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WO2020241822A1 - Copolymère méthacrylique et article moulé - Google Patents

Copolymère méthacrylique et article moulé Download PDF

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Publication number
WO2020241822A1
WO2020241822A1 PCT/JP2020/021319 JP2020021319W WO2020241822A1 WO 2020241822 A1 WO2020241822 A1 WO 2020241822A1 JP 2020021319 W JP2020021319 W JP 2020021319W WO 2020241822 A1 WO2020241822 A1 WO 2020241822A1
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WO
WIPO (PCT)
Prior art keywords
mass
methacrylic copolymer
less
molecular weight
average molecular
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/JP2020/021319
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English (en)
Japanese (ja)
Inventor
伸崇 平岡
広大 松橋
英孝 田村
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
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Kuraray Co Ltd
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Priority to JP2021522896A priority Critical patent/JP7442520B2/ja
Publication of WO2020241822A1 publication Critical patent/WO2020241822A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to methacrylic copolymers and molded articles. More specifically, the present invention relates to a methacrylic copolymer having excellent fluidity during heat molding and less mold stain, and a molded product having high heat resistance and high mechanical strength.
  • Methacrylic resin has high transparency and is useful as a material for molded products used for optical members, lighting members, signboard members, decorative members and the like. In some fields where molded products of methacrylic resin are used, there is a demand for weight reduction or thinning of molded products. In order to obtain a thin-walled molded product, it is necessary for the methacrylic resin to have high fluidity when melted. As measures for increasing the fluidity of the resin, it is generally known to lower the softening temperature or the glass transition temperature, lower the molecular weight, widen the molecular weight distribution, and the like. However, when these measures are applied to methacrylic resin, the heat resistance is lowered and the mechanical strength is lowered. In consideration of such a situation, Cited Documents 1 to 3 propose various methacrylic resins and methods for producing the same.
  • An object of the present invention is to provide a methacrylic copolymer having excellent fluidity during heat molding and less mold stain, and a molded product having high heat resistance and high mechanical strength.
  • Weight average molecular weight Mw is 48,000-59000, The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2.1 or less, and the ratio Tg / R of the glass transition temperature Tg to the melt flow rate R under the conditions of 230 ° C. and a 3.8 kg load is 5.0.
  • thermoplastic resin composition containing the methacrylic copolymer according to [1] or [2] and acrylic rubber particles.
  • the amount of the acetone-insoluble content contained in the thermoplastic resin composition is 59% by mass or less, and the acetone-soluble content contained in the thermoplastic resin composition is under the conditions of 230 ° C. and a load of 3.8 kg.
  • the thermoplastic resin composition according to [3] or [4], wherein the ratio Tg / R of the glass transition temperature Tg to the melt flow rate R in the above is 6.0 to 1.5 ° C. for 10 minutes / g.
  • Weight average molecular weight Mw is 48,000-59000, The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2.1 or less, and the ratio Tg / R of the glass transition temperature Tg to the melt flow rate R under the conditions of 230 ° C. and a 3.8 kg load is 5.0.
  • the methacrylic copolymer of the present invention has excellent fluidity and is unlikely to cause molding defects such as silver streaks, cracks, sink marks, flow marks, resin burns, gas stains, and coloring.
  • the molding material containing the methacrylic copolymer of the present invention is suitable for injection molding.
  • the molding material containing the methacrylic copolymer of the present invention is suitable for obtaining a thin-walled molded product, for example, a plate having a thickness of 0.5 mm or less.
  • the molded product containing the methacrylic copolymer of the present invention has high heat resistance and mechanical strength, and has no appearance defects such as coloring.
  • the molding material containing the methacrylic copolymer of the present invention has low heat generation due to shearing, and an injection-molded product having a good appearance can be obtained even at a low temperature and a high injection pressure.
  • the methacrylic copolymer of the present invention comprises a monomer unit derived from methyl methacrylate and a monomer unit derived from an acrylic acid ester.
  • the content of the monomer unit derived from methyl methacrylate is 85.0 to 95.0% by mass, preferably 85.0 to 93.5% by mass, and more preferably 87.5 to 93.5% by mass. More preferably, it is 88 to 93.5% by mass.
  • the content of the monomer unit derived from the acrylic acid ester is 5.0 to 15.0% by mass, preferably 6.5 to 15.0% by mass, and more preferably 6.5 to 12.5% by mass. More preferably, it is 6.5 to 12% by mass.
  • the total of the monomer unit derived from methyl methacrylate and the monomer unit derived from the acrylic acid ester is preferably 99% by mass or more, preferably 100% by mass. Is more preferable.
  • Acrylate esters include acrylic acids such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, myristyl acrylate, dodecyl acrylate, palmityl acrylate, stearyl acrylate, and behenyl acrylate.
  • Acrylic acid branched alkyl ester such as isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate; Acrylic acid cyclic alkyl ester such as cyclohexyl acrylate; Acrylic acid aryl ester such as phenyl acrylate; benzyl acrylate and the like Acrylate aralkyl ester; etc.
  • acrylic acid linear, branched or cyclic alkyl esters are preferred, and acrylic acid linear alkyl esters are more preferred.
  • the alkyl group in the acrylic acid alkyl ester preferably has 1 to 18, more preferably 1 or 2, and even more preferably 1.
  • the methacrylic copolymer of the present invention may have a monomer unit other than a monomer unit derived from methyl methacrylate and a monomer unit derived from an acrylic acid ester, and such a single amount may be present.
  • an alkyl ester of acyclic C2 or more of methacrylic acid such as ethyl methacrylate, butyl butyl methacrylate, hexyl methacrylate, and heptyl methacrylate, preferably an alkyl ester of acyclic C2 or more and C7 or less of methacrylic acid; bicyclo methacrylate [3].
  • the methacrylic copolymer of the present invention has a weight average molecular weight Mw and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn, both of which are within the following ranges. That is, the methacrylic copolymer of the present invention has a weight average molecular weight Mw of 48,000 to 59000, preferably 48,000 to 55,000, and more preferably 49000 to 53000, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is Mw / Mn. However, it is 2.1 or less, preferably 1.7 or more and 2.0 or less.
  • the weight average molecular weight Mw and the number average molecular weight Mn are values calculated by converting the chart measured by gel permeation chromatography into the molecular weight of standard polystyrene.
  • the ratio Tg / R of the glass transition temperature Tg to the melt flow rate R under the conditions of 230 ° C. and a 3.8 kg load is preferably 5.0 to 1.5 ° C. for 10 minutes / g. Is 4.0 to 1.5 ° C. for 10 minutes / g, more preferably 3.5 to 1.5 ° C. for 10 minutes / g, and even more preferably 3.3 to 1.5 ° C. for 10 minutes / g. ..
  • the glass transition temperature is once raised to 230 ° C.
  • the DSC curve was measured under the condition that the temperature was raised from 1 to 230 ° C. at 10 ° C./min. It is an intermediate point glass transition temperature (Tmg) determined based on the DSC curve measured at the time of the second temperature rise.
  • Tmg intermediate point glass transition temperature
  • the lower limit of the melt flow rate R of the methacrylic copolymer of the present invention measured at 230 ° C. and a load of 3.8 kg is preferably 15 g / 10 minutes, more preferably 25 g / 10 from the viewpoint of moldability, toughness and the like. Minutes, with an upper limit of preferably 60 g / 10 minutes.
  • the amount of bound sulfur atom with respect to the monomer unit derived from methyl methacrylate is preferably 0.4 mol% or less, more preferably 0.3 to 0.38 mol%, still more preferably. It is 0.31 to 0.36 mol%.
  • the amount of sulfur bond is related to imparting good moldability, low mold stain, and high fluidity to the methacrylic copolymer.
  • the amount of bound sulfur atom is a value S p which is determined as follows. The methacrylic copolymer is dissolved in chloroform to obtain a solution. This solution is added to n-hexane to give a precipitate. The precipitate is dried at 80 ° C. for 12 hours or longer under vacuum.
  • An appropriate amount of the obtained dried product is precisely weighed, set in a sulfur combustion device, decomposed in a reactor having a temperature of 400 ° C., and the generated gas is passed through a furnace having a temperature of 900 ° C., and then 0.3% hydrogen peroxide solution is used. Absorb with.
  • the obtained liquid (decomposition gas aqueous solution) is appropriately diluted with pure water, and sulfate ions are quantified by ion chromatography (ICS-1500 manufactured by DIONEX, column: AS12A). From the mass W p (mass%) of sulfur atoms per mass of the dried product, the amount of bound sulfur atoms (mol%) with respect to the monomer unit derived from methyl methacrylate is calculated.
  • the method for producing the methacrylic copolymer of the present invention is not particularly limited.
  • it can be produced by a known polymerization reaction such as a radical polymerization reaction or an anionic polymerization reaction.
  • a radical polymerization reaction is preferable.
  • the polymerization reaction can be carried out by a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method.
  • the massive polymerization method is preferable because it contains less impurities.
  • the polymerization conversion rate is preferably 35 to 65%.
  • the bulk polymerization method is preferably carried out by a continuous flow method. In the continuous flow type massive polymerization method, the average residence time in the reactor is preferably 1.5 to 3 hours.
  • a preferred method for producing the methacrylic copolymer of the present invention is a monomer containing methyl methacrylate and an acrylic acid ester, preferably methyl methacrylate 81.0 to 94.2% by mass and an acrylic acid ester 5.8 to 19.
  • a monomer containing at least 0% by mass, more preferably a monomer containing 81.0 to 91.9% by mass of methyl methacrylate and 8.1 to 19.0% by mass of an acrylic acid ester are polymerized by a massive polymerization method. Including that.
  • Acrylic acid esters are involved in imparting high fluidity and high melt flow rate R to methacrylic copolymers.
  • the monomers used for polymerization include methacrylic acid acyclic C2 or more alkyl ester (preferably methacrylic acid acyclic C2 or more and C7 or less alkyl ester), methacrylic acid cyclic alkyl ester; Aromatic vinyl such as styrene and methylstyrene may be contained.
  • the content of these monomers other than methyl methacrylate and acrylic acid ester is preferably 1% by mass or less.
  • the total amount of methyl methacrylate and acrylic acid ester contained in the monomer to be polymerized is preferably 99% by mass or more, and more preferably 100% by mass.
  • the polymerization reaction is carried out using a polymerization initiator, a predetermined monomer, and if necessary, a chain transfer agent or the like.
  • the temperature at the time of polymerization is preferably 100 to 150 ° C, more preferably 110 to 140 ° C, and even more preferably 120 to 140 ° C. The lower the polymerization temperature, the higher the heat resistance of the methacrylic copolymer of the present invention tends to be.
  • the polymerization initiator used in the present invention is not particularly limited.
  • an azo-based polymerization initiator such as azobisisobutyronitrile
  • a peroxide-based polymerization initiator such as t-hexyl peroxyisopropyl monocarbonate and the like
  • the polymerization initiator used in the present invention preferably has a half-life of 1 second to 1 minute at the temperature at the time of polymerization. When the amount of the polymerization initiator used is small, the methacrylic copolymer of the present invention tends to have less mold stain.
  • azobisisobutyronitrile is preferably 0.02 parts by mass or less, more preferably 0 parts by mass, based on a total of 100 parts by mass of the monomers to be polymerized. It can be used in an amount of .002 parts by mass or more and 0.01 parts by mass or less.
  • the chain transfer agent used in the present invention is not particularly limited.
  • mercaptan chain transfer agents such as n-octyl mercaptan and n-dodecyl mercaptan; ⁇ -methylstyrene dimer; terpinolene and the like can be mentioned.
  • the amount of the chain transfer agent used is preferably 0.42 to 0.52 parts by mass with respect to a total of 100 parts by mass of the monomers to be polymerized. As the amount of the mercaptan chain transfer agent used increases, the amount of bound sulfur atoms with respect to the monomer unit derived from methyl methacrylate increases.
  • n-octyl mercaptan is preferably 0.3 mass by mass with respect to 100 parts by mass of the total amount of the monomers to be polymerized. It can be used in an amount of 0.6 parts by mass or more, more preferably 0.41 parts by mass or more and 0.50 parts by mass or less.
  • the unreacted monomer is preferably removed by a thermal devolatile method at a temperature of 220 to 260 ° C.
  • volatile components are removed from a device for heating a liquid containing a reaction product discharged from a reactor, for example, a heat exchanger and a liquid heated to a predetermined temperature by the device for heating.
  • An extruder with a vent for removal is preferably used.
  • a vented extruder usually consists of a cylinder and a screw.
  • the cylinder is provided with a hopper (introduction port for liquid including reaction products), a rear vent on the upstream side of the hopper, a front vent on the downstream side of the hopper, and a polymer discharge port on the most downstream side. Then, it is preferable to set the temperature and pressure in the hopper and the cylinder so that the liquid heated in the hopper evaporates in a flash. The removed volatile matter is discharged from the rear vent and the front vent. Then, it is preferable to add an inert gas such as nitrogen gas at the rear vent and / or the front vent to the volatile matter discharged through the rear vent and / or the front vent. Further, the screw may be either a single shaft type or a biaxial type.
  • the screw may, for example, have a smaller shaft diameter of the screw in that portion than that of the other portion so as to release pressure at the portion corresponding to the front vent.
  • a valve mechanism for providing a dynamic valve immediately before the front vent, or a bypass mechanism for providing a reverse screw portion on the screw immediately before the front vent and providing a bypass connecting immediately before and after the front vent in the cylinder may be provided.
  • thermoplastic resin composition of the present invention contains the methacrylic copolymer of the present invention and acrylic rubber particles.
  • the acrylic rubber particles include those composed of an outer layer made of a thermoplastic polymer (P) and an inner layer made of a crosslinked elastic body in contact with and covered with the outer layer, and the inner layer and the outer layer are a core and a shell. It is preferable that the above is formed.
  • the inner layer consists of a core and an inner shell.
  • the core (inner layer) is a crosslinked rubber polymer (Q)
  • the outer shell (outer layer) is a thermoplastic polymer (P)
  • the core (inner layer) is a crosslinked polymer (R).
  • -Inner shell (inner layer) is a crosslinked rubber polymer
  • Q) -Outer shell (outer layer) is a three-layer polymer of thermoplastic polymer (P)
  • core (inner layer) is a crosslinked rubber polymer (Q) -First
  • a four-layer polymer in which the inner shell (inner layer) is a crosslinked polymer (R) -the second inner shell (inner layer) is a crosslinked rubber polymer (Q) -the outer shell (outer layer) is a thermoplastic polymer (P).
  • 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 outer layer of the acrylic rubber particles is preferably 60/40 to 95/5, more preferably 70/30 to 90/10.
  • the ratio of the layer containing the crosslinked rubber polymer (Q) is preferably 20 to 70% by mass, more preferably 30 to 50% by mass.
  • the acrylic rubber particles have an average particle diameter of preferably 0.05 to 3 ⁇ m, more preferably 0.1 to 1 ⁇ m, and even more preferably 0.15 to 0.2 ⁇ m.
  • an average particle size within such a range particularly an average particle size of 0.15 to 0.2 ⁇ m, toughness can be exhibited with a small amount of compounding, and therefore rigidity and surface hardness are not impaired. ..
  • 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 (P) 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.
  • the thermoplastic polymer (P) 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 (P) is preferably 80 to 100% by mass with respect to the mass of the thermoplastic polymer (P). More preferably, it is 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 C1-8 alkyl ester), for example, methyl methacrylate is preferable.
  • the amount of the monofunctional monomer unit other than the methacrylic acid C1-8 alkyl ester constituting the thermoplastic polymer (P) is preferably 0 to 20% by mass with respect to the mass of the thermoplastic polymer (P). More preferably, it is 5 to 15% by mass.
  • monofunctional monomers other than methacrylic acid C1-8 alkyl ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and prol acrylate; aromatic vinyl such as styrene. Compounds can be mentioned.
  • the amount of the thermoplastic polymer (P) is preferably 40 to 75% by mass, more preferably 45 to 70% by mass, and further preferably 50 to 65% by mass with respect to the acrylic rubber particles.
  • the crosslinked elastic layer which is an inner layer, has an intermediate layer made of a crosslinked rubber polymer (Q) and an inner layer made of a crosslinked polymer (R) and covered in contact with the intermediate layer.
  • the crosslinked polymer (R) 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 (R) is preferably 40 to 98.5% by mass, more preferably 45 to 95% by mass, based on the mass of the crosslinked polymer (R).
  • the amount of the monofunctional monomer unit other than methyl methacrylate constituting the crosslinked polymer (R) is 1 to 59.5% by mass, preferably 5 to 55% by mass, based on the mass of the crosslinked polymer (R). %.
  • 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 (R) is preferably 0.05 to 0.4% by mass, more preferably 0.1 to 0.1, based on the mass of the crosslinked polymer (R). It is 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 (R) is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and further preferably 10 to 30% by mass with respect to the acrylic rubber particles.
  • the crosslinked rubber polymer (Q) 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 (Q) is preferable with respect to the mass of the crosslinked rubber polymer (Q). It is 85 to 99% by mass, more preferably 95 to 98% by mass.
  • 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.
  • the amount of the polyfunctional monomer unit constituting the crosslinked rubber polymer (Q) is preferably 1 to 1.7% by mass, more preferably 1.2 to 1% by mass, based on the mass of the crosslinked rubber polymer (Q). It is 1.6% by mass, more preferably 1.3 to 1.5% by mass.
  • Examples of the polyfunctional monomer include those mentioned in the crosslinked polymer (R).
  • the ratio of the mass of the polyfunctional monomer unit in the crosslinked rubber polymer (Q) to the mass of the polyfunctional monomer unit in the crosslinked polymer (R) is preferable. It is 0.05 to 0.25, more preferably 0.1 to 0.2.
  • the glass transition temperature of the crosslinked rubber polymer (Q) is preferably lower than the glass transition temperature of the crosslinked polymer (R).
  • the amount of the crosslinked rubber polymer (Q) is preferably 20 to 55% by mass, more preferably 25 to 45% by mass, and further preferably 30 to 40% by mass with respect to the amount of acrylic rubber particles.
  • the average diameter of the inner layer of the acrylic rubber particles is preferably 60 to 110 nm, more preferably 65 to 105 nm, and further preferably 70 to 100 nm.
  • the average diameter of the inner layer can be determined as follows. Using a hydraulic press molding machine, mold size 50 mm x 120 mm, press temperature 250 ° C, preheating time 3 minutes, press pressure 50 kg / cm 2 , press time 30 seconds, cooling temperature 20 ° C, cooling pressure 50 kg / cm 2. Under the condition that the cooling time is 10 minutes, the resin composition containing the acrylic rubber particles is molded into a flat plate having a thickness of 3 mm. Using a microtome, the obtained flat plate is cut at ⁇ 100 ° C.
  • the slice is dyed with ruthenium.
  • the dyed flakes are observed with a scanning transmission electron microscope (JSM7600F manufactured by JEOL Ltd.) at an accelerating voltage of 25 kV and a photograph is taken.
  • JSM7600F scanning transmission electron microscope
  • the acrylic rubber particles are not particularly limited depending on the production method thereof.
  • emulsion polymerization and the like can be mentioned.
  • the monomer (r) for forming the crosslinked polymer (R) is emulsion-polymerized to obtain a latex containing the crosslinked polymer (R), and the crosslinked rubber polymer (R) is obtained.
  • a monomer (q) for constituting Q) is added, and the monomer (q) is seed-emulsified polymerized to obtain a latex containing a crosslinked polymer (R) and a crosslinked rubber polymer (q).
  • a monomer (p) for forming a thermoplastic polymer (P) is added thereto, and the monomer (p) is seed-emulsified polymerized to obtain a latex containing acrylic rubber particles.
  • 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.
  • thermoplastic resin composition of the present invention can further contain an acrylic block copolymer.
  • the acrylic block copolymer is preferably composed of a polymer block (b1) having a methacrylic acid ester unit as a main component and a polymer block (b2) having an acrylic acid ester unit as a main component.
  • the number of polymer blocks (b1) in one molecule of the acrylic block copolymer may be 1, or may be 2 or more. Further, the number of polymer blocks (b2) in one molecule of the acrylic block copolymer may be 1, or may be 2 or more.
  • 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 for the polymer block (b1).
  • the amount of the polymer block (b1) contained in the acrylic block copolymer is preferable from the viewpoints of transparency, flexibility, bending resistance, impact resistance, flexibility, molding processability, surface smoothness, and the like. Is 40% by mass or more and 90% by mass or less, 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 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 monomer units 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 acrylic block copolymer is not particularly limited.
  • a block (b1) in which one end is connected (b1-b2-b1 triblock copolymer) is preferable.
  • the weight average molecular weight of the acrylic block copolymer is preferably 52,000 or more and 400,000 or less, and more preferably 60,000 or more and 300,000 or less. Further, in the acrylic block copolymer, the ratio of the weight average molecular weight to the number average molecular weight 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 acrylic block copolymer 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 acrylic block copolymer is not particularly limited depending on the production method thereof, and can be obtained by a known method.
  • a method including living polymerization of the monomers constituting each polymer block is generally used.
  • a living polymerization method a method including anionic polymerization in the presence of an organoalkali metal compound and an organoaluminum compound is a method in which the molecular weight and composition ratio can be easily controlled, the production cost, and the obtained acrylic block copolymer. It is preferable from the viewpoint of purity.
  • the amount of acetone insoluble matter contained in the thermoplastic resin composition of the present invention is preferably 59% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass.
  • the amount of acetone insoluble matter contained in the thermoplastic resin composition is determined as follows. 2 g (w0) of the precisely weighed thermoplastic resin composition is added to 50 ml of acetone, and the mixture is stirred at room temperature for 24 hours. The obtained liquid is placed in a centrifuge tube and centrifuged at 0 ° C. and 20000 rpm for 180 minutes. The supernatant is then removed by decantation. Acetone is added to the centrifuge tube and stirred. Centrifuge at 5 ° C. and 20000 rpm for 120 minutes. The supernatant is then removed by decantation. The centrifuge is taken out from the bottom of the centrifuge tube, dried at 50 ° C. under reduced pressure, and its mass w1 is measured.
  • the amount (percentage) of acetone insoluble matter is calculated by the formula: 100 ⁇ w1 / w0.
  • the amount (percentage) of the acetone-soluble component is calculated by the formula: 100 ⁇ (w0-w1) / w0.
  • the acetone-soluble component contained in the thermoplastic resin composition of the present invention can be obtained by drying the supernatant at 50 ° C. under reduced pressure.
  • the ratio Tg / R of the glass transition temperature Tg to the melt flow rate R under the conditions of 230 ° C. and a 3.8 kg load is preferably 6.0 to 1.5 ° C. for 10 minutes / g, more preferably. Is 5.6 to 2.0 ° C. for 10 minutes / g.
  • the acetone-soluble component contained in the thermoplastic resin composition of the present invention has a glass transition temperature of preferably 90 to 115 ° C, more preferably 95 to 110 ° C.
  • the acetone-soluble component contained in the thermoplastic resin composition of the present invention has a melt flow rate R of preferably 15 to 60 g / 10 minutes, more preferably 20 to 55 g / 10 under the conditions of 230 ° C. and a load of 3.8 kg. Minutes.
  • the molding material of the present invention contains the methacrylic copolymer (or thermoplastic resin composition) of the present invention.
  • the molding material of the present invention is an antioxidant, a heat deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, as long as the effects of the present invention are not impaired.
  • Additives such as flame retardant, dye pigment, light diffusing agent, organic dye, matting agent, impact resistance modifier, and phosphor may be further contained.
  • 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.
  • 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.
  • a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used in combination, it is recommended to use a phosphorus-based antioxidant / hindered phenol-based antioxidant in a mass ratio of 0.2 / 1 to 2/1. It is preferably used at 0.5 / 1/1 to 1/1, more preferably.
  • Phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (manufactured by ADEKA; trade name: ADEKA STAB HP-10), tris (2,4-di-). t-butylphenyl) phosphite (manufactured by BASF; trade name: IRUGAFOS168), 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa 3 , 9-Diphosphaspiro [5.5] Undecan (manufactured by ADEKA; trade name: ADEKA STAB PEP-36) and the like.
  • pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANOX1010), octadecyl-3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF; trade name IRGANOX1076) and the like are preferable.
  • the heat deterioration of the resin can be prevented by capturing the polymer radicals generated when exposed to high heat under a substantially oxygen-free state.
  • the heat deterioration inhibitor include 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-dit-amyl-6- (3', 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilyzer GS) and the like are preferable. ..
  • the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays, and is said to have a function of mainly converting light energy into heat energy.
  • the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like.
  • benzotriazoles, triazines, and ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max of 100 dm 3 ⁇ mol -1 cm -1 or less at a wavelength of 380 to 450 nm are preferable.
  • Benzotriazoles are highly effective in suppressing deterioration of optical properties such as coloring due to exposure to ultraviolet rays, and are therefore preferable as an ultraviolet absorber used when the molded product of the present invention is applied to optical applications.
  • benzotriazoles 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-t-octylphenol] (manufactured by ADEKA; LA-31) and the like are preferable.
  • an ultraviolet absorber having a maximum molar extinction coefficient ⁇ max of 1200 dm 3 ⁇ mol -1 cm -1 or less at a wavelength of 380 to 450 nm can suppress discoloration of the obtained molded product.
  • examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd .; trade name: Sandeuboa VSU).
  • benzotriazoles are preferably used from the viewpoint of suppressing resin deterioration due to UV exposure.
  • 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; LA-F70).
  • examples thereof include hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; TINUVIN 477 and TINUVIN 460), which are related thereto.
  • the maximum value ⁇ max of the molar extinction coefficient of the ultraviolet absorber is measured as follows. 10.00 mg of an ultraviolet absorber is added to 1 L of cyclohexane and dissolved so that there is no undissolved substance by visual observation. This solution is injected into a quartz glass cell of 1 cm ⁇ 1 cm ⁇ 3 cm, and the absorbance at a wavelength of 380 to 450 nm and an optical path length of 1 cm is measured using a U-3410 spectrophotometer manufactured by Hitachi, Ltd.
  • the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light.
  • Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
  • lubricant examples include stearic acid, behenic acid, stearoamic acid, methylene bisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hydrogenated oil. Increasing the amount of lubricant used tends to increase the melt flow rate R of the molding material of the present invention and increase the fluidity.
  • the mold release agent is a compound having a function of facilitating separation of a molded product from a mold.
  • the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • higher alcohols and glycerin fatty acid monoester in combination as a release agent.
  • the mass ratio of the higher alcohols / glycerin fatty acid monoester is preferably in the range of 2.5 / 1 to 3.5 / 1, 2.8. It is more preferable to use it in the range of / 1 to 3.2 / 1.
  • polymer particles having a particle size of 0.05 to 0.5 ⁇ m can be used.
  • the polymer particles may be single-layer particles composed of polymers having a single composition ratio and a single ultimate viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or ultimate viscosities. You may. Among these, 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.
  • the amount of the polymer processing aid used is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the methacrylic copolymer. Good processing characteristics are obtained when the amount of the polymer processing aid used is 0.1 parts by mass or more, and surface smoothness is good when the amount of the polymer processing aid used is 5 parts by mass or less.
  • the impact resistance modifier examples include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; and a modifier containing a plurality of rubber particles.
  • the organic dye a compound having a function of converting ultraviolet rays, which are considered to be harmful to the resin, 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 fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, and fluorescent bleaching agents.
  • additives may be used alone or in combination of two or more. These additives may be added at the time of producing the methacrylic copolymer, or may be added to the produced methacrylic copolymer.
  • the total amount of the additives contained in the methacrylic copolymer of the present invention is preferably 1% by mass or less, more preferably 0.% by mass, based on the methacrylic copolymer resin, from the viewpoint of suppressing poor appearance of the molded product. It is 8% by mass or less, more preferably 0.5% by mass or less.
  • the methacrylic copolymer or thermoplastic resin composition of the present invention can be used as a molding material in any form such as pellets, granules, and powder in order to enhance convenience such as transportation and storage.
  • the molded product of the present invention can be obtained by molding the methacrylic copolymer (or thermoplastic resin composition or molding material) of the present invention. Molding can be performed by a known method such as an injection molding method, a compression molding method, an extrusion molding method, a vacuum forming method, or a cast molding method. Of these, the injection molding method is preferable.
  • the methacrylic copolymer of the present invention can provide a thin-walled and wide-area molded product with little residual strain and almost no coloring even when injection-molded at a low cylinder temperature and a high injection pressure with high production efficiency. it can.
  • the maximum value of the ratio of the resin flow length to the thickness of the mold that can be used in injection molding is preferably 450 or more.
  • the methacrylic copolymer of the present invention is suitable for producing a thin-walled molded product.
  • the molded product of the preferred form of the present invention has a plate shape, and the thickness thereof is preferably 0.5 mm or less, more preferably 0.45 mm or less, still more preferably 0.4 mm or less, still more preferably 0.35 mm. It is as follows.
  • the methacrylic copolymer (or thermoplastic resin composition or molding material) of the present invention is suitable for manufacturing a housing of a mobile phone terminal.
  • a mobile phone terminal is a terminal used for a telephone service (that is, a mobile phone) capable of making a call while moving.
  • a mobile phone terminal consists of at least an antenna, a speaker, a microphone, an input / output device, a display device, an electronic circuit and a power supply, and a housing for accommodating them.
  • the housing for mobile phone terminals is required to be thinned while ensuring the strength at a practical level.
  • the methacrylic copolymer (or thermoplastic resin composition or molding material) of the present invention can secure the strength at a practical level even if it is thinned.
  • the housing for the mobile phone terminal of the present invention is made of the methacrylic copolymer (or thermoplastic resin composition or molding material) of the present invention, and has, for example, a thickness of preferably 0.8 mm. Below, more preferably 0.7 mm or less, still more preferably 0.6 mm or less, the portion is composed of the methacrylic copolymer (or thermoplastic resin composition or molding material) of the present invention.
  • Examples of the molded product of the present invention include signboard parts such as advertising towers, stand signs, sleeve signs, column signboards, and roof signboards; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting covers, etc.
  • signboard parts such as advertising towers, stand signs, sleeve signs, column signboards, and roof signboards
  • display parts such as showcases, dividers, and store displays
  • Lighting parts such as lamp shades, light ceilings, light walls, chandeliers; Interior parts such as pendants and mirrors; Building parts such as doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, roofs of leisure buildings Transport equipment related parts such as aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shading plates, automobile side visors, rear visors, head wings, headlight covers; audiovisual nameplates, stereo covers, TV protective masks, Electronic equipment parts such as vending machines; Medical equipment parts such as incubators and roentgen parts; Equipment-related parts such as machine covers, instrument covers, experimental equipment, rulers, dials, observation windows; LCD protective plates, light guide plates, guides Optical parts such as optical films, frennel lenses, lenticular lenses, front plates of various displays, diffusers, polarizer protective films, polarizing plate protective films, retardation films, housings for mobile phones; road signs, information boards, Traffic-related parts such as curved mirrors and soundproof walls; Surface materials for
  • the light guide is used, for example, as a member of the backlight of the liquid crystal display element. It guides the light from the light source on the side or back so that the light can be radiated uniformly from the entire plate surface.
  • the plate surface of the light guide may be provided with micron-sized irregularities for uniformly radiating light.
  • Examples 1 to 7 and Comparative Examples 1 to 4 Purified methyl methacrylate (MMA), methyl acrylate (MA), 2,2'-azobis (2-methylpropionitrile) (AIBN) and n-octyl mercaptan (n-OM) in an autoclave with a stirrer. was charged at the ratio shown in Table 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 temperature of 140 ° C. at 1.5 kg / hr, and the polymerization reaction is carried out by a massive polymerization method with an average residence time of 120 minutes, and the polymerization reaction is carried out from the tank reactor.
  • the liquid containing the methacrylic copolymer was continuously discharged.
  • the polymerization conversion rate was 57% by mass.
  • the liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C.
  • the twin-screw extruder the volatile matter containing the unreacted monomer as a main component was separated and removed, and the methacrylic copolymer was extruded as a strand.
  • the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic copolymer.
  • the physical properties of the methacrylic copolymer were measured by the following method. The results are shown in Table 1.
  • the amount of the unit derived from MMA is the amount of the unit other than the MA unit, so the description in the table is omitted.
  • the amount of the bonded sulfur atom of the methacrylic copolymer is a value determined as follows.
  • the methacrylic copolymer is dissolved in chloroform to obtain a solution.
  • This solution is added to n-hexane to give a precipitate.
  • the precipitate is dried at 80 ° C. for 12 hours or longer under vacuum.
  • An appropriate amount of the obtained dried product is precisely weighed, set in a sulfur combustion device, decomposed in a reactor having a temperature of 400 ° C., and the generated gas is passed through a furnace having a temperature of 900 ° C., and then 0.3% hydrogen peroxide solution is used. Absorb with.
  • the obtained liquid (decomposition gas aqueous solution) is appropriately diluted with pure water, and sulfate ions are quantified by ion chromatography (ICS-1500 manufactured by DIONEX, column: AS12A).
  • ICS-1500 manufactured by DIONEX, column: AS12A.
  • Glass transition temperature Tg Glass transition temperature Tg
  • the acetone-insoluble content of the methacrylic copolymer and the thermoplastic resin obtained in the examples was 250 using a differential scanning calorimetry device (manufactured by Shimadzu Corporation, DSC-50 (product number)) in accordance with JIS K7121.
  • the DSC curve was measured under the condition that the temperature was raised once to ° C., then cooled to room temperature, and then 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.
  • injection moldability Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: SE-180DU-HP), injection molding is performed in a cylinder temperature of 280 ° C., a mold temperature of 75 ° C., and a molding cycle of 1 minute, and the long side is 205 mm and the short side is 160 mm.
  • a flat plate S having a thickness of 0.4 mm was manufactured.
  • the appearance of the flat plate S was observed and evaluated by the following indexes.
  • C There is a crack.
  • the methacrylic copolymer of the present invention has high fluidity, excellent injection moldability, and is less likely to cause mold stains.
  • Production Example 1 (Acrylic rubber particles) 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 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.
  • Examples 8 to 13 and Comparative Examples 5 to 7 The methacrylic copolymer, the acrylic rubber particles, and the acrylic block copolymer are mixed at the ratios shown in Table 2, melt-kneaded at 250 ° C. with a twin-screw extruder having a shaft diameter of 20 mm, extruded, and thermoplastic. A resin composition was obtained.
  • thermoplastic resin composition The physical properties of the thermoplastic resin composition were measured by the following method. The results are shown in Table 2.
  • the composition was injection molded to obtain a square injection molded piece having a thickness of 3 mm and a side of 50 mm.
  • Each test piece was evaluated by the following indexes by measuring the total light transmittance Tt and haze H using a spectrocolor difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the method described in JIS K7361-1. Was done.
  • C Tt is less than 80% or H is greater than 10%
  • the composition was injection molded to obtain a square injection molded piece having a thickness of 3 mm and a side of 50 mm.
  • a table-movable pencil scratching tester model P (manufactured by Toyo Seiki Co., Ltd.)
  • Pencil hardness is 2H or more
  • Pencil hardness is F or more and less than 2H
  • Pencil hardness is less than F
  • the composition was injection-molded to obtain a strip-shaped injection-molded piece having a thickness of 4 mm, a long side of 80 mm, and a short side of 10 mm.
  • the flatwise method measured by performing a Charpy impact test on each test piece in accordance with the method described in ISO179-1, and the Charpy impact strength without a notch is defined as the Charpy impact strength, and the obtained Charpy impact strength is obtained.
  • Charpy impact strength is 60 kJ / m 2 or more
  • Charpy impact strength is 40 kJ / m 2 or more and less than 60 kJ / m 2
  • Charpy impact strength is less than 40 kJ / m 2
  • thermoplastic resin composition of the present invention can provide a thin-walled molded product having excellent transparency, surface hardness, and impact resistance.

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Abstract

L'invention concerne un copolymère méthacrylique qui comprend 85,0 à 95,0 % en masse d'unités monomères dérivées de méthacrylate de méthyle et 5,0 à 15,0 % en masse d'unités monomères dérivées d'un ester acrylique et a un poids moléculaire moyen en poids Mw de 48 000 à 59 000 et dans lequel le rapport du poids moléculaire moyen en poids Mw au poids moléculaire moyen en nombre Mn, Mw/Mn, est de 2,1 ou moins et le rapport de la température de transition vitreuse Tg à l'indice de fusion R mesuré dans les conditions de 230°C et une charge de 3,8 kg, Tg/R, est de 5,0 à 1,5°C·10-min/g.
PCT/JP2020/021319 2019-05-29 2020-05-29 Copolymère méthacrylique et article moulé Ceased WO2020241822A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2016167292A1 (fr) * 2015-04-17 2016-10-20 株式会社クラレ Composition de résine méthacrylique
WO2017146169A1 (fr) * 2016-02-26 2017-08-31 株式会社クラレ Composition de résine méthacrylique et objet moulé par injection
JP2017178975A (ja) * 2016-03-28 2017-10-05 三菱ケミカル株式会社 アクリル樹脂、成形体、導光体及びアクリル樹脂の製造方法

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JP6284483B2 (ja) 2012-11-09 2018-02-28 株式会社クラレ メタクリル樹脂組成物
EP2998328B1 (fr) 2013-05-16 2018-06-27 Kuraray Co., Ltd. Film
TWI633147B (zh) 2013-11-25 2018-08-21 Kuraray Co., Ltd. 丙烯酸樹脂薄膜及其製造方法
JP6317131B2 (ja) 2014-02-21 2018-04-25 株式会社クラレ メタクリル樹脂組成物からなる板状成形体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016167292A1 (fr) * 2015-04-17 2016-10-20 株式会社クラレ Composition de résine méthacrylique
WO2017146169A1 (fr) * 2016-02-26 2017-08-31 株式会社クラレ Composition de résine méthacrylique et objet moulé par injection
JP2017178975A (ja) * 2016-03-28 2017-10-05 三菱ケミカル株式会社 アクリル樹脂、成形体、導光体及びアクリル樹脂の製造方法

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