.60 or less.
  • the weight average molecular weight and the number average molecular weight of the block copolymer elastomer can be appropriately set from the viewpoints of moldability, tensile strength, appearance and the like.
  • the weight average molecular weight and the number average molecular weight are standard polystyrene-equivalent values measured by GPC (gel permeation chromatography).
  • the block copolymer elastomer (B-2) is not particularly limited depending on the production method thereof, and can be obtained by a known method. For example, a method including living polymerization of the monomers constituting each polymer block is generally used. As a living polymerization method, a high-purity block copolymer elastomer can be obtained, the molecular weight and composition ratio can be easily controlled, and the cost is low. Therefore, in the presence of an organoalkali metal compound and an organoaluminum compound. A method involving anionic polymerization is preferred. (Methyl resin (C)) In the laminate of the present invention, it is preferable that the methacrylic resin (C) is contained in the layer made of the resin composition (I).
  • the content of the methacrylic resin (C) in the resin composition (I) is preferably 1 to 49% by mass, more preferably 5 to 45% by mass, and in the range of 10 to 40% by mass. Is even more preferable.
  • the fluidity of the laminate of the present invention is improved when the content of the methacrylic resin (C) is in the range of 1 to 49% by mass.
  • the methacrylic resin (C) contains, among all the monomer units, a structural unit derived from methyl methacrylate (hereinafter referred to as “MMA”) in an amount of preferably 70% by mass or more, more preferably 80% by mass or more, and further. It preferably contains 90% by mass.
  • MMA structural unit derived from methyl methacrylate
  • the content of the structural unit derived from MMA of the methacrylic resin (C) is that the resin purified by reprecipitating the methacrylic resin (C) in methanol is pyrolyzed and volatile components using pyrolysis gas chromatography. Can be calculated from the ratio of the peak area of the obtained MMA and the copolymerization component (mainly methyl acrylate).
  • the methacrylic resin (C) can contain structural units derived from monomers other than MMA among all the monomer units.
  • methyl acrylate (hereinafter referred to as "MA") and ethyl (meth) acrylate are preferable from the viewpoint of availability.
  • the total content of structural units derived from these other monomers in the methacrylic resin (C) is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less. It is also preferable that the structural unit derived from a monomer other than the methacrylic acid ester is not contained.
  • the methacrylic resin (C) can be obtained by polymerizing MMA alone or another monomer which is an optional component.
  • a plurality of types of monomers are used in such polymerization, usually, the plurality of types of monomers are mixed to prepare a monomer mixture, which is then subjected to polymerization.
  • the polymerization method is not particularly limited, but from the viewpoint of productivity, radical polymerization is preferably carried out by a method such as a massive polymerization method, a suspension polymerization method, a solution polymerization method, or an emulsion polymerization method.
  • the lower limit of the syndiotacticity (rr) of the triplet display of the methacrylic resin (C) is preferably 56% or more, more preferably 57% or more, and further preferably 58% or more. preferable.
  • the resin composition (I) according to the present invention has excellent heat resistance.
  • syndiotacticity (rr) of the triplet display (hereinafter, may be simply referred to as “syngiotacticity (rr)”) is a chain of three consecutive structural units (triple, triad). ) Has two chains (double element, diad), both of which are racemo (denoted as rr). In the chain of structural units (doubles, diads) in the polymer molecule, those having the same configuration are referred to as meso, and the opposite ones are referred to as racemo, which are referred to as m and r, respectively.
  • the syndiotacticity (rr) (%) of the methacrylic resin (A) was measured in 1 H-NMR spectrum at 30 ° C. in deuterated chloroform, and tetramethylsilane (TMS) was defined as 0 ppm from the spectrum.
  • TMS tetramethylsilane
  • the area (Y) of the region of 0.6 to 0.95 ppm and the area (Z) of the region of 0.6 to 1.35 ppm are measured and calculated by the formula: (Y / Z) ⁇ 100. be able to.
  • the weight average molecular weight (hereinafter referred to as "Mw") of the methacrylic resin (C) is preferably 40,000 to 500,000, more preferably 60,000 to 300,000, still more preferably 80,000 to 200,000. ..
  • Mw weight average molecular weight
  • the resin composition (I) according to the present invention has excellent mechanical strength, and when it is 500,000 or less, the fluidity is good.
  • the glass transition temperature of the methacrylic resin (C) is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and even more preferably 110 ° C. or higher.
  • the resin composition (I) according to the present invention has excellent heat resistance.
  • the glass transition temperature in the present specification is a temperature when measured by a differential scanning calorimeter at a heating rate of 10 ° C./min and calculated by the midpoint method.
  • the saturated water absorption rate of the methacrylic resin (C) in water at 23 ° C. is preferably 2.5% by mass or less, more preferably 2.3% by mass or less, and preferably 2.1% by mass or less. More preferred.
  • the saturated water absorption rate is 2.5% by mass or less, the resin composition (I) according to the present invention has excellent moisture resistance, and warpage of the laminate due to moisture absorption can be suppressed.
  • the saturated water absorption rate in the present specification is the mass at the time when the molded product is vacuum-dried for 3 days or more, the molded product is immersed in distilled water at 23 ° C., the mass is measured over time, and the equilibrium is reached. It is a value measured as an increase rate of.
  • the melt flow rate of the methacrylic resin (C) (hereinafter referred to as "MFR") is preferably in the range of 1 to 10 g / 10 minutes.
  • the lower limit of such MFR is more preferably 1.2 g / 10 minutes or more, and further preferably 1.5 g / 10 minutes or more.
  • the upper limit of the MFR is more preferably 7.0 g / 10 minutes or less, and further preferably 4.0 g / 10 minutes or less.
  • the MFR of the resin composition (I) according to the present invention in the present specification is a value measured using a melt indexer at a temperature of 230 ° C. under a load of 3.8 kg.
  • the resin composition (I) according to the present invention has a melt flow rate of preferably 1 g / 10 minutes or more, more preferably 1.5 to 35 g / 10 minutes, still more preferably, under the conditions of 230 ° C. and a load of 3.8 kg. 2 to 20 g / 10 minutes.
  • the melt flow rate is a value of the melt mass flow rate measured in accordance with JIS K7210.
  • the resin composition (I) according to the present invention has a glass transition temperature of preferably 100 to 160 ° C, more preferably 105 to 155 ° C, and even more preferably 110 to 150 ° C.
  • the glass transition temperature is 100 ° C. or lower, the heat resistance tends to decrease, and when the glass transition temperature is 160 ° C. or higher, the moldability tends to decrease.
  • the resin composition (I) according to the present invention has a saturated water absorption rate of 2.5% or less, more preferably 2.1% or less, which is measured under the same conditions as the measurement of the saturated water absorption rate of the acrylic copolymer (A). , More preferably 2.0% or less. Since the saturated water absorption rate is 2.5% or less, the dimensional stability at high humidity is excellent.
  • the resin composition (I) according to the present invention may contain a filler, if necessary, as long as the effects of the present invention are not impaired.
  • the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate and the like.
  • the amount of the filler that can be contained in the resin composition (I) is preferably 3% by mass or less, more preferably 1.5% by mass or less.
  • the resin composition (I) according to the present invention may contain other polymers as long as the effects of the present invention are not impaired.
  • Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymers, high-impact polystyrene, etc.
  • Sterite resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-based polymers other than acrylic copolymer (A), methyl methacrylate-styrene copolymer; polyethylene terephthalate, Polyester resin such as polybutylene terephthalate; polyamide such as nylon 6, nylon 66, polyamide elastomer; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, vinylidene fluoride, polyurethane, phenoxy resin, Modified polyphenylene ethers, polyphenylene sulfides, silicone-modified resins; silicone rubbers; styrene-based thermoplastic polymers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM can be mentioned.
  • the amount of the other polymer is preferably 10% by
  • the resin composition (I) according to the present invention contains an antioxidant, a heat deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, and a polymer processing aid as long as the effects of the present invention are not impaired. It may contain additives such as agents, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes, matting agents and phosphors.
  • the antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen.
  • phosphorus-based antioxidants hindered phenol-based antioxidants, thioether-based antioxidants, and the like can be mentioned. These antioxidants can be used alone or in combination of two or more.
  • phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. preferable.
  • the ratio is not particularly limited, but the mass ratio of the phosphorus-based antioxidant / hindered phenol-based antioxidant is preferably 1/5. It is ⁇ 2/1, more preferably 1/2 ⁇ 1/1.
  • Phosphorus antioxidants include 2,2-methylenebis (4,6-dit-butylphenyl) octylphosphite (manufactured by ADEKA; trade name: ADEKA STAB HP-10), tris (2,4-dit-). Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRUGAFOS168), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10- Examples thereof include tetraoxa-3,9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADEKA STAB PEP-36).
  • pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals; trade name IRGANOX1010)
  • examples thereof include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals Co., Ltd .; trade name IRGANOX1076).
  • the thermal deterioration inhibitor is a compound capable of preventing thermal deterioration of a resin by capturing polymer radicals generated when exposed to high heat under a substantially oxygen-free state, and is, for example, 2-t-butyl-6-. (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilyzer GM), 2,4-di-t-amyl-6- (3', Examples thereof include 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilyzer GS).
  • An ultraviolet absorber is a compound having an ability to absorb ultraviolet rays.
  • the ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
  • Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These may be used alone or in combination of two or more.
  • benzotriazoles, triazines, and ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol -1 cm -1 or less are preferable.
  • benzotriazoles examples include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H-).
  • Benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2'-methylenebis [6- (2H-benzotriazole-2) -Il) -4-tert-octylphenol] (manufactured by ADEKA; trade name LA-31), 2- (5-octylthio-2H-benzotriazole-2-yl) -6-tert-butyl-4-methylphenol, etc. Is preferable.
  • a triazine-type ultraviolet absorber is preferably used.
  • examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; trade name LA-F70). And its relatives, hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; trade names TINUVIN477, TINUVIN460 and TINUVIN479), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1, Examples include 3,5-triazine.
  • the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light, and examples thereof include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. Be done.
  • lubricant examples include stearic acid, behenic acid, stearoamic acid, methylene bisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hydrogenated oil.
  • the mold release agent is a compound having a function of facilitating the mold release of a molded product from a mold, and is, for example, higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acids such as stearic acid monoglyceride and stearic acid diglyceride. Esters and the like can be mentioned. Since the use of glycerin higher fatty acid ester may cause gel-like foreign substances, it is preferable to use higher alcohols.
  • the polymer processing aid is a compound that exerts an effect on thickness accuracy and thinning when molding the resin composition (I).
  • the polymer processing aid can usually be produced by an emulsification polymerization method.
  • the polymer processing aid is preferably polymer particles having a particle size of 0.05 to 0.5 ⁇ m.
  • the polymer particles may be single-layer particles composed of a polymer having a single composition ratio and a single extreme viscosity, or may be multilayer particles composed of two or more kinds of polymers having different composition ratios or ultimate viscosities. You may.
  • particles having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl / g or more in the outer layer are preferable.
  • the polymer processing aid preferably has an ultimate viscosity of 3 to 6 dl / g. If the ultimate viscosity is too small, the effect of improving moldability is low. If the ultimate viscosity is too large, the melt fluidity of the resin composition (I) tends to decrease.
  • Antistatic agents include sodium heptyl sulfonate, sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium cetyl sulfonate, sodium octadecyl sulfonate, sodium diheptyl sulfonate, heptyl sulfonic acid.
  • potassium octyl sulfonate potassium nonyl sulfonate, potassium decyl sulfonate, potassium dodecyl sulfonate, potassium cetyl sulfonate, potassium octadecyl sulfonate, potassium diheptyl sulfonate, lithium heptyl sulfonate, lithium octyl sulfonate, nonyl sulfonate
  • alkyl sulfonates such as lithium acid, lithium decyl sulfonate, lithium dodecyl sulfonate, lithium cetyl sulfonate, lithium octadecyl sulfonate, and lithium diheptyl sulfonate.
  • Examples of the flame retardant include metal hydrates having a hydroxyl group or crystalline water such as magnesium hydroxide, aluminum hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, and hydrotalcite, and phosphoric acid such as polyphosphate amine and phosphoric acid ester.
  • Examples include compounds and silicon compounds, including trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and dimethyl ethyl.
  • Phosphate-based flame retardants such as phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, and hydroxyphenyldiphenyl phosphate are preferred.
  • Dyes and pigments include red organic pigments such as parared, fire red, pyrazolone red, thioindigo red, and perylene red, blue organic pigments such as cyanine blue and indanslen blue, and green organic pigments such as cyanine green and naphthol green. These can be mentioned, and one or more of these can be used.
  • the organic dye a compound having a function of converting ultraviolet rays into visible light is preferably used.
  • the light diffusing agent and the matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.
  • the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, and a fluorescent bleaching agent.
  • additives may be used alone or in combination of two or more. Further, these additives may be added to the polymerization reaction solution for producing the acrylic copolymer (A) and the elastomer (B), or the produced acrylic copolymer (A) or crosslinks may be added. It may be added to the rubber (B) or may be added when preparing the resin composition (I).
  • the total amount of the additives is preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, based on the resin composition (I), from the viewpoint of suppressing poor appearance of the molded product. Is.
  • the resin composition (T) used for the laminate of the present invention is a resin composition containing polycarbonate.
  • Polycarbonate is preferably obtained by copolymerizing a divalent phenol such as bisphenol A with a carbonate precursor.
  • the Mw of the polycarbonate is preferably in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 70,000.
  • the laminate of the present invention is excellent in impact resistance and heat resistance, and when it is 100,000 or less, the polycarbonate is excellent in molding processability, and the laminate of the present invention is produced. You can improve your sex.
  • the resin composition (T) may contain other polymers as long as the effects of the present invention are not impaired.
  • other polymers the same ones as other polymers which may be contained in the methacrylic resin, the resin composition (I) and the above-mentioned resin composition (I) can be used. These other polymers may be used alone or in combination of two or more.
  • the content of these other polymers in the resin composition (T) is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the resin composition (T) may contain various additives, if necessary.
  • the additive the same additive as the additive that may be contained in the resin composition (I) described above can be used.
  • the content of these additives can be appropriately set within a range that does not impair the effects of the present invention.
  • the content of the antioxidant is 0.01 to 1 part by mass and the content of the ultraviolet absorber is 0.01 to 1 part by mass with respect to 100 parts by mass of the polycarbonate. 0.01 to 3 parts by mass, light stabilizer content 0.01 to 3 parts by mass, lubricant content 0.01 to 3 parts by mass, dye / pigment content 0.01 to 3 parts by mass Is preferable.
  • the resin composition (T) used in the present invention preferably has a glass transition temperature of 120 to 160 ° C. Further, it is preferable that the glass transition temperature of the resin composition (T) is about the same as the glass transition temperature of the resin composition (I).
  • of the difference between the glass transition temperature of the resin composition (T) and the glass transition temperature of the resin composition (I) is preferably 30 ° C. or lower, more preferably 20 ° C. or lower. ..
  • is 30 ° C. or less, the effect of suppressing the occurrence of warpage of the laminated body under high temperature and high humidity becomes higher.
  • the resin composition (T) used in the present invention preferably has a saturated water absorption rate of 0.1 to 1.0% by mass in water at 23 ° C. Further, it is preferable that the saturated water absorption rate of the resin composition (T) is about the same as the saturated water absorption rate of the resin composition (I). Specifically, the absolute value
  • the MFR of the resin composition (T) used in the present invention is preferably in the range of 1 to 30 g / 10 minutes, more preferably in the range of 3 to 20 g / 10 minutes, and 5 to 10 g / 10 minutes. It is more preferably in the range. When the MFR is in the range of 1 to 30 g / 10 minutes, the stability of heat melt molding is good.
  • the MFR of the resin composition (T) in the present specification is measured using a melt indexer under the conditions of a temperature of 300 ° C. and a load of 1.2 kg.
  • the laminate of the present invention may have a plurality of layers made of the resin composition (I) and / or a plurality of layers made of the resin composition (T).
  • the laminate of the present invention may have a layer made of another resin (another resin layer) in addition to the layer made of the resin composition (I) and the layer made of the resin composition (T).
  • the resin contained in the other resin layer include various thermoplastic resins other than the resin composition (I) and the resin composition (T); thermosetting resin; energy ray-curable resin; and the like.
  • Examples of the other resin layer described above include a scratch resistant layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, an adhesive layer, and an impact strength imparting layer.
  • the other resin layers may be one layer or a plurality of layers. When there are a plurality of these other resin layers, they may be made of the same resin or different resins.
  • the arrangement order of the other resin layers is not particularly limited, and may be a surface layer or an inner layer.
  • the thickness of the laminate of the present invention is preferably in the range of 0.03 to 6.0 mm, preferably in the range of 0.05 to 5.0 mm, from the viewpoint of producing with good productivity while maintaining an excellent appearance. It is more preferably in the range of 0.1 to 4.0 mm.
  • the thickness of the layer made of the resin composition (I) in the laminate of the present invention is preferably in the range of 0.01 to 0.6 mm, more preferably in the range of 0.015 to 0.5 mm. It is more preferably in the range of 0.02 to 0.4 mm. If the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. If it exceeds 0.6 mm, the impact resistance may be insufficient.
  • the thickness of the layer made of the resin composition (T) in the laminate of the present invention is preferably in the range of 0.02 to 5.4 mm, more preferably in the range of 0.035 to 4.5 mm. It is more preferably in the range of 0.08 to 3.6 mm. If the thickness is less than 0.02 mm, the impact resistance may be insufficient. If it exceeds 5.4 mm, the productivity may decrease.
  • the thickness of the layer made of the resin composition (I) in the laminate of the present invention is preferably in the range of 2 to 15%, preferably in the range of 3 to 12%, based on the thickness of the laminate. Is more preferable, and the range of 4 to 10% is further preferable. If the thickness ratio is less than 2%, scratch resistance and weather resistance may be insufficient. If it exceeds 15%, the impact resistance may be insufficient.
  • the thickness of the layer made of the resin composition (T) in the laminate of the present invention is preferably in the range of 85 to 98%, preferably in the range of 88 to 97%, based on the thickness of the laminate. Is more preferable, and more preferably in the range of 90 to 96%. If the ratio of such thickness is less than 85%, the impact resistance may be insufficient. If it is 15% or more, the weather resistance may be insufficient.
  • the layer made of the resin composition (I) is (1), and the resin composition (T) is used.
  • the stacking order of the laminated body of the present invention is (1)-(2); (1)-(2)-(1); (2)-(1)-. (2); (1)-(2)-(1)-(2)-(1); and the like, and from the viewpoint of enhancing scratch resistance, (1)-(2); (1)-( 2)-(1); (1)-(2)-(1)-(2)-(1); etc., at least one surface is laminated so as to be a layer made of the resin composition (I). It is preferable to have.
  • the stacking order of the laminated body of the present invention is (1)-(2). -(3); (3)-(1)-(2); (3)-(1)-(2)-(3); (3)-(1)-(2)-(1)-( 3); (1)-(2)-(3)-(2)-(1); and the like.
  • (3) is a scratch-resistant layer
  • the stacking order of the laminated body of the present invention is (3')-(1)-(2) when the scratch-resistant layer is described as (3').
  • At least one surface is scratch resistant, such as (3')-(1)-(2)-(3'), (3')-(1)-(2)-(1)-(3'). It is preferable that the layers are laminated.
  • the stacking order of the laminated body of the present invention is (1)-(2)-(3)-(4); (4)-(3)-(1)-(2); (4)-( 3)-(1)-(2)-(3); (4)-(1)-(2)-(3); (4)-(3)-(1)-(2)-(3) -(4); (4)-(3)-(1)-(2)-(1)-(3)-(4); and the like.
  • the antireflection layer is described as (4'), (4')-(3')-(1)- (2); (4')-(3')-(1)-(2)-(3'); (4')-(3')-(1)-(2)-(3')- It is preferable that the layers are laminated in the order of (4'); (4')-(3')-(1)-(2)-(1)-(3')-(4') ;.
  • the laminated body of the present invention has a symmetrical stacking order in the thickness direction, and the thickness of each layer is also symmetrical. preferable.
  • the total light transmittance of the laminate of the present invention is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the laminate obtained in the present invention is excellent in appearance quality.
  • the total light transmittance can be measured by a method according to JIS K7105.
  • the method for producing the laminated body of the present invention is not particularly limited, it is usually preferable to laminate the layer made of the resin composition (I) and the layer made of the resin composition (T) by multi-layer molding.
  • the multi-layer molding include a laminating synthetic molding method such as multi-layer extrusion molding, multi-layer blow molding, multi-layer press molding, multi-color injection molding, and insert injection molding, and multi-layer extrusion molding is preferable from the viewpoint of productivity.
  • Examples of the method of further laminating other resin layers include a method of multi-layer molding by the above-mentioned method together with a layer made of the resin composition (I) and a layer made of polycarbonate, and a layer or resin made of the resin composition (I) prepared in advance.
  • the method of multi-layer extrusion molding is not particularly limited, and a known multi-layer extrusion molding method used for producing a multi-layer laminate of a thermoplastic resin can be preferably adopted, and more preferably a flat T-die and polishing having a mirror-finished surface. Molded by a device with rolls.
  • the T-die method includes a feed block method in which the resin composition (I) and the resin composition (T) in a heated and melted state are laminated before the inflow of the T-die, the resin composition (I) and the resin composition ( A multi-manifold system in which T) is laminated inside the T die can be adopted.
  • the multi-manifold method is preferable from the viewpoint of improving the smoothness of the interface between the layers constituting the laminated body.
  • examples of the polishing roll in this case include a metal roll and an elastic roll having a metal thin film on the outer periphery (hereinafter, may be referred to as a metal elastic roll).
  • the metal roll is not particularly limited as long as it has high rigidity, and examples thereof include a drilled roll and a spiral roll.
  • the surface state of the metal roll is not particularly limited, and may be, for example, a mirror surface, or may have a pattern, unevenness, or the like.
  • the metal elastic roll is, for example, a shaft roll provided rotatably in a substantially columnar shape, a cylindrical metal thin film arranged so as to cover the outer peripheral surface of the shaft roll and in contact with a film-like object, and a shaft thereof.
  • the shaft roll is not particularly limited, and is made of, for example, stainless steel.
  • the metal thin film is made of, for example, stainless steel, and its thickness is preferably about 2 to 5 mm.
  • the metal thin film preferably has flexibility, flexibility, and the like, and preferably has a seamless structure without weld joints.
  • a metal elastic roll provided with such a metal thin film has excellent durability, and if the metal thin film is mirror-finished, it can be handled in the same manner as a normal mirror-finished roll. It is easy to use because it becomes a roll that can transfer the shape.
  • the resin composition (I) and the resin composition (T) are preferably melt-filtered by a filter before and / or during multi-layer molding.
  • a filter medium of the filter used is not particularly limited, and is appropriately selected depending on the operating temperature, viscosity, and filtration accuracy.
  • Nonwoven fabric made of, for example, polypropylene, cotton, polyester, rayon, glass fiber, etc .; phenol resin impregnated cellulose film; metal fiber non-woven fabric baked. Yui film; metal powder sintered film; wire mesh; or a combination thereof can be used. Above all, from the viewpoint of heat resistance and durability, it is preferable to use a plurality of laminated metal fiber non-woven fabric sintered films.
  • the filtration accuracy of the filter is not particularly limited, but is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 5 ⁇ m or less.
  • the scratch resistant layer will be described in detail as an example of the layer made of another resin composition.
  • the scratch resistant layer is a layer for increasing the hardness by the pencil scratch test, and is a layer showing a hardness of "4H" or more in the pencil scratch test defined by JIS-K5600-5-4. Is preferable.
  • the scratch resistant layer is preferably provided on the surface of the layer made of the resin composition (I).
  • the thickness of the scratch resistant layer is preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, and even more preferably 4 to 7 ⁇ m. When the thickness is 2 ⁇ m or more, the scratch resistance tends to be maintained, and when the thickness is 10 ⁇ m or less, the impact resistance of the laminated body tends to be excellent.
  • the scratch-resistant layer is usually a fluid curable composition made of a monomer, an oligomer, a resin, or the like, which is made of another layer (for example, a layer made of the resin composition (I) or a layer made of the resin composition (T)). It can be formed by applying it to the surface and curing it.
  • curable compositions are, for example, thermosetting compositions that are cured by heat and energy ray-curable compositions that are cured by energy rays such as electron beams, radiation, and ultraviolet rays.
  • thermosetting composition examples include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-.
  • examples thereof include compositions containing a urea cocondensate resin, a silicon resin, a polysiloxane resin and the like.
  • thermosetting compositions may contain, for example, a cross-linking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, or the like, if necessary.
  • isocyanates organic sulfonic acids and the like are usually used for polyester resins and polyurethane resins
  • amines are used for epoxy resins
  • peroxides such as methyl ethyl ketone peroxide
  • radical initiators such as azobisisobutyl ester are used. Used for unsaturated polyester-based resins.
  • Examples of the curable compound contained in the energy ray-curable composition include oligomers and / or monomers having a polymerizable unsaturated bond such as an acryloyl group or a metaacryloyl group, a thiol group, or an epoxy group in the molecule. From the viewpoint of enhancing scratch resistance, oligomers and / or monomers having a plurality of acryloyl groups or metaacryloyl groups are preferable.
  • the energy ray-curable composition may contain a photopolymerization initiator and / or a photosensitizer in addition to the curable compound.
  • photopolymerization initiators include carbonyl compounds such as benzoin methyl ether, acetophenone, 3-methylacetophenone, benzophenone and 4-chlorobenzophenone; sulfur compounds such as tetramethylthium monosulfide and tetramethylthiuram disulfide; 2, 4, 6 -Methylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide and the like can be mentioned, and examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like.
  • the content of these curable compounds is preferably in the range of 30 to 100% by mass, more preferably in the range of 40 to 95% by mass, and in the range of 50 to 95% by mass. It is more preferable to have.
  • These curable compounds may be used alone or in combination of two or more.
  • the curable composition is, if necessary, a monofunctional monomer; an organic solvent; a leveling agent, an antiblocking agent, a dispersion stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antifoaming agent, a thickener, and the like.
  • Additives such as lubricants, antistatic agents, antifouling agents, antifoaming agents, fillers and catalysts; may be appropriately contained. The content of these additives can be appropriately set as long as the effects of the present invention are not impaired.
  • Examples of the method for applying the curable composition described above include a spin coating method, a dip method, a spray method, a slide coating method, a bar coating method, a roll coating method, a gravure coating method, a meniscus coating method, a flexographic printing method, and a screen printing method. Can be mentioned.
  • inventions include, for example, signboard parts such as advertising towers, stand signs, sleeve signs, column signs, roof signs, marking films; display parts such as showcases, dividers, store displays; fluorescent lamp covers, etc.
  • Mood lighting parts such as lighting covers, lamp shades, light ceilings, light walls, chandeliers; interior parts such as furniture, pendants, mirrors; doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, leisure buildings Building parts such as roofs; aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shading plates, automobile side visors, rear visors, head wings, headlight covers, automobile interior parts, automobile exterior parts such as bumpers, etc.
  • Transport machine-related parts nameplates for audiovisual images, stereo covers, TV protective masks, vending machines, mobile phones, personal computers and other electronic equipment parts; incubators, roentgen parts and other medical equipment parts; machine covers, instrument covers, experimental equipment Equipment-related parts such as rulers, dials, observation windows; optical parts such as liquid crystal protective plates, light guide plates, light guide films, frennel lenses, lenticular lenses, front plates of various displays, diffuser plates; road signs, guide plates , Curved mirrors, soundproof walls, and other traffic-related parts; Others, greenhouses, large water tanks, box water tanks, bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, musical instruments, face protection masks during welding, Examples include solar cell back sheets, flexible solar cell front sheets, decorative films; surface materials used for personal computers, mobile phones, furniture, vending machines, bathroom materials, and the like.
  • the weight average molecular weight (Mw) of the resin obtained in the production example was determined by the GPC method (gel permeation chromatography method).
  • a sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran.
  • the temperature of the column oven was set to 40 ° C., the eluent flow rate was 0.35 ml / min, 20 ⁇ l of the sample solution was injected into the apparatus, and the chromatogram was measured.
  • Ten standard polystyrenes having a molecular weight in the range of 400 to 5,000,000 were GPC-measured to prepare a calibration curve showing the relationship between the retention time and the molecular weight.
  • the Mw of the resin to be measured was determined based on this calibration curve. From the chromatogram measured by GPC, the value corresponding to the molecular weight of standard polystyrene was taken as the molecular weight of the copolymer.
  • Equipment Tosoh GPC equipment
  • Eluent tetrahydrofuran
  • Eluent flow rate 0.35 mL / min
  • Column temperature 40 ° C.
  • Detection method Differential refractometer (RI)
  • composition of each unit in the copolymer 1
  • the proton ratio of the phenyl group of ⁇ -methylstyrene unit to the methoxy group of methyl methacrylate was determined by 1 H-NMR, and the ⁇ -methylstyrene unit was calculated by this.
  • Glass transition temperature Tg Glass transition temperature Tg
  • the resin composition obtained in the production example is once heated to 250 ° C. using a differential scanning calorimetry device (manufactured by Shimadzu Corporation, DSC-50 (product number)) in accordance with JIS K7121, and then to room temperature. After cooling, the DSC curve was measured under the condition that the temperature was raised from room temperature to 200 ° C. at 10 ° C./min. The midpoint glass transition temperature obtained from the DSC curve measured at the time of the second temperature rise was defined as the glass transition temperature in the present invention.
  • composition of each unit of acrylic copolymer The ⁇ -methylstyrene unit and the styrene unit had the same composition as each unit composition of the precursor polymer. Using 1 H-NMR (manufactured by Bruker; trade name ULTRA SHIELD 400 PLUS), 1 H-NMR measurement of the acrylic copolymer was performed, and glutarialimide units and methyl methacrylate units in the acrylic copolymer were measured. Obtain the content (mol%) of each monomer unit such as aromatic vinyl ( ⁇ -methylstyrene and styrene) unit, and use the molecular weight of each monomer unit to determine the content (mol%). Converted to content (% by weight).
  • thermogravimetric reduction temperature Using a thermogravimetric analyzer (manufactured by Shimadzu Corporation, TGA-50), the resin composition obtained in the production example was heated at 10 ° C./min under a nitrogen atmosphere, and the temperature at the time when the weight was reduced by 1% was adjusted. The temperature was set to 1% thermogravimetric reduction temperature.
  • the resin composition obtained in the production example was placed in a rectangular mold frame having a short side of 110 mm and a long side of 150 mm and pressed at 230 ° C. and 50 kg / cm 2 for 5 minutes to have a thickness of 2 mm and a short length.
  • a sheet having a side of 110 mm and a long side of 150 mm was produced.
  • a test piece prepared by cutting the obtained sheet into a square having a side of 50 mm was dried under reduced pressure (1 kPa) at 80 ° C. for 24 hours, and then allowed to cool in a desiccator at a temperature of 23 ° C. and a relative humidity of 50%. The mass was measured promptly and used as the initial mass.
  • the resin composition obtained in the production example was placed in a rectangular mold frame having a short side of 110 mm and a long side of 150 mm and pressed at 230 ° C. and 50 kg / cm 2 for 5 minutes to have a thickness of 2 mm and a short length.
  • a sheet having a side of 110 mm and a long side of 150 mm was produced.
  • a table-movable pencil scratch tester model P (manufactured by Toyo Seiki Co., Ltd.)
  • the hardness of the pencil lead was gradually increased, and the hardness of the lead, which was one step softer than the time when the scar was generated, was defined as the pencil scratch hardness.
  • Test piece was prepared. Place the test piece on the surface plate so that both ends of the test piece are in contact with the surface plate (that is, the test piece is convex upward), and use a feeler gauge to maximize the gap between the test piece and the surface plate. was measured and used as the initial amount of warpage. Next, each test piece was left in a hot air dryer set at a temperature of 100 ° C.
  • test piece whose short side was clipped was placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%. After being suspended and left in that state for 72 hours, it was allowed to cool and regulate humidity for 120 hours in an environment of 23 ° C. and 50% relative humidity. As a result, all the test pieces were bowed along the long sides of the test pieces, with the layer made of the resin composition (I) on the outside and the layer made of the resin composition (T) on the inside. ..
  • test piece Place the test piece on the surface plate so that both ends of the test piece with the bow-shaped warp are in contact with the surface plate (that is, the test piece has an upward convex shape), and use a feeler gauge to attach the test piece to the surface plate.
  • the maximum value of the gap with the surface plate was measured and used as the amount of warpage under high temperature and high humidity.
  • the amount of change in warpage under high temperature and high humidity was calculated from the following formula, and the quality of dimensional stability was judged from the amount of change.
  • Warp change amount under high temperature and high humidity Warp amount under high temperature and high humidity ⁇
  • Warpage change amount under high temperature and high humidity is larger than 3 mm (surface hardness)
  • the laminates of Examples and Comparative Examples are cut into rectangles so that the direction parallel to the extrusion flow direction is the long side and the direction perpendicular to the extrusion flow direction is the short side, and the long side is 200 mm and the short side is 120 mm. Test piece was prepared.
  • Pencil hardness of the resin composition (I) surface of the laminate is 3H or more
  • Pencil hardness of the resin composition (I) surface of the laminate is 2H
  • Pencil hardness of the resin composition (I) surface of the laminate is H or less (weather resistance)
  • the laminates of Examples and Comparative Examples were cut out to a size of 50 mm ⁇ 50 mm to prepare test pieces.
  • a super UV tester manufactured by Iwasaki Denki Co., Ltd., SUV-W161
  • the black panel temperature was 83 ° C.
  • the relative humidity was 50%
  • the irradiation energy was 100 mW / cm 2 .
  • Precursor polymer The precursor polymers Aa to Ag according to this production example were produced by the following methods. Precursor polymers A-a-A-f Tables of purified methyl methacrylate (MMA), ⁇ -methylstyrene, 2,2'-azobis (2-methylpropionitrile) (AIBN) and n-octyl mercaptan (n-OM) in an autoclave with a stirrer. The mixture was charged at the ratio described in 1 and uniformly dissolved to obtain a polymerization raw material. The polymerization raw material is continuously supplied from the autoclave to a tank reactor controlled at a polymerization temperature of 120 ° C.
  • MMA methyl methacrylate
  • AIBN 2,2'-azobis (2-methylpropionitrile)
  • n-OM n-octyl mercaptan
  • the polymerization reaction is carried out by a massive polymerization method with an average residence time of 3 hours, and the tank reactor is subjected to a polymerization reaction.
  • the liquid containing the acrylic copolymer was continuously discharged from the water.
  • the polymerization conversion rate was the value shown in Table 1.
  • the liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C. In the twin-screw extruder, the volatile matter containing the unreacted monomer as a main component was separated and removed, and the acrylic copolymer was extruded into strands.
  • the strands were cut with a pelletizer to give precursor polymers Aa-Af.
  • the weight average molecular weight Mw, the ratio of ⁇ -methylstyrene structural units, and the glass transition temperature Tg of the obtained precursor polymers Aa to Af were measured. The results are shown in Table 1.
  • the amount (mass%) of the unit derived from MMA is ⁇ 100- (mass% of the unit other than ⁇ -methylstyrene unit) ⁇ , so the description in Table 1 is omitted.
  • Precursor polymer Ag MS resin (copolymer of methyl methacrylate (MMA) and styrene (St)) is produced according to the method for producing a copolymer (A) described in the section of [Example] of JP-A-2003-231785. bottom.
  • Got% The MMA unit of the precursor polymer Ag was 90% by mass.
  • Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 120 rpm and a temperature of 250 ° C.
  • the precursor polymer [AA] was supplied at 2 kg / hr, and monomethylamine was injected at 0.10 kg / hr at the melt-kneading section where the kneading block was installed from the additive supply port of the twin-screw extruder.
  • the precursor polymer [AA] was reacted with monomethylamine.
  • a reverse flight was installed on the screw at the end of the reaction zone.
  • by-products and excess monomethylamine were volatilized from the molten resin that had passed through the melt kneading section and discharged through the vent.
  • the molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to form a pellet-shaped acrylic copolymer (A-a-1). ) was obtained.
  • Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 230 ° C.
  • a liquid consisting of 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine in a melt-kneaded portion in which an acrylic copolymer (A-a-1) is supplied at 1 kg / hr and a kneading block is installed.
  • the molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to form a pellet-shaped acrylic copolymer (A-a-2). ) was obtained.
  • Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 230 ° C.
  • the acrylic copolymer (A-a-2) was supplied at 1 kg / hr.
  • the devolatilization section set to 20 Torr (about 2.7 kPa), volatile components such as unreacted substances were volatilized from the molten resin that had passed through the melt-kneading section and discharged through the vent.
  • the molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped acrylic copolymer (A-1). Obtained.
  • the content of the glutarimide unit (ratio of the structural unit (R)) of the acrylic copolymer (A-1) was 9 wt%.
  • the precursor polymer [Ab] was used, and the amount of monomethylamine added was 0.07 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-2) and the resin composition (I-2) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.018 kg / hr. The evaluation results are shown in Table 1.
  • the precursor polymer [Ab] was used, and the amount of monomethylamine added was 0.14 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-3) and the resin composition (I-3) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.036 kg / hr. The evaluation results are shown in Table 1.
  • the precursor polymer [Aa] was used, and the amount of monomethylamine added was 0.07 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-4) and the resin composition (I-4) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.018 kg / hr. The evaluation results are shown in Table 1.
  • Production example 5 instead of the precursor polymer [AA], the precursor polymer [Ad] was used, and the amount of monomethylamine added was 0.07 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-5) and the resin composition (I-5) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.008 kg / hr.
  • Production Example 6 whose evaluation results are shown in Table 1.
  • the precursor polymer [Aa] instead of the precursor polymer [Ae] was used, and the amount of monomethylamine added was 0.08 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-6) and the resin composition (I-6) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.008 kg / hr.
  • Production Example 7 whose evaluation results are shown in Table 1.
  • the precursor polymer [AF] was used, and the amount of monomethylamine added was 0.03 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-7) and the resin composition (I-7) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.008 kg / hr. The evaluation results are shown in Table 1.
  • Production Example 8 Acrylic was added in the same manner as in Production Example 1 except that a liquid consisting of 0.30 kg / hr of monomethylamine, 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine was injected at 0.075 kg / hr. A system copolymer (A-8) and a resin composition (I-8) were obtained. The evaluation results are shown in Table 1.
  • the precursor polymer [Aa] was used, and the amount of monomethylamine added was 0.07 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-9) and the resin composition (I-9) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.018 kg / hr. The evaluation results are shown in Table 1.
  • Production Example 10 instead of the precursor polymer [Aa], the precursor polymer [Ag] was used, and the amount of monomethylamine added was 0.45 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine.
  • the acrylic copolymer (A-10) and the resin composition (I-10) were obtained by the same method as in Production Example 1 except that the solution was injected at 0.125 kg / hr. The evaluation results are shown in Table 1.
  • Production Example 11 An acrylic copolymer was used in the same manner as in Production Example 1 except that the precursor polymer [Ab] was used instead of the precursor polymer [Aa], no additives were added, and the extruder was passed through the extruder. (A-11) and a resin composition (I-11) were obtained. The evaluation results are shown in Table 1.
  • Multilayer copolymer elastomer (B-1) In a reactor equipped with a stirrer, thermometer, nitrogen gas introduction tube, monomer introduction tube and reflux condenser, 1050 parts by mass of ion-exchanged water, 0.44 parts by mass of polyoxyethylene tridecyl ether sodium acetate and sodium carbonate 0.7 parts by mass was charged, and the inside of the reactor was sufficiently replaced with nitrogen gas. Then, the internal temperature was adjusted to 80 ° C. 0.25 parts by mass of potassium persulfate was added thereto, and the mixture was stirred for 5 minutes.
  • the latex was frozen and solidified. Then, it was washed with water and dried to obtain a multilayer copolymer elastomer (B-1).
  • the average particle size of the multilayer copolymer elastomer (B-1) was 0.2 ⁇ m. 80 parts by mass of acrylic copolymer (A-1), 20 parts by mass of multilayer copolymer elastomer (B-1), 0.15 parts by mass of Calcol 8098 (manufactured by Kao Co., Ltd.), 0.9 parts by mass Adecaster LA-31 (manufactured by ADEKA Co., Ltd.) was mixed, melt-kneaded at 250 ° C. with a twin-screw extruder having a shaft diameter of 20 mm, and extruded to obtain a pellet-shaped resin composition (I-12).
  • Table 2 The evaluation results are shown in Table 2.
  • Block Copolymer Elastow (B-2) Dry toluene at room temperature 735 kg, hexamethyltriethylenetetramine 0.4 kg, and isobutylbis (2,6) in a glass-lined 3 m 3 reaction vessel with a degassed, nitrogen-replaced brine-coolable jacket and stirrer.
  • -Di-t-Butyl-4-methylphenoxy 39.4 kg of a toluene solution containing 20 mol of aluminum was added, and 1.17 mol of sec-butyllithium was further added.
  • Methyl methacrylate (35.0 kg) was added thereto, and the mixture was reacted at room temperature for 1 hour to obtain a methyl methacrylate polymer having a weight average molecular weight (hereinafter referred to as Mw (b1-1)) of 40,000 (polymer block (b1). -1)) was obtained.
  • Mw (b1-1) weight average molecular weight
  • b1-1 weight average molecular weight of 40,000
  • a polymer block (b2) composed of a copolymer of n-butyl acrylate and benzyl acrylate was grown from one end to obtain a diblock copolymer elastomer (B-2) having a weight average molecular weight of 80,000. .. Since the weight average molecular weight of the polymer block (b1-1) was 40,000, it was determined that the weight average molecular weight (Mw (b2)) of the polymer block (b2) was 40,000.
  • the block copolymer elastomer (B-2) has a content of the polymer block (b2) having an acrylic acid ester unit in an amount of 50% by mass.
  • Production example 14 80 parts by mass of acrylic copolymer (A-1), 10 parts by mass of multilayer copolymer elastomer (B-1), 10 parts by mass of block copolymer elastomer (B-2), 0.15 parts by mass Polymer 8098 (manufactured by Kao Co., Ltd.) and 0.9 parts by mass of Adecaster LA-31 (manufactured by ADEKA Co., Ltd.) are mixed, melt-kneaded at 250 ° C. with a twin-screw extruder having a shaft diameter of 20 mm, and extruded. A pellet-shaped resin composition (I-14) was obtained. The evaluation results are shown in Table 2.
  • Production example 15 80 parts by mass of acrylic copolymer (A-1), 20 parts by mass of methacrylic resin (C) (Parapet HR-S, manufactured by Kuraray Co., Ltd.), 0.15 parts by mass of Calcol 8098 (manufactured by Kao Corporation) , 0.9 parts by mass of Adecaster LA-31 (manufactured by ADEKA Co., Ltd.) is mixed, melt-kneaded at 250 ° C. with a twin-screw extruder having a shaft diameter of 20 mm, extruded, and pelletized resin composition (I-). 15) was obtained. The evaluation results are shown in Table 2.
  • Production example 16 30 parts by mass of methacrylic resin (C), 70 parts by mass of styrene copolymer (S-1), 0.15 parts by mass of Calcol 8098 (manufactured by Kao Co., Ltd.), 0.9 parts by mass of ADEKA STAB LA-31 (Manufactured by ADEKA Corporation) was mixed, melt-kneaded at 250 ° C. with a twin-screw extruder having a shaft diameter of 20 mm, and extruded to obtain a pellet-shaped resin composition (I-16). The evaluation results are shown in Table 2.
  • Production example 17 50 parts by mass of methacrylic resin (C), 50 parts by mass of styrene copolymer (S-2), 0.15 parts by mass of Calcol 8098 (manufactured by Kao Co., Ltd.), 0.9 parts by mass of ADEKA STAB LA-31 (Manufactured by ADEKA Corporation) was mixed, melt-kneaded at 250 ° C. with a twin-screw extruder having a shaft diameter of 20 mm, and extruded to obtain a pellet-shaped resin composition (I-17). The evaluation results are shown in Table 2.
  • Example 1 Polycarbonate pellets were continuously put into a single-screw extruder having a shaft diameter of 50 mm, and extruded in a molten state at a cylinder temperature of 280 ° C.
  • pellets of the resin composition (I-1) were continuously put into a single-screw extruder having a shaft diameter of 30 mm and extruded in a molten state at a cylinder temperature of 220 ° C.
  • the molten polycarbonate and the resin composition (I-1) are introduced into a junction block, laminated with a multi-manifold die set at 250 ° C., extruded into a sheet, and a resin composition (I-) having a thickness of 80 ⁇ m.
  • a laminated body having a thickness of 1000 ⁇ m formed of two layers of a layer made of 1) (first layer) and a layer made of polycarbonate having a thickness of 920 ⁇ m (second layer) was produced.
  • the evaluation results of such a laminated body are shown in Table 3.
  • Example 2 A layer made of a resin composition (I-1) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-2) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 3 A layer made of a resin composition (I-3) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-3) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 4 A layer made of a resin composition (I-4) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-4) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 5 A layer made of a resin composition (I-5) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-5) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 6 A layer made of a resin composition (I-6) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-6) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m.
  • the evaluation results of such a laminated body are shown in Table 3.
  • Example 7 A layer made of a resin composition (I-12) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-12) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 8 A layer made of a resin composition (I-13) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-13) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 9 A layer made of a resin composition (I-14) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-14) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 10 A layer made of a resin composition (I-15) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-15) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Example 11 Polycarbonate pellets were continuously put into a single-screw extruder having a shaft diameter of 50 mm, and extruded in a molten state at a cylinder temperature of 280 ° C.
  • pellets of the resin composition (I-1) were continuously put into a single-screw extruder having a shaft diameter of 30 mm and extruded in a molten state at a cylinder temperature of 220 ° C.
  • the molten polycarbonate and the resin composition (I-1) are introduced into a junction block, laminated with a multi-manifold die set at 250 ° C., extruded into a sheet, and a resin composition (I-) having a thickness of 200 ⁇ m.
  • a laminated body having a thickness of 1000 ⁇ m formed of two layers of a layer made of 1) (first layer) and a layer made of polycarbonate having a thickness of 800 ⁇ m (second layer) was produced.
  • the evaluation results of such a laminated body are shown in Table 3.
  • Example 12 Polycarbonate pellets were continuously put into a single-screw extruder having a shaft diameter of 50 mm, and extruded in a molten state at a cylinder temperature of 280 ° C.
  • pellets of the resin composition (I-1) were continuously put into a single-screw extruder having a shaft diameter of 30 mm and extruded in a molten state at a cylinder temperature of 220 ° C.
  • the molten polycarbonate and the resin composition (I-1) are introduced into a junction block, laminated with a multi-manifold die set at 250 ° C., extruded into a sheet, and a resin composition (I-) having a thickness of 50 ⁇ m.
  • a laminate having a thickness of 3000 ⁇ m formed of two layers of a layer made of 1) (first layer) and a layer made of polycarbonate having a thickness of 2950 ⁇ m (second layer) was produced.
  • the evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 1 A layer made of a resin composition (I-7) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-7) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 2 A layer made of a resin composition (I-8) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-8) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 3 A layer made of a resin composition (I-9) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-9) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 4 A layer made of a resin composition (I-10) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-10) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 5 A layer made of a resin composition (I-11) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-11) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 6 A layer made of a resin composition (I-16) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-16) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • Comparative Example 7 A layer made of a resin composition (I-17) having a thickness of 80 ⁇ m as in Example 1 except that the resin composition (I-17) was used instead of the resin composition (I-1) of Example 1.
  • a laminate having a total thickness of 1000 ⁇ m was produced, which was composed of a layer made of polycarbonate having a thickness of 920 ⁇ m and a thickness of 920 ⁇ m. The evaluation results of such a laminated body are shown in Table 3.
  • the laminates of the present invention are resin compositions (I-1) containing an acrylic copolymer having excellent heat resistance and low water absorption.
  • (I-6) the glass transition temperature difference and the saturated water absorption rate difference from the resin composition (T) containing polycarbonate are reduced, and the dimensional stability is excellent.
  • the resin composition is excellent in heat-resistant decomposition property and high pencil hardness, the laminate of the present invention is excellent in moldability and surface hardness. Furthermore, it has excellent weather resistance.
  • the laminate of the present invention is a resin composition (I-12) to which an elastomer or a methacrylic resin is added by containing an acrylic copolymer having excellent heat resistance, pencil hardness, and weather resistance. )-(I-15), there is no deterioration in performance.
  • the laminated bodies (Comparative Examples 1 to 4) using the resin compositions (I-7) to (I-10) having low heat resistance and water absorption deteriorate in dimensional stability.
  • the laminate (Comparative Example 5) using the resin composition (I-11) having low heat-resistant decomposition property deteriorates in moldability.
  • the laminates (Comparative Examples 6 and 7) using the resin compositions (I-16) and (I-17) containing the styrene-based copolymer have low surface hardness and poor weather resistance.
  • the laminate of the present invention has excellent appearance quality, dimensional stability, and surface hardness, and is used for a cover or housing of a display device, a window material or a cover for interior or exterior of a vehicle, or the like. Suitable for use.

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WO2025070509A1 (ja) 2023-09-27 2025-04-03 三菱瓦斯化学株式会社 多層体、および、ヘッドアップディスプレイ用防塵カバー
WO2025070510A1 (ja) 2023-09-27 2025-04-03 三菱瓦斯化学株式会社 多層体、および、ヘッドアップディスプレイ用防塵カバー
WO2025070511A1 (ja) 2023-09-27 2025-04-03 三菱瓦斯化学株式会社 多層体、および、ヘッドアップディスプレイ用防塵カバー

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WO2024101410A1 (ja) 2022-11-10 2024-05-16 三菱瓦斯化学株式会社 多層体およびヘッドアップディスプレイ用防塵カバー
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