WO2015182750A1 - メタクリル樹脂組成物 - Google Patents

メタクリル樹脂組成物 Download PDF

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Publication number
WO2015182750A1
WO2015182750A1 PCT/JP2015/065578 JP2015065578W WO2015182750A1 WO 2015182750 A1 WO2015182750 A1 WO 2015182750A1 JP 2015065578 W JP2015065578 W JP 2015065578W WO 2015182750 A1 WO2015182750 A1 WO 2015182750A1
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Prior art keywords
methacrylic resin
mass
resin composition
acrylate
film
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PCT/JP2015/065578
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English (en)
French (fr)
Japanese (ja)
Inventor
達 阿部
淳裕 中原
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株式会社クラレ
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Priority to CN201580028984.7A priority Critical patent/CN106414599B/zh
Priority to KR1020167033293A priority patent/KR102221882B1/ko
Priority to JP2016523578A priority patent/JP6407270B2/ja
Publication of WO2015182750A1 publication Critical patent/WO2015182750A1/ja

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    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • 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
    • 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
    • C08F220/14—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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state

Definitions

  • the present invention relates to a methacrylic resin composition. More specifically, the present invention can obtain a molded article having high transparency, small change in haze in a wide temperature range, small thickness direction retardation, small thermal shrinkage, and high strength.
  • the present invention relates to a methacrylic resin composition having excellent moldability and a high glass transition temperature.
  • a methacrylic resin having a high syndiotacticity is known as a methacrylic resin having a high glass transition temperature (see Patent Documents 1 and 2).
  • methacrylic resins having high syndiotacticity are inferior in molding processability and it is difficult to obtain a molded article having a smooth surface.
  • methacrylic resins with high syndiotacticity are excellent in solvent resistance and heat resistance, but have low mechanical strength, tend to be brittle and easy to break.
  • the graft copolymer of a core-shell structure containing a rubbery polymer having a glass transition temperature of 0 ° C. or less has been proposed to blend a polymer (see, for example, Patent Document 3).
  • the object of the present invention is to provide a molding process with high transparency, a small change in haze over a wide temperature range, a small phase difference in the thickness direction, a small thermal shrinkage rate and a large strength. And a methacrylic resin composition having a high glass transition temperature.
  • the acrylic ester polymer block (b2) comprises 50 to 90% by mass of structural units derived from alkyl acrylate ester and 50 to 10% by mass of structural units derived from (meth) acrylic aromatic ester.
  • the methacrylic resin composition as described in [1].
  • the methacrylic resin (A) has a total content of structural units derived from methyl methacrylate of 99% by mass or more, and has a refractive index n 23D of 1 at a wavelength of 587.6 nm (D line) and 23 ° C. .488 to 1.490,
  • the block copolymer (B) has a wavelength of 587.6 nm (D line) and a refractive index n 23D at 23 ° C. of 1.485 to 1.495, as described in any one of [1] to [3] Methacrylic resin composition.
  • the methacrylic resin (A) has a weight average molecular weight of 50,000 to 150,000, a content of a component having a molecular weight of 200,000 or more is 0.1 to 10%, and a content of a component having a molecular weight of less than 15,000 is 0.00.
  • the methacrylic resin composition according to any one of [1] to [4], which is 2 to 5%.
  • the methacrylic resin (A) has a syndiotacticity (rr) with a triplet indication of 65% or more, and a syndiotacticity (rr) with a triplet indication of 45- 58% methacrylic resin (a2) is contained in any one of [1] to [5], containing a methacrylic resin (a1) / methacrylic resin (a2) mass ratio of 40/60 to 70/30 Methacrylic resin composition.
  • the methacrylic resin composition according to any one of [1] to [7], further comprising an ultraviolet absorber. [9] Any one of [1] to [8], further comprising 1 to 10 parts by weight of a polycarbonate resin with respect to 100 parts by weight of the total amount of the methacrylic resin (A) and the block copolymer (B). The methacrylic resin composition as described.
  • a molded article comprising the methacrylic resin composition according to any one of [1] to [10].
  • a film comprising the methacrylic resin composition according to any one of [1] to [10].
  • the film according to [12] stretched in at least one direction by 1.5 to 8 times in area ratio.
  • a polarizer protective film comprising the film according to [12] or [13].
  • the methacrylic resin composition of the present invention is excellent in moldability and has a high glass transition temperature.
  • a molded article having high transparency, a small change in haze in a wide temperature range, a small retardation in the thickness direction, a small thermal contraction rate and a large strength.
  • Such a molded body is suitable for a polarizer protective film, a liquid crystal protective plate, a surface material for a portable information terminal, a display window protective film for a portable information terminal, a light guide film, a front plate for various displays, and the like.
  • the methacrylic resin composition of the present invention contains a methacrylic resin (A) and a block copolymer (B).
  • the methacrylic resin (A) used in the present invention has a triplet display syndiotacticity (rr) of 58% or more, preferably 59% or more, more preferably 60% or more.
  • the upper limit of the tridentated syndiotacticity (rr) of the methacrylic resin (A) is not particularly limited, but is preferably 99%, more preferably 85%, and even more preferably 77 from the viewpoint of moldability. %, More preferably 70%, even more preferably 65%, and most preferably 64%.
  • a triplet display syndiotacticity (hereinafter sometimes simply referred to as “syndiotacticity (rr)”) is a chain of three consecutive structural units (triplet, triad).
  • the two chains (doublet, diad) present in are both a racemo (denoted as rr).
  • rr racemo
  • messages those having the same configuration are referred to as “meso”, and those opposite to each other are referred to as “racemo”, which are expressed as m and r, respectively.
  • the triplet-represented syndiotacticity (rr) (%) is a value obtained by measuring a 1 H-NMR spectrum in deuterated chloroform at 30 ° C.
  • the area (X) of the region of ⁇ 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.
  • the methacrylic resin (A) used in the present invention has a weight average molecular weight Mw A of preferably 50,000 to 150,000, more preferably 60,000 to 140,000, still more preferably 70,000 to 120,000.
  • Mw A weight average molecular weight
  • rr syndiotacticity
  • the resulting film has high strength, is difficult to break, and is easy to stretch. Therefore, the film can be made thinner.
  • Mw A is 150,000 or less, since the methacrylic resin is improved moldability tends to thickness of the resulting film is excellent in uniform and surface smoothness.
  • the ratio (Mw A / Mn A ) between Mw A and the number average molecular weight Mn A is preferably 1.2 to 5.0, more preferably 1.3 to 3. 5.
  • Mw A / Mn A is 1.2 or more, the fluidity of the methacrylic resin is improved, and the resulting film tends to be excellent in surface smoothness.
  • a film obtained when Mw A / Mn A is 5.0 or less tends to be excellent in impact resistance and toughness.
  • Mw A and Mn A are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.
  • the content of a component having a molecular weight of 200,000 or more is preferably 0.1 to 10%, more preferably 0.5 to 5%.
  • the content of a component having a molecular weight of less than 15000 (low molecular weight component) is preferably 0.2 to 5%, more preferably 1 to 4.5%.
  • the content of a component having a molecular weight of 200,000 or more is the chromatogram and the baseline detected before the retention time of the standard polystyrene having a molecular weight of 200,000 in the area surrounded by the chromatogram and the baseline measured by GPC. It is calculated as a ratio of the area of the portion surrounded by.
  • the content of the component having a molecular weight of less than 15000 is determined by the chromatogram and the baseline detected after the retention time of the standard polystyrene having a molecular weight of 15000 in the area surrounded by the chromatogram obtained by GPC and the baseline. Calculated as the ratio of the area of the enclosed part.
  • GPC measurement is performed as follows. Tetrahydrofuran is used as the eluent, and TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 are connected in series as the column.
  • HLC-8320 product number
  • RI detector differential refractive index detector
  • As a sample a solution in which 4 mg of methacrylic resin was dissolved in 5 ml of tetrahydrofuran was used.
  • the column oven temperature was set to 40 ° C., 20 ⁇ l of sample solution was injected at an eluent flow rate of 0.35 ml / min, and the chromatogram was measured.
  • Standard polystyrene having a molecular weight in the range of 400 to 5000000 was measured, and a calibration curve showing the relationship between retention time and molecular weight was created.
  • the baseline connecting the point where the slope on the high molecular weight side of the chromatogram changes from zero to positive and the point where the slope of the peak on the low molecular weight side changes from negative to zero was taken as the baseline. If the chromatogram shows multiple peaks, connect the line connecting the point where the slope of the highest molecular weight peak changes from zero to positive and the point where the slope of the lowest molecular weight peak changes from negative to zero. Baseline.
  • the methacrylic resin (A) used in the present invention has a melt flow rate of preferably 0.1 to 20 g / 10 min, measured under conditions of 230 ° C. and 3.8 kg load in accordance with JIS K7210. Preferably it is 0.5 to 15 g / 10 min, and most preferably 1.0 to 10 g / 10 min.
  • the content of the structural unit derived from methyl methacrylate is more preferably 90% by mass or more based on the mass of the methacrylic resin (A) from the viewpoint of improving heat resistance. Is 93% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass.
  • the methacrylic resin (A) used in the present invention may contain structural units other than the structural units derived from methyl methacrylate, such as ethyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, isobornyl methacrylate.
  • Methacrylic acid alkyl esters other than methyl methacrylate such as 8-tricyclo [5.2.1.0 2,6 ] decanyl methacrylate and 4-t-butylcyclohexyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid Acrylic acid alkyl esters such as propyl, butyl acrylate and 2-ethylhexyl acrylate; acrylic acid aryl esters such as phenyl acrylate; acrylic acid cycloalkyl esters such as cyclohexyl acrylate and norbornenyl acrylate; ; Methacrylamide; acrylonitrile; methacrylonitrile; polymerizable carbon in one molecule, such as a - can be exemplified a structural unit derived from a vinyl monomer having only one carbon-carbon double bond.
  • the glass transition temperature of the methacrylic resin (A) used in the present invention is preferably 120 ° C. or higher, more preferably 123 ° C. or higher, and still more preferably 124 ° C. or higher.
  • the upper limit of the glass transition temperature of the methacrylic resin is preferably 135 ° C, more preferably 130 ° C.
  • the glass transition temperature can be controlled by adjusting the molecular weight and syndiotacticity (rr). When the glass transition temperature is in this range, deformation such as heat shrinkage of the obtained film is difficult to occur.
  • the glass transition temperature is a midpoint glass transition temperature measured according to JIS K7121.
  • the DSC curve was measured under the condition that the sample was heated to 230 ° C., then cooled to room temperature, and then heated from room temperature to 230 ° C. at 10 ° C./min.
  • the midpoint glass transition temperature determined from the DSC curve measured at the second temperature increase was determined.
  • the refractive index n 23D at a wavelength of 587.6 nm (D line) measured at 23 ° C. and 50% RH of the methacrylic resin (A) used in the present invention is preferably from the viewpoint of transparency of the resulting methacrylic resin composition. Is from 1.488 to 1.490, more preferably from 1.4885 to 1.4897.
  • the methacrylic resin (A) used in the present invention may be one that satisfies the above characteristics with one kind of methacrylic resin, or one that satisfies the above characteristics with a mixture of a plurality of kinds of methacrylic resins. There may be.
  • methacrylic resin which comprises the methacrylic resin (A) used for this invention can be manufactured by a well-known polymerization method.
  • Each characteristic of the methacrylic resin (A) described above can be realized by adjusting polymerization conditions such as polymerization temperature, polymerization time, type and amount of chain transfer agent, and type and amount of polymerization initiator.
  • Examples of the polymerization reaction form used for the production of the methacrylic resin include a radical polymerization method and an anionic polymerization method.
  • a polymerization method such as a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method can be employed.
  • the suspension polymerization method and the bulk polymerization method are preferable from the viewpoints of productivity and thermal decomposition resistance.
  • a polymerization method such as a bulk polymerization method or a solution polymerization method can be employed.
  • the polymerization reaction is initiated by a polymerization initiator.
  • the polymerization initiator used for radical polymerization is not particularly limited as long as it generates a reactive radical.
  • Such a polymerization initiator has a one-hour half-life temperature of preferably 60 to 140 ° C., more preferably 80 to 120 ° C.
  • Examples of the polymerization initiator used in radical polymerization include t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethyl.
  • t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2′-azobis (2-methylpropionate) are preferable.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the addition amount and addition method of the polymerization initiator are not particularly limited as long as they are appropriately set according to the purpose.
  • the amount of the polymerization initiator used in the suspension polymerization method is preferably 0.0001 to 0.1 parts by mass, more preferably 0.001 parts by mass with respect to 100 parts by mass of all monomers subjected to the polymerization reaction. 001 to 0.07 parts by mass.
  • the polymerization initiator used for anionic polymerization is not particularly limited as long as it generates a reactive anion.
  • examples of such a polymerization initiator include organic alkali metal compounds, alkali metal or alkaline earth metal mineral salts, those composed of combinations of organic alkali metal compounds and organic aluminum compounds, and organic rare earth metal complexes.
  • Specific examples of the polymerization initiator used in the anionic polymerization method include alkyllithium such as n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium.
  • the organoaluminum compound include a compound represented by AlR 1 R 2 R 3.
  • R 1 , R 2 and R 3 may each independently have an alkyl group which may have a substituent, an cycloalkyl group which may have a substituent, or a substituent.
  • R 2 and R 3 may be an aryleneoxy group which may have a substituent formed by bonding them.
  • organoaluminum compound examples include isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2 And '-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum.
  • a chain transfer agent in radical polymerization and a polymerization terminator in anionic polymerization can be added to the reaction system.
  • the chain transfer agent used for radical polymerization is not particularly limited.
  • n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiol Alkyl mercaptans such as propionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- ( ⁇ -thiopropionate), pentaerythritol tetrakisthiopropionate; ⁇ -methylstyrene Dimer; terpinolene and the like can be mentioned.
  • alkyl mercaptans such as n-octyl mercaptan and pentaerythritol tetrakisthiopropionate are preferred.
  • chain transfer agents can be used alone or in combination of two or more.
  • the amount of the chain transfer agent used is preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.8 part by weight, and still more preferably 100 parts by weight of the total monomer subjected to the polymerization reaction. 0.2 to 0.6 parts by mass, most preferably 0.2 to 0.5 parts by mass.
  • the amount of the chain transfer agent used is preferably 2500 to 10000 parts by mass, more preferably 3000 to 9000 parts by mass, and further preferably 3500 to 6000 parts by mass with respect to 100 parts by mass of the polymerization initiator. When the amount of the chain transfer agent used is in the above range, the molecular weight of the resulting methacrylic resin can be controlled, so that good moldability and high mechanical strength can be obtained.
  • Examples of the polymerization terminator used in the anionic polymerization method include alcohol and water.
  • the amount of the polymerization terminator used is not particularly limited, but is preferably less than the amount of the polymerization initiator during the polymerization reaction, specifically, preferably 1 mol% to 50 mol% with respect to the amount of the polymerization initiator, More preferably, it is 2 mol% to 20 mol%, still more preferably 5 mol% to 10 mol%.
  • a polymerization initiator can be additionally added during the polymerization reaction in order to adjust the weight average molecular weight, number average molecular weight, and molecular weight distribution of the resulting methacrylic resin.
  • the amount of the polymerization initiator additionally added during the polymerization reaction is preferably 1 mol% to 50 mol%, more preferably 2 mol% to 20 mol%, based on the amount of the polymerization initiator added at the start of the polymerization. More preferably, it is 5 mol% to 10 mol%.
  • Each monomer, polymerization initiator, and chain transfer agent used in the production of the methacrylic resin may be supplied all at once to the reaction vessel, or may be supplied separately to the reaction vessel. .
  • the solvent used in the solution polymerization method is not particularly limited as long as it can dissolve monomers and methacrylic resins and does not deactivate radicals and anions.
  • aromatic hydrocarbons such as benzene, toluene and ethylbenzene are preferable. These solvents can be used alone or in combination of two or more.
  • the usage-amount of a solvent can be suitably set from a viewpoint of the viscosity and productivity of a reaction liquid.
  • the amount of the solvent used is, for example, preferably 100 parts by mass or less, more preferably 90 parts by mass or less with respect to 100 parts by mass of the polymerization reaction raw material.
  • the temperature at the time of the polymerization reaction can be appropriately set depending on the reaction form or from the viewpoint of the polymerization reaction rate, the viscosity of the polymerization reaction solution, the suppression of the formation of by-products.
  • the temperature during the polymerization reaction is preferably 50 to 180 ° C, more preferably 60 to 140 ° C.
  • the temperature during the polymerization reaction is preferably 100 to 200 ° C, more preferably 110 to 180 ° C.
  • the polymerization reaction for producing the methacrylic resin can be carried out by a batch reaction or a continuous flow reaction.
  • a raw material for polymerization reaction for example, a raw material for polymerization reaction (mixed liquid containing monomer, polymerization initiator, chain transfer agent, etc.) is prepared in a nitrogen atmosphere, etc., all of which are charged into a reactor, and the reaction is performed for a predetermined time. And take out the reaction product.
  • a continuous flow reaction for example, a polymerization reaction raw material (mixed liquid containing a monomer, a polymerization initiator, a chain transfer agent, etc.) is prepared under a nitrogen atmosphere, and the mixture is supplied to the reactor at a constant flow rate.
  • the liquid in the reactor is extracted at a flow rate corresponding to the supply amount.
  • the continuous flow type is preferable from the viewpoint of productivity and stability.
  • a tubular reactor that can be brought into a state close to plug flow and / or a tank reactor that can be brought into a state close to complete mixing can be used.
  • continuous flow polymerization may be performed in one reactor, or continuous flow polymerization may be performed by connecting two or more reactors.
  • the amount of liquid in the tank reactor during the polymerization reaction is preferably 1/4 to 3/4, more preferably 1/3 to 2/3 with respect to the volume of the tank reactor.
  • the reactor is usually equipped with a stirring device.
  • Examples of the stirring device include a static stirring device and a dynamic stirring device.
  • Examples of the dynamic agitation device include a Max blend type agitation device, an agitation device having a lattice-like blade rotating around a vertical rotation shaft arranged in the center, a propeller type agitation device, a screw type agitation device, and the like. .
  • a Max blend type stirring apparatus is preferably used from the point of uniform mixing property.
  • the removal method is not particularly limited.
  • the suspension medium, solvent, or emulsion medium may be removed by a known operation, and the remaining resin component may be washed and dried as necessary. it can.
  • unreacted monomers can be removed, and the remaining resin components can be dried as necessary.
  • a known devolatilization method can be employed for removing the suspending medium, the solvent, the emulsifying medium or the unreacted monomer. Examples of the devolatilization method include an equilibrium flash method and an adiabatic flash method.
  • the devolatilization temperature by the adiabatic flash method is preferably 200 to 280 ° C, more preferably 220 to 260 ° C.
  • the time for heating the resin by the adiabatic flash method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and further preferably 0.5 to 2 minutes.
  • the removed unreacted monomer can be recovered and used again for the polymerization reaction.
  • the yellow index of the recovered monomer may be high due to heat applied during the recovery operation.
  • the recovered monomer is preferably purified by an appropriate method to reduce the yellow index.
  • a known kneading method for example, a kneading machine such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer is used. Can be used.
  • the temperature at the time of kneading can be appropriately adjusted according to the melting temperature of the methacrylic resin to be used, and is usually 150 ° C. to 300 ° C.
  • a method of polymerizing a monomer capable of obtaining another type of methacrylic resin in the presence of one type of methacrylic resin can be employed.
  • Such polymerization can be performed by the radical polymerization method or the anion polymerization method described above. In this method, since the heat history applied to the methacrylic resin is shorter than the method by kneading, the thermal decomposition of the methacrylic resin is suppressed, and a film with less coloring and foreign matter is easily obtained.
  • the mixture of a plurality of methacrylic resins as the methacrylic resin (A) preferably contains a methacrylic resin (a1) and a methacrylic resin (a2).
  • the methacrylic resin (a1) contains a structural unit derived from methyl methacrylate.
  • the content of the structural unit derived from methyl methacrylate is preferably 92% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass, based on the mass of the methacrylic resin (a1). % Or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.
  • the methacrylic resin (a1) may contain a structural unit derived from a monomer other than methyl methacrylate.
  • monomers other than methyl methacrylate include, for example, ethyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, isobornyl methacrylate, 8-tricyclo [5.2.1.0 2,6 ] decanyl methacrylate, Alkyl methacrylates other than methyl methacrylate, such as 4-t-butylcyclohexyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; One molecule of acrylic acid aryl ester such as phenyl acrylate; cycloalkyl acrylate, cycloalkyl ester such as norbornenyl acrylate; acrylamide; meth
  • the methacrylic resin (a1) has a triplet display syndiotacticity (rr) of preferably 65% or more, more preferably 70 to 90%, and still more preferably 72 to 85%.
  • the syndiotacticity (rr) is 65% or more.
  • the weight average molecular weight Mw a1 of the methacrylic resin (a1) is preferably 40,000 to 150,000, more preferably 40,000 to 120,000, and still more preferably 50,000 to 100,000.
  • Mwa1 is 40,000 or more, impact resistance and toughness tend to be improved. If Mwa1 is 150,000 or less, the moldability tends to be improved.
  • the ratio of Mw a1 to the number average molecular weight Mn a1 is preferably 1.01 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.05 to 1.5.
  • Mw a1 and Mn a1 can be controlled by adjusting the type and amount of the polymerization initiator used in the production of the methacrylic resin (a1).
  • Mwa1 and Mna1 are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.
  • the glass transition temperature of the methacrylic resin (a1) is preferably 125 ° C. or higher, more preferably 128 ° C. or higher, and further preferably 130 ° C. or higher.
  • the upper limit of the glass transition temperature of the methacrylic resin (a1) is preferably 140 ° C.
  • the glass transition temperature can be controlled by adjusting the molecular weight, syndiotacticity (rr) and the like. As the glass transition temperature of the methacrylic resin (a1) increases, the glass transition temperature of the resulting methacrylic resin composition increases, and the molded body made of the methacrylic resin composition hardly undergoes deformation such as heat shrinkage.
  • the methacrylic resin (a2) contains a structural unit derived from a methacrylic acid ester.
  • the amount of the structural unit derived from the methacrylic acid ester contained in the methacrylic resin (a2) is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and still more preferably 99% by mass. As mentioned above, Most preferably, it is 100 mass%.
  • methacrylic acid ester examples include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylates such as phenyl methacrylate; cycloalkyl methacrylates such as cyclohexyl methacrylate and norbornenyl methacrylate. Esters can be mentioned, alkyl methacrylates are preferred, and methyl methacrylate is most preferred.
  • the content of the structural unit derived from methyl methacrylate among the structural units derived from the methacrylic acid ester is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98%. % By mass or more, more preferably 99% by mass or more, and most preferably 100% by mass.
  • the methacrylic resin (a2) may contain structural units derived from monomers other than methacrylic acid esters.
  • monomers other than methacrylic acid esters include, for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; acrylic acid such as phenyl acrylate Aryl ester; Acrylic acid cycloalkyl ester such as cyclohexyl acrylate and norbornenyl acrylate; Aromatic vinyl compound such as styrene and ⁇ -methylstyrene; Acrylamide; Methacrylamide; Acrylonitrile; Methacrylonitrile; Examples thereof include vinyl monomers having only one polymerizable carbon-carbon double bond.
  • the methacrylic resin (a2) has a triplet display syndiotacticity (rr) of preferably 45 to 58%, more preferably 49 to 55%.
  • the weight average molecular weight Mw a2 of the methacrylic resin (a2) is preferably 80,000 to 150,000, more preferably 80,000 to 140,000, still more preferably 80,000 to 130,000.
  • Mwa2 is 80,000 or more, impact resistance and toughness tend to be improved.
  • Mwa2 is 150,000 or less, moldability tends to be improved.
  • the ratio of Mw a2 to the number average molecular weight Mn a2 is preferably 1.7 to 2.6, more preferably 1.7 to 2.3, still more preferably 1.7 to 2.0.
  • Mw a2 and Mn a2 can be controlled by adjusting the type and amount of the polymerization initiator used in the production of the methacrylic resin (a2).
  • Mwa2 and Mna2 are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.
  • the glass transition temperature of the methacrylic resin (a2) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 115 ° C. or higher, and most preferably 117 ° C. or higher.
  • the upper limit of the glass transition temperature of the methacrylic resin (a2) is preferably 125 ° C.
  • the glass transition temperature can be controlled by adjusting the molecular weight, syndiotacticity (rr) and the like. When the glass transition temperature of the methacrylic resin (a2) is within this range, the heat resistance becomes high, and a molded body that is unlikely to undergo deformation such as heat shrinkage is easily obtained.
  • a methacryl resin (a1) and a methacryl resin (a2) there is no restriction
  • the radical polymerization method and the anionic polymerization method described above can be employed.
  • an anionic polymerization method or a suspension polymerization method at a low temperature is preferable from the viewpoint of high syndiotacticity (rr) and a high glass transition temperature.
  • the content of the methacrylic resin (a1) is preferably 40. 95%, more preferably 40-70% by mass, still more preferably 45-65% by mass, and most preferably 50-60% by mass.
  • the content of the methacrylic resin (a2) is preferably 5-60%, More preferably, it is 30 to 60% by mass, still more preferably 35 to 55% by mass, and most preferably 40 to 50% by mass.
  • the mass ratio of the methacrylic resin (a1) / methacrylic resin (a2) is preferably 40/60 to 95/5, more preferably 40/60 to 70/30, still more preferably 45/55 to 65/35, Most preferably, it is 50/50 to 60/40.
  • the methacrylic resin composition of the present invention contains a methacrylic resin (A) and a block copolymer (B).
  • a methacrylic resin (A) a methacrylic resin (A) and a block copolymer (B).
  • the transparency is high, the change in haze is small in a wide temperature range, the glass transition temperature is high, the mechanical strength is high, and the bleed of a low molecular compound (ultraviolet absorber).
  • a methacrylic resin composition with suppressed out can be obtained.
  • the block copolymer (B) used in the present invention has a methacrylic acid ester polymer block (b1) and an acrylate polymer block (b2).
  • the block copolymer (B) may have only one methacrylic acid ester polymer block (b1), or two or more.
  • the ratio and molecular weight of the structural units constituting each methacrylic acid ester polymer block (b1) may be the same or different.
  • the block copolymer (B) may have only one acrylate polymer block (b2), or two or more.
  • the ratio and molecular weight of the structural units constituting each acrylate polymer block (b2) may be the same or different.
  • the methacrylic acid ester polymer block (b1) is mainly composed of structural units derived from methacrylic acid esters.
  • the proportion of structural units derived from the methacrylic acid ester in the methacrylic acid ester polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass. % Or more.
  • Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, Isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxy methacrylate Examples thereof include ethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacryl
  • methacrylic acid such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate.
  • Alkyl esters are preferred, and methyl methacrylate is more preferred.
  • These methacrylic acid esters can be used alone or in combination of two or more.
  • the methacrylic acid ester polymer block (b1) may contain a structural unit derived from a monomer other than the methacrylic acid ester as long as the object and effect of the present invention are not hindered.
  • the proportion of structural units derived from monomers other than methacrylate ester contained in the methacrylate polymer block (b1) is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass. Hereinafter, it is particularly preferably 2% by mass or less.
  • Monomers other than methacrylic acid esters include acrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, and chloride. Examples thereof include vinyl, vinylidene chloride, and vinylidene fluoride. These monomers other than methacrylic acid esters can be used alone or in combination of two or more.
  • the methacrylic acid ester polymer block (b1) preferably has a refractive index at a wavelength of 587.6 nm (D line) measured at 23 ° C. and 50% RH. Is 1.485 to 1.495.
  • the lower limit of the weight average molecular weight Mw b1 of the methacrylic acid ester polymer block (b1) is preferably 5,000, more preferably 8,000, more preferably 12,000, even more preferably 15,000, and most preferably.
  • the upper limit is preferably 150,000, more preferably 120,000, and even more preferably 100,000.
  • the weight average molecular weight Mw b1 is as follows for all methacrylate polymer blocks (b1). The weight average molecular weight is calculated and defined as the sum of the numerical values.
  • Mw A / Mw b1 is preferably 0.5 or more and 6 or less, more preferably 0.5 or more and 3.5 or less, further preferably 0.6 or more and 2.7 or less, and most preferably 0.7 or more and 2 or less. .5 or less. If Mw A / Mw b1 is too small, the impact resistance of the molded product produced from the methacrylic resin composition tends to be lowered. On the other hand, if Mw A / Mw b1 is too large, the surface smoothness and haze temperature dependency of a molded product produced from the methacrylic resin composition tend to deteriorate.
  • the ratio of the methacrylic ester polymer block (b1) in the block copolymer (B) is preferably 10% by mass or more and 80% by mass or less from the viewpoint of transparency, flexibility, molding processability, and surface smoothness. Preferably they are 20 mass% or more and 70 mass% or less, More preferably, they are 40 mass% or more and 60 mass% or less.
  • the proportion of the methacrylic acid ester polymer block (b1) in the block copolymer (B) is within the above range, the transparency, flexibility, and bending resistance of the methacrylic resin composition of the present invention or a molded product comprising the same. Excellent in impact resistance and flexibility.
  • the above ratio is calculated based on the total mass of all methacrylate ester polymer blocks (b1).
  • the acrylic ester polymer block (b2) is mainly composed of a structural unit derived from an acrylic ester.
  • the proportion of structural units derived from the acrylate ester in the acrylate polymer block (b2) is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 90% by mass. % Or more.
  • the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylic acid.
  • acrylic acid esters can be used alone or in combination of two or more.
  • the acrylic ester polymer block (b2) may contain a structural unit derived from a monomer other than the acrylic ester as long as it does not interfere with the object and effect of the present invention.
  • the amount of structural units derived from monomers other than the acrylate ester contained in the acrylate polymer block (b2) is preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass. Hereinafter, it is particularly preferably 10% by mass or less.
  • acrylic acid esters methacrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, chloride Examples thereof include vinyl, vinylidene chloride, and vinylidene fluoride.
  • acrylic acid esters methacrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, chloride Examples thereof include vinyl, vinylidene chloride, and vinylidene fluoride.
  • the acrylic ester polymer block (b2) is preferably composed of an acrylic acid alkyl ester and a (meth) acrylic aromatic hydrocarbon ester from the viewpoint of improving the transparency of the methacrylic resin composition of the present invention.
  • the alkyl acrylate include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and the like. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.
  • (Meth) acrylic acid aromatic hydrocarbon ester means acrylic acid aromatic hydrocarbon ester or methacrylic acid aromatic hydrocarbon ester.
  • Examples of (meth) acrylic aromatic hydrocarbon esters include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styryl acrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styryl methacrylate.
  • phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred.
  • the acrylic acid ester polymer block (b2) composed of an acrylic acid alkyl ester and a (meth) acrylic aromatic hydrocarbon ester is preferably 50 to 90% by mass, more preferably a structural unit derived from an acrylic acid alkyl ester.
  • the structural unit is preferably contained in an amount of 60 to 80% by mass and derived from a (meth) acrylic acid aromatic ester, preferably 50 to 10% by mass, more preferably 40 to 20% by mass.
  • the acrylic ester polymer block (b2) preferably has a refractive index at a wavelength of 587.6 nm (D line) measured at 23 ° C. and 50% RH, preferably 1.485. ⁇ 1.495.
  • the lower limit of the weight average molecular weight Mw b2 of the acrylate polymer block (b2) is preferably 5,000, more preferably 15,000, more preferably 20,000, still more preferably 30,000, most preferably 4.
  • the upper limit is preferably 120,000, more preferably 110,000, and still more preferably 100,000.
  • the weight average molecular weight Mw b2 is as follows for all acrylate polymer blocks (b2). The weight average molecular weight is calculated and defined as the sum of the numerical values.
  • Mw b1 and Mw b2 are the respective stages of the production of the block copolymer (B), specifically, at the end of the polymerization for producing the methacrylic ester polymer block (b1) and the acrylate polymer.
  • the weight average molecular weight is measured at the end of the polymerization for producing the block (b2), and the difference between the measured value of the weight average molecular weight before the start of the polymerization and the measured value of the weight average molecular weight at the end of the polymerization is measured. This is a value obtained by considering it as the weight average molecular weight of the polymer block obtained in 1.
  • Each weight average molecular weight is a standard polystyrene conversion value measured by GPC (gel permeation chromatography).
  • the proportion of the acrylate polymer block (b2) in the block copolymer (B) is preferably 20% by mass or more and 90% by mass or less from the viewpoint of transparency, flexibility, molding processability, and surface smoothness. Preferably they are 30 mass% or more and 80 mass% or less.
  • the ratio of the acrylate polymer block (b2) in the block copolymer (B) is within the above range, the methacrylic resin composition of the present invention or a molded product made thereof is excellent in impact resistance, flexibility and the like.
  • a plurality of acrylic ester polymer blocks (b2) are contained in the block copolymer (B), the above ratio is calculated based on the total mass of all the acrylic ester polymer blocks (b2).
  • the block copolymer (B) is not particularly limited by the bonding form of the methacrylic ester polymer block (b1) and the acrylate polymer block (b2).
  • a methacrylic acid ester polymer block (b1) having one end connected to one end of an acrylic acid ester polymer block (b2) (diblock copolymer having a (b1)-(b2) structure); methacrylic acid A polymer in which one end of an acrylate polymer block (b2) is connected to each of both ends of the ester polymer block (b1) (a triblock copolymer having a structure (b2)-(b1)-(b2)); A triblock copolymer having a (b1)-(b2)-(b1) structure in which one end of a methacrylic ester polymer block (b1) is connected to each of both ends of the acrylate polymer block (b2) )
  • methacrylic acid ester polymer blocks (b1) and acrylic acid ester polymer blocks (b2) are connected in series
  • a block copolymer [(b1)-(b2)-] m X-structure star block in which one end of a plurality of arm block copolymers having the structure (b1)-(b2) are connected to each other to form a radial structure Copolymer); a block copolymer ([(b2)-(b1)-] m X structure in which one end of a plurality of arm block copolymers having the structure (b2)-(b1) is connected to form a radial structure) Star block copolymer); a block copolymer ([(b1)-([(b1)-(b1)-(b1)-(b1)-(b1)-(b1)-(b1)-(b1)-(b1) b2)-(b1)-] m X-structure star block copolymer); one end of a plurality of (b2)-(b1)-(b2) -structured arm block copolymers are connected to form a radial structure.
  • block copolymer ([(b2) - (b1) - (b2) - ] m X structure star block Polymer) and star block copolymers such as, and the like block copolymer having a branched structure.
  • X represents a coupling agent residue.
  • a diblock copolymer, a triblock copolymer, and a star block copolymer are preferable, and a diblock copolymer having a (b1)-(b2) structure, (b1)-(b2)-(b1 ) Structure triblock copolymer, [(b1)-(b2)-] m X structure star block copolymer, [(b1)-(b2)-(b1)-] m X structure star A block copolymer is more preferred.
  • Each m independently represents the number of arm block copolymers.
  • the block copolymer (B) may have a polymer block (b3) other than the methacrylic ester polymer block (b1) and the acrylate polymer block (b2).
  • the main structural units constituting the polymer block (b3) are structural units derived from monomers other than methacrylic acid esters and acrylic acid esters.
  • Examples of such monomers include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, ⁇ -methylstyrene, p-methylstyrene, m- Aromatic vinyl compounds such as methylstyrene; vinyl acetate, vinyl pyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ⁇ -caprolactone, valerolactone, etc. .
  • the bonding form of the methacrylic ester polymer block (b1), the acrylate polymer block (b2) and the polymer block (b3) is not particularly limited.
  • the bonding form of the block copolymer (B) comprising the methacrylic ester polymer block (b1), the acrylate polymer block (b2) and the polymer block (b3) for example, (b1)-(b2)
  • Examples thereof include a block copolymer having a structure of (b1)-(b3) and a block copolymer having a structure of (b3)-(b1)-(b2)-(b1)-(b3).
  • the composition ratio and molecular weight of the structural units constituting each polymer block (b3) may be the same as each other, May be different.
  • the block copolymer (B) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain end as necessary.
  • the block copolymer (B) has a weight average molecular weight Mw B of preferably 32,000 to 300,000, more preferably 45,000 to 230,000.
  • Mw B weight average molecular weight
  • Mw B weight average molecular weight
  • the ratio (Mw B / Mn B ) between Mw B and the number average molecular weight Mn B is preferably 1.0 or more and 2.0 or less, more preferably 1.0 or more and 1 .6 or less.
  • the refractive index of the block copolymer (B) is preferably 1.485 to 1.495, more preferably 1.487 to 1.493. When the refractive index is within this range, the transparency of the methacrylic resin composition of the present invention increases.
  • the “refractive index” means a value measured at a wavelength of 587.6 nm (D-line) as in Examples described later.
  • the method for producing the block copolymer (B) is not particularly limited, and a method according to a known method can be employed.
  • a method of living polymerizing monomers constituting each polymer block is generally used.
  • living polymerization methods include anionic polymerization in the presence of mineral acid salts such as alkali metals or alkaline earth metal salts using organic alkali metal compounds as polymerization initiators, and polymerization of organic alkali metal compounds.
  • a method for anionic polymerization in the presence of an organoaluminum compound as an initiator a method for polymerization using an organic rare earth metal complex as a polymerization initiator, a method for radical polymerization in the presence of a copper compound using an ⁇ -halogenated ester compound as an initiator And so on.
  • a method of producing a mixture containing the block copolymer (B) used in the present invention by polymerizing monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent, etc.
  • the block copolymer (B) can be obtained with high purity, the molecular weight and the composition ratio can be easily controlled, and it is economical.
  • a method in which anionic polymerization is used in the presence of an organoaluminum compound is preferred.
  • the mass ratio (B / A) of the block copolymer (B) to the methacrylic resin (A) is preferably 1/99 to 90/10, more preferably 5/95 to 85/15, more preferably 5/95 to 25/75.
  • the mass ratio of the block copolymer (B) to the methacrylic resin (A) is large, fine streak-like irregularities are generated on the surface of the plate-like molded body obtained by melt extrusion using a T-die, and the surface is smooth. There is a tendency that it is difficult to obtain a plate-like molded article having good properties.
  • the mass ratio of the block copolymer (B) to the methacrylic resin (A) is small, the tensile elastic modulus of the methacrylic resin composition and the plate-shaped molded body made thereof increases, and the flexibility tends to decrease. .
  • the methacrylic resin composition according to a preferred embodiment of the present invention contains a methacrylic resin (A), a block copolymer (B), and a polycarbonate resin.
  • a methacrylic resin composition that can easily adjust the retardation can be obtained.
  • the amount of the polycarbonate resin is preferably 1 to 10 parts by mass, more preferably 2 to 7 parts by mass, and still more preferably with respect to 100 parts by mass of the total amount of the methacrylic resin (A) and the methacrylic resin block copolymer (B). Is 3 to 6 parts by mass.
  • MVR value at 1.2Kg is preferably 130 ⁇ 250 cm 3 / 10 min, more preferably 0.99 ⁇ 230 cm 3/10 min, more preferably from 180 ⁇ 220 cm 3/10 min.
  • the MVR value is a value measured under conditions of 300 ° C., 1.2 kg load, and 10 minutes in accordance with JIS K7210.
  • the polycarbonate resin used in the present invention has a weight average molecular weight Mw p of preferably 15000 to 28000, more preferably 18000 to 27000, still more preferably 20000 to 24000.
  • MVR value and the weight average molecular weight of the polycarbonate resin can be adjusted by adjusting the amounts of the end terminator and the branching agent.
  • Mw p is the molecular weight in terms of standard polystyrene measured by GPC (gel permeation chromatography).
  • the glass transition temperature of the polycarbonate resin used in the present invention is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, and further preferably 140 ° C. or higher.
  • the upper limit of the glass transition temperature of the polycarbonate resin is preferably 180 ° C.
  • the polycarbonate resin used in the present invention is not particularly limited by its production method.
  • the phosgene method interfacial polymerization method
  • the melt polymerization method transesterification method
  • the aromatic polycarbonate resin preferably used in the present invention may be one obtained by subjecting a polycarbonate resin produced by a melt polymerization method to a post-treatment for adjusting the amount of terminal hydroxy groups.
  • Polyfunctional hydroxy compounds that are raw materials for producing polycarbonate resins include 4,4′-dihydroxybiphenyls optionally having substituents; bis (hydroxyphenyl) alkanes optionally having substituents Bis (4-hydroxyphenyl) ethers optionally having substituents; bis (4-hydroxyphenyl) sulfides optionally having substituents; bis optionally having substituents (4-hydroxyphenyl) sulfoxides; bis (4-hydroxyphenyl) sulfones optionally having substituents; bis (4-hydroxyphenyl) ketones optionally having substituents; Bis (hydroxyphenyl) fluorenes that may have; dihydroxy-p-terphenyls that may have a substituent; Dihydroxy-p-quaterphenyls which may be substituted; bis (hydroxyphenyl) pyrazines which may have a substituent; bis (hydroxyphenyl) menthanes which may have a substituent; Bis [2- (4-hydroxyphenyl) -2-
  • carbonate ester-forming compounds include various dihalogenated carbonyls such as phosgene, haloformates such as chloroformate, and carbonate ester compounds such as bisaryl carbonate.
  • the amount of the carbonate ester-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio in the reaction with the polyfunctional hydroxy compound.
  • the polymerization reaction is usually performed in a solvent in the presence of an acid binder.
  • the acid binder include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; trimethylamine, triethylamine, tributylamine, N, Tertiary amines such as N-dimethylcyclohexylamine, pyridine, dimethylaniline; quaternaries such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide Ammonium salts; quaternary phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide Rukot
  • an antioxidant such as sodium sulfite or hydrosulfide may be added to this reaction system.
  • the amount of the acid binder may be appropriately adjusted in consideration of the stoichiometric ratio in the reaction. Specifically, the acid binder is preferably used in an amount of 1 gram equivalent or more, preferably 1 to 5 gram equivalent, relative to 1 mole of hydroxyl group of the starting polyfunctional hydroxy compound.
  • End terminators include p-tert-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluorohexylphenyl) Phenol, p-tert-perfluorobutylphenol, 1- (P-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3 -Hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H- Perfluoronona
  • branching agents include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6-dimethyl-2,4,6-tris (4- Hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (2-hydroxyphenyl) benzene, 1,3,5- Tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) ) Cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy) 5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl)
  • the polycarbonate resin may contain a unit having a polyester structure, a polyurethane structure, a polyether structure or a polysiloxane structure in addition to the polycarbonate unit.
  • the methacrylic resin composition according to a preferred embodiment of the present invention contains a methacrylic resin (A), a block copolymer (B), and a phenoxy resin.
  • a methacrylic resin composition that can easily adjust the retardation can be obtained.
  • the amount of the phenoxy resin is preferably 1 to 10 parts by mass, more preferably 2 to 7 parts by mass, further preferably 100 parts by mass of the total amount of the methacrylic resin (A) and the methacrylic resin block copolymer (B). Is 3 to 6 parts by mass.
  • the phenoxy resin is a thermoplastic polyhydroxy polyether resin.
  • the phenoxy resin contains, for example, one or more structural units represented by the formula (1) and 50 mass% or more structural units represented by the formula (1).
  • X is a divalent group containing at least one benzene ring
  • R is a linear or branched alkylene group having 1 to 6 carbon atoms.
  • the structural unit represented by Formula (1) may be connected in any form of random, alternating, or block.
  • the phenoxy resin preferably contains 10 to 1000 structural units represented by the formula (1), more preferably 15 to 500, and still more preferably 30 to 300.
  • the phenoxy resin preferably has no epoxy group at the end.
  • a phenoxy resin having no epoxy group at the end is used, a film with few gel defects can be easily obtained.
  • the number average molecular weight of the phenoxy resin is preferably 3,000 to 2,000,000, more preferably 5,000 to 100,000, and most preferably 10,000 to 50,000. When the number average molecular weight is in this range, a methacrylic resin composition having high heat resistance and high strength can be obtained.
  • the glass transition temperature of the phenoxy resin is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and most preferably 95 ° C. or higher. If the glass transition temperature of the phenoxy resin is low, the heat resistance of the resulting methacrylic resin composition will be low.
  • the upper limit of the glass transition temperature of the phenoxy resin is not particularly limited, but is generally 150 ° C. If the glass transition temperature of the phenoxy resin is too high, the resulting molded product made of the methacrylic resin composition becomes brittle.
  • the phenoxy resin can be obtained from a condensation reaction between a dihydric phenol compound and an epihalohydrin or a polyaddition reaction between a dihydric phenol compound and a bifunctional epoxy resin.
  • the reaction can be carried out in solution or without solvent.
  • dihydric phenol compound used for the production of phenoxy resin examples include hydroquinone, resorcin, 4,4-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ketone, 2,2-bis (4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy Phenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (3-phenyl) -4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 1,3-
  • 4,4-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ketone, 2,2-bis (4-hydroxyphenyl) propane, or 9,9′-bis (4-hydroxyphenyl) is particularly preferred from the viewpoint of physical properties and cost.
  • Fluorene is preferred.
  • Examples of the bifunctional epoxy resins used in the production of the phenoxy resin include epoxy oligomers obtained by condensation reaction of the above divalent phenol compound and epihalohydrin, such as hydroquinone diglycidyl ether, resorcin diglycidyl ether, bisphenol S type epoxy resin, Bisphenol A type epoxy resin, bisphenol F type epoxy resin, methyl hydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl oxide diglycidyl ether, 2,6-dihydroxynaphthalenediglycidyl ether, dichlorobisphenol A di Glycidyl ether, tetrabromobisphenol A type epoxy resin, 9,9'-bis (4) -hydroxyphenyl) Diglycidyl ether, and the like can be mentioned.
  • bisphenol A type epoxy resin bisphenol S type epoxy resin, hydroquinone diglycidyl ether, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, or 9,9′-bis (4 ) -Hydroxyphenyl) full orange glycidyl ether is preferred.
  • reaction solvent that can be used in the production of the phenoxy resin
  • aprotic organic solvents such as methyl ethyl ketone, dioxane, tetrahydrofuran, acetophenone, N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, sulfolane and the like are preferably used.
  • reaction catalyst that can be used for the production of the phenoxy resin, alkali metal hydroxides, tertiary amine compounds, quaternary ammonium compounds, tertiary phosphine compounds, and quaternary phosphonium compounds are suitable as conventionally known polymerization catalysts. used.
  • X in the formula (1) is preferably a divalent group derived from the compounds represented by the formulas (2) to (8).
  • the position of the hands of the two bonds constituting the divalent group is not particularly limited as long as it is a chemically possible position.
  • X in formula (1) is preferably a divalent group having a bond that can be formed by extracting two hydrogen atoms from the benzene ring in the compounds represented by formulas (2) to (8).
  • the divalent group is preferably a divalent group having a bond that can be formed by extracting one hydrogen atom from any two benzene rings in the compounds represented by formulas (3) to (8).
  • R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms, and p is 1 It is an integer of any one of .about.4.
  • R 1 is a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a cycloalkylidene group having 3 to 20 carbon atoms.
  • R 2 and R 3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 2 to 6 carbon atoms.
  • An alkenyl group of the chain, and n and m are each independently an integer of 1 to 4.
  • R 6 and R 7 are each independently a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or A cycloalkylidene group having 3 to 20 carbon atoms.
  • R 5 and R 8 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a carbon number 2 to 6 linear or branched alkenyl groups, and q and r are each independently an integer of 1 to 4.
  • X may be a divalent group derived from a compound formed by condensing a plurality of benzene rings with an alicyclic ring or a heterocyclic ring.
  • a divalent group derived from a compound having a fluorene structure or a carbazole structure can be given.
  • Examples of the divalent group derived from the compounds represented by the above formulas (2) to (8) include the following. In addition, this illustration does not mean that X in this invention is limited to these.
  • the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (9) or (10), more preferably a structural unit represented by the formula (11).
  • a preferred embodiment of the phenoxy resin preferably contains 10 to 1000 structural units.
  • R 9 is a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a cycloalkylidene group having 3 to 20 carbon atoms.
  • R 10 is a linear or branched alkylene group having 1 to 6 carbon atoms.
  • phenoxy resins YP-50 and YP-50S of Nippon Steel & Sumikin Chemical, jER series of Mitsubishi Chemical, PKFE and PKHJ which are phenoxy resins of InChem, etc. can be used.
  • the methacrylic resin composition of the present invention may contain other polymers in addition to the methacrylic resin (A), the block copolymer (B), and the polycarbonate resin or phenoxy resin.
  • polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and 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 polymer, methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; nylon 6 Polyamide such as nylon 66 and polyamide elastomer; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinyl fluoride Examples include redene, polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone
  • the methacrylic resin composition according to the present invention includes fillers, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes. Additives that may be blended in ordinary resins such as pigments, light diffusing agents, organic dyes, matting agents, and phosphors may be included. These may be added to either one or both of the polymerization reaction liquid when producing the methacrylic resin (A) or the block copolymer (B), or the methacrylic resin (A) produced by the polymerization reaction or You may add to any one or both of a block copolymer (B).
  • fillers examples include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
  • the amount of filler that can be contained in the methacrylic resin composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.
  • the antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen.
  • phosphorus antioxidants hindered phenol antioxidants, thioether antioxidants and the like can be mentioned. These antioxidants may be used alone or in combination of two or more.
  • a phosphorus-based antioxidant and a hindered phenol-based antioxidant are preferable, and a combination of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is more preferable.
  • the amount of phosphorus antioxidant used is 1: 5 to 2: 1 is preferable, and 1: 2 to 1: 1 is more preferable.
  • Examples of phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: ADK STAB HP-10), tris (2,4-di-t- Butylphenyl) phosphite (manufactured by BASF; trade name: IRGAFOS 168), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9 -Diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADK STAB PEP-36) is preferable.
  • pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name: IRGANO01010)
  • octadecyl-3- 3,5-di-t-butyl-4-hydroxyphenyl) propionate
  • BASF trade name IRGANO01076
  • the thermal degradation inhibitor can prevent thermal degradation of the resin by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
  • the thermal degradation inhibitor include 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilizer GS) 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. These may be used alone or in combination of two or more.
  • 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.
  • Benzotriazoles are preferable as ultraviolet absorbers used when the methacrylic resin composition of the present invention is applied to applications requiring such properties 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 (manufactured by BASF; trade name TINUVIN329), 2- (2H- Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis [6- (2H-benzotriazole-2 -Yl) -4-tert-octylphenol] (manufactured by ADEKA; LA-31), 2- (5-octylthio-2H-benzotriazol-2-yl) -6
  • an ultraviolet absorber having a maximum molar extinction coefficient ⁇ max at wavelengths of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less can suppress the yellowness of the resulting molded article.
  • examples of such an ultraviolet absorber include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, trade name: Sundebore VSU). Of these ultraviolet absorbers, benzotriazoles are preferably used from the viewpoint of suppressing resin degradation due to ultraviolet irradiation.
  • a triazine UV 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), Its analogs are hydroxyphenyltriazine ultraviolet absorbers (manufactured by BASF; CGL777MPA-D and TINUVIN460), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5- A triazine etc. can be mentioned.
  • WO2011 / 089794A1 WO2012 / 124395A1, JP2012-012476, JP2013-023461, JP2013-112790
  • Metal complexes having a heterocyclic ligand disclosed in JP2013-194037, JP2014-62228, JP2014-88542, JP2014-88543, and the like for example, A compound having a structure represented by the formula (A) is preferably used as the ultraviolet absorber.
  • M is a metal atom.
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently a divalent group other than a carbon atom (oxygen atom, sulfur atom, NH, NR 5 etc.).
  • R 5 is each independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, and an aralkyl group. The substituent may further have a substituent on the substituent.
  • Z 1 and Z 2 are each independently a trivalent group (nitrogen atom, CH, CR 6 etc.).
  • R 6 is each independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, and an aralkyl group.
  • the substituent may further have a substituent on the substituent.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, alkyl group, hydroxyl group, carboxyl group, alkoxyl group, halogeno group, alkylsulfonyl group, monophorinosulfonyl group, piperidinosulfonyl group, thio Substituents such as a morpholinosulfonyl group and a piperazinosulfonyl group.
  • the substituent may further have a substituent on the substituent.
  • a, b, c and d each represent the number of R 1 , R 2 , R 3 and R 4 and are any integer of 1 to 4; ]
  • Examples of the ligand of the heterocyclic structure include 2,2′-iminobisbenzothiazole, 2- (2-benzothiazolylamino) benzoxazole, 2- (2-benzothiazolylamino) benzimidazole, ( 2-benzothiazolyl) (2-benzimidazolyl) methane, bis (2-benzoxazolyl) methane, bis (2-benzothiazolyl) methane, bis [2- (N-substituted) benzimidazolyl] methane, and their derivatives .
  • As the central metal of such a metal complex copper, nickel, cobalt, and zinc are preferably used.
  • the metal complexes In order to use these metal complexes as ultraviolet absorbers, it is preferable to disperse the metal complexes in a medium such as a low molecular compound or a polymer.
  • the addition amount of the metal complex is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the film of the present invention. Since the metal complex has a large molar extinction coefficient at a wavelength of 380 nm to 400 nm, the amount to be added is small in order to obtain a sufficient ultraviolet absorption effect. If the amount added is small, deterioration of the resin film appearance due to bleeding out or the like can be suppressed. Moreover, since the metal complex has high heat resistance, there is little deterioration and decomposition during molding. Furthermore, since the metal complex has high light resistance, the ultraviolet absorption performance can be maintained for a long time.
  • 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-tetraalkylpiperidine skeleton.
  • lubricant examples include stearic acid, behenic acid, stearamide acid, methylene bisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.
  • the release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • higher alcohols and glycerin fatty acid monoester are used in combination, the ratio is not particularly limited, but the amount of higher alcohol used: the amount of glycerin fatty acid monoester is 2.5: 1 to 3. 5: 1 is preferable, and 2.8: 1 to 3.2: 1 is more preferable.
  • polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m which can be usually produced by an emulsion polymerization method, are used.
  • the polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be.
  • particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.
  • the polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g.
  • the intrinsic viscosity is too small, the effect of improving moldability tends to be low. If the intrinsic viscosity is too large, the molding processability of the methacrylic resin composition tends to be lowered.
  • Specific examples include Metablene-P series manufactured by Mitsubishi Rayon Co. and Paraloid series manufactured by Rohm and Haas.
  • organic dye a compound having a function of converting ultraviolet light into visible light is preferably used.
  • Examples of the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
  • Fluorescent materials include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent brighteners, fluorescent bleaches, and the like.
  • the total amount of the light diffusing agent, the organic dye, the matting agent, and the phosphor is preferably 7% by mass or less, more preferably 5% by mass or less, and further preferably 4% by mass or less.
  • the methacrylic resin composition of the present invention can be produced by a known method.
  • the methacrylic resin composition of this invention can manufacture a methacrylic resin composition by melt-kneading a methacrylic resin (A), a block copolymer (B), another polymer, etc., for example.
  • the melt kneading can be performed using a melt kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer.
  • the temperature at the time of kneading can be appropriately set according to the softening temperature of the methacrylic resin (A), the block copolymer (B), and other polymers, and is preferably 150 ° C. to 300 ° C.
  • the methacrylic resin composition can also be produced by polymerizing a monomer that is a raw material of the methacrylic resin (A) in the presence of the block copolymer (B). Such polymerization can be performed in the same manner as the polymerization method for producing the methacrylic resin (A).
  • the manufacturing method by polymerizing the monomer which is a raw material of the methacrylic resin (A) in the presence of the block copolymer (B) includes melt-kneading the methacrylic resin (A) and the block copolymer (B). Since the thermal history applied to the methacrylic resin is shortened as compared with the method produced by the above, the thermal decomposition of the methacrylic resin is suppressed, and a molded product with less coloring and foreign matter is easily obtained.
  • the methacrylic resin composition of the present invention has a weight average molecular weight Mw c of preferably 32,000 to 300,000, more preferably 45,000 to 230,000, and still more preferably 60,000 to 200,000.
  • the ratio Mw c / Mn c of Mw c and number average molecular weight Mn c is preferably 1.2 to 2.5, more preferably 1.3 to 2.0.
  • Mw c and Mw c / Mn c are in this range, the molding processability of the methacrylic resin composition becomes good, and it becomes easy to obtain a molded article excellent in impact resistance and toughness.
  • Mw c and M n c are molecular weights in terms of standard polystyrene measured by GPC (gel permeation chromatography).
  • the methacrylic resin composition of the present invention has a melt flow rate determined by measurement under conditions of 230 ° C. and a load of 3.8 kg, preferably 0.1 g / 10 min or more, more preferably 0.2 to 30 g / 10. Min, more preferably 0.5 to 20 g / 10 min, most preferably 1.0 to 10 g / 10 min.
  • the glass transition temperature of the methacrylic resin composition of the present invention is preferably 120 ° C. or higher, more preferably 123 ° C. or higher, and further preferably 124 ° C. or higher.
  • the upper limit of the glass transition temperature of the methacrylic resin composition is not particularly limited, but is preferably 130 ° C.
  • the methacrylic resin composition of the present invention can be in the form of pellets or the like in order to enhance convenience during storage, transportation or molding.
  • the molded product of the present invention is composed of the methacrylic resin composition of the present invention.
  • the manufacturing method of the molded object of this invention is not specifically limited.
  • T-die method laminate method, co-extrusion method, etc.
  • inflation method co-extrusion method, etc.
  • compression molding method blow molding method
  • calendar molding method vacuum molding method
  • injection molding method insert method, two-color method
  • Press molding core back method, sandwich method, etc.
  • melt casting methods and solution casting methods.
  • the T die method, the inflation method, or the injection molding method is preferable from the viewpoint of high productivity and cost.
  • molded article of the present invention include, for example, billboard parts such as advertising towers, stand signboards, sleeve signboards, billboard signs, and rooftop signs; display parts such as showcases, partition plates, and store displays; fluorescent lamp covers, mood lighting Lighting parts such as covers, lamp shades, light ceilings, light walls, and chandeliers; interior parts such as pendants and mirrors; architectures such as doors, domes, safety window glass, partitions, staircases, balcony waistboards, and roofs for leisure buildings Parts: Aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, and other transport related parts; audio visual nameplates, stereo covers, TV protection Electronic devices such as masks and display covers for vending machines Parts: Medical equipment parts such as incubators and X-ray parts; machine-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; light guide plates and films for front lights of display devices, guides for back
  • the molded body of the present invention has high transparency, small change in haze over a wide temperature range, high glass transition temperature, small thickness direction retardation, small thermal shrinkage, high strength and moldability. Excellent.
  • the molded body of the present invention includes, for example, various covers, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, watches, and other optical equipment, and also related to video / optical recording / optical communication / information equipment.
  • the molded article of the present invention includes, for example, various liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, liquid crystal displays for vehicles, liquid crystal monitors, light control panels, displays for OA devices, displays for AV devices, It can be used for an electroluminescence display element or a touch panel.
  • the molded article of the present invention can be used for, for example, building interior / exterior members, curtain walls, roof members, roof materials, window members, gutters, exteriors, etc.
  • building material applications such as wall materials, flooring materials, construction materials, road construction members, retroreflective films / sheets, agricultural films / sheets, lighting covers, signboards, translucent sound insulation walls, etc. It is.
  • the film of the present invention comprises the methacrylic resin composition of the present invention.
  • the film of the present invention preferably contains 1 to 9% by mass, more preferably 2 to 7% by mass, and further preferably 3 to 6% by mass of a polycarbonate resin from the viewpoint of reducing the retardation in the thickness direction. It consists of the methacrylic resin composition of the invention.
  • the film of the present invention can be produced by a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, or the like. Of these, the extrusion molding method is preferred from the viewpoint that a film having excellent transparency, improved toughness, excellent handleability, and excellent balance between toughness, surface hardness and rigidity can be obtained.
  • the temperature of the methacrylic resin composition discharged from the extruder is preferably set to 160 to 270 ° C., more preferably 220 to 260 ° C.
  • the methacrylic resin composition is extruded from a T die in a molten state, and then it is applied to two or more specular rolls. Or the method including pinching with a mirror surface belt and shape
  • the mirror roll or mirror belt is preferably made of metal.
  • the linear pressure between the pair of mirror rolls or the mirror belt is preferably 10 N / mm or more, more preferably 30 N / mm or more.
  • the surface temperature of the mirror roll or the mirror belt is preferably 130 ° C. or less.
  • the pair of mirror rolls or mirror belts preferably have at least one surface temperature of 60 ° C. or higher.
  • the methacrylic resin composition discharged from the extruder can be cooled at a speed faster than natural cooling, and a film having excellent surface smoothness and low haze can be easily produced.
  • the thickness of the unstretched film obtained by extrusion molding is preferably 10 to 300 ⁇ m.
  • the haze of the film is preferably 0.5% or less, more preferably 0.3% or less at a thickness of 100 ⁇ m.
  • the film of the present invention may be subjected to stretching treatment.
  • the film subjected to the stretching treatment has high mechanical strength and is difficult to crack.
  • the method for the stretching treatment is not particularly limited, and examples thereof include uniaxial stretching, simultaneous biaxial stretching, sequential biaxial stretching, and tuber stretching.
  • the temperature during stretching is preferably from 100 to 200 ° C., more preferably from 120 to 160 ° C. from the viewpoint that uniform stretching can be performed and a high-strength film can be obtained. Stretching is usually performed at 100 to 5000% / min on a length basis. A film with less heat shrinkage can be obtained by heat setting after stretching.
  • the film of the present invention is not particularly limited by its thickness, but when used as an optical film, the thickness is preferably 1 to 300 ⁇ m, more preferably 10 to 50 ⁇ m, still more preferably 15 to 40 ⁇ m.
  • the film of the present invention has a haze at a thickness of 50 ⁇ m, preferably 0.2% or less, more preferably 0.1% or less. Thereby, it is excellent in surface glossiness and transparency. Further, in optical applications such as a liquid crystal protective film and a light guide film, the use efficiency of the light source is preferably increased. Furthermore, it is preferable because it is excellent in shaping accuracy when performing surface shaping.
  • a functional layer may be provided on the surface of the film of the present invention.
  • the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, an anti-sticking layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer, and a slippery layer such as fine particles.
  • the hard coat layer is a layer having a function of protecting the surface of the film of the present invention by increasing the hardness.
  • the hard coat layer can be appropriately selected from conventionally known ones.
  • the hard coat layer is preferably a layer made of a cured product of the curable resin composition.
  • an ionizing radiation curable resin other known curable resins, or the like may be appropriately employed depending on the required performance.
  • the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins.
  • acrylate-based ionizing radiation curable resins include monofunctional (meth) acrylate monomers, bifunctional (meth) acrylate monomer monomers, (meth) acrylate monomers such as trifunctional or higher (meth) acrylate monomers, urethane ( It consists of (meth) acrylic acid ester oligomers such as (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate, or (meth) acrylic acid ester prepolymers.
  • examples of the trifunctional or higher functional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
  • the hard coat layer is obtained by applying the resin composition for hard coat layer containing the curable resin directly to the film of the present invention or by applying and curing the primer layer surface of the film of the present invention coated with the primer layer. can get.
  • the antireflection layer is a layer that prevents reflection of a background due to specular reflection of extraneous light.
  • the antireflection layer laminated on the surface of the film of the present invention can be appropriately selected from conventionally known antireflection layers.
  • As the antireflection layer for example, a high refractive index layer and a low refractive index layer are alternately laminated, and a multilayered (multi-coated) resin layer such that the outermost surface is a low refractive index layer, a fine uneven shape, etc. Examples thereof include an antireflection layer in which the nanostructure is formed.
  • the high refractive index layer examples include a resin composition for forming a high refractive index layer containing metal oxide fine particles such as titanium, tantalum, zirconium, and indium, and a cured product thereof.
  • the low refractive index layer examples include a resin composition for forming a low refractive index layer containing a fluorine-based resin, hollow silica fine particles, and the like, and a cured product thereof.
  • the antiglare layer is a layer that scatters or diffuses extraneous light.
  • extraneous light can be diffused by roughening the light incident surface.
  • This roughening treatment includes a method of forming fine irregularities on the surface of the substrate itself, such as a sand blasting method or an embossing method, and an organic filler such as an inorganic filler such as silica or / and resin particles on the surface of the substrate.
  • a method of applying a radiation curable or thermosetting resin composition containing a filler to form a rough surface by rough coating, and applying a resin composition capable of forming a sea-island structure to form a porous film The method of forming and roughening a surface can be mentioned.
  • a curable acrylic resin, an ionizing radiation curable resin that can be used for the hard coat layer, and the like are preferably used from the viewpoint of increasing the strength of the surface layer.
  • an antistatic layer may be provided.
  • the antistatic layer can be appropriately selected from conventionally known ones. For example, it can be set as an antistatic layer by mixing and using a well-known antistatic agent in the said resin composition for hard-coat layers.
  • Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, phosphate ester bases.
  • a polymerizable compound such as an organometallic compound such as an agent can be used as an antistatic agent.
  • An adhesive layer may be provided on the surface of the film of the present invention.
  • an adhesive constituting the adhesive layer for example, a water-based adhesive, a solvent-based adhesive, a hot-melt adhesive, an active energy ray-curable adhesive, or the like can be used. Of these, water-based adhesives and active energy ray-curable adhesives are suitable.
  • the methacrylic resin composition of the present invention Since the methacrylic resin composition of the present invention has small birefringence, it is easy to obtain a film having a small in-plane direction retardation or thickness direction retardation.
  • the film of the present invention has an in-plane retardation Re for light having a wavelength of 590 nm and a film thickness of 40 ⁇ m, it is preferably 5 nm or less, more preferably 4 nm or less, still more preferably 3 nm or less, particularly preferably 2 nm or less, Most preferably, it is 1 nm or less.
  • the film of the present invention preferably has a thickness direction retardation Rth for light having a wavelength of 590 nm of ⁇ 5 nm to 5 nm, more preferably ⁇ 4 nm to 4 nm, and still more preferably ⁇ 40 nm when the film thickness is 40 ⁇ m. It is 3 nm to 3 nm, particularly preferably ⁇ 2 nm to 2 nm, and most preferably ⁇ 1 nm to 1 nm. If the in-plane direction phase difference and the thickness direction phase difference are within such ranges, the influence on the display characteristics of the image display apparatus due to the phase difference can be significantly suppressed.
  • the in-plane direction phase difference Re and the thickness direction phase difference Rth are values defined by the following equations, respectively.
  • Re (n x ⁇ n y ) ⁇ d
  • Rth ((n x + n y ) / 2 ⁇ n z ) ⁇ d
  • n x is a refractive index in a slow axis direction of the film
  • n y is a refractive index in a fast axis direction of the film
  • n z is a refractive index in the thickness direction of the film
  • d (nm ) Is the thickness of the film.
  • the slow axis refers to the direction in which the in-plane refractive index is maximized
  • the fast axis refers to the direction perpendicular to the slow axis in the plane.
  • the methacrylic resin composition of the present invention has high transparency and high heat resistance, and can be formed into a thin film.
  • the film according to the present invention has a polarizer protective film, a retardation film, a liquid crystal protective plate, a surface material for a portable information terminal, a display window protective film for a portable information terminal, a light guide film, silver nanowires and carbon nanotubes on the surface. It is suitable for a transparent conductive film coated on the front surface of various displays, front plates of various displays, and the like. In particular, a film having a small retardation obtained by the present invention is suitable for a polarizer protective film.
  • the film of the present invention is an IR cut film, a crime prevention film, a scattering prevention film, a decorative film, a metal decorative film, a solar cell backsheet, a flexible solar cell front sheet, a shrink film, an in-mold label film, It can be used as a base film for window films and gas barrier films.
  • the film of the present invention When the film of the present invention is used as a polarizer protective film or a retardation film, it may be laminated only on one side of the polarizer film or on both sides. When laminating with a polarizer film, it can be laminated via an adhesive layer or an adhesive layer.
  • a stretched film made of a polyvinyl alcohol resin and iodine can be used, and the film thickness is 1 ⁇ m to 100 ⁇ m.
  • the polarizing plate using the polarizer protective film of the present invention includes at least one polarizer protective film of the present invention.
  • a polarizer formed from a polyvinyl alcohol-based resin and the polarizer protective film of the present invention are laminated via an adhesive layer.
  • the adhesive layer 12 and the polarizer protective film 14 of the present invention are laminated in this order on one surface of the polarizer 11,
  • the adhesive layer 15 and the optical film 16 are laminated in this order on the other surface of the polarizer 11.
  • the easy-adhesion layer 13 may be provided on the surface of the polarizer protective film 14 of the present invention in contact with the adhesive layer 12 (see FIG. 2)
  • the polarizer protective film 14 of the present invention is preferably easy-adhesive. Adhesion can be maintained without providing the layer 13.
  • the easy-adhesion layer 13 it is preferable in terms of better adhesion between the adhesive layer 12 and the polarizer protective film 14, but is inferior in terms of productivity and cost.
  • the polarizer formed from the polyvinyl alcohol-based resin can be obtained, for example, by dyeing a polyvinyl alcohol-based resin film with a dichroic substance (typically iodine or a dichroic dye) and uniaxially stretching.
  • the polyvinyl alcohol-based resin film is formed by any suitable method (for example, casting method, casting method, extrusion method for casting a solution obtained by dissolving a resin in water or an organic solvent). Can be obtained.
  • the degree of polymerization of the polyvinyl alcohol resin is preferably 100 to 8000, more preferably 1400 to 6000.
  • the thickness of the polyvinyl alcohol-based resin film used for the polarizer can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is typically 1 to 80 ⁇ m.
  • the adhesive layer that can be provided on the polarizing plate using the polarizer protective film of the present invention is not particularly limited as long as it is optically transparent.
  • an adhesive constituting the adhesive layer for example, a water-based adhesive, a solvent-based adhesive, a hot-melt adhesive, a UV curable adhesive, or the like can be used. Of these, water-based adhesives and UV curable adhesives are preferred.
  • the water-based adhesive is not particularly limited, and examples thereof include a vinyl polymer, gelatin, vinyl latex, polyurethane, isocyanate, polyester, and epoxy.
  • a catalyst such as a crosslinking agent, other additives, and an acid can be blended as necessary.
  • an adhesive containing a vinyl polymer is preferably used, and the vinyl polymer is preferably a polyvinyl alcohol resin.
  • the polyvinyl alcohol-based resin can contain a water-soluble crosslinking agent such as boric acid, borax, glutaraldehyde, melamine, or oxalic acid.
  • aqueous adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by mass of a solid content.
  • the adhesive may contain a metal compound filler. With the metal compound filler, the fluidity of the adhesive layer can be controlled, the film thickness can be stabilized, and a polarizing plate having a good appearance, uniform in-plane and no adhesive variation can be obtained.
  • the method for forming the adhesive layer is not particularly limited. For example, it can be formed by applying the adhesive to an object and then heating or drying.
  • coating of an adhesive agent may be performed with respect to the polarizer protective film or optical film of this invention, and may be performed with respect to a polarizer.
  • the polarizer protective film or the optical film and the polarizer can be pressed together to laminate them. In the lamination, a roll press machine or a flat plate press machine can be used.
  • the heating and drying temperature and drying time are appropriately determined according to the type of adhesive.
  • the thickness of the adhesive layer is preferably 0.01 to 10 ⁇ m, more preferably 0.03 to 5 ⁇ m in the dry state.
  • the easy adhesion treatment that can be applied to the polarizing plate using the polarizer protective film of the present invention improves the adhesion of the surface where the polarizer protective film and the polarizer are in contact.
  • Examples of the easy adhesion treatment include surface treatment such as corona treatment, plasma treatment, and low-pressure UV treatment.
  • the silicone layer which has a reactive functional group can be mentioned, for example.
  • the material of the silicone layer having a reactive functional group is not particularly limited.
  • an isocyanate group-containing alkoxysilanol, an amino group-containing alkoxysilanol, a mercapto group-containing alkoxysilanol, a carboxy-containing alkoxysilanol, an epoxy group-containing Examples include alkoxysilanols, vinyl type unsaturated group-containing alkoxysilanols, halogen group-containing alkoxylanols, and isocyanate group-containing alkoxysilanols.
  • amino silanols are preferred.
  • a titanium-based catalyst or tin-based catalyst for efficiently reacting silanol to the silanol the adhesive strength can be strengthened.
  • other additives include tackifiers such as terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins; stabilizers such as ultraviolet absorbers, antioxidants, and heat stabilizers.
  • the layer which consists of what saponified cellulose acetate butyrate resin as an easily bonding layer is also mentioned.
  • the easy-adhesion layer is formed by coating and drying by a known technique.
  • the thickness of the easy-adhesion layer is preferably 1 to 100 nm, more preferably 10 to 50 nm in a dry state.
  • the chemical solution for forming an easy adhesion layer may be diluted with a solvent.
  • the dilution solvent is not particularly limited, and examples thereof include alcohols.
  • the dilution concentration is not particularly limited, but is preferably 1 to 5% by mass, more preferably 1 to 3% by mass.
  • the optical film 16 may be the polarizer protective film of the present invention, or any other appropriate optical film.
  • the optical film can exhibit functions such as a polarizer protection function, a brightness enhancement function, a viewing angle adjustment function, and a light diffusion function.
  • the optical film is not particularly limited depending on the material, and examples thereof include a film made of cellulose resin, polycarbonate resin, cyclic polyolefin resin, methacrylic resin, polyethylene terephthalate resin, and the like.
  • Cellulose resin is an ester of cellulose and fatty acid.
  • Specific examples of the cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among these, cellulose triacetate is particularly preferable.
  • Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available cellulose triacetate products are trade names “UV-50”, “UV-80”, “SH-80”, “TD-80U”, “TD-TAC”, “UZ-” manufactured by FUJIFILM Corporation. TAC ",” KC series "manufactured by Konica Minolta, and the like.
  • the cyclic polyolefin resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Can be mentioned. Specific examples include cyclic olefin ring-opening (co) polymers, cyclic olefin addition polymers, cyclic olefins and ⁇ -olefins such as ethylene and propylene (typically random copolymers), And the graft polymer which modified these by unsaturated carboxylic acid or its derivative (s), those hydrides, etc. can be mentioned. Specific examples of the cyclic olefin include norbornene monomers.
  • cyclic polyolefin resins Various products are commercially available as cyclic polyolefin resins. Specific examples include trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION, product names “ARTON” manufactured by JSR Corporation, “TOPASS” manufactured by Polyplastics Corporation, and products manufactured by Mitsui Chemicals, Inc. Product name “APEL”.
  • any appropriate methacrylic resin can be adopted as long as the effects of the present invention are not impaired.
  • polymethacrylate such as polymethylmethacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (meth) Acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), polymer having alicyclic hydrocarbon group (eg, methyl methacrylate- methacrylic acid cyclohexyl copolymer, methyl methacrylate) -(Meth) acrylic acid norbornyl copolymer).
  • methacrylic resin constituting the optical film 16 include, for example, methyl methacrylate and maleimide-based singles described in Acrypet VH and Acrypet VRL20A, manufactured by Mitsubishi Rayon Co., Ltd., JP2013-033237A and WO2013 / 005634.
  • Acrylic resin copolymerized with a monomer acrylic resin having a ring structure in the molecule described in WO2005 / 108438, methacrylic resin having a ring structure in the molecule described in JP2009-197151, intramolecular crosslinking And a high glass transition temperature (Tg) methacrylic resin obtained by intramolecular cyclization reaction.
  • Tg glass transition temperature
  • a methacrylic resin having a lactone ring structure can also be used. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.
  • Examples of the methacrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, JP 2005-146084, and the like. And a methacrylic resin having a lactone ring structure as described in 1. above.
  • Examples of the polyethylene terephthalate resin constituting the optical film 16 include polyethylene terephthalate resins described in WO2011-162198, WO2015-037527, WO2007-020909, and JP2010-204630.
  • the polarizing plate using the polarizer protective film of the present invention can be used for an image display device.
  • the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED), and a liquid crystal display device.
  • the liquid crystal display device includes a liquid crystal cell and the polarizing plate disposed on at least one side of the liquid crystal cell.
  • the chromatogram was measured under the following conditions by gel permeation chromatography (GPC), and the value converted into the molecular weight of standard polystyrene was calculated.
  • the baseline is that the slope of the peak on the high molecular weight side of the GPC chart changes from zero to positive when viewed from the earlier retention time, and the slope of the peak on the low molecular weight side is from negative to zero when viewed from the earlier retention time. A line connecting the points that change to.
  • Glass transition temperature Tg Glass transition temperature Tg
  • DSC-50 product number manufactured by Shimadzu Corporation
  • n 23D Refractive index n 23D of methacrylic resin (A) and block copolymer (B)
  • a sheet of 3 cm ⁇ 3 cm and a thickness of 3 mm was produced by press molding, and a refractive index at a wavelength of 587.6 nm (D line) at 23 ° C. and 50% RH using Kalnew Optical Co., Ltd. “KPR-200”. n23D was measured.
  • MFR Melt Mass Flow Rate
  • Production Example 1 (Production of methacrylic resin [A-1]) The inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, at room temperature, 1600 g of toluene, 2.49 g (1,0.8 mmol) of 1,1,4,7,10,10-hexamethyltriethylenetetramine, isobutyl bis (2,6-dioxy) having a concentration of 0.45M. 5.
  • the diluted solution was poured into 100 kg of methanol to obtain a precipitate.
  • the obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours, Mw A 79400, Mw A / Mn A 1.08, syndiotacticity (rr) 70%, glass transition temperature 130 ° C., low molecular weight Component content 0.19% by mass, high molecular weight component content 0.02% by mass, MFR 0.9 g / 10 min, n 23D 1.489, and content of structural unit derived from methyl methacrylate 100% by mass A methacrylic resin [A-1] was obtained.
  • Production Example 2 (Production of methacrylic resin [A-2]) The inside of the autoclave equipped with the stirrer and the sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate, 0.0052 parts by mass of 2,2′-azobis (2-methylpropionitrile (hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.), and 0.23 parts by mass of n-octyl mercaptan was added and stirred to obtain a raw material liquid, and nitrogen was fed into the raw material liquid to remove dissolved oxygen in the raw material liquid. The raw material liquid was put to 2/3 of the capacity in a tank reactor connected to the autoclave by piping.
  • the polymerization reaction was started in a batch mode while maintaining the temperature at 140 ° C.
  • the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate of an average residence time of 150 minutes, and the reaction liquid is supplied at a flow rate corresponding to the supply flow rate of the raw material liquid.
  • the reaction liquid temperature in the reactor was maintained at 140 ° C., and the polymerization reaction was switched to a continuous flow system. After switching, the polymerization conversion in the steady state was 55% by mass.
  • the reaction liquid withdrawn from the tank reactor in a steady state was heated by supplying it to a multi-tubular heat exchanger having an internal temperature of 230 ° C. at a flow rate with an average residence time of 2 minutes.
  • the heated reaction liquid was introduced into a flash evaporator, and volatile components mainly composed of unreacted monomers were removed to obtain a molten resin.
  • the molten resin from which volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 260 ° C., discharged into a strand, cut with a pelletizer, Mw A 101000, Mw A / Mn A 1.87, syndiotactic City (rr) 52%, glass transition temperature 120 ° C., low molecular weight component content 2.54% by mass, high molecular weight component content 0.73% by mass, MFR 1.6 g / 10 min, n 23D 1.491, and methacryl A pellet-shaped methacrylic resin [A-2] having a structural unit content derived from methyl acid of 100% by mass was obtained.
  • Production Example 3 (Production of methacrylic resin [A-3]) A mixture of 57 parts by weight of methacrylic resin [A-1] and 43 parts by weight of methacrylic resin [A-2] was mixed at 250 ° C. with a twin-screw extruder (manufactured by Technobel Co., Ltd., trade name: KZW20TW-45MG-NH-600).
  • Production Example 4 (Production of methacrylic resin [A-4]) 0.07 part by mass of a polymerization initiator (2,2′-azobis (2,4-dimethylvaleronitrile), hydrogen abstraction capacity: 1%, 10 hour half-life temperature: 51 ° C.) and 100 parts by mass of methyl methacrylate 0.26 parts by mass of a chain transfer agent (n-octyl mercaptan) was added and dissolved to obtain a raw material solution. 0.03 parts by mass of sodium sulfate and 0.46 parts by mass of the suspension dispersant were mixed with 100 parts by mass of ion-exchanged water to obtain a mixed solution.
  • a polymerization initiator (2,2′-azobis (2,4-dimethylvaleronitrile), hydrogen abstraction capacity: 1%, 10 hour half-life temperature: 51 ° C.
  • a chain transfer agent n-octyl mercaptan
  • a pressure-resistant polymerization tank 420 parts by mass of the mixed solution and 210 parts by mass of the raw material liquid were charged, and the polymerization reaction was started at a temperature of 60 ° C. while stirring in a nitrogen atmosphere.
  • the temperature was raised to 70 ° C., and stirring was continued at 70 ° C. for 1 hour to obtain a dispersion in which bead-shaped fine particles were dispersed. Fine particles are collected from the dispersion, washed with ion-exchanged water, and then dried under reduced pressure at 80 ° C.
  • a bead-shaped methacrylic resin [A-4] having a structural unit content of 100% by mass was obtained.
  • Production Example 5 (Production of methacrylic resin [A-5]) 0.10 parts by weight of a polymerization initiator (2,2′-azobis (2-methylpropionitrile), 85% by weight of methyl methacrylate and 15 parts by weight of methyl acrylate, hydrogen abstraction capacity: 1%, half-life for 1 hour Temperature: 83 ° C.) and 0.2 parts by mass of a chain transfer agent (n-octyl mercaptan) were added and dissolved to obtain a raw material solution. 0.03 parts by mass of sodium sulfate and 0.46 parts by mass of the suspension dispersant were mixed with 100 parts by mass of ion-exchanged water to obtain a mixed solution.
  • a polymerization initiator 2,2′-azobis (2-methylpropionitrile)
  • 85% by weight of methyl methacrylate and 15 parts by weight of methyl acrylate hydrogen abstraction capacity: 1%, half-life for 1 hour Temperature: 83 ° C.
  • a chain transfer agent
  • Mw A-5 having a derived structural unit content of 85 mass% was obtained.
  • Production Example 6 (Production of methacrylic resin [A-6]) The inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, at room temperature, 1600 g of toluene, 3.19 g (1,3.9 mmol) of 1,1,4,7,10,10-hexamethyltriethylenetetramine, isobutylbis (2,6-dioxy) having a concentration of 0.45 M were added.
  • the obtained solution was diluted by adding 1500 g of toluene. Next, the diluted solution was poured into 100 kg of methanol to obtain a precipitate.
  • the obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours, Mw A 58900, Mw A / Mn A 1.06, syndiotacticity (rr) 74%, glass transition temperature 130 ° C., low molecular weight component Methacrylic resin having a content of 0.02% by mass, a high molecular weight component of 0.01% by mass, MFR 2.1 g / 10 min, n 23D 1.489, and a structural unit content derived from methyl methacrylate of 100% by mass [A-6] was obtained.
  • Production Example 7 (Production of methacrylic resin [A-7]) 20% maleic anhydride solution dissolved in methyl isobutyl ketone so that maleic anhydride has a concentration of 20% by mass and methyl so that t-butylperoxy-2-ethylhexanoate becomes 2% by mass.
  • a 10 L autoclave equipped with a stirrer was charged with 28 g of a 20% maleic anhydride solution, 224 g of styrene, 130 g of methyl methacrylate, and 0.4 g of t-dodecyl mercaptan.
  • the temperature was raised to 88 ° C over a period of minutes. While maintaining 88 ° C. after the temperature rise, the 20% maleic anhydride solution was continuously fed at a rate of 21 g / hr and the 2% t-butylperoxy-2-ethylhexanoate solution was continuously fed at a rate of 3.75 g / hr. The addition was continued over 8 hours.
  • the diluted solution was poured into 200 kg of methanol to obtain a precipitate.
  • the resulting precipitate was dried at 80 ° C. and 140 Pa for 24 hours to obtain a methacrylic resin [A-7].
  • the composition of the obtained resin was as follows: the structural unit derived from methyl methacrylate was 26% by mass, the structural unit derived from maleic anhydride having a cyclic structure was 18% by mass, The derived structural unit was 56% by mass.
  • the obtained resin was Mw: 169000, Mw / Mn: 2.47, Tg: 137 degreeC.
  • Table 1 shows the physical properties of the methacrylic resins (A-1) to (A-7).
  • Production Example 8 (Production of diblock copolymer [B-1]) Into a three-necked flask purged with nitrogen and replaced with nitrogen, 735 g of dry toluene, 0.4 g of hexamethyltriethylenetetramine, and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum at room temperature 39.4 g of a toluene solution containing 20 mmol was added. To this was added 1.17 mmol of sec-butyllithium. Further, 39.0 g of methyl methacrylate was added thereto and reacted at room temperature for 1 hour to obtain a methyl methacrylate polymer (b1 1 ). The weight average molecular weight Mw b11 of the methyl methacrylate polymer (b1 1 ) contained in the reaction solution was 45800.
  • the reaction solution was brought to ⁇ 25 ° C., and a mixed solution of 29.0 g of n-butyl acrylate and 10.0 g of benzyl acrylate was added dropwise over 0.5 hour to terminate the end of the methyl methacrylate polymer (b1 1 ).
  • the diblock copolymer [B- 1 ] comprising a methyl methacrylate polymer block (b1 1 ) and an acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate 1] was obtained.
  • the block copolymer [B-1] contained in the reaction solution had a weight average molecular weight Mw B of 92000 and a weight average molecular weight Mw B / number average molecular weight Mn B of 1.06. Since the weight average molecular weight of the methyl methacrylate polymer (b1 1 ) was 45800, the weight average molecular weight of the acrylate polymer (b2) composed of n-butyl acrylate and benzyl acrylate was determined to be 46200. The proportion of benzyl acrylate contained in the acrylate polymer (b2) was 25.6% by mass.
  • Production Example 9 (Production of diblock copolymer [B-2]) Changing the amount of methyl methacrylate in 78 g, changing the amount of acrylic acid n- butyl 58 g, except for changing the amount of benzyl acrylate in 20g in the same manner as in Preparation Example 7 methyl methacrylate polymer block (b1 1 ) And an acrylate polymer (b2) consisting of n-butyl acrylate and benzyl acrylate was obtained.
  • the methyl methacrylate polymer block (b1 1 ) had an Mw b11 of 74300.
  • Mw b2 was 81700, and the proportion of benzyl acrylate was 25.6% by mass.
  • the diblock copolymer [B-2] had Mw B of 156000, Mw B / Mn B of 1.08, and n 23D of 1.490.
  • the ratio of the mass of the methacrylic ester polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 48/52.
  • reaction solution was brought to ⁇ 30 ° C., and a mixture of 219.6 g of n-butyl acrylate and 77.1 g of benzyl acrylate was added dropwise over 0.5 hour, whereby methyl methacrylate polymer (b1 1 )
  • a diblock copolymer comprising a methyl methacrylate polymer block (b1 1 ) and an acrylate polymer block (b2) comprising n-butyl acrylate and benzyl acrylate is obtained. It was.
  • the weight average molecular weight of the diblock polymer contained in the reaction solution was 57800.
  • the weight average molecular weight of the methyl methacrylate polymer block (b1 1 ) was 19000
  • the weight average molecular weight of the acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate was determined to be 38800.
  • the proportion of benzyl acrylate contained in the acrylate polymer (b2) was 25.6% by mass.
  • a triblock copolymer comprising a polymer block (b1 1 ), an acrylate polymer block (b2) composed of n-butyl acrylate and benzyl acrylate, and a methyl methacrylate polymer block (b1 2 ) [B- 3] was obtained.
  • the obtained triblock copolymer [B-3] had a weight average molecular weight Mw B of 75800, Mw B / Mn B of 1.10, and n 23D of 1.490. Since the weight average molecular weight of the diblock copolymer was 57800, the weight average molecular weight of the methyl methacrylate polymer block (b1 2 ) was determined to be 18,000. The ratio of the total mass of the methacrylic ester polymer blocks (b1 1 ) and (b1 2 ) to the mass of the acrylate polymer block (b2) was 49/51.
  • the weight average molecular weight of the methyl methacrylate polymer block (b1 1 ) is 19000 and the weight average molecular weight of the methyl methacrylate polymer block (b1 2 ) is 18000, the weight of the methyl methacrylate polymer block (b1)
  • the average molecular weight Mw b1 is 37000.
  • Production Example 12 (Production of diblock copolymer [B-5])
  • the methyl methacrylate polymer block (b1 1 ) had an Mw b11 of 4500.
  • the acrylate polymer (b2) had an Mw b2 of 88300 and a proportion of benzyl acrylate of 26.0% by mass.
  • the diblock copolymer [B-5] had Mw B of 92800, Mw B / Mn B of 1.10, and n 23D of 1.490.
  • the ratio of the mass of the methacrylic ester polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 5/95.
  • Production Example 13 (Production of diblock copolymer [B-6]) Changing the amount of methyl methacrylate in 50 g, changing the amount of acrylic acid n- butyl 50 g, except for changing the amount of benzyl acrylate in 0g in the same manner as in Preparation Example 7 methyl methacrylate polymer block (b1 1 And a diblock copolymer [B-6] consisting of an acrylic ester polymer (b2) consisting of n-butyl acrylate.
  • the methyl methacrylate polymer block (b1 1 ) had an Mw b11 of 45,000.
  • the acrylate polymer (b2) had an Mw b2 of 45000 and a proportion of benzyl acrylate of 0% by mass.
  • the diblock copolymer [B-6] had Mw B of 90000, Mw B / Mn B of 1.08, and n 23D of 1.476.
  • the ratio of the mass of the methacrylic ester polymer block (b1 1 ) to the mass of the acrylate polymer block (b2) was 50/50.
  • Production Example 14 (Production of emulsion containing multilayer polymer particles (A))
  • a reaction vessel 100 liters equipped with a condenser, thermometer and stirrer was charged with 48 kg of ion-exchanged water, followed by 416 g of sodium stearate, 128 g of sodium lauryl sarcosinate and 16 g of sodium carbonate. And dissolved.
  • 11.2 kg of methyl methacrylate and 110 g of allyl methacrylate were added and the temperature was raised to 70 ° C. while stirring. Thereafter, 560 g of a 2% aqueous potassium persulfate solution was added to initiate polymerization.
  • 720 g of a 2% sodium persulfate aqueous solution was added to the obtained emulsion.
  • a monomer mixture composed of 12.4 kg of butyl acrylate, 1.76 kg of styrene and 280 g of allyl methacrylate was dropped over 60 minutes, and graft polymerization was performed until 60 minutes passed.
  • Production Example 15 (Production of emulsion containing (meth) acrylic acid ester polymer particles (B)) Into a glass-lined reaction tank (100 liters) equipped with a condenser, thermometer and stirrer, 48 kg of ion-exchanged water is added, and then 252 g of a surfactant (“PEREX SS-H” manufactured by Kao Corporation) is added. And dissolved. The temperature was raised to 70 ° C.
  • a surfactant (“PEREX SS-H” manufactured by Kao Corporation)
  • Phenoxy1 (manufactured by NS
  • UVA1 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70)
  • UVA2 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (manufactured by ADEKA; LA-31)
  • Example 1 90 parts by weight of methacrylic resin [A-3], 10 parts by weight of block copolymer [B-1], 4 parts by weight of polycarbonate resin [PC1] and 2 parts by weight of processing aid (Paraloid K125-P (manufactured by Kureha)) Were mixed and extruded at 250 ° C. with a twin-screw extruder (trade name: KZW20TW-45MG-NH-600, manufactured by Technobel Co., Ltd.) to produce a methacrylic resin composition [C-1].
  • processing aid Paraloid K125-P (manufactured by Kureha)
  • Total light transmittance The methacrylic resin composition [C-1] was hot press molded to obtain a plate-like molded body of 130 mm ⁇ 50 mm ⁇ 3.2 mm. According to JIS K7361-1, the total light transmittance of 3.2 mm thickness was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150).
  • the methacrylic resin composition [C-1] was hot press molded to obtain a plate-like molded body of 130 mm ⁇ 50 mm ⁇ 3.2 mm. Based on JIS K7136, a haze of 3.2 mm thick part was measured at 23 ° C. using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150).
  • the methacrylic resin composition [C-1] was hot press molded to obtain a plate-like molded body of 130 mm ⁇ 50 mm ⁇ 3.2 mm. It was left in a thermostat at 70 ° C. for 30 minutes. The plate-shaped molded body was taken out of the thermostat, and immediately, the haze of 3.2 mm thick part was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) in accordance with JIS K7136.
  • the methacrylic resin composition [C-1] was injection molded at 230 ° C. to obtain a test piece of 80 mm ⁇ 10 mm ⁇ 4.0 mm in thickness. Except that only the notch angle was changed to 45 ° using the test piece, three-point bending at 23 ° C. was performed using an autograph (manufactured by Shimadzu Corporation) in accordance with ASTM E399-83. The maximum point stress at that time was defined as the bending strength with notches.
  • Table 3 shows the physical properties of the methacrylic resin composition [C-1].
  • Methacrylic resin compositions [C-2] to [C-26] were produced in the same manner as in Example 1 except that the composition shown in Table 3, 4 or 5 was used.
  • the physical properties of the methacrylic resin compositions [C-2] to [C-26] are shown in Tables 3, 4 and 5.
  • the methacrylic resin composition (Example) of the present invention has high transparency, small change in haze over a wide temperature range, high glass transition temperature, and high mechanical strength.
  • a section having a size of 100 mm ⁇ 100 mm was cut out from the unstretched film.
  • the section was set in a pantograph type biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.), and stretched in the machine direction at a stretching temperature: glass transition temperature + 20 ° C., a stretching speed of 1000% / min, and a stretching ratio of 2 times.
  • the film was stretched in the transverse direction at a stretching temperature: glass transition temperature + 20 ° C., a stretching speed of 1000% / min, and a stretching ratio of 2 times.
  • the film biaxially stretched successively in an area ratio of 4 times was gradually cooled to obtain a biaxially stretched film having a thickness of 40 ⁇ m.
  • Total light transmittance In accordance with JIS K7361-1, the total light transmittance of the film was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150).
  • n x is a plane slow axis direction of the refractive index
  • n y is the refractive index of the direction perpendicular in the plane with respect to the slow axis
  • n z is a refractive index in the thickness direction.
  • the thickness d [nm] of the test piece was measured using a digimatic indicator (manufactured by Mitutoyo Corporation).
  • the average refractive index n required for calculating the refractive indices n x, n y and n z are the average refraction at digital precision refractometer wavelength 587.6 nm (D line) measured at (Kalnew Optical Industry Co., Ltd. KPR-200) Rate values were used.
  • the biaxially stretched film obtained using the methacrylic resin composition according to the present invention has high transparency, good stretchability, and can reduce the thickness direction retardation. Further, since the film of the present invention has good stretchability, a thin stretched film can be obtained in this way.

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JPWO2018003788A1 (ja) * 2016-06-27 2019-04-18 株式会社クラレ アクリル系樹脂組成物からなる成形体
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CN107282868A (zh) * 2017-06-22 2017-10-24 安徽银力铸造有限公司 一种铸造用抗静电呋喃树脂砂的制备方法
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JP7326726B2 (ja) 2017-11-15 2023-08-16 東レ株式会社 積層フィルム
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JP7096842B2 (ja) 2017-12-27 2022-07-06 株式会社クラレ アクリル系樹脂フィルムおよびその製造方法
JPWO2019131831A1 (ja) * 2017-12-27 2021-01-14 株式会社クラレ アクリル系樹脂フィルムおよびその製造方法
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