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WO2017030147A1 - Composition de résine, article moulé et stratifié - Google Patents

Composition de résine, article moulé et stratifié Download PDF

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Publication number
WO2017030147A1
WO2017030147A1 PCT/JP2016/074019 JP2016074019W WO2017030147A1 WO 2017030147 A1 WO2017030147 A1 WO 2017030147A1 JP 2016074019 W JP2016074019 W JP 2016074019W WO 2017030147 A1 WO2017030147 A1 WO 2017030147A1
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Prior art keywords
resin composition
mass
resin
layer
composition according
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PCT/JP2016/074019
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English (en)
Japanese (ja)
Inventor
祐作 野本
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株式会社クラレ
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Priority to CN201680043738.3A priority Critical patent/CN107849327B/zh
Priority to JP2017535552A priority patent/JP6743024B2/ja
Priority to KR1020177027321A priority patent/KR102516911B1/ko
Publication of WO2017030147A1 publication Critical patent/WO2017030147A1/fr

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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
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/378—Thiols containing heterocyclic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/16—Syndiotactic

Definitions

  • the present invention relates to a resin composition comprising a methacrylic resin and a vinyl copolymer. Moreover, it is related with the molded article and laminated body containing the said resin composition.
  • a methacrylic resin excellent in transparency, scratch resistance, weather resistance and the like is useful as a material for a molded product used for an optical member, a lighting member, a signboard member, a decorative member, and the like.
  • a methacrylic resin has a low glass transition temperature of about 110 ° C.
  • a molded body made of the resin has a problem that it is easily deformed by heat.
  • a method for increasing the glass transition temperature of a methacrylic resin a method of polymer blending a methacrylic resin with a copolymer resin (SMA resin) composed of styrene and maleic anhydride is known.
  • Non-Patent Document 1 discusses polymer blends of various SMA resins having different copolymerization ratios of methacrylic resin and maleic anhydride.
  • An SMA resin containing 8 to 33% by mass of maleic anhydride is methacrylic resin. It has been reported that it is compatible with a resin and has a higher glass transition temperature than a methacrylic resin.
  • Patent Document 1 reports that a polymer blend of a copolymer of styrene, maleic anhydride, and methyl methacrylate and a methacrylic resin has a high glass transition temperature and low water absorption.
  • Patent Document 2 discloses a laminate including a layer made of a resin composition containing a methacrylic resin and an SMA resin and a layer made of a polycarbonate.
  • JP2015-105371A International Publication No. 2015/050051
  • the resin composition obtained by these methods has a problem that the surface hardness and chemical resistance decrease due to the influence of the SMA resin.
  • the composition ratio of the SMA resin it is possible to suppress a decrease in surface hardness and chemical resistance, but the glass transition temperature of the resulting resin composition becomes insufficient.
  • the present invention has been made in view of the above problems.
  • the object is to provide a resin composition containing a methacrylic resin and an SMA resin, which has high surface hardness, chemical resistance, and high glass transition temperature without deteriorating the high transparency characteristic of the methacrylic resin. And a molded article and a laminate comprising the same.
  • a methacrylic resin A containing 99% by mass or more of a structural unit derived from methyl methacrylate and a structure derived from at least an aromatic vinyl compound (b1) represented by the following general formula (1)
  • a resin composition comprising 10 to 95% by mass of a vinyl copolymer (B) comprising a unit and a structural unit derived from a cyclic acid anhydride (b2) represented by the following general formula (2).
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group.
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group.
  • [2] The resin composition according to [1], wherein the methacrylic resin (A) contains 99.5% by mass or more of a structural unit derived from methyl methacrylate.
  • [3] The resin composition as described in [1] or [2], wherein the methacrylic resin (A) has a triadic syndiotacticity (rr) of 50% or more.
  • the vinyl copolymer (B) contains 50 to 84% by mass of structural units derived from the aromatic vinyl compound (b1), and 15 to 49 structural units derived from the cyclic acid anhydride (b2).
  • the resin composition according to any one of [1] to [4] which is contained in an amount of 1% by mass and contains 1 to 35% by mass of structural units derived from the methacrylic acid ester (b3).
  • a molded article comprising the resin composition according to any one of [1] to [12].
  • the laminate according to [14] or [15] which has an absolute value of 30 ° C. or less of a difference in Tg between the thermoplastic resin composition (T) and the resin composition.
  • the laminate according to any one of [14] to [16] further comprising a scratch-resistant layer on at least one surface.
  • the resin composition according to the present invention is a resin composition containing a methacrylic resin and an SMA resin, and has high surface hardness, chemical resistance, and high glass transition temperature without reducing the high transparency characteristic of the methacrylic resin.
  • the resin composition and a molded product and a laminate including the resin composition can be provided.
  • the numerical value specified by this specification shows the value obtained when it measures by the method described in the Example mentioned later.
  • the weight average molecular weight Mw is a standard polystyrene conversion value measured by GPC (gel permeation chromatography), and shows a value obtained when measured by the method described in Examples described later.
  • the numerical values “A to B” specified in the present specification indicate ranges that are larger than the numerical values A and A and satisfy the values smaller than the numerical values B and B.
  • the resin composition of the present invention comprises a methacrylic resin (A), a structural unit derived from an aromatic vinyl compound (b1) represented by the following general formula (1), and a cyclic acid anhydride represented by the following general formula (2) It contains a vinyl copolymer (B) containing a structural unit derived from (b2) (hereinafter referred to as “SMA resin (B)”).
  • SMA resin (B) a vinyl copolymer containing a structural unit derived from (b2)
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group.
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group.
  • the content of the methacrylic resin (A) in the resin composition of the present invention is in the range of 5 to 90% by mass.
  • the content of the methacrylic resin (A) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and 30% by mass. The above is most preferable.
  • the content of the methacrylic resin (A) in the resin composition is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less, Most preferably, it is at most mass%.
  • the layer composed of the resin composition of the present invention has excellent scratch resistance when the content of the methacrylic resin (A) in the resin composition is 5% by mass or more, and is 90% by mass or less. When laminated with other layers, the occurrence of warpage under high temperature and high humidity can be suppressed.
  • the methacrylic resin (A) is 99% by mass or more, preferably 99.5% by mass or more, more preferably a structural unit derived from methyl methacrylate (hereinafter referred to as “MMA”) among all monomer units. Contains 100% by mass.
  • MMA methyl methacrylate
  • the content of the structural unit derived from MMA of the methacrylic resin (A) is obtained by subjecting the resin purified by reprecipitation of the methacrylic resin (A) in methanol to pyrolysis and volatile components using pyrolysis gas chromatography. Can be calculated from the ratio of the peak areas of the obtained MMA and the copolymerization component (mainly methyl acrylate).
  • the methacrylic resin (A) contained in the resin composition of the present invention can contain a structural unit derived from a monomer other than MMA at 1% by mass or less, among all monomer units.
  • the structural unit is preferably not included.
  • Examples of the monomer include structural units derived from methacrylic acid esters other than MMA.
  • Examples of the methacrylic acid ester include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, methacrylic acid.
  • Methacrylic acid alkyl esters such as 2-ethylhexyl acid, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclomethacrylate [5. 2.1.0 2,6] cycloalkyl methacrylate esters such as deca-8-yl; methacrylic acid aryl esters such as phenyl methacrylate; meta Methacrylic acid aralkyl esters such as acrylic acid benzyl; and the like.
  • ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferred.
  • the content of structural units derived from methacrylic esters other than MMA in the methacrylic resin (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and derived from methacrylic esters other than MMA. Most preferably, no structural unit is included.
  • examples of the monomer include structural units derived from monomers other than methacrylic acid esters.
  • Such other monomers include methyl acrylate (hereinafter referred to as “MA”), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-acrylate Butyl, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic Cyclohexyl acid, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate,
  • MA ethyl acrylate, n-propyl acrylate, acrylic acid Acrylic esters such as isopropyl, n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate are preferred, MA and ethyl acrylate are more preferred, and MA is most preferred.
  • the total content of structural units derived from these other monomers in the methacrylic resin (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and other single quantities other than methacrylic acid esters. Most preferably, it does not contain structural units derived from the body.
  • the methacrylic resin (A) can be obtained by polymerizing MMA alone or other monomer which is an optional component.
  • a plurality of types of monomers in such polymerization usually, such a plurality of types of monomers are mixed to prepare a monomer mixture and then subjected to polymerization.
  • radical polymerization is preferably performed by a method such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method from the viewpoint of productivity.
  • the lower limit of the triplet-represented syndiotacticity (rr) is preferably 50% or more, more preferably 51% or more, and further preferably 52% or more. preferable.
  • the resin composition of the present invention has excellent heat resistance.
  • syndiotacticity (rr) in triplet display is a chain of three consecutive structural units (triplet, triad). ) Is a ratio in which both chains (doublet, diad) are racemo (represented as rr).
  • meo those having the same configuration
  • racemo those opposite to each other are referred to as “racemo”, which are expressed as m and r, respectively.
  • the syndiotacticity (rr) (%) of the methacrylic resin (A) was determined by measuring a 1 H-NMR spectrum at 30 ° C. in deuterated chloroform and setting tetramethylsilane (TMS) to 0 ppm from the spectrum.
  • TMS tetramethylsilane
  • the area (X) of the region of 0.6 to 0.95 ppm and the area (Y) of the region of 0.6 to 1.35 ppm are measured and calculated by the formula: (X / Y) ⁇ 100 be able to.
  • the weight average molecular weight (hereinafter referred to as “Mw”) of the methacrylic resin (A) 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 of the present invention is excellent in mechanical strength, and when it is 500,000 or less, the compatibility with the SMA resin is good, and the resin of the present invention. Transparency of the molded body made of the composition can be increased.
  • the glass transition temperature of the methacrylic resin (A) is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher.
  • the glass transition temperature in this specification is a temperature when it measures with the temperature increase rate of 10 degree-C / min using a differential scanning calorimeter, and is calculated by the midpoint method.
  • the saturated water absorption in 23 ° C. water of the methacrylic resin (A) is preferably 2.5% by mass or less, more preferably 2.3% by mass or less, and 2.1% by mass or less. Further preferred.
  • the resin composition of the present invention has excellent moisture resistance and can suppress warping of the laminate due to moisture absorption.
  • the saturated water absorption in this specification is the mass at the time when the molded product is immersed in 23 ° C. distilled water with respect to the mass of the molded product vacuum-dried for 3 days or more, the mass is measured over time, and the equilibrium is reached. It is a value measured as the rate of increase of.
  • the melt flow rate (hereinafter referred to as “MFR”) of the methacrylic resin (A) is preferably in the range of 1 to 10 g / 10 minutes.
  • the lower limit value of MFR is more preferably 1.2 g / 10 minutes or more, and further preferably 1.5 g / 10 minutes.
  • the upper limit value of MFR is more preferably 7.0 g / 10 min or less, and further preferably 4.0 g / 10 min or less.
  • the MFR of the resin composition of the present invention is a value measured using a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg.
  • the content of the SMA resin (B) in the resin composition of the present invention is in the range of 10 to 95% by mass.
  • the content of the SMA resin (B) in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and 40% by mass or more. Most preferably. Further, the content of the SMA resin (B) in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and 70% by mass. % Is most preferred.
  • the laminate of the present invention is laminated with another layer because the content of the SMA resin (B) in the resin composition is 10% by mass or more, the occurrence of warpage under high temperature and high humidity can be suppressed, It is excellent in abrasion resistance because it is 95% by mass or less.
  • the SMA resin (B) is a vinyl copolymer (B) comprising at least a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a cyclic acid anhydride.
  • Examples of the alkyl group independently represented by R 1 and R 2 in the general formula (1) and R 3 and R 4 in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl Group, decyl group, dodecyl group and the like, preferably an alkyl group having 12 or less carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group
  • R 1 is preferably a hydrogen atom, a methyl group, an ethyl group or a t-butyl group.
  • R 2 , R 3 and R 4 are preferably a hydrogen atom, a methyl group and an ethyl group.
  • the content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and 60% by mass or more. More preferably. Further, the content of the structural unit derived from the aromatic vinyl compound (b1) in the SMA resin (B) is preferably 84% by mass or less, more preferably 82% by mass or less, and 80% by mass or less. More preferably. When the content is in the range of 50 to 84% by mass, the resin composition of the present invention is excellent in moisture resistance and transparency.
  • the aromatic vinyl compound (b1) in the SMA resin (B) is used.
  • the content of the structural unit derived from) is preferably in the range of 50 to 85% by mass.
  • aromatic vinyl compound (b1) examples include styrene; alkyl substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene; ⁇ -methylstyrene , ⁇ -alkyl-substituted styrene such as 4-methyl- ⁇ -methylstyrene; and styrene is preferable from the viewpoint of availability.
  • aromatic vinyl compounds (b1) may be used alone or in combination of two or more.
  • the content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 15% by mass or more, more preferably 18% by mass or more, and 20% by mass or more. More preferably.
  • the content of the structural unit derived from the cyclic acid anhydride (b2) in the SMA resin (B) is preferably 49% by mass or less, more preferably 45% by mass or less, and 40% by mass or less. More preferably. When the content is in the range of 15 to 49% by mass, the resin composition of the present invention is excellent in heat resistance and transparency.
  • the SMA resin (B) consists of only two monomers, the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2), the cyclic acid anhydride (b2) in the SMA resin (B)
  • the content of the structural unit derived from is preferably in the range of 15 to 50% by mass
  • Examples of the cyclic acid anhydride (b2) include maleic anhydride, citraconic anhydride, and dimethylmaleic anhydride, and maleic anhydride is preferable from the viewpoint of availability.
  • a cyclic acid anhydride (b2) may be used individually by 1 type, or may use multiple types together.
  • the SMA resin (B) preferably contains a structural unit derived from the methacrylic acid ester (b3) in addition to the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2).
  • the content of the structural unit derived from the methacrylic acid ester (b3) in the SMA resin (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass or more. Even more preferably, it is most preferably 10% by mass or more.
  • the content of the structural unit derived from the methacrylic acid ester (b3) in the SMA resin (B) is preferably 35% by mass or less, more preferably 30% by mass or less, and 26% by mass or less. More preferably it is. When the content is in the range of 1 to 35% by mass, the transparency and thermal stability are further improved.
  • Examples of the methacrylic acid ester (b3) include MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate t -Butyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate; and the like.
  • methacrylic acid esters methacrylic acid alkyl esters having 1 to 7 carbon atoms in the alkyl group are preferable, and MMA is particularly preferable because the obtained SMA resin is excellent in heat resistance and transparency.
  • methacrylic acid ester may be used individually by 1 type, or may use multiple types together.
  • the SMA resin (B) may have a structural unit derived from another monomer other than the aromatic vinyl compound (b1), the cyclic acid anhydride (b2), and the methacrylic acid ester (b3).
  • Such other monomers include MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate.
  • the content of the structural unit derived from the other monomer in the SMA resin (B) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
  • the SMA resin (B) is obtained by polymerizing at least the monomers of the aromatic vinyl compound (b1) and the cyclic acid anhydride (b2).
  • the monomer may be polymerized by adding the methacrylic acid ester (b3) and other optional monomers.
  • the monomers to be used are mixed to prepare a monomer mixture and then subjected to polymerization.
  • radical-polymerize by methods, such as a block polymerization method and a solution polymerization method.
  • the Mw of the SMA resin (B) is preferably in the range of 40,000 to 300,000.
  • the resin composition of the present invention is excellent in mechanical strength, and when it is 300,000 or less, the compatibility with the methacrylic resin is improved, and the resin composition of the present invention.
  • the transparency of a molded product made of a product can be increased.
  • the glass transition temperature of the SMA resin (B) is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 125 ° C. or higher.
  • the resin composition of the present invention has excellent heat resistance, and the warpage of the laminate due to heat can be suppressed.
  • the saturated water absorption of the SMA resin (B) in 23 ° C. water is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and 0.6% by mass or less. Further preferred.
  • the resin composition of the present invention has excellent moisture resistance and can suppress warping of the laminate due to moisture absorption.
  • the MFR of the SMA resin (B) is preferably in the range of 1 to 10 g / 10 minutes.
  • the lower limit value of MFR is more preferably 1.2 g / 10 minutes or more, and further preferably 1.5 g / 10 minutes.
  • the upper limit value of MFR is more preferably 7.0 g / 10 min or less, and further preferably 4.0 g / 10 min or less.
  • the mass ratio of the methacrylic resin (A) and the SMA resin (B) contained in the resin composition of the present invention suppresses the occurrence of warpage at high temperatures and is transparent. From the viewpoint of scratch resistance, it is preferably in the range of 5/95 to 90/10.
  • the mass ratio is more preferably 10/90 or more, further preferably 15/85 or more, and particularly preferably 20/80 or more. Further, the mass ratio is more preferably 85/15 or less, further preferably 80/20 or less, and particularly preferably 75/25 or less.
  • a melt mixing method for example, a solution mixing method, or the like can be used.
  • a melt mixing method for example, using a melt kneader such as a uniaxial or multiaxial kneader, an open roll, a Banbury mixer, a kneader, and the like, under an inert gas atmosphere such as nitrogen gas, argon gas, helium gas, etc. Perform melt-kneading.
  • the methacrylic resin (A) and the SMA resin (B) are dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran, or methyl ethyl ketone.
  • the resin composition of the present invention may contain a polymer other than the methacrylic resin (A) and the SMA resin (B) as long as the effects of the present invention are not impaired.
  • examples of such other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene, ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide elastomer Polyamides such as polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide
  • the resin composition of the present invention may contain various additives as necessary.
  • additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, and light diffusing agents. , Matting agents, impact resistance modifiers, phosphors and the like.
  • the content of these additives can be appropriately set within a range not impairing the effects of the present invention.
  • the content of the antioxidant is 0.01 to 1 part by mass with respect to 100 parts by mass of the resin composition
  • Absorber content is 0.01-3 parts by weight
  • light stabilizer content is 0.01-3 parts by weight
  • lubricant content is 0.01-3 parts by weight
  • dye / pigment content is 0.
  • the content is 0.01 to 3 parts by mass.
  • An antioxidant is effective in preventing oxidative degradation of a resin alone in the presence of oxygen.
  • phosphorus antioxidants for example, phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, amine antioxidants and the like can be mentioned.
  • a phosphorus-based antioxidant and a phenol-based antioxidant are preferable, and a combined use of a phosphorus-based antioxidant and a phenol-based antioxidant is more preferable.
  • a phosphorus antioxidant and a phenolic antioxidant it is preferable to use a phosphorus antioxidant / phenolic antioxidant at a mass ratio of 0.2 / 1 to 2/1. It is more preferable to use 5/1 to 1/1.
  • phosphorus antioxidants examples include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (“ADEKA STAB HP-10” manufactured by ADEKA Corporation), tris (2,4-di-t-butyl). Phenyl) phosphite (“IRGAFOS168” manufactured by BASF Japan Ltd.), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9 -Diphosphaspiro [5.5] undecane (“ADEKA STAB PEP-36” manufactured by ADEKA Corporation) is preferable.
  • IRGANOX1010 pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
  • IRGANOX1076 octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate
  • the thermal degradation of the resin can be prevented by supplementing polymer radicals generated when exposed to high temperatures under substantially oxygen-free conditions.
  • the thermal degradation inhibitor include 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (“Sumilyzer GM” manufactured by Sumitomo Chemical Co., Ltd.), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (“Sumilyzer GS” manufactured by Sumitomo Chemical Co., Ltd.) is preferred.
  • the 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, succinic anilides, malonic esters, formamidines, and the like.
  • benzotriazoles, triazines, or 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.
  • These ultraviolet absorbers may be used alone or in combination of two or more.
  • Benzotriazoles are preferable as ultraviolet absorbers used when the resin composition of the present invention is applied to optical applications because it has a high effect of suppressing deterioration of optical properties such as coloring due to ultraviolet irradiation.
  • benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name “TINUVIN329” manufactured by BASF Japan Ltd.), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name “TINUVIN234” manufactured by BASF Japan Ltd.), 2,2′-methylenebis [6- ( 2H-benzotriazol-2-yl) -4-tert-octylphenol] (“ADEKA STAB LA-31” manufactured by ADEKA Corporation) is preferable.
  • a triazine UV absorber is preferably used.
  • an ultraviolet absorber 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (“ADEKA STAB LA-F70” manufactured by ADEKA Corporation) And hydroxyphenyltriazine-based ultraviolet absorbers (“TINUVIN477” and “TINUVIN460” manufactured by BASF Japan Ltd.) which are analogs thereof.
  • the ultraviolet absorber containing sulfur in the skeleton can increase the refractive index of the resin composition in addition to the ultraviolet absorbing ability, it is preferable when the resin composition of the present invention is applied to optical applications.
  • the ultraviolet absorber containing sulfur in the skeleton include 2- (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (Compound A) as benzotriazoles, 2- (5-dodecylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (Compound B).
  • the ultraviolet absorber containing sulfur in the skeleton can increase the refractive index of the resin composition, it may have absorption in the visible light region having a wavelength of 380 nm or more, which causes the resin composition to be colored. There is. Therefore, it is preferable to use together with other ultraviolet absorbers.
  • the ultraviolet absorber contained is labeled [3], for example, [1] and [2]; [1] and [3]; [2] and [3]: [1], [2] and [3] A combination of; Furthermore, [4] may be used in combination with an ultraviolet absorber not corresponding to any of [1] to [3].
  • the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
  • Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6 monotetraalkylpiperidine skeleton. Examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (“ADEKA STAB LA-77Y” manufactured by ADEKA Corporation).
  • Lubricants are compounds that are said to have the effect of improving mold releasability and workability by adjusting the slip between the polymer and the metal surface and preventing adhesion and adhesion.
  • examples thereof include higher alcohols, hydrocarbons, fatty acids, fatty acid metal salts, aliphatic amides, fatty acid esters and the like.
  • aliphatic monohydric alcohols having 12 to 18 carbon atoms are preferred from the viewpoint of compatibility with the resin composition of the present invention. Examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.
  • the methacrylic resin (A) may be added even when the methacrylic resin (A) and / or SMA resin (B) is polymerized. And it may add when mixing SMA resin (B), or may add after mixing methacryl resin (A) and SMA resin (B).
  • the glass transition temperature of the resin composition of the present invention is preferably in the range of 115 to 160 ° C.
  • the lower limit of the glass transition temperature is more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and most preferably 140 ° C. or higher.
  • the upper limit value of the glass transition temperature is more preferably 155 ° C. or less, and further preferably 150 ° C. or less.
  • the saturated water absorption in 23 ° C. water of the resin composition of the present invention is preferably 1.9% by mass or less, more preferably 1.5% by mass or less, and 1.0% by mass or less. Is more preferable.
  • the saturated water absorption is 1.9% by mass or less, the resin composition of the present invention has excellent moisture resistance, and the warpage of the laminate due to moisture absorption can be suppressed.
  • the MFR of the resin composition of the present invention is preferably in the range of 1 to 10 g / 10 minutes.
  • the lower limit value of MFR is more preferably 1.5 g / 10 min or more, and further preferably 2.0 g / 10 min.
  • the upper limit value of MFR is more preferably 7.0 g / 10 min or less, and further preferably 4.0 g / 10 min or less.
  • the resin composition of the present invention is formed by extrusion molding methods such as co-extrusion molding, T-die lamination molding, and extrusion coating; insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, Various molded products can be obtained by heat-melt molding by an injection molding method such as an injection breath molding method; blow molding method; calendar molding method; press molding method; slush molding method.
  • the resin composition of the present invention is also suitable for the production of molded products that require high temperature and long-term residence conditions because gels are unlikely to form even when melt molded for a long time at high temperatures.
  • the resin composition of the present invention is suitable for production of thin and wide molded articles such as sheets, films, and plates.
  • the laminate of the present invention has at least one layer composed of the resin composition of the present invention (hereinafter also referred to as resin composition [C1]) and at least one layer composed of another material.
  • resin composition [C1] the resin composition of the present invention
  • Other materials used for the laminate of the present invention are not particularly limited. Examples thereof include organic materials such as resins; inorganic materials such as simple metals and metal oxides.
  • the laminate according to an embodiment of the present invention has at least one layer made of the resin composition [C1] and at least one layer made of the resin composition [C2] which is another layer.
  • Resin contained in the resin composition [C2] is not particularly limited.
  • the resin include polyolefin such as polyethylene and polypropylene, polystyrene, (meth) acrylic resin, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyfluoride.
  • Resin of resin composition [C2] can be used individually by 1 type or in combination of 2 or more types. Of these, thermoplastic resins are preferable, and polycarbonate is more preferable.
  • the amount of polycarbonate contained in the resin composition [C2] is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably.
  • the weight average molecular weight of the polycarbonate is preferably 20,000 to 100,000. When the weight average molecular weight of the polycarbonate is within the above range, the heat resistance and impact resistance of the resin composition [C2] are improved, and a laminated sheet comprising the resin composition [C1] and the resin composition [C2] is obtained. It can be manufactured with excellent moldability and high productivity.
  • the polycarbonate has Mw / Mn of preferably 1.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0.
  • polycarbonate Commercially available products may be used as the polycarbonate.
  • “Taflon (registered trademark)” manufactured by Teijin Chemicals Ltd. and “Panlite (registered trademark)” manufactured by Teijin Chemicals Ltd. can be suitably used.
  • the resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a glass transition temperature of 130 to 160 ° C.
  • the thermoplastic resin composition (T) is preferably a resin composition containing polycarbonate.
  • the glass transition temperature of resin composition [C2] is comparable as the glass transition temperature of resin composition [C1].
  • of the difference between the glass transition temperature of the resin composition [C2] and the glass transition temperature of the resin composition [C1] is preferably 30 ° C. or less, more preferably 20 ° C. or less. .
  • is 30 ° C. or lower, the effect of suppressing the occurrence of warpage of the laminate under high temperature and high humidity becomes higher.
  • the resin composition [C2] used in the present invention is preferably a thermoplastic resin composition (T) having a saturated water absorption rate of 0.1 to 1.0% by mass in 23 ° C. water.
  • the thermoplastic resin composition (T) is preferably a resin composition containing polycarbonate.
  • the resin composition [C2] has the same saturated water absorption as that of the resin composition [C1].
  • of the difference between the saturated water absorption rate of the resin composition [C2] and the saturated water absorption rate of the resin composition [C1] is preferably 1.5% by mass or less. Is 1.0 mass% or less. When the saturated water absorption difference between the two resins is 1.5% by mass or less, the effect of suppressing the occurrence of warpage of the laminate under high temperature and high humidity becomes higher.
  • the resin composition used in the present invention [C2] have a melt volume rate (hereinafter, referred to as "MVR") is preferably a thermoplastic resin composition in the range of 1 ⁇ 30cm 3/10 min (T) .
  • the MVR is more preferably in the range of 3 ⁇ 20cm 3/10 minutes, more preferably in the range of 6 ⁇ 10cm 3/10 minutes.
  • MVR in this specification is measured using a melt indexer under conditions of a temperature of 300 ° C. and a load of 1.2 kg.
  • the resin composition [C2] used in the present invention may contain a known additive in order to improve heat decomposition resistance, heat discoloration resistance, light resistance and the like.
  • Additives include antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes , Matting agents, impact resistance modifiers, phosphors and the like.
  • the laminate according to another embodiment of the present invention includes at least one layer [L1] composed of the resin composition [C1], at least one layer [L2] composed of the resin composition [C2], and at least one function. And a property-imparting layer [L3].
  • the functionality-imparting layer [L3] is not particularly limited. Examples thereof include a scratch-resistant layer, a hard coat 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 functional layer [L3] can be formed by a known method.
  • the hard coat layer can be obtained by applying a resin solution for hard coat, drying and curing.
  • the antireflection layer can be obtained by laminating a low refractive index film and a high refractive index film by vapor deposition or the like.
  • the scratch-resistant layer, the hard coat layer, the antistatic layer, the antifouling layer, the friction reducing layer, the antiglare layer, the antireflection layer and the like are generally on the outermost side of the laminate.
  • Only 1 type may be provided for functional provision layer [L3], and multiple types may be provided.
  • the laminate of the present invention preferably has a scratch-resistant layer on at least one surface.
  • the layer structure in the laminate of the present invention is not particularly limited.
  • the layer composed of the resin composition [C1] is the [L1] layer
  • the layer composed of the resin composition [C2] is the [L2] layer
  • the functional layer [L3] is “ For example, [L1] layer / [L2] layer, [L1] layer / [L2] layer / [L1] layer, [L2] layer / [L1] layer / [L2] layer, [L1] layer / [L2] layer / [L1] layer / [L2] layer / [L1] layer, [L1] layer / [L2] layer / [L3] layer, [L3] layer / [L1] layer / [ [L2] layer, [L3] layer / [L1] layer / [ [L2] layer, [L3] layer / [L1] layer / [ [L2] layer, [L3] layer / [L1] layer / [
  • [L3] layer / [L1] layer / [L2] layer when the [L3] layer is a hard coat layer, [L3] layer / [L1] layer / [L2] layer / [L3] layer, L3] layer / [L1] layer / [L2] layer / [L1] layer / [L3] layer are preferable.
  • the present invention is useful in a laminate having a shape such as a sheet, a thin plate, or a film.
  • the laminated body which concerns on this invention as a protective cover, it arrange
  • a laminate having a layer configuration of [L1] layer / [L2] layer is arranged in the order of [L1] layer / [L2] layer / protected surface, or [L1] layer / [L2] layer / [ It is preferable to arrange the laminated body having the layer configuration of the L1 layer in the order of [L1] layer / [L2] layer / [L1] layer / protected surface.
  • the total thickness of the laminate according to the present invention can be set depending on the application, but is preferably 0.2 to 2 mm, more preferably 0.3 to 1.5 mm. If it is too thin, the rigidity tends to be insufficient. If it is too thick, it tends to hinder weight reduction of liquid crystal display devices.
  • the thickness of the layer made of the resin composition [C1] in the laminate according to the present invention is preferably in the range of 0.02 to 0.5 mm.
  • the lower limit value of the thickness of the layer is more preferably 0.03 mm or more, and further preferably 0.05 mm or more.
  • the upper limit value of the thickness of the layer is more preferably 0.3 mm or less, and further preferably 0.1 mm or less.
  • the laminate according to the present invention is preferably arranged in a lamination order that is symmetric in the thickness direction, and more preferably, the thickness of each layer is also symmetric. .
  • the laminate according to the present invention is not particularly limited by the production method, and can be produced by a multilayer molding method such as multilayer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding, or the like. .
  • multilayer extrusion molding of the resin composition [C1] and the resin composition [C2] is preferable from the viewpoint of productivity.
  • the method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for the production of multilayer laminates of thermoplastic resins is adopted, and includes, for example, a flat T die and a polishing roll having a mirror-finished surface. Molded by the machine.
  • a heat-melted resin composition [C1] and a resin composition [C2] are laminated before the T die is flown, or a resin composition [C1] and a resin composition [C2].
  • the resin composition [C1] and the resin composition [C2] are preferably melt filtered through a filter before multilayer molding.
  • a filter used for melt filtration is not particularly limited.
  • the filter is appropriately selected from known ones in terms of operating temperature, viscosity, required filtration accuracy, and the like.
  • Specific examples of the filter include nonwoven fabric made of polypropylene, cotton, polyester, viscose rayon, glass fiber, etc .; phenol resin impregnated cellulose film; metal fiber nonwoven fabric sintered film; metal powder sintered film; wire mesh; Can be mentioned.
  • a plurality of laminated metal fiber nonwoven fabric sintered films it is preferable to use a plurality of laminated metal fiber nonwoven fabric sintered films.
  • the resin composition of the present invention has excellent transparency, surface hardness and heat resistance. Therefore, a molded product and a laminate obtained by melt-molding the resin composition according to the present invention have good appearance, excellent scratch resistance, and small dimensional change, and therefore can be suitably used for optical members and the like. it can.
  • Examples of uses of the molded product, molded product and laminate according to the present invention include billboard components such as advertising towers, stand billboards, sleeve billboards, field billboards, and rooftop billboards; display components such as showcases, partition plates, and store displays.
  • billboard components such as advertising towers, stand billboards, sleeve billboards, field billboards, and rooftop billboards
  • display components such as showcases, partition plates, and store displays.
  • the resin composition according to the present invention is injection molded under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 75 ° C., and a molding cycle of 1 minute.
  • a square test piece having a thickness of 2 mm and a side of 50 mm was obtained.
  • Each test piece was measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the method of JIS-K7361-1.
  • a test piece made of the resin composition according to the present invention was obtained by the same method as described above. Each test piece was measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of JIS-K7361.
  • a test piece made of the resin composition according to the present invention was obtained by the same method as described above. Each test piece was measured on the M scale using a Rockwell hardness tester DXT-FA manufactured by Toyo Seiki Co., Ltd. in accordance with the method of JIS-K7202-2.
  • ⁇ Glass transition temperature (Tg)> In accordance with JIS K7121, the resin composition according to the present invention was heated from room temperature to 250 ° C. at 20 ° C./min, held for 5 minutes, cooled to ⁇ 100 ° C. at 10 ° C./min, and then ⁇ 100 Differential scanning calorimetry (DSC) analysis was performed at a temperature condition where the temperature was raised from 10 ° C. to 250 ° C. at 10 / min. The midpoint glass transition temperature obtained from the DSC curve measured at the second temperature increase was adopted as the glass transition temperature in the present invention. Q-20 manufactured by TA INSTRUMENTS was used as a measuring device.
  • DSC Differential scanning calorimetry
  • a test piece made of the resin composition according to the present invention was obtained by the same method as described above.
  • the test piece was vacuum-dried for 24 hours under the conditions of a temperature of 80 ° C. and 5 mmHg.
  • the test piece was then allowed to cool in a desiccator.
  • the mass was measured.
  • this test piece was immersed in 23 degreeC distilled water.
  • the test piece was taken out of the water, the water adhering to the surface was wiped off, and the mass was measured.
  • the test piece was immersed in distilled water, and the mass was measured in the same manner as described above.
  • a test piece made of the resin composition according to the present invention was obtained by the same method as described above.
  • the sunscreen agent 0.05g shown in Table 1 was uniformly apply
  • ⁇ There is an attached white cloth trace, markedly whitened
  • methacrylic resin (A) and the vinyl copolymer (B) containing the resin composition according to the present invention the following materials were used.
  • Methacrylic resin (A2) Parapet made by Kuraray Co., Ltd.
  • Example 1a 70 parts by mass of methacrylic resin (A1) and 30 parts by mass of vinyl copolymer (B) were melt-kneaded at a cylinder temperature of 230 ° C. using a biaxial kneader. Thereafter, the molten resin was extruded to obtain a pellet-shaped resin composition [1].
  • the composition and properties of the resin composition [1] are shown in Table 2.
  • Example 2a Resin composition [2] was obtained in the same manner as in Example 1a, except that the composition ratio of the resin composition was 50 parts by mass of methacrylic resin (A1) and 50 parts by mass of vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [2].
  • Example 3a Resin composition [3] was obtained in the same manner as in Example 1a except that the composition ratio of the resin composition was 30 parts by mass of methacrylic resin (A1) and 70 parts by mass of vinyl copolymer (B). Table 2 shows the composition and physical properties of the resin composition [3].
  • the resin compositions according to the present invention maintained transparency compared to the resin compositions according to the present invention (Comparative Examples 1a to 6a). Since it has a high glass transition temperature, surface hardness and low saturated water absorption, it has excellent heat resistance, scratch resistance and moisture resistance. Moreover, it is excellent in chemical resistance.
  • the total light transmittance of the laminate according to the present invention was measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of JIS-K7361-1. Further, the haze of the laminate according to the present invention was measured using an apparatus similar to the total light transmittance based on the method of JIS-K7361. ⁇ when the total light transmittance is 90% or more and haze is 0.3% or less, ⁇ when the total light transmittance is 90% or more or haze is 0.3% or less, and the total light transmittance is less than 90% And the thing whose haze exceeds 0.3% was made into x.
  • a rectangular test piece having a short side of 65 mm and a long side of 110 mm is formed so that the direction perpendicular to the extrusion flow direction is the short side and the direction parallel to the extrusion flow direction is the long side. Cut out. After picking and hanging the short side of the test piece and leaving it in an environmental tester set at a temperature of 75 ° C. and a relative humidity of 50% for 4 hours, the test piece was allowed to cool to 25 ° C. Warped. This seems to be a warp caused by the influence of molding conditions.
  • test piece Place the test piece warped in a bow shape on the surface plate so that the end of the test piece is in contact with the surface plate (that is, the test piece is chevron-shaped), and the gap between the surface plate and the test piece is The maximum distance (usually, the vicinity of the center of the long side of the test piece is maximum) was measured using a gap gauge. This value was used as the initial warpage amount. Subsequently, the short side of the bowed test piece was picked and hung and left in an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85% for 72 hours. The specimen was allowed to cool in an environmental testing machine set at 25 ° C.
  • warpage change amount The absolute value of the amount of warp change was less than 0.5 mm, the case where the absolute value was less than 0.5 and less than 1.0 was ⁇ , and the case where the absolute value was 1.0 mm or more was x.
  • the laminate was cut into a square with a side of 50 mm and used as a test piece.
  • the sunscreen agent 0.05g shown in Table 1 is uniformly apply
  • ⁇ There is no attached white cloth trace, but slightly whitened
  • ⁇ There is an attached white cloth trace, markedly whitened
  • Example 1b Polycarbonate ("SD Polyca (registered trademark) PCX" manufactured by Sumika Stylon Polycarbonate Co., Ltd., the same shall apply hereinafter) to a single-screw extruder [I] with a shaft diameter of 150 mm set at a cylinder temperature of 245 to 260 ° C and a discharge rate of 430 kg / hour Of pellets were continuously charged.
  • the pellets of the resin composition [1] were continuously charged into a single screw extruder [II] with a shaft diameter of 65 mm set at a cylinder temperature of 215 to 230 ° C. and a discharge rate of 37 kg / hour.
  • a pleated cylindrical filter with a filter pore size of 20 ⁇ m (manufactured by Fuji Filter Industry Co., Ltd.), which is extruded from the extruder [I] and the extruder [II] simultaneously with the polycarbonate and the resin composition [1], and filled with the resin in advance. Is then introduced into the junction block, and then polycarbonate and resin composition [1] are co-extruded with a multi-manifold die (Nordson Co., Ltd.) having a resin discharge port width of 1600 mm and a lip interval of 2.0 mm at a temperature of 245 ° C. And made into a sheet. This sheet was formed into a bank between No. 1 and No.
  • Example 2b Except for changing the resin composition [1] to the resin composition [2], a layer composed of the resin composition [2] having a thickness of 80 ⁇ m and a layer composed of a polycarbonate having a thickness of 920 ⁇ m were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 ⁇ m was obtained.
  • Example 3b Except for changing the resin composition [1] to the resin composition [3], a layer composed of the resin composition [3] having a thickness of 80 ⁇ m and a layer composed of a polycarbonate having a thickness of 920 ⁇ m were prepared in the same manner as in Example 1b. A laminate having a total thickness of 1000 ⁇ m was obtained.
  • Example 1b a laminate was obtained in the same manner except that 1.0 part by mass of a benzotriazole-based ultraviolet absorber (LA31RG; manufactured by Adeka) was added per 100 parts by mass of the resin composition [1].
  • LA31RG benzotriazole-based ultraviolet absorber
  • ⁇ E of the polycarbonate layer by UV irradiation was 15 or more in Example 1b, but 0.5 or less in Example 1c.
  • Example 2c> A laminate was obtained in the same manner as in Example 1c, except that the resin composition [2] was used.
  • the ⁇ E of the polycarbonate layer was 15 or more in Example 2b, but 0.5 or less in Example 2c.
  • Example 3c> A laminate was obtained in the same manner as in Example 1c, except that the resin composition [3] was used.
  • the ⁇ E of the polycarbonate layer was 15 or more in Example 3b, but 0.5 or less in Example 3c.
  • Table 3 shows the evaluation results of Examples 1b to 3b and Comparative Examples 1b to 6b.
  • the laminates (Examples 1b to 3b) according to the present invention have high pencil hardness and chemical resistance while maintaining transparency. Furthermore, it turns out that the laminated body which concerns on this invention has few curvature even if it is left to stand under high temperature and high humidity.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Problème] Proposer une composition de résine caractérisée par une grande transparence, une grande dureté de surface et une grande résistance chimique, et qui présente aussi une température de transition vitreuse élevée. Il s'agit également de proposer un article moulé et un stratifié, qui utilisent cette composition de résine. [Solution] Une composition de résine qui contient : 5 à 90 % en poids de (A) une résine méthacrylique contenant au moins 99 % en poids d'un motif structural issu du méthacrylate de méthyle ; et 10 à 95 % en poids de (B) un copolymère de vinyle qui est composé d'au moins une unité structurale, issue d'un composé vinylique aromatique (b1) représenté par la formule générale (1), et d'une unité structurale issue d'un anhydride d'acide cyclique (b2) représenté par la formule générale (2). (Dans la formule générale (1), R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle) (Dans la formule générale (2), R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle) AA%%%Formule générale
PCT/JP2016/074019 2015-08-18 2016-08-17 Composition de résine, article moulé et stratifié WO2017030147A1 (fr)

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KR1020177027321A KR102516911B1 (ko) 2015-08-18 2016-08-17 수지 조성물, 성형품 및 적층체

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JP2017155184A (ja) * 2016-03-04 2017-09-07 住友化学株式会社 樹脂フィルム
WO2018084068A1 (fr) * 2016-11-01 2018-05-11 デンカ株式会社 Film décoratif
WO2018230260A1 (fr) * 2017-06-13 2018-12-20 リケンテクノス株式会社 Film multicouche
WO2020022426A1 (fr) * 2018-07-27 2020-01-30 株式会社クラレ Feuille multicouche à protection contre la lumière infrarouge et procédé de production associé
WO2020149254A1 (fr) * 2019-01-18 2020-07-23 株式会社クラレ Corps stratifié de résine extrudée et corps stratifié de résine extrudée fixé à un revêtement durci
CN111670105A (zh) * 2018-02-02 2020-09-15 三菱化学株式会社 三维造型用材料、三维造型用细丝、该细丝的卷绕体和三维打印机用盒
US11465323B2 (en) 2016-09-05 2022-10-11 Riken Technos Corporation Method for producing multilayer film

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JP6844570B2 (ja) * 2018-03-29 2021-03-17 信越化学工業株式会社 シリコーンゴム−シリコーン変性ポリイミド樹脂積層体
EP3978238A4 (fr) * 2019-05-31 2023-06-28 Kuraray Co., Ltd. Ionomère, feuille de résine et verre feuilleté
CN115427227B (zh) * 2020-04-22 2024-10-22 株式会社可乐丽 层叠体

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JP2003019759A (ja) * 2001-07-10 2003-01-21 Kuraray Co Ltd 活性エネルギー線硬化樹脂層を含む積層体の製造方法
WO2015050051A1 (fr) * 2013-10-02 2015-04-09 株式会社クラレ Stratifié
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JP2003019759A (ja) * 2001-07-10 2003-01-21 Kuraray Co Ltd 活性エネルギー線硬化樹脂層を含む積層体の製造方法
WO2015050051A1 (fr) * 2013-10-02 2015-04-09 株式会社クラレ Stratifié
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WO2017150153A1 (fr) * 2016-03-04 2017-09-08 住友化学株式会社 Film de résine
JP2017155184A (ja) * 2016-03-04 2017-09-07 住友化学株式会社 樹脂フィルム
US11465323B2 (en) 2016-09-05 2022-10-11 Riken Technos Corporation Method for producing multilayer film
WO2018084068A1 (fr) * 2016-11-01 2018-05-11 デンカ株式会社 Film décoratif
JPWO2018084068A1 (ja) * 2016-11-01 2019-09-19 デンカ株式会社 加飾フィルム
WO2018230260A1 (fr) * 2017-06-13 2018-12-20 リケンテクノス株式会社 Film multicouche
US11396165B2 (en) 2017-06-13 2022-07-26 Riken Technos Corporation Multilayer film
CN111670105A (zh) * 2018-02-02 2020-09-15 三菱化学株式会社 三维造型用材料、三维造型用细丝、该细丝的卷绕体和三维打印机用盒
WO2020022426A1 (fr) * 2018-07-27 2020-01-30 株式会社クラレ Feuille multicouche à protection contre la lumière infrarouge et procédé de production associé
JPWO2020022426A1 (ja) * 2018-07-27 2021-08-05 株式会社クラレ 赤外線遮蔽性積層シートとその製造方法
JP7329515B2 (ja) 2018-07-27 2023-08-18 株式会社クラレ 赤外線遮蔽性積層シートとその製造方法
WO2020149254A1 (fr) * 2019-01-18 2020-07-23 株式会社クラレ Corps stratifié de résine extrudée et corps stratifié de résine extrudée fixé à un revêtement durci
JPWO2020149254A1 (ja) * 2019-01-18 2021-11-25 株式会社クラレ 押出樹脂積層体及び硬化被膜付き押出樹脂積層体
JP7449873B2 (ja) 2019-01-18 2024-03-14 株式会社クラレ 押出樹脂積層体及び硬化被膜付き押出樹脂積層体

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TW201716493A (zh) 2017-05-16
KR20180041616A (ko) 2018-04-24
CN107849327B (zh) 2020-10-16

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