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WO2019088025A1 - Résine méthacrylique, composition de résine méthacrylique et corps moulé - Google Patents

Résine méthacrylique, composition de résine méthacrylique et corps moulé Download PDF

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Publication number
WO2019088025A1
WO2019088025A1 PCT/JP2018/040128 JP2018040128W WO2019088025A1 WO 2019088025 A1 WO2019088025 A1 WO 2019088025A1 JP 2018040128 W JP2018040128 W JP 2018040128W WO 2019088025 A1 WO2019088025 A1 WO 2019088025A1
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WO
WIPO (PCT)
Prior art keywords
methacrylic resin
mass
methyl methacrylate
parts
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/040128
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English (en)
Japanese (ja)
Inventor
達 阿部
竹友 山下
淳裕 中原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP2019550374A priority Critical patent/JP7184793B2/ja
Publication of WO2019088025A1 publication Critical patent/WO2019088025A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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

Definitions

  • the present invention relates to methacrylic resins. More particularly, the present invention relates to a methacrylic resin having high thermal decomposition resistance, low foaming during molding, and high heat resistance.
  • the present invention also relates to a methacrylic resin composition and a molded article.
  • the methacrylic resin has high transparency and is useful as a material of a molded body used for an optical member, a lighting member, a signboard member, a decoration member and the like.
  • Patent Document 1 A methacrylic resin composition having improved thermal decomposition resistance, heat resistance and moldability is known (Patent Document 1). By using this resin composition, there is no foaming at the time of molding processing, and a molded article having high surface smoothness and relatively high heat resistance can be obtained. However, heat resistance is not sufficient in applications requiring heat resistance such as in-vehicle displays.
  • the present invention has been made in view of the above background, and the object of the present invention is a methacrylic resin, a methacrylic resin composition and a molded article having high heat decomposition resistance, low foaming at the time of molding, and heat resistance. To provide.
  • the present invention provides the following methacrylic resin, methacrylic resin composition and molded article.
  • [1] Comprising 99% by mass to 100% by mass of methyl methacrylate-derived structural units and 0% by mass to 1% by mass of acrylic acid ester-derived structural units,
  • the syndiotacticity (rr) in ternary notation is X%
  • the weight average molecular weight is Y
  • the amount of methyl methacrylate remaining is Z mass% in the methacrylic resin (A)
  • the remaining chain A methacrylic resin whose value calculated by the formula: X ⁇ Y / (10000 ⁇ Z ⁇ W) is 20 or more and 30 or less when the amount of transfer agent is W ppm in the methacrylic resin (A).
  • the amount of methyl methacrylate remaining is 55 to 58%, and the amount of methyl methacrylate remaining is 0.7% by mass or less in the methacrylic resin (A), and the methyl methacrylate dimer remaining
  • the amount of methyl methacrylate in the methacrylic resin (A) is 1,000 ppm or less, the amount of methyl methacrylate trimer remaining is 300 ppm or less in the methacrylic resin (A), and the amount of residual chain transfer agent is 200 ppm in the methacrylic resin (A) It is the following, The methacrylic resin as described in [1] whose glass transition temperature (Tg) satisfy
  • a methacrylic resin composition which further comprises 5 to 50 parts by mass of a crosslinked rubber with respect to 100 parts by mass of the methacrylic resin according to any one of [1] to [5].
  • a methacrylic resin composition further comprising 0.0001 to 0.1 parts by mass of light diffusing particles with respect to 100 parts by mass of the methacrylic resin according to any one of [1] to [5].
  • a molded article comprising the methacrylic resin according to any one of [1] to [5] or the methacrylic resin composition according to [6] or the methacrylic resin composition according to [7].
  • the molded object as described in [8] whose molded object is a film.
  • a methacrylic resin a methacrylic resin composition, and a molded article having high thermal decomposition resistance, low foaming at the time of molding, and heat resistance.
  • the methacrylic resin (A) of the present invention contains 99% by mass or more of a structural unit derived from methyl methacrylate.
  • the content of structural units derived from methyl methacrylate is preferably 99.5% by mass or more, and more preferably 100% by mass.
  • the “structural unit” is derived from a monomer, and the calculation of the ratio of each structural unit does not include components other than the monomer such as a chain transfer agent and a polymerization initiator.
  • the proportion of “structural units” is calculated based on a tetramer or higher methacrylic resin, and monomers, dimers and trimers of the raw materials such as methyl methacrylate and acrylic esters are proportions of structural units. Not considered in the calculation.
  • methyl methacrylate for example, methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate (Meth) acrylic acid alkyl esters such as hexyl; aryl acrylates such as phenyl acrylate; acrylic acid cycloalkylates such as cyclohexyl acrylate and norbornenyl acrylate; aromatic vinyls such as styrene and ⁇ -methylstyrene Acrylamide; methacrylamide; acrylonitrile; methacrylonitrile; and the like.
  • Examples include structural units derived from a vinyl-based monomer having only one polymerizable carbon-carbon double bond in one molecule.
  • structural units of (meth) acrylic acid ester are preferable in that they are easily copolymerized and a resin having high transparency can be obtained.
  • acrylic acid ester includes acrylic acid alkyl ester, acrylic acid aryl ester, acrylic acid cycloalkyl ester.
  • the content of structural units other than structural units derived from methyl methacrylate is preferably 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.1% by mass or less.
  • the content of the structural unit derived from the acrylic ester is 0% by mass to 1% by mass.
  • 0% by mass that is, it is desirable not to contain.
  • the acid value of the methacrylic resin (A) tends to increase.
  • the syndiotacticity (rr) in ternary notation is X%
  • the weight average molecular weight is Y
  • the amount of methyl methacrylate remaining in the methacrylic resin (A) is The value calculated by the formula: X ⁇ Y / (10000 ⁇ Z ⁇ W) is 20 when the amount of remaining chain transfer agent is W ppm or less in the methacrylic resin (A). 30 or more, preferably 21 or more and 29 or less.
  • the value calculated by the formula: X ⁇ Y / (10000 ⁇ Z ⁇ W) is small, the heat resistance tends to be low, and the impact resistance and the toughness of the obtained film tend to be low. If the value calculated by the formula: X ⁇ Y / (10000 ⁇ Z ⁇ W) is large, the moldability tends to be poor and the thermal decomposition resistance tends to be low.
  • the methacrylic resin (A) of the present invention has a syndiotacticity (rr) of triad indication of 55% to 60%, preferably 56% to 59% or 55% to 58%. If the syndiotacticity is more than 60%, the glass transition temperature of the methacrylic resin will be high, and the thermal decomposition will not only decrease, but the molding processing temperature must be set high, and the resin will be easily foamed. On the other hand, when the syndiotacticity is less than 55%, the glass transition temperature is low and the resin becomes low in heat resistance.
  • syndiotacticity (rr) displayed in triples will be described.
  • meso chain of structural units in a polymer molecule
  • racemo chain of structural units in a polymer molecule
  • m and r racemo
  • a syndiotacticity in which a ratio in which two chains (bi-dim, diad) of three successive structural units (tri-d, triad) are both racemo (denoted as rr) is represented by a triad It is a city (rr) (hereinafter simply referred to as "syndiotacticity (rr)").
  • the syndiotacticity (rr) (%) in ternary notation is measured at 30 ° C. in deuterated chloroform, and the 1 H-NMR spectrum is measured.
  • the area (P) of the region of ⁇ 0.95 ppm and the area (Q) of the region of 0.6 ⁇ 1.35 ppm are measured, and the value is calculated by the formula: (P / Q) ⁇ 100.
  • the methacrylic resin (A) of the present invention preferably has a weight average molecular weight (hereinafter referred to as "Mw") of 50000 to 150000, more preferably 55000 to 120000, and still more preferably 57000 to 100000.
  • Mw weight average molecular weight
  • a film obtained when the Mw is 50,000 or more tends to be excellent in impact resistance and toughness.
  • the molecular weight is 150000 or less, the molding processability of the methacrylic resin is enhanced, so that the thickness of the obtained film tends to be uniform and the surface smoothness is excellent.
  • Mw weight average molecular weight
  • the ratio of Mw to number average molecular weight (hereinafter referred to as “Mn”) (Mw / Mn: hereinafter referred to as “molecular weight distribution”) is preferably 1.2. It is -2.5, more preferably 1.5-2.0.
  • Mw and Mn are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.
  • the methacrylic resin (A) of the present invention preferably has a melt flow rate of 0.1 g / 10 min or more, more preferably 0, which is measured at 230 ° C. under a load of 3.8 kg in accordance with JIS K 7210. 0.5 to 30 g / 10 min, more preferably 1.0 to 20 g / 10 min, and most preferably 1.1 to 5 g / 10 min.
  • the glass transition temperature of the methacrylic resin (A) satisfies the following formula.
  • the glass transition temperature of the methacrylic resin (A) is preferably 120 ° C. or more, more preferably 121 ° C. or more, still more preferably 122 ° C. or more.
  • the upper limit of the glass transition temperature of the methacrylic resin is usually 125 ° C. or less, preferably 124 ° C. or less, more preferably 123 ° C. or less.
  • 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 thermal contraction of the obtained film hardly occurs, and thermal decomposition of the resin at the time of molding of a molded article such as a film is easily suppressed.
  • the acid value of acetic acid conversion of the methacrylic resin (A) of the present invention is 40 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less from the viewpoint of good thermal decomposition resistance. If the acid value in terms of acetic acid is too high, it is not only inferior in thermal decomposition resistance, but also reacts with other compounds at the time of molding to generate gel and the like, which may cause a defect of the molded article, which is not preferable.
  • the evaluation of the acid value is a value calculated as the amount of acetic acid contained with respect to the weight of the methacrylic resin (A) after converting the acid value of JIS K 0070: 1992 into the amount of acetic acid instead of KOH conversion. Specifically, it may be measured by the method described in the examples.
  • the thermal weight retention measured at a constant temperature of 290 ° C. for 10 minutes in the air atmosphere of the methacrylic resin (A) of the present invention is preferably 90% or more, more preferably 91% or more, and more preferably 92% from the viewpoint of heat decomposition resistance The above is the most preferable.
  • the measurement of the thermal weight retention ratio is from 50 ° C. to 290 ° C. at a flow rate of 50 ml / min of the dry air at a flow rate of 50 ml / min of the methacrylic resin (A) under an air atmosphere using a thermogravimetric measurement device (manufactured by Shimadzu Corporation, TGA). After the temperature is raised at 20 ° C./min, the thermal weight loss may be measured under the condition of maintaining at 290 ° C. for 10 minutes as it is in the air atmosphere. For example, based on the weight (X1) of 50 ° C. (retention 100%), the heat decomposition resistance can be evaluated by the following equation based on the weight (X2) when held at 290 ° C. for 10 minutes. It can be said that the higher the thermal weight retention, the higher the thermal decomposition resistance.
  • the method for producing the methacrylic resin (A) is preferably a radical polymerization method from the viewpoints of low coloring, small acid value, good thermal decomposition resistance, and good productivity.
  • the radical polymerization method is preferably continuous bulk polymerization without solvent from the viewpoint of obtaining a low impurity concentration methacrylic resin (A).
  • the polymerization reaction is preferably performed with a low amount of dissolved oxygen.
  • the polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas.
  • the polymerization initiator used in the radical polymerization method for producing the methacrylic resin (A) is not particularly limited as long as it generates reactive radicals.
  • t-hexylperoxyisopropyl monocarbonate t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate T-Hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 1,1-Bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis (2-methylpropionitrile), 2, 2
  • t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane and dimethyl 2,2'-azobis (2-methylpropionate) are preferable.
  • the one-hour half-life temperature of such a polymerization initiator is preferably 60 to 140 ° C., more preferably 80 to 120 ° C.
  • the polymerization initiator used for producing the methacrylic resin (A) preferably has a hydrogen extraction ability of 20% or less, more preferably 10% or less, and still more preferably 5% or less.
  • Such polymerization initiators can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass, and more preferably 100 parts by mass of the monomer to be subjected to the polymerization reaction. Is from 0.005 to 0.007 parts by mass.
  • hydrogen extraction ability can be known from the technical data of polymerization initiator manufacturer (for example, Nippon Oil and Fats Co., Ltd. technical data "Hydrogen extraction ability and initiator efficiency of organic peroxide" (prepared in April 2003) etc. .
  • it can be measured by a radical trapping method using ⁇ -methylstyrene dimer, ie, ⁇ -methylstyrene dimer trapping method. The said measurement is generally performed as follows. First, the polymerization initiator is cleaved in the coexistence of ⁇ -methylstyrene dimer as a radical trapping agent to form radical fragments.
  • radical fragments having low hydrogen abstraction ability are captured by being attached to the double bond of ⁇ -methylstyrene dimer.
  • radical fragments having high hydrogen abstraction ability abstract hydrogen from cyclohexane to generate cyclohexyl radicals, and the cyclohexyl radicals are added and captured to the double bond of ⁇ -methylstyrene dimer to form a cyclohexane capture product. Therefore, the hydrogen extraction ability is defined as the ratio (molar fraction) of radical fragments having a high hydrogen extraction ability to the theoretical amount of radical fragment generation, which is determined by quantifying cyclohexane or a cyclohexane scavenging product.
  • n-octyl mercaptan As a chain transfer agent used in the radical polymerization method for producing the methacrylic resin (A), n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol Ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- ( ⁇ -thiopropio) And alkyl mercaptans such as pentaerythritol tetrakisthiopropionate.
  • monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable.
  • 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 mass, more preferably 0.15 to 0.8 parts by mass, still more preferably 0 based on 100 parts by mass of the monomer to be subjected to the polymerization reaction. 2 to 0.6 parts by weight, most preferably 0.2 to 0.5 parts by weight.
  • 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 still more preferably 3500 to 6000 parts by mass with respect to 100 parts by mass of the polymerization initiator. When the amount of chain transfer agent used is in the above range, the resulting methacrylic resin (A) tends to have good moldability and high mechanical strength.
  • the temperature during the polymerization reaction is preferably 80 to 115 ° C., more preferably 90 to 110 ° C., and even more preferably 95 to 105 ° C.
  • productivity tends to be improved due to the improvement of the polymerization rate, the decrease in viscosity of the polymerization solution, and the like.
  • the polymerization temperature is 115 ° C. or less, the control of the polymerization rate is facilitated, the formation of by-products is suppressed, and a methacrylic resin having a desired glass transition temperature can be obtained.
  • the temperature at the time of the polymerization reaction can be controlled by the temperature of the reactor jacket and the polymerization rate.
  • the polymerization reaction time is preferably 0.5 to 4 hours, more preferably 1.5 to 3.5 hours, and still more preferably 1.5 to 3 hours. In the case of a continuous flow reactor, the polymerization reaction time is the average residence time in the reactor. When the temperature at the time of the polymerization reaction and the time of the polymerization reaction are in the above range, the methacrylic resin (A) having excellent transparency can be produced with high efficiency.
  • the polymerization conversion in the radical polymerization method for producing the methacrylic resin (A) is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and still more preferably 35 to 55% by mass.
  • the conversion rate of polymerization is at least 20% by mass, removal of the remaining unreacted monomer is facilitated when the volatile matter removal step is provided, and the resulting methacrylic resin is difficult to foam, and a molded article obtained The appearance of the tends to be good.
  • the polymerization conversion rate is 70% by mass or less, the viscosity of the polymerization solution tends to be low, and the productivity tends to be improved.
  • the radical polymerization may be carried out using a batch reactor, but from the viewpoint of productivity, it is preferable to carry out using a continuous flow reactor.
  • a polymerization reaction raw material a mixed solution containing a monomer, a polymerization initiator, a chain transfer agent, etc.
  • a polymerization reaction raw material a mixed solution containing a monomer, a polymerization initiator, a chain transfer agent, etc.
  • the liquid in the reactor is withdrawn at a flow rate corresponding to the volume.
  • a tubular reactor which can be brought into a state close to a plug flow and / or a tank reactor which 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.
  • a continuous flow type tank reactor for at least one unit.
  • the liquid volume in the tank reactor at the time of 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 fitted with a stirrer.
  • a stirring apparatus a static stirring apparatus and a dynamic stirring apparatus are mentioned.
  • the dynamic stirring device include a Max-blend type stirring device, a stirring device having a grid-like blade rotating around a vertical rotation shaft disposed at the center, a propeller type stirring device, a screw type stirring device and the like.
  • the Max Blend type stirring apparatus is preferably used from the viewpoint of uniform mixing.
  • the volatilization method may, for example, be an equilibrium flash method or an adiabatic flash method.
  • the volatilization temperature by the adiabatic flash method is preferably 200 to 270 ° C., more preferably 220 to 260 ° C.
  • the heating time of the resin in the adiabatic flush method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and still more preferably 0.5 to 2 minutes.
  • the unreacted monomers removed can be recovered and used again for the polymerization reaction.
  • the yellow index of the recovered monomer may be high due to the heat applied during the recovery operation and the like.
  • the recovered monomer is preferably purified by an appropriate method such as distillation or adsorption purification using a column to reduce the acid value and the yellow index.
  • a resin mixture containing volatile matter such as polymer, monomer, dimer, trimer, chain transfer agent, etc. obtained after the polymerization is transferred from the reactor to a twin-screw extruder equipped with a vent. It can be transported continuously. This can be followed by equilibration or adiabatic flush at the twin screw extruder inlet, followed by devolatilization via the twin screw extruder vent.
  • the pressure of the resin melt immediately before the flash in the adiabatic flash is preferably 1.5 to 3.0 MPa, more preferably 2.0 to 2.5 MPa. If the pressure is less than 1.5 MPa, the flash tends to be insufficient and the amount of residual monomers tends to be large. On the other hand, when the pressure exceeds 3.0 MPa, stable production tends to be difficult to obtain.
  • the twin-screw extruder used in the present invention is preferably equipped with a vent.
  • the vent is preferably a vacuum vent or an open vent. At least one vent is provided downstream of the polymer inflow portion.
  • the pressure in the vacuum vent is preferably 30 Torr or less, more preferably 15 Torr or less, still more preferably 9 Torr or less, and most preferably 6 Torr or less. If the pressure in the vacuum vent is within the above range, the degassing efficiency is good, and monomers, dimers, trimers, chain transfer agents, etc. remaining in the methacrylic resin (A) can be reduced. .
  • the screw of the twin screw extruder is preferably a co-directional twin screw.
  • the shear energy applied to the resin is greater than in the single-axial case, and the degree of surface renewal is large, so degassing can be performed efficiently, so that the amount of remaining unreacted monomers, dimers, trimers, etc. can be reduced.
  • the screw configuration has a kneading segment portion of 5% or more with respect to the total screw length.
  • the kneading segment may, for example, be a rotor segment, a forward feed kneading disc, a reverse feed kneading disc, a mixing gear or the like.
  • the cylinder heating temperature of the twin-screw extruder is preferably 200 to 270 ° C., more preferably 220 to 260 ° C., and still more preferably 230 to 250 ° C. If it is less than 210 ° C., it takes a long time to degas, and the degassing tends to be insufficient. When degassing is insufficient, appearance defects such as silver may occur on the molded body. Conversely, if the temperature exceeds 270 ° C., the amount of terminal double bonds in the methacrylic resin (A) increases, and the acid value increases, making it difficult to ensure the thermal decomposition resistance. Also, the formation of the aforementioned dimers and trimers may be increased.
  • the methacrylic resin (A) of the present invention is preferably composed only of a methacrylic resin, but actually, when obtained as a methacrylic resin (A), a small amount of other optional components resulting from the production conditions is present There is.
  • Other components resulting from the production conditions include unreacted monomers, dimers, trimers, chain transfer agents and the like. In the present specification, for the sake of convenience, those containing these other components are also referred to as methacrylic resin (A).
  • the content of the other component is preferably 1% by mass or less in the methacrylic resin (A).
  • the content of the other components is in this range, the decrease in the glass transition temperature is reduced.
  • the amount of methyl methacrylate remaining in the remaining unreacted monomer is preferably 0.7% by mass or less, more preferably 0.6 in the methacrylic resin (A). It is at most mass%, more preferably at most 0.5 mass%.
  • the amount of methyl methacrylate dimer remaining in the methacrylic resin (A) of the present invention is preferably 1000 ppm or less, more preferably 500 ppm or less, and still more preferably 300 ppm or less in the methacrylic resin (A).
  • the amount of methyl methacrylate trimer remaining in the methacrylic resin (A) of the present invention is preferably 300 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less, particularly 0 ppm, in the methacrylic resin (A).
  • the amount of the chain transfer agent remaining in the methacrylic resin (A) of the present invention is preferably 200 ppm or less, more preferably 150 ppm or less, still more preferably 100 ppm or less, in the methacrylic resin (A).
  • the methacrylic resin (A) of the present invention can be used as a methacrylic resin composition (B) by adding an ultraviolet light absorber, a polycarbonate resin, a phenoxy resin, a crosslinked rubber, light diffusing particles and the like.
  • an ultraviolet light absorber can be added to the methacrylic resin (A) of the present invention to use it as a methacrylic resin composition (B). That is, the methacrylic resin composition (B) can contain the methacrylic resin (A) and an ultraviolet absorber.
  • the ultraviolet absorber used in the present invention is a known ultraviolet absorber which may be blended into a thermoplastic resin. If the molecular weight of the ultraviolet absorber is 200 or less, problems such as foaming may occur when molding the methacrylic resin composition (B), so the lower limit of the molecular weight of the ultraviolet absorber is preferably 300. Or more, more preferably 500 or more, and still more preferably 600 or more.
  • the amount of the ultraviolet absorber which can be contained in the methacrylic resin composition (B) of the present invention is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the methacrylic resin (A). It is more preferably part, still more preferably 1 to 2 parts by mass.
  • UV absorbers are compounds having the ability to absorb UV light. UV absorbers are compounds that are said to mainly have the function of converting light energy into thermal energy.
  • UV absorbers examples include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic esters, formamidines and the like. One of these may be used alone, or two or more of these may be used in combination. Among these, benzotriazoles (compounds having a benzotriazole skeleton) and triazines (compounds having a triazine skeleton) are preferable.
  • the benzotriazoles or triazines have a high effect of suppressing deterioration (for example, yellowing etc.) of the resin due to ultraviolet light.
  • triazines examples include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70) and analogues thereof.
  • Certain hydroxyphenyl triazine UV absorbers BASF; CGL777, TINUVIN 460, TINUVIN 479, etc.
  • a polycarbonate resin or a phenoxy resin can be added to the methacrylic resin (A) of the present invention to be used as a methacrylic resin composition (B).
  • a polycarbonate resin or a phenoxy resin By containing a polycarbonate resin or a phenoxy resin, it is possible to obtain a methacrylic resin composition (B) whose retardation can be easily adjusted.
  • the amount of the polycarbonate resin or phenoxy resin is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and still more preferably 0.8 to 4 parts by mass with respect to 100 parts by mass of the methacrylic resin (A). It is a mass part.
  • a cross-linked rubber can be added to the methacrylic resin (A) of the present invention to use it as a methacrylic resin composition (B). That is, the methacrylic resin composition (B) can contain the methacrylic resin (A) and a crosslinked rubber.
  • the content of the crosslinked rubber in the methacrylic resin composition (B) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, still more preferably 15 to 30 with respect to 100 parts by mass of the methacrylic resin (A). It is a mass part.
  • the crosslinked rubber used in the present invention is a polymer exhibiting rubber elasticity in which a polymer chain is crosslinked by a structural unit derived from a crosslinkable monomer.
  • the crosslinkable monomer is one having two or more polymerizable functional groups in one monomer.
  • crosslinked rubber examples include acrylic crosslinked rubber and diene based crosslinked rubber, and more specifically, acrylic acid alkyl ester monomers, crosslinkable monomers and other vinyl monomers Copolymer rubber, copolymer rubber of conjugated diene monomer, crosslinkable monomer and other vinyl monomer, acrylic acid alkyl ester monomer and conjugated diene monomer and crosslinkable monomer Copolymer rubbers of monomers and other vinyl monomers can be mentioned.
  • the crosslinked rubber is preferably contained in the form of particles in the methacrylic resin composition.
  • the crosslinked rubber particle may be a single layer particle consisting only of a crosslinked rubber, or may be a multilayer particle consisting of a crosslinked rubber and another polymer.
  • core-shell type particles comprising a core comprising a crosslinked rubber and a shell comprising another polymer are preferred.
  • the volume-based average particle diameter of the crosslinked rubber particles used in the present invention is preferably 0.02 to 1 ⁇ m, more preferably 0.05 to 0.5 ⁇ m, and still more preferably 0.1 to 0.3 ⁇ m.
  • the volume-based average particle diameter in the present specification is a value calculated based on electron microscopic observation of the methacrylic resin composition (B) containing crosslinked rubber particles.
  • Light diffusing particles can be added to the methacrylic resin (A) of the present invention to be used as a methacrylic resin composition (B). That is, the methacrylic resin composition (B) can contain the methacrylic resin (A) and light diffusing particles.
  • the content of the light diffusing particles in the methacrylic resin composition (B) is preferably 0.0001 to 0.1 parts by mass, more preferably 0.0002 to 0.01 based on 100 parts by mass of the methacrylic resin (A). It is a mass part.
  • the light diffusing particle used in the present invention is a particle having a refractive index different from that of the methacrylic resin (A) and scattering light. Light diffusing particles described in WO 2010/113422 are preferred.
  • the volume average particle diameter (volume average diameter) d of the light diffusion particles is preferably 0.5 to 5 ⁇ m, more preferably 0.75 to 4 ⁇ m, and particularly preferably 1 to 3 ⁇ m.
  • the volume average particle diameter d of the light diffusion particles is smaller than 0.5 ⁇ m, a difference in color may occur between the vicinity of the light incident end face of the molded body and the position away therefrom.
  • the volume average particle diameter d of the light diffusing particles is larger than 5 ⁇ m, the light diffusing particles having a relatively large particle diameter may become bright spots when the light source is turned on and may deteriorate the appearance.
  • the volume average particle diameter d in the present specification is a particle diameter obtained by photographing an electron micrograph of primary particles and determining by image analysis type particle size distribution measurement software.
  • the refractive index difference ( ⁇ n) between the methacrylic resin (A) and the light diffusing particles is preferably 0.3 to 3.
  • the refractive index difference ( ⁇ n) is smaller than 0.3, light can not be extracted efficiently, and the transparency may be inferior to the brightness when the light source is turned on.
  • the refractive index difference ( ⁇ n) is more preferably 0.4 or more.
  • the refractive index difference ( ⁇ n) is larger than 3, backscattering is dominant in scattered light, so that light can not be extracted efficiently, and the transparency at the time of lighting the light source is poor There is a case.
  • inorganic compound particles having a large difference in refractive index with respect to the methacrylic resin (A) are preferably used.
  • titanium oxide, zinc oxide and the like are preferably used.
  • the volume average particle diameter d of the light diffusion particles is too small, a change in color such as coloring which may be attributed to the Rayleigh scattering phenomenon may occur.
  • a change in color such as coloring that may be caused by the Rayleigh scattering phenomenon may occur.
  • the scattered light may be bluish near the light source and may be yellowish at a position away from the light source.
  • ⁇ d) of the volume average particle diameter d ( ⁇ m) of the light diffusing particle and the absolute value of the refractive index difference ( ⁇ n) in order to suppress the change in color such as coloring that is considered to be caused by the Rayleigh scattering phenomenon Is preferably 0.1 ⁇ m or more.
  • methacrylic resin composition (B) of the present invention may be contained in the methacrylic resin composition (B) of the present invention in addition to the methacrylic resin (A), the ultraviolet absorber, the polycarbonate resin, the phenoxy resin, the crosslinked rubber, and the light diffusing particles.
  • 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, Styrene 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, polybutylene terephthalate; nylon 6 , Nylon 66, polyamides such as polyamide elastomer; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyfluorinated vinyl Silicone rubber, acrylic thermoplastic elastomer; styrene thermoplastic elastomer such
  • a filler In the methacrylic resin composition (B) according to the present invention, a filler, an antioxidant, a thermal deterioration inhibitor, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic, in addition to the ultraviolet absorber.
  • the additive which may be mix
  • the filler examples include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate and magnesium carbonate.
  • the amount of the 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, and still more preferably 0% by mass.
  • the antioxidant has an effect of preventing oxidative deterioration of the resin alone in the presence of oxygen.
  • phosphorus-based antioxidants, hindered phenol-based antioxidants, thioether-based antioxidants and the like can be mentioned.
  • One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and a combination of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable.
  • the usage of the phosphorus-based antioxidant is 1: 5 to 2: 2 in mass ratio 1 is preferable, and 1: 2 to 1: 1 is more preferable.
  • phosphorus-based antioxidants examples include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: Adekastab HP-10), tris (2,4-di-t-).
  • Butylphenyl) phosphite (manufactured by BASF AG; 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: Adekastab PEP-36) and the like are preferable.
  • a hindered phenol-based antioxidant pentaerythrityl-tetrakis [3- (3,5-di t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANOX1010), octadecyl-3- ( Preferred is 3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF AG; trade name IRGANOX 1076).
  • the thermal deterioration inhibitor is capable of preventing thermal deterioration of the resin by trapping polymer radicals generated when exposed to high heat under substantially oxygen-free conditions.
  • thermal degradation inhibitor 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: SMILIZER GM), Preferred is 2,4-di t-amyl-6- (3 ′, 5′-di t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: SMILIZER GS).
  • a light stabilizer is a compound that is said to have the function of capturing radicals generated mainly by oxidation by light.
  • Suitable light stabilizers can include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
  • stearic acid for example, stearic acid, behenic acid, stearoamic acid, methylene bis stearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, hydrogenated oil and the like can be mentioned.
  • the mold release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as monoglyceride stearate and diglyceride stearate.
  • higher alcohols such as cetyl alcohol and stearyl alcohol
  • glycerin higher fatty acid esters such as monoglyceride stearate and diglyceride stearate.
  • the ratio is not particularly limited, but the amount of the higher alcohol used: the used amount of the glycerin fatty acid monoester is 2.5: 1 to 3.3 by mass ratio. 5: 1 is preferable, and 2.8: 1 to 3.2: 1 is more preferable.
  • the polymer processing aid is a polymer compound having an average polymerization degree of 3,000 to 40,000, and preferably 60% by mass or more of a methyl methacrylate unit and 40 mass of a vinyl monomer unit copolymerizable therewith. % Or less.
  • the average degree of polymerization of the polymer processing aid can be determined as a degree of polymerization in terms of PMMA using an automatic dilution capillary viscometer (Ubbelohde type) and measurement at 20 ° C. using chloroform as a solvent.
  • polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m which can usually be produced by emulsion polymerization, can be used.
  • the polymer particle may be a single layer particle consisting of a polymer having a single composition ratio and a single intrinsic viscosity, or a multilayer particle consisting of two or more polymers different in composition ratio or intrinsic viscosity. May be Among these, particles of 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 preferably mentioned.
  • the polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g. If the intrinsic viscosity is too small, the effect of improving formability tends to be low. When the intrinsic viscosity is too large, the molding processability of the methacrylic resin composition tends to decrease. Specifically, there may be mentioned Metabrene-P series manufactured by Mitsubishi Rayon Co., Ltd. and Paraloid series manufactured by Dow Chemical Co.
  • flame retardants include organic halogen flame retardants such as tetrabromobisphenol A, decabromodiphenyl oxide and brominated polycarbonate; non-halogen flame retardants such as antimony oxide, aluminum hydroxide, zinc borate and tricresyl phosphate Etc.
  • organic halogen flame retardants such as tetrabromobisphenol A, decabromodiphenyl oxide and brominated polycarbonate
  • non-halogen flame retardants such as antimony oxide, aluminum hydroxide, zinc borate and tricresyl phosphate Etc.
  • antistatic agent for example, stearoamidopropyl dimethyl- ⁇ -hydroxyethyl ammonium nitrate and the like can be mentioned.
  • dyes and pigments examples include titanium oxide and bengala.
  • organic dye a compound having a function of converting ultraviolet light into visible light is preferably used.
  • Examples of the light diffusing agent and the matting agent include glass particles, polysiloxane based crosslinked particles, crosslinked polymer particles, talc, calcium carbonate and barium sulfate.
  • a fluorescent substance As a fluorescent substance, a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, a fluorescent bleaching agent etc. can be mentioned.
  • 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, still more preferably 4% by mass or less, most preferably 1% by mass or less is there.
  • the methacrylic resin composition (B) of the present invention preferably contains 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more of the methacrylic resin (A) of the present invention.
  • the haze of 3.2 mm thickness of the methacrylic resin (A) or the methacrylic resin composition (B) of the present invention is preferably 3.0% or less, more preferably 2.0% or less, and 1.5% or less More preferable.
  • the methacrylic resin (A) or the methacrylic resin composition (B) 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 methacrylic resin (A) or the methacrylic resin composition (B) of the present invention can be reacted with a polymer by a known method.
  • a polymer reaction the imidization reaction described in JP-A-2008-273140, JP-A-2008-274187, JP-A-2010-254742 or JP-A-2010-261025, or the grafting described in JP-A-2012-20183. Reaction is mentioned.
  • the methacrylic resin (A) or the methacrylic resin composition (B) of the present invention can be formed into a molded product by a known molding method.
  • a molding method for example, T-die method (lamination 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 Examples include melt-forming methods such as a method, a two-color method, a pressing method, a core back method, a sandwich method, and the like, and a solution casting method.
  • a mold is generally used to mold a resin.
  • the mold is often made of metal, but other than metal, for example, a rubber roll, tempered glass, etc. are also present.
  • the shape of the molded object of this invention is arbitrary and is not specifically limited, For example, a film, a sheet, a board, etc. may be sufficient.
  • billboard parts such as advertising towers, stand signs, sleeve signs, cross signs, roof signs and the like; display parts such as showcases, dividers, store displays; fluorescent light covers, mood lighting Lighting parts such as covers, lampshades, light ceilings, light walls and chandeliers; interior parts such as pendants and mirrors; constructions such as doors, domes, safety glass panes, partitions, stairwells, balcony waistboards, roofs of leisure buildings Components for aircraft windshields, visors for pilots, motorcycles, motor boat windshields, light shields for buses, side visors for cars, rear visors, head wings, headlight covers, glazing materials, sunroofs, head-up displays, etc.
  • Transport parts Picture nameplate, stereo cover, TV Electronic parts such as protective masks, display covers for vending machines; Medical equipment parts such as incubators and X-ray parts; Machine-related parts such as instrument covers, instrument covers, laboratory equipment, rulers, dials, observation windows; Display equipment Light guide plate for front light and film, light guide plate and film for back light, liquid crystal protective plate, Fresnel lens, lenticular lens, front plate of various displays, diffusion plate, optical member such as reflector, road sign, guide plate, Transportation parts such as curved mirrors and sound barriers; surface materials for car interiors; surface materials for mobile phones; film members such as marking films; for household appliances such as lids and control panels for washing machines and top panels for rice cookers Other members, greenhouse, large water tank, box water tank, clock panel, bathtub, sanitary, deskma Door, game parts, toys, and the like face protective mask at the time of welding.
  • the molded article of the present invention is an optical device represented by, for example, various covers, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, watches and the like from the viewpoint of excellent weather resistance, and also video and optical recording.
  • Optical communication Information equipment related parts as cameras, finders such as VTRs, projection TVs, filters, prisms, Fresnel lenses, protective films for various optical disc (VD, CD, DVD, MD, LD etc.) substrates, optical switches, optical connectors Liquid Crystal Display, Light Guide Film for Liquid Crystal Display, Flat Panel Display, Light Guide Film for Flat Panel Display, Plasma Display, Light Guide Film for Plasma Display, Sheet, Light Guide Film for Electronic Paper, Retardation Film sheet, polarizing film ⁇ Sheets, polarizing plate protective films / sheets, polarizer protective films / sheets, wave plates, light diffusion films / sheets, prismatic films / sheets, reflective films / sheets, antireflective films / sheets, viewing angle widening films / sheets,
  • 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 equipment, displays for AV equipment, etc. and electroluminescence display It can be used for an element or a touch panel.
  • interior / exterior members for buildings, curtain walls, roof members, roof members, window members, gutters, exteriors, wall materials, floor materials, construction materials It can be particularly suitably applied to known building materials such as road construction members, retroreflective films / sheets, agricultural films / sheets, lighting covers, signs, light-transmitting sound barriers, and the like.
  • the molded article of the present invention is also applied to solar cell surface protective films, solar cell satire films, solar cell rear surface protective films, solar cell base films, gas barrier film substrates, gas barrier film protective films and the like as solar cell applications It is possible.
  • the film of the present invention which is one form of a molded article, is not particularly limited by the production method.
  • the film of the present invention can be prepared, for example, by using the above-mentioned methacrylic resin (A) or methacrylic resin composition (B) by a known method such as solution casting, melt casting, extrusion molding, inflation molding, blow molding and the like. It can be obtained by film formation.
  • the extrusion method is preferred. According to the extrusion method, it is possible to obtain a film having an improved toughness, an excellent handleability, and an excellent balance of toughness and surface hardness and rigidity.
  • the temperature of the methacrylic resin (A) or the methacrylic resin composition (B) discharged from the extruder is preferably set to 160 to 270 ° C., more preferably 220 to 260 ° C.
  • the polymer filter preferably has a filtration accuracy of 1 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m, and still more preferably 2 ⁇ m to 3 ⁇ m.
  • a polymer filter well-known things, such as a leaf disc type and a candle type, can be used.
  • heat generation may occur due to heat generation when it is filtered through a polymer filter, which may cause foaming to deteriorate the quality of the film.
  • the above-mentioned methacrylic resin (A) or methacrylic resin composition (B) is extruded from a T-die in a molten state from the viewpoint of obtaining a film with good surface smoothness, good mirror gloss and low haze. Then, a method including sandwiching and molding it with two or more mirror rolls or mirror belts is preferable.
  • the mirror roll or mirror belt is preferably made of metal.
  • the linear pressure between the pair of mirror rolls or mirror belts is preferably 2 N / mm or more, more preferably 10 N / mm or more, still more preferably 30 N / mm or more.
  • the surface temperature of a mirror surface roll or a mirror surface belt is both 130 degrees C or less. Moreover, it is preferable that at least one surface temperature of a pair of mirror surface roll or mirror surface belts is 60 degreeC or more.
  • the methacrylic resin (A) or the methacrylic resin composition (B) discharged from the extruder can be cooled at a speed faster than natural cooling, and the surface smoothness is excellent and It is easy to produce a low haze film.
  • the film of the present invention may be stretched.
  • the stretching method is not particularly limited, and examples thereof include uniaxial stretching method, simultaneous biaxial stretching method, sequential biaxial stretching method, and Tumbrer stretching method.
  • the temperature at the time of stretching is preferably 100 to 200 ° C., and more preferably 120 ° C. 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 based on length.
  • the stretching is preferably performed so as to have an area ratio of 1.5 to 8 times.
  • the thickness of the film of the present invention is not particularly limited, but when used as an optical film, the thickness is preferably 1 to 300 ⁇ m, more preferably 10 to 50 ⁇ m, and still more preferably 15 to 40 ⁇ m.
  • the film of the present invention has a haze of preferably 0.2% or less, more preferably 0.1% or less at a thickness of 40 ⁇ m. This is excellent in surface gloss and transparency.
  • the utilization efficiency of the light source is preferably increased. Furthermore, since it is excellent in the shaping precision at the time of performing surface shaping, it is preferable.
  • the film of the present invention has high heat decomposition resistance, low foaming at the time of molding, and heat resistance, so it has a polarizer protective film, a retardation film, a liquid crystal protective plate, a surface material of a portable information terminal, a portable information terminal
  • a polarizer protective film for the above, a light guide film, a transparent conductive film coated with silver nanowires or carbon nanotubes on the surface, a front plate of various displays, etc. are suitable.
  • the film of the present invention can reduce the retardation, it is suitable for a polarizer protective film.
  • the film of the present invention has transparency and heat resistance, IR cut films, crime prevention films, shatterproof films, decorative films, metal decorative films, solar cell backs are used as applications other than optical applications. It can be used for sheets, front sheets for flexible solar cells, shrink films, films for in-mold labels.
  • HLC-8320 Detector Differential Refractive Index Detector Column: Two TSKgel SuperMultipore HZM-M's manufactured by Tosoh Corporation and Super HZ 4000 connected in series were used. Eluent: Tetrahydrofuran Eluent flow rate: 0.35 ml / min Column temperature: 40 ° C. Calibration curve: made using data of 10 standard polystyrene
  • the 1 H-NMR spectrum of the methacrylic resin was measured using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS manufactured by Bruker) using deuterated chloroform as a solvent under conditions of room temperature and 64 integrations. From the spectrum, measure the area (X) of the region of 0.6 to 0.95 ppm when TMS is 0 ppm and the area (Y) of the region of 0.6 to 1.35 ppm, and then The syndiotacticity (rr) shown was calculated by the formula: (X / Y) ⁇ 100.
  • Glass transition temperature Tg Glass transition temperature Tg
  • DSC-50 product number manufactured by Shimadzu Corporation
  • JIS K 7121 room temperature
  • the DSC curve was measured under the condition that the temperature was raised from room temperature to 230 ° C. at 10 ° C./min a second time.
  • the midpoint glass transition temperature determined from the DSC curve measured at the second temperature rise was taken as the glass transition temperature in the present invention.
  • MFR melt flow rate
  • Example 1 Production of Methacrylic Resin [A-1]
  • MMA methyl methacrylate
  • 2,2'-azobis (2-methylpropionitrile) hydrolysis capacity: 1%, 1 hour half-life temperature: 83 ° C.
  • Nitrogen was fed into the raw material solution to remove dissolved oxygen in the raw material solution.
  • the feed solution was charged to 2/3 of the volume in a tank reactor connected by an autoclave and piping.
  • the temperature was maintained at 100 ° C. and the polymerization reaction was first initiated in a batch mode.
  • the feed solution is supplied from the autoclave to the tank reactor at a flow rate that achieves an average residence time of 120 minutes when the polymerization conversion ratio reaches 55% by mass, and the reaction solution is delivered at a flow rate corresponding to the feed flow rate of the feed solution.
  • the reactor was withdrawn from the tank reactor, maintained at a temperature of 100 ° C., and switched to a continuous flow polymerization reaction. After switching, the polymerization conversion at steady state was 45% by mass.
  • the reaction liquid withdrawn from the tank reactor in a steady state was supplied to a multi-tube heat exchanger with an internal temperature of 230 ° C. and heated at a flow rate at which the average residence time is 2 minutes. Then, the heated reaction solution was introduced into a flash evaporator to remove volatile components mainly composed of unreacted monomers to obtain a molten resin.
  • the molten resin from which volatile components had been removed was supplied to a twin-screw extruder having an internal temperature of 230 ° C., discharged into strands, and cut with a pelletizer to obtain a methacrylic resin [A-1].
  • the methacrylic resin composition [A-1] After drying the methacrylic resin composition [A-1] at 80 ° C. for 12 hours, it was melt-kneaded at a discharge rate of 30 kg / hr using a 50 mm ⁇ ⁇ ⁇ vent type single screw extruder of L / D 34. After melt-kneading, use a gear pump, pass through a leaf disc filter with a filtration area of 0.75 m 2 and a filtration accuracy of 5 ⁇ m, extrude from a 130 mm wide T-die at a temperature of 270 ° C, and film on a 90 ° C metal mirror roll. It shape
  • the unstretched film with a thickness of 160 ⁇ m obtained by the above method is cut into small pieces of 100 mm ⁇ 100 mm so that the two sides are parallel to the extrusion direction, and a pantograph type biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.) ), The stretching temperature of glass transition temperature + 10 ° C, the stretching speed of 150% / min in one direction, the stretching ratio of 2 times in one direction, the direction parallel to the extrusion direction first, and then the biaxial direction
  • the film was stretched under the condition of holding for 10 seconds and then quenched by taking it out at room temperature to obtain a biaxially stretched film with a thickness of 40 ⁇ m.
  • the measurement results of the obtained methacrylic resin [A-1] and biaxially stretched film are shown in Table 1.
  • Example 2 (Production of Methacrylic Resin [A-2]) Methacrylic resin [A-2] and 2 in the same manner as in Example 1 except that 0.0102 parts by mass of 2,2′-azobis (2-methylpropionitrile) and 0.315 parts by mass of n-octylmercaptan were used. An axial stretched film was obtained. The evaluation results are shown in Table 1.
  • Example 3 (Production of Methacrylic Resin [A-3]) Methacrylic resin [A-3] and a dimethacrylate resin in the same manner as in Example 1 except that 0.0094 parts by mass of 2,2'-azobis (2-methylpropionitrile) and 0.260 parts by mass of n-octylmercaptan were used. An axial stretched film was obtained. The evaluation results are shown in Table 1.
  • Comparative Example 2 (Production of Methacrylic Resin [A-5]) Methacrylic resin [A-5] and di-methyl methacrylate resin in the same manner as in Comparative Example 1 except that 0.0070 parts by mass of 2,2′-azobis (2-methylpropionitrile) and 0.275 parts by mass of n-octylmercaptan were used. An axial stretched film was obtained. The evaluation results are shown in Table 1.
  • Comparative Example 3 (Production of Methacrylic Resin [A-6]) Methacrylic resin [A-6] and di-methyl methacrylate in the same manner as in Comparative Example 1 except that 0.0066 parts by mass of 2,2'-azobis (2-methylpropionitrile) and 0.230 parts by mass of n-octylmercaptan were used. An axial stretched film was obtained. The evaluation results are shown in Table 1.
  • Comparative Example 5 (Production of Methacrylic Resin [A-8]) 100 parts by mass of methyl methacrylate, 8 parts by mass of methyl acrylate (MA), 0.0065 parts by mass of 2,2'-azobis (2-methylpropionitrile), 0.13 parts by mass of n-octylmercaptan, polymerization temperature A methacrylic resin [A-8] and a biaxially stretched film were obtained in the same manner as in Comparative Example 1 except that the temperature was changed to 150 ° C. The MMA content and the MA content were confirmed by 1 H-NMR. The evaluation results are shown in Table 1.
  • Comparative Example 6 (Production of Methacrylic Resin [A-9]) 100 parts by mass of methyl methacrylate, 1.1 parts by mass of methyl acrylate, 0.0068 parts by mass of 2,2'-azobis (2-methylpropionitrile), 0.235 parts by mass of n-octylmercaptan A methacrylic resin [A-9] and a biaxially stretched film were obtained in the same manner as in Comparative Example 1. The MMA content and the MA content were confirmed by 1 H-NMR. The evaluation results are shown in Table 1.
  • Comparative Example 7 (Production of Methacrylic Resin [A-10]) To 100 parts by mass of methyl methacrylate, 0.451 parts by mass of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 0.2 parts by mass of n-octylmercaptan are added and dissolved to prepare a raw material solution. Obtained. 150 parts by mass of ion exchange water, 0.03 parts by mass of sodium sulfate and 0.46 parts by mass of the suspension dispersant were mixed to obtain a liquid mixture. The mixed solution and the raw material solution were charged into a pressure resistant polymerization tank, and the temperature was set to 35 ° C. to initiate a polymerization reaction while stirring under a nitrogen atmosphere.

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Abstract

La présente invention concerne une résine méthacrylique contenant 99-100 % en masse d'un motif structural dérivé de méthacrylate de méthyle et 0-1 % en masse d'un motif structural dérivé d'ester acrylique, la valeur calculée par l'équation X·Y/(10000·Z·W) valant 20-30 (dans l'équation, X (%) est la syndiotacticité triade (rr), Y est le poids moléculaire moyen en poids, Z (% en masse) est la quantité de méthacrylate de méthyle restant dans la résine méthacrylique (A) et W (ppm) est la quantité d'agent de transfert de chaîne restant dans la résine méthacrylique (A)).
PCT/JP2018/040128 2017-10-30 2018-10-29 Résine méthacrylique, composition de résine méthacrylique et corps moulé Ceased WO2019088025A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023238885A1 (fr) * 2022-06-07 2023-12-14 株式会社カネカ Résine méthacrylique ainsi que procédé de fabrication de celle-ci, composition de résine, et film de résine
WO2024161763A1 (fr) * 2023-01-31 2024-08-08 住友化学株式会社 Composition de résine (méth)acrylique et objet moulé
CN119039730A (zh) * 2024-08-20 2024-11-29 武汉美格科技股份有限公司 一种透明前板及其制备方法、光伏组件

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JP2000026507A (ja) * 1998-07-14 2000-01-25 Mitsubishi Rayon Co Ltd メタクリル系重合体およびその製造方法
WO2010113422A1 (fr) * 2009-03-31 2010-10-07 株式会社クラレ Illuminant
WO2014185508A1 (fr) * 2013-05-16 2014-11-20 株式会社クラレ Film
WO2015037691A1 (fr) * 2013-09-11 2015-03-19 住友化学株式会社 Composition de résine méthacrylique
JP2017048344A (ja) * 2015-09-04 2017-03-09 株式会社クラレ メタクリル樹脂、メタクリル樹脂組成物及び成形体

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2000026507A (ja) * 1998-07-14 2000-01-25 Mitsubishi Rayon Co Ltd メタクリル系重合体およびその製造方法
WO2010113422A1 (fr) * 2009-03-31 2010-10-07 株式会社クラレ Illuminant
WO2014185508A1 (fr) * 2013-05-16 2014-11-20 株式会社クラレ Film
WO2015037691A1 (fr) * 2013-09-11 2015-03-19 住友化学株式会社 Composition de résine méthacrylique
JP2017048344A (ja) * 2015-09-04 2017-03-09 株式会社クラレ メタクリル樹脂、メタクリル樹脂組成物及び成形体

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023238885A1 (fr) * 2022-06-07 2023-12-14 株式会社カネカ Résine méthacrylique ainsi que procédé de fabrication de celle-ci, composition de résine, et film de résine
WO2024161763A1 (fr) * 2023-01-31 2024-08-08 住友化学株式会社 Composition de résine (méth)acrylique et objet moulé
CN119039730A (zh) * 2024-08-20 2024-11-29 武汉美格科技股份有限公司 一种透明前板及其制备方法、光伏组件

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