WO2021020426A1 - Composition de résine méthacrylique, modificateur de résine, corps moulé, et film ainsi que procédé de fabrication de celui-ci - Google Patents

Composition de résine méthacrylique, modificateur de résine, corps moulé, et film ainsi que procédé de fabrication de celui-ci Download PDF

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WO2021020426A1
WO2021020426A1 PCT/JP2020/028996 JP2020028996W WO2021020426A1 WO 2021020426 A1 WO2021020426 A1 WO 2021020426A1 JP 2020028996 W JP2020028996 W JP 2020028996W WO 2021020426 A1 WO2021020426 A1 WO 2021020426A1
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molecular weight
methacrylic
mass
weight
polymer
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PCT/JP2020/028996
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伸崇 平岡
広大 松橋
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株式会社クラレ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—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 a methacrylic resin composition, a resin modifier, a molded product and a film, and a method for producing a film.
  • Methacrylic resin (a polymer mainly containing structural units derived from methacrylic acid ester) is excellent in transparency, light resistance, surface hardness and the like.
  • Various optical members such as a light guide plate, a lens, a sheet, and a film can be obtained by molding a resin composition containing a methacrylic resin.
  • Patent Document 1 describes a (meth) acrylic resin A having a weight average molecular weight of preferably 200,000 or less, and a glass transition temperature lower than that of the (meth) acrylic resin A, and a weight average molecular weight of preferably 100,000 or more and 1,000,000 or less.
  • a (meth) acrylic resin B contains a (meth) acrylic resin A in a weight ratio of preferably 80/20 to 40/60 of the (meth) acrylic resin B.
  • the composition and the film containing the composition are disclosed.
  • Patent Document 1 states that if the content of the (meth) acrylic resin B is excessively large, the heat shrinkage rate of the obtained (meth) acrylic resin film tends to increase.
  • the ⁇ relaxation temperature T ⁇ 1 when measured in dynamic viscoelasticity at 1 Hz in a tensile mode is 137 ° C. or higher
  • the molecular weight distribution is preferably 1.0 to 1.4
  • the weight average molecular weight is 40,000 to 40,000.
  • a methacrylic resin composition having a molecular weight ratio of methacryl resin (M1) / methacryl resin (M2) of 2/98 to 29/71 is disclosed.
  • Patent Document 3 discloses a dope composition containing a methacrylic resin having a weight average molecular weight of 250,000 or more and additives such as a phenolic compound having a weight average molecular weight of less than 50,000, a styrene copolymer, and a novolak resin. doing.
  • An object of the present invention is to provide a novel methacrylic resin composition, resin modifier, molded product and film, and a method for producing a film.
  • the present invention includes the following forms.
  • the peak top molecular weight M Pt having the mass ratio of the methacrylic polymer (A) to the methacrylic polymer (B) of 2/98 to 39/61 and having the highest weight fraction differential value in the weight-based differential molecular weight distribution curve is 100,000 to 2000,000, Methacrylic resin.
  • the sum of the weight fraction differential values of the components having a molecular weight of 1/20 or less of the peak top molecular weight M Ph having the highest molecular weight is the sum of the weight fraction differential values of all the components.
  • the total of the weight fraction derivative values of the components having a molecular weight of 15,000 or less is 2% or less with respect to the total weight fraction derivative values of all the components.
  • [6] has a weight average molecular weight Mw of from 40,000 to 140,000, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of 1.0-1.4, the refractive index n d be from 1.485 to 1.495 , A methacrylic polymer (A) having a triad syndiotacticity (rr) of 63 to 80%, a glass transition temperature of 125 ° C. or higher, and containing 100% by mass of a structural unit derived from methyl methacrylate. Resin modifier.
  • the total weight fraction differential values of the components having a molecular weight of 15,000 or less in the weight-based differential molecular weight distribution curve is 2% of the total weight fraction differential values of all the components.
  • the doping according to [11] is cast on a casting support, and the doping is cast.
  • a method for producing a film which comprises then removing the organic solvent.
  • the production method according to [12], wherein the thickness of the film is 20 ⁇ m or more and 200 ⁇ m or less.
  • the methacrylic resin or resin composition of the present invention has high transparency and high heat resistance.
  • the molded product of the present invention for example, a film, has high transparency, high heat resistance, and high mechanical strength, and is also excellent in surface smoothness, surface hardness, or impact resistance.
  • the method for producing a film of the present invention has a short time required for evaporation of an organic solvent, and has high production efficiency for a film having excellent surface smoothness, surface hardness, or impact resistance.
  • the methacrylic resin of the present invention contains a methacrylic polymer (A) and a methacrylic polymer (B).
  • the methacrylic polymer (A) is a random polymer mainly containing a structural unit derived from a methacrylic acid ester. This methacrylic polymer (A) can be used as a resin modifier.
  • methacrylic acid ester examples include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylate esters such as phenyl methacrylate; and cycloalkyl methacrylates such as cyclohexyl methacrylate and norbornenyl methacrylate. ; Can be mentioned. Of these, alkyl methacrylate esters are preferred, and methyl methacrylate is most preferred.
  • the amount of the structural unit derived from the methacrylic acid ester contained in the methacrylic polymer (A) is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total structural units of the methacrylic polymer (A). It is more preferably 98% by mass or more, even more preferably 99% by mass or more, and most preferably 100% by mass.
  • the content of the structural unit derived from methyl methacrylate of the methacrylic acid polymer (A) is preferably 90% by mass with respect to all the structural units of the methacrylic acid polymer (A). % Or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, and most preferably 100% by mass.
  • the methacrylic polymer (A) may contain a structural unit derived from a monomer other than the methacrylic acid ester.
  • the monomer other than the methacrylic acid ester include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; acrylic acids such as phenyl acrylate.
  • Acrylic ester Acrylic acid cycloalkyl ester such as cyclohexyl acrylate and norbornenyl acrylate; Aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; acrylamide; Methalamide; Acrylonitrile; Methacronitrile; Examples thereof include vinyl-based monomers having only one polymerizable carbon-carbon double bond.
  • the weight average molecular weight Mw A of the methacrylic polymer (A) is usually 30,000 or more, preferably 40,000 to 200,000, more preferably 40,000 to 140,000, and further preferably 40,000 to 100,000.
  • Mw A is 30,000 or more, the impact resistance and toughness of the molded product tend to be improved.
  • the upper limit of Mw A is not particularly limited, the Mw A is 200,000 or less, the flowability of the methacrylic resin or resin composition, to provide good moldability tends to be a sufficient level.
  • the methacrylic polymer (A) has a ratio of weight average molecular weight Mw A to number average molecular weight Mn A (Mw A / Mn A ) of usually 1.0 to 1.4, preferably 1.01 to 1.4. It is more preferably 1.05 to 1.4, still more preferably 1.05 to 1.3.
  • Mw A and Mn A are values calculated by converting into the molecular weight of standard polystyrene based on the chromatogram measured by gel permeation chromatography.
  • the temperature of the column oven is set to 40 ° C., 20 ⁇ l of the sample solution is injected at an eluent flow rate of 0.35 ml / min, and the chromatogram is measured.
  • the chromatogram is a chart obtained by plotting an electric signal (detection intensity Y) derived from the difference in refractive index between the sample solution and the reference solution with respect to the elution time (retention time). Conversion of standard polystyrene to molecular weight is performed based on the calibration curve.
  • a calibration curve is created by measuring the chromatogram by gel permeation chromatography for each standard polystyrene in the range of 400 to 500000 molecular weight and plotting the elution time and the logarithmic value of the molecular weight.
  • the sum of the weight fraction differential values of the components (M ⁇ 15,000) having a molecular weight of 15,000 or less is the sum of the weight fraction differential values of all the components in the weight-based differential molecular weight distribution curve.
  • it is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less.
  • the horizontal axis is the logarithmic log (M) of the molecular weight
  • the vertical axis is the weight fraction differential value (the value dw obtained by differentiating the weight fraction W with the logarithmic log (M) of the molecular weight). It is a plot of / d (log (M))), and is obtained by converting the horizontal axis to the molecular weight of standard polystyrene based on the chromatogram used in calculating Mw A and Mn A. ..
  • the glass transition temperature of the methacrylic polymer (A) is preferably 125 ° C. or higher, more preferably 127 ° C. or higher, and even more preferably 129 ° C. or higher.
  • the upper limit of the glass transition temperature of the methacrylic polymer (A) is preferably 140 ° C. The higher the glass transition temperature of the methacrylic polymer (A), the higher the heat resistance of the methacrylic resin or resin composition of the present invention, and the less likely it is that deformation such as heat shrinkage will occur.
  • the lower limit of the triad syndiotacticity (rr) of the methacrylic polymer (A) is 63%, preferably 65%, more preferably 72%, and the upper limit is preferably 90%, more preferably 85%. More preferably, it is 80%.
  • the triad syndiotacticity (rr) of the methacrylic polymer (A) is 63% or more, the methacrylic resin or resin composition of the present invention has high heat resistance and tends to be less likely to be deformed such as heat shrinkage. is there.
  • the strength of the methacrylic resin or the resin composition of the present invention is particularly improved. It is considered that this is because the carbonyl-carbonyl interaction between the methacrylic polymer (A) and the methacrylic polymer (B) is improved.
  • triad syndiotacticity two chains (doubles, diad) of a chain of three consecutive structural units (triple, triad) are both racemo (denoted as rr). Is the ratio.
  • meso those having the same configuration
  • racemo which are referred to as m and r, respectively.
  • the triad syndiotacticity (rr) (%) is a region of 0.6 to 0.95 ppm when 1 1 H-NMR spectrum is measured at 30 ° C. in deuterated chloroform and TMS is 0 ppm.
  • the area (X) of the above and the area (Y) of the region of 0.6 to 1.35 ppm can be measured and calculated by the formula: (X / Y) ⁇ 100.
  • the method for producing the methacrylic polymer (A) is not particularly limited as long as the methacrylic polymer (A) satisfying the above physical characteristics can be obtained.
  • the anion polymerization method is preferable. More preferably, in the anion polymerization method, the polymerization temperature, the polymerization time, the type and amount of the chain transfer agent, the type and amount of the polymerization initiator, and the like are appropriately set so as to satisfy the above-mentioned physical property values. Produces methacrylic polymer (A).
  • anionic polymerization method examples include a method in which an organic alkali metal compound is used as a polymerization initiator and anionic polymerization is carried out in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt (see Special Fair 7-25859), and organic.
  • a method of anionic polymerization using an alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound see JP-A-11-335432
  • a method of anionic polymerization using an organic rare earth metal complex as a polymerization initiator see JP-A-6-93060.
  • alkyllithium such as n-butyllithium, sec-butyllithium, isobutyllithium and tert-butyllithium
  • the organoaluminum compound coexists.
  • the organic aluminum the compound represented by Al R 1 R 2 R 3 (R 1 , R 2 and R 3 may have an alkyl group or a substituent which may independently have a substituent, respectively.
  • it represents an N, N-disubstituted amino group.
  • R 2 and R 3 may be an arylenoxy group which may have a substituent formed by binding them.) be able to.
  • organoaluminum compound examples include isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, and isobutyl [2,2].
  • '-Methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum and the like can be mentioned.
  • an ether, a nitrogen-containing compound, or the like can coexist in order to control the polymerization reaction.
  • the methacrylic polymer (A) is useful as a resin modifier, and is particularly useful as a modifier for the methacrylic polymer (B).
  • the methacrylic polymer (B) is a random polymer mainly containing a structural unit derived from a methacrylic acid ester.
  • methacrylic acid ester examples include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; aryl methacrylate esters such as phenyl methacrylate; and cycloalkyl methacrylates such as cyclohexyl methacrylate and norbornenyl methacrylate. ; Can be mentioned. Of these, alkyl methacrylate esters are preferred, and methyl methacrylate is most preferred.
  • the amount of the structural unit derived from the methacrylic acid ester contained in the methacrylic polymer (B) is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total structural units of the methacrylic polymer (B). ..
  • the methacrylic polymer (B) may contain a structural unit derived from an acrylic acid ester.
  • acrylic acid ester include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid aryl esters such as phenyl acrylate; to cyclo acrylate.
  • acrylic acid cycloalkyl esters such as xyl and norbornenyl acrylate.
  • the amount of the structural unit derived from the acrylic acid ester contained in the methacrylic polymer (B) is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the total structural units of the methacrylic polymer (B). %.
  • the methacrylic polymer (B) may contain a structural unit derived from a monomer other than the methacrylic acid ester and the acrylic acid ester.
  • monomers other than methacrylic acid ester and acrylic acid ester include ⁇ , ⁇ -unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; unsaturated group-containing divalent carboxylic acids such as maleic anhydride, fumaric acid and itaconic acid.
  • Aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; ⁇ and ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile; maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like can be mentioned. ..
  • the amount of structural units derived from monomers other than methyl methacrylate and acrylic acid ester contained in the methacrylic polymer (B) is preferably 20% by mass or less based on the total structural units of the methacrylic polymer (B). , More preferably 10% by mass or less.
  • the weight average molecular weight Mw B of the methacrylic polymer (B) is preferably 80,000 or more, more preferably 80,000 to 3,000, more preferably 120,000 to 2,500,000, still more preferably 16,000 to 20,000,000.
  • Mw B is 80,000 or more
  • the upper limit of Mw B is not particularly limited from the viewpoint of impact resistance and toughness, but the methacrylic polymer (B) having Mw B exceeding 3,000,000 tends to be difficult to produce.
  • Mw B is 160,000 or more, the strength of the methacrylic resin or the resin composition is particularly improved. It is considered that this is because the carbonyl-carbonyl interaction between the methacrylic polymer (A) and the methacrylic polymer (B) is improved.
  • the ratio (Mw B / Mn B ) of the weight average molecular weight Mw B to the number average molecular weight Mn B of the methacrylic polymer (B) is preferably 1.7 to 2.6, more preferably 1.7 to 2. 5, more preferably 1.7 to 2.3.
  • Mw B and Mn B are values calculated by converting into the molecular weight of standard polystyrene based on the chromatogram measured by gel permeation chromatography.
  • the methacrylic polymer (B) has a glass transition temperature of preferably 100 ° C. or higher, more preferably 105 ° C. or higher.
  • the upper limit of the glass transition temperature of the methacrylic polymer (B) is preferably 140 ° C. When the glass transition temperature of the methacrylic polymer (B) is in this range, the heat resistance of the methacrylic resin or the resin composition becomes high, and deformation such as heat shrinkage tends to be difficult to occur.
  • the methacrylic polymer (B) has a triad syndiotacticity (rr) of preferably 45 to 63%, more preferably 49 to 60%.
  • triad syndiotacticity (rr) of the methacrylic polymer (B) is in the above range, the heat resistance of the methacrylic resin or the resin composition and the moldability tend to be well balanced.
  • the method for producing the methacrylic polymer (B) is not particularly limited as long as the methacrylic polymer (B) satisfying the above physical characteristics can be obtained.
  • Examples of the method for producing the methacrylic polymer (B) include radical polymerization and anionic polymerization from the viewpoint of the reaction active site.
  • the method for producing the methacrylic polymer (B) includes emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like from the viewpoint of the form of the polymerization reaction solution. Of these, radical emulsion polymerization, radical bulk polymerization, or radical suspension polymerization is preferable, and radical bulk polymerization is more preferable, from the viewpoint of high productivity and ease of polymerization.
  • polymerization initiator used in bulk polymerization or suspension polymerization include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy2-ethylhexanoate, and 1,1,3,3-tetramethylbutyl.
  • Peroxides 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), etc. Azo compounds and the like can be mentioned. Of these, t-hexyl peroxy2-ethylhexanoate, 1,1-bis (t-hexyl peroxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) are preferable.
  • polymerization initiator used in emulsion polymerization are persulfate-based initiators such as potassium persulfate and ammonium persulfate; and redox-based initiators such as persulfoxylate / organic peroxide and persulfate / sulfite. Agents can be mentioned.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be set so that a methacrylic polymer (B) satisfying the above physical property values can be obtained.
  • methacrylic polymer (B) satisfying the above physical property values
  • the polymerization initiator used in bulk polymerization is one that generates reactive radicals.
  • the polymerization initiator has a 1-hour half-life temperature of preferably 60 to 140 ° C, more preferably 80 to 120 ° C. Further, the polymerization initiator has a hydrogen extraction ability of preferably 20% or less, more preferably 10% or less, still more preferably 5% or less.
  • the hydrogen abstraction ability can be known from the technical data of the polymerization initiator manufacturer (for example, the technical data of Nippon Oil & Fats Co., Ltd. "Hydrogen extraction ability of organic peroxide and initiator efficiency" (created in April 2003)). .. Further, the hydrogen extraction ability can be measured by a radical trapping method using an ⁇ -methylstyrene dimer, that is, an ⁇ -methylstyrene dimer trapping method. The measurement is generally performed as follows. First, the polymerization initiator is cleaved in the coexistence of ⁇ -methylstyrene dimer as a radical trapping agent to generate a radical fragment.
  • the radical fragment having a low hydrogen abstraction force is added to the double bond of the ⁇ -methylstyrene dimer and captured.
  • a radical fragment having a high hydrogen abstraction force abstracts hydrogen from cyclohexane to generate a cyclohexyl radical, and the cyclohexyl radical is added to and trapped in the double bond of ⁇ -methylstyrene dimer to generate a cyclohexane trapping product. Therefore, cyclohexane or cyclohexane capture product is quantified, the ratio (mole fraction) of radical fragments having high hydrogen abstraction power to the theoretical amount of radical fragment generation is calculated, and this is used as the hydrogen abstraction ability.
  • Chain transfer agents used in massive polymerization include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol.
  • Alkyl mercaptans and the like can be mentioned. Of these, monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable.
  • These chain transfer agents may be used alone or in combination of two or more.
  • the amount of the chain transfer agent used may be set so that the methacrylic polymer (B) satisfying the above physical property values can be obtained. For example, with respect to 100 parts by mass of the monomer subjected to the polymerization reaction. It can be appropriately set within the range of preferably 0 to 0.5 parts by mass, more preferably 0.05 to 0.4 parts by mass, and further preferably 0.06 to 0.25 parts by mass.
  • the amount of the chain transfer agent used can be appropriately set within the range of preferably 2500 to 10000 parts by mass, more preferably 3000 to 9000 parts by mass with respect to 100 parts by mass of the polymerization initiator.
  • a suspension stabilizer can be used in suspension polymerization.
  • the suspension stabilizer include an organic colloidal polymer substance, an inorganic colloidal polymer substance, inorganic fine particles, and a combination thereof with a surfactant.
  • An emulsifier can be used in emulsion polymerization.
  • the emulsifier include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and alkyl sulfates such as sodium dodecyl sulphate; nonions.
  • Polyoxyethylene alkyl ether sulfate such as sodium, alkyl ether carboxylate such as polyoxyethylene tridecyl ether sodium acetate; can be mentioned.
  • These emulsifiers may be used alone or in combination of two or more.
  • the average number of repeating units of ethylene oxide units in the examples of the nonionic emulsifier and the nonionic / anion emulsifier is preferably 30 or less, more preferably 20 or less, in order to prevent the foaming property of the emulsifier from becoming extremely large. More preferably, it is 10 or less.
  • the resin is taken out from the reaction product solution by a known method after the completion of the polymerization reaction.
  • the resin can be taken out from the reaction product liquid (emulsion) by a salting out coagulation method, a freeze coagulation method, a spray drying method or the like.
  • the salting out coagulation method and the freeze coagulation method are preferable from the viewpoint that impurities contained in the resin can be easily removed by washing with water. It is preferable to filter the emulsion with a wire mesh having a mesh size of 50 ⁇ m or less before the coagulation step because foreign substances mixed in the emulsion can be removed.
  • the methacrylic polymer (B) has a shear rate of 122 seconds- 1 and a melt viscosity ⁇ B at a temperature of 260 ° C.
  • the methacrylic polymer (A) has a shear rate of 122 seconds- 1 and a temperature of 260 ° C. Higher than viscosity ⁇ A.
  • the difference between the melt viscosity ⁇ B and the melt viscosity ⁇ A is preferably 1000 Pa ⁇ s or more, and more preferably 1500 Pa ⁇ s or more.
  • the weight average molecular weight Mw B of the methacrylic polymer (B) is 2.5 times or more, preferably 3 times or more the weight average molecular weight Mw A.
  • the methacrylic resin of the present invention has an absolute value of the difference between the refractive index n dA of the methacrylic polymer (A) and the refractive index n dB of the methacrylic polymer (B)
  • the amount of the methacrylic polymer (A) contained in the methacrylic resin of the present invention is preferably 2 to 39 with respect to the methacrylic resin from the viewpoint of achieving both heat resistance and molding processability or surface smoothness in a good state. It is by mass, more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and most preferably 5 to 16% by mass.
  • the amount of the methacrylic polymer (B) contained in the methacrylic resin of the present invention is preferably 61 to 98 mass with respect to the methacrylic resin from the viewpoint of achieving both heat resistance or mechanical strength and molding processability in a good state. %, More preferably 70 to 95% by mass, still more preferably 80 to 95% by mass, and most preferably 84 to 95% by mass.
  • the methacrylic resin of the present invention has a mass ratio of the methacrylic polymer (A) to the methacrylic polymer (B) of 2/98 to 39/61, more preferably 5/95 to 30/70, still more preferably 5/95. ⁇ 20/80.
  • the highest peak top molecular weight M Pt weight fraction differential value in the differential molecular weight distribution curve of the weight is preferably from 100000 to 2000000, more preferably 120000 to 2000000, more preferably at from 160,000 to 2,000,000 is there.
  • the peak top molecular weight MPt is in this range, a molded product having excellent strength, hardness, and surface smoothness can be obtained.
  • the methacrylic resin of the present invention has a weight fraction differential value of a component (M ⁇ 1/20 M Ph ) having a molecular weight of 1/20 or less of the peak top molecular weight M Ph having the highest molecular weight in the weight-based differential molecular weight distribution curve.
  • the total is preferably 2% or less, more preferably 1.5% or less, based on the total weight fraction derivative values of all the components.
  • the total of the weight fraction differential values of the components having a molecular weight of 15,000 or less (M ⁇ 15,000) is relative to the total weight fraction differential values of all the components. It is preferably 2% or less, more preferably 1.75% or less.
  • the effect of the methacrylic resin or resin composition of the present invention is further improved by the small amount of the low molecular weight component as described above.
  • the methacrylic resin composition of the present invention contains the methacrylic resin of the present invention.
  • the methacrylic resin composition of the present invention may contain the methacrylic resin of the present invention and a resin other than the methacrylic resin (additional resin).
  • additional resin examples include olefin-based thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); halogen-containing heat such as vinyl chloride and vinyl chlorinated resins.
  • Plastic resin Acrylic thermoplastic resin
  • Polystyrene-based thermoplastic resin such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer; polyethylene terephthalate, polybutylene terephthalate, Polyesters such as polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetals; polycarbonates; polyphenylene oxides; polyphenylene sulfides; polyether ether ketones; polysulphons; polyether salphons; Examples thereof include rubbery polymers such as ABS resin and ASA resin containing acrylic rubber, and cellulose resins such as polyvinyl butyral and cellulose acylate.
  • these other resins may be in a compatible state or a phase-separated state with the methacrylic resin of
  • the methacrylic resin composition of the present invention may contain the methacrylic resin of the present invention, an elastomer, and if necessary, the other resin described above.
  • Elastomer is a mixture of methacrylic resin in a compatible state or a phase-separated state.
  • the elastomer is preferably mixed with a methacrylic resin in a phase-separated state to form a dispersed phase.
  • the shape of the dispersed phase is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a rod shape, a flat body shape, and a string shape.
  • the size of the dispersed phase is not particularly limited, but for example, the average particle size is preferably 0.05 to 1 ⁇ m, more preferably 0.07 to 0.5 ⁇ m, and further preferably 0.10 to 0.4 ⁇ m.
  • the elastomer is preferably a polymer containing a structural unit derived from an acrylic acid ester.
  • acrylic acid ester include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; acrylic acids such as cyclohexyl acrylate and norbornenyl acrylate.
  • Acrylic acid cycloalkyl ester Of these, alkyl acrylate esters are preferred, and butyl acrylate is most preferred.
  • the amount of the structural unit derived from the acrylic acid ester contained in the elastomer is preferably 30% by mass or more, more preferably 35% by mass or more and 90% by mass or less, and further preferably 40% by mass or more and 80% by mass or less.
  • the elastomer may have a structural unit derived from a vinyl-based monomer having only one polymerizable carbon-carbon double bond in one molecule.
  • the vinyl-based monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; and aryl methacrylates such as phenyl methacrylate; Cycloalkyl methacrylic acid esters such as cyclohexyl methacrylate and norbornenyl methacrylate; aralkyl esters of methacrylic acid such as benzyl methacrylate, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; acrylamide; methacrylicamide; acrylonitrile; methacrylic nitrile ; And so on.
  • the amount of elastomer contained in the methacrylic resin composition of the present invention is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and further preferably 0 to 30% by mass with respect to the methacrylic resin composition. ..
  • the amount of elastomer can be appropriately set from the viewpoints of chemical resistance, heat resistance, flexural modulus, workability, and the like.
  • the elastomer is not particularly limited by the form of its molecular chain, and is, for example, a linear polymer elastomer (for example, a random copolymer elastomer, a block copolymer elastomer, etc.), a branched chain polymer elastomer (for example, a graft elastomer). Elastomer, star-type block copolymer elastomer), and the like.
  • the elastomer preferably contains a block copolymer elastomer composed of a polymer block mainly having a structural unit derived from a methacrylic acid ester and a polymer block having a structural unit derived from an acrylic acid ester. ..
  • the elastomer may be particles containing a crosslinked rubber polymer containing a structural unit derived from an acrylic acid ester (hereinafter, referred to as crosslinked rubber particles).
  • the crosslinked rubber particles have an average particle diameter of preferably 0.05 to 1 ⁇ m, more preferably 0.07 to 0.5 ⁇ m, and even more preferably 0.10 to 0.4 ⁇ m.
  • the average particle size is an average value in a volume-based particle size distribution measured by a light scattering method.
  • the crosslinked rubber particles are preferably composed of an inner layer and an outermost layer covering the inner layer.
  • the inner layer may be composed of only a core layer, or may be composed of a core layer and an intermediate layer covering the core layer.
  • the intermediate layer may be a single layer made of one polymer, or may be a multilayer made of different polymers.
  • the crosslinked rubber particles have a difference in refractive index nd between the two adjacent layers, preferably less than 0.01, more preferably less than 0.008, and further preferably less than 0.005. Is preferable.
  • the mass ratio of the inner layer to the outermost layer of the crosslinked rubber particles is preferably 60/40 to 95/5, more preferably 70/30 to 90/10.
  • the crosslinked rubber particles include, for example, two-layer particles of a core layer made of a crosslinked rubber polymer (II) and an outermost layer made of a thermoplastic polymer (III) covering the core layer; the crosslinked polymer (I).
  • the thermoplastic polymer (III) is a structural unit derived from a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and, if necessary, a structural unit derived from a monofunctional monomer other than the methacrylic acid alkyl ester. It is a polymer composed of.
  • the thermoplastic polymer (III) preferably does not contain structural units derived from the polyfunctional monomer.
  • the amount of the structural unit derived from the methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms constituting the thermoplastic polymer (III) is 80 to 100 mass with respect to the mass of the thermoplastic polymer (III). %, Preferably 85-95% by mass.
  • methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2 methacrylic acid.
  • methacrylic acid C1-8 alkyl ester examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2 methacrylic acid.
  • -Ethylhexyl, propyl methacrylate, cyclohexyl methacrylate and the like can be mentioned. Of these, methyl methacrylate is preferable.
  • the amount of the structural unit derived from the monofunctional monomer other than the methacrylic acid C1-8 alkyl ester constituting the thermoplastic polymer (III) is 0 to 20 mass with respect to the mass of the thermoplastic polymer (III). %, Preferably 5 to 15% by mass.
  • the monofunctional monomer other than the methacrylic acid C1-8 alkyl ester include acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate; styrene and p-methylstyrene. , ⁇ -Methylstyrene and other aromatic vinyl compounds; examples thereof include maleimide compounds such as N-propyl maleimide, N-cyclohexyl maleimide and NO-chlorophenyl maleimide.
  • the amount of the thermoplastic polymer (III) is preferably 40 to 75% by mass, more preferably 50 to 70% by mass, and further preferably 55 to 65% by mass with respect to the mass of the crosslinked rubber particles.
  • the crosslinked polymer (I) is composed of a structural unit derived from methyl methacrylate, a structural unit derived from a monofunctional monomer other than methyl methacrylate, and a structural unit derived from a polyfunctional monomer.
  • the amount of the structural unit derived from methyl methacrylate constituting the crosslinked polymer (I) is 40 to 98.5% by mass, preferably 45 to 95% by mass, based on the mass of the crosslinked polymer (I). ..
  • the amount of the structural unit derived from the monofunctional monomer other than methyl methacrylate constituting the crosslinked polymer (I) is 1 to 59.5% by mass, preferably 1 to 59.5% by mass, based on the mass of the crosslinked polymer (I). It is 5 to 55% by mass.
  • the monofunctional monomer other than methyl methacrylate include methacrylic ester other than methyl methacrylate such as ethyl methacrylate, butyl methacrylate and cyclohexyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, and 2 acrylate.
  • Acrylic esters such as ethylhexyl and propyl acrylate; aromatic vinyl compounds such as styrene, p-methylstyrene and ⁇ -methylstyrene; maleimide compounds such as N-propylmaleimide, N-cyclohexylmaleimide and No-chlorophenylmaleimide Can be mentioned.
  • the amount of the structural unit derived from the polyfunctional monomer constituting the crosslinked polymer (I) is 0.05 to 0.4% by mass, preferably 0.1, based on the mass of the crosslinked polymer (I). It is about 0.3% by mass.
  • the polyfunctional monomer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl. Isocyanurate and the like can be mentioned.
  • the amount of the crosslinked polymer (I) is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and further preferably 10 to 30% by mass with respect to the mass of the crosslinked rubber particles.
  • the crosslinked rubber polymer (II) is a structural unit derived from an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and / or a structural unit derived from a conjugated diene, and a structural unit derived from a polyfunctional monomer. Consists of.
  • the amount of the structural unit derived from the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and / or the structural unit derived from the conjugated diene constituting the crosslinked rubber polymer (II) is determined by the crosslinked rubber polymer (II). It is 98.3 to 99% by mass, preferably 95 to 98% by mass, based on the mass of.
  • acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate.
  • conjugated diene examples include 1,3-butadiene, isoprene and the like.
  • the amount of the structural unit derived from the polyfunctional monomer constituting the crosslinked rubber polymer (II) is 1 to 1.7% by mass, preferably 1.2, based on the mass of the crosslinked rubber polymer (II). It is ⁇ 1.6% by mass, more preferably 1.3 to 1.5% by mass.
  • the polyfunctional monomer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl. Isocyanurate and the like can be mentioned.
  • the structural unit derived from the polyfunctional monomer in the crosslinked polymer (I) is relative to the mass of the structural unit derived from the polyfunctional monomer in the crosslinked rubber polymer (II).
  • the mass ratio of is preferably 0.05 to 0.25, more preferably 0.1 to 0.2.
  • the glass transition temperature of the crosslinked rubber polymer (II) is preferably lower than the glass transition temperature of the crosslinked polymer (I).
  • the amount of the crosslinked rubber polymer (II) is preferably 20 to 55% by mass, more preferably 25 to 45% by mass, and further preferably 30 to 40% by mass with respect to the mass of the crosslinked rubber particles.
  • the molecular chains of the crosslinked polymer (I) and the crosslinked rubber polymer (II) are connected by a graft bond. Further, it is preferable that the molecular chains of the crosslinked rubber polymer (II) and the thermoplastic polymer (III) are connected by a graft bond.
  • the graft bond is generated by a polymerization method (graft polymerization method) in which a substituent bonded to the main chain of the already completed polymer is used as a reaction active point and a branch portion is newly extended from the reaction active point. It is a bond that connects the main chain and the branch part.
  • the resin composition of the present invention may contain a conventional additive as long as it does not impair physical properties such as transparency and strength.
  • Additives include, for example, UV absorbers, stabilizers, mold release agents, antistatic agents, flame retardants, plasticizers, dispersants, flow modifiers, leveling agents, defoamers, surface modifiers, heat resistance improvements. Agents, water repellency improvers, optical expression agents and the like can be used.
  • plasticizer examples include phthalate ester type, fatty acid ester type, trimellitic acid ester type, phosphoric acid ester type, polyester type, epoxy type and the like.
  • UV absorber examples include benzotriazole-based, 2-hydroxybenzophenone-based, and salicylic acid phenyl ester-based agents.
  • the release agent examples include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • the flame retardant examples include organic halogen-based 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. And so on.
  • organic halogen-based 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. And so on.
  • antistatic agent examples include stearoamide propyl dimethyl- ⁇ -hydroxyethylammonium nitrate.
  • Examples of the surface modifier include polybutadiene and CTBN (terminal carboxylic acid-modified nitrile butadiene rubber).
  • stabilizer examples include 2,6-di-t-butyl-4-methylphenol, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline and the like.
  • leveling agent examples include fluorine-based surfactants.
  • Examples of the defoaming agent include acrylic copolymers and silicones.
  • additives can be used alone or in combination of two or more.
  • the amount of the additive is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the methacrylic resin composition. May be good.
  • the resin composition of the present invention may be in the form of a solid or in the form of a liquid.
  • the solid resin composition can be produced by mixing the methacrylic polymer (A), the methacrylic polymer (B) and other components (additional components) such as other resins, elastomers and additives as required. Can be prepared. Mixing can be performed by, for example, melt-kneading using a mixer such as a ribbon blender, a tumble mixer, or a Henschel mixer, or a mixing means using a kneader such as an open roller, a kneader, a Banbury mixer, or an extruder. These mixing means may be used alone or in combination of two or more.
  • the resin composition of the present invention is not limited by the mixing order of the methacrylic polymer (A), the methacrylic polymer (B) and other components to be mixed as needed.
  • the methacrylic polymer (A) and the methacrylic polymer (B) may be mixed to obtain the methacrylic resin of the present invention, and then other components may be mixed thereto to obtain the resin composition of the present invention.
  • the methacrylic polymer (A), the methacrylic polymer (B) and other components may be mixed together to obtain the resin composition of the present invention, or the methacrylic polymer (A) and other components may be mixed.
  • the resin composition of the present invention may be obtained by mixing and then mixing the methacrylic polymer (B) with the methacrylic polymer (B), or the methacrylic polymer (B) and other components are mixed with the methacrylic polymer. (A) may be mixed to obtain the resin composition of the present invention.
  • the liquid resin composition is formed by dissolving or dispersing the methacrylic polymer (A), the methacrylic polymer (B) and, if necessary, other components in a liquid medium.
  • the liquid medium include hydrocarbons (benzene, toluene, etc.), halogen-based solvents (dichloromethane, etc.), ethers (diethyl ether, tetrahydrofuran, etc.), esters (ethyl acetate, etc.), ketones (acetone, ethylmethyl, etc.).
  • examples include alcohols (methanol, ethanol, butanol, etc.) such as ketones, diisopropyl ketones, cyclohexanone, etc.
  • These liquid media may be used alone or in combination of two or more.
  • the procedure for adding the methacrylic polymer (A), the methacrylic polymer (B) and, if necessary, other components to the liquid medium is not particularly limited.
  • the molded product of the present invention contains the methacrylic resin or resin composition of the present invention.
  • the molded product of the present invention can be applied to the methacrylic resin or solid resin composition of the present invention, for example, injection molding method, injection compression molding method, extrusion molding method (for example, T-die method, inflation method, etc.), calendar method, heat. It can be obtained by performing molding using a molding method (particularly, a hot press method), a transfer molding method, a blow molding method, a melt casting method, or the like. Further, the molded product of the present invention can be obtained by subjecting the liquid resin composition of the present invention (for example, doping) to molding using, for example, a solvent casting method.
  • the film or sheet which is one aspect of the molded product of the present invention may be one that has not been stretched (unstretched film) or may be a stretched film that has been stretched.
  • the film of the present invention can be used as an optical film or an optical sheet.
  • the stretching may be either uniaxial stretching (for example, longitudinal stretching or transverse stretching) or biaxial stretching (for example, iso-stretching or partial stretching).
  • the draw ratio may be, for example, about 1.1 to 10 times in each direction (or one direction) in uniaxial stretching and biaxial stretching, preferably 1.2 to 5 times, and more preferably 1.3. It is about 3 times.
  • the strength of the film of the present invention may be improved by the stretching treatment.
  • the thickness of the film is, for example, 1 to 1000 ⁇ m, preferably 3 to 800 ⁇ m, more preferably 5 to 500 ⁇ m, and most preferably 20 to 200 ⁇ m.
  • the doping of the present invention contains the methacrylic resin of the present invention, an organic solvent, and, if necessary, other components.
  • Halogenized hydrocarbons such as dichloromethane are preferably used for doping; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl- Alcohols such as 2-butanol and cyclohexanol can be mentioned.
  • the amount of the methacrylic resin of the present invention contained in the dope is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 15 to 50% by mass.
  • the amount of the organic solvent contained in the doping is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and further preferably 50 to 85% by mass.
  • the dope of the present invention may contain an additive for solvent casting.
  • Additives for solvent casting include moisture permeability reducing compounds; peeling accelerators; retardation (Rth) control agents; inorganic fine particles (matting agents); plasticizers such as phthalates and phosphate ester compounds; Re-expressing agents; Ultraviolet absorbers; antioxidants and the like can be mentioned.
  • Doping is preferably prepared at a temperature of 0 ° C. or higher (normal temperature or high temperature).
  • the doping can be prepared by mixing a methacrylic resin, an organic solvent, other components if necessary, and a solvent casting additive if necessary.
  • the mixing procedure is not particularly limited, and for example, a mixture of each component may be added to an organic solvent to dissolve it, or each component may be sequentially added to and dissolved in an organic solvent being stirred. Solutions of each component may be prepared in advance and the solutions may be mixed.
  • the methacrylic resin or resin composition of the present invention may be dissolved at normal pressure, below the boiling point of the main solvent, or pressurized above the boiling point of the main solvent.
  • the method for producing a film of the present invention includes casting the doping of the present invention on a support to obtain a liquid film, and removing the organic solvent from the liquid film. Doping casting is performed, for example, by pumping the dope from the storage tank to the die, draining the dope from the die slit, and applying it to a rotating metal endless belt.
  • the thickness of the liquid film is adjusted so that the thickness of the film is preferably 20 to 200 ⁇ m from the viewpoint of the strength and processability of the film.
  • the thickness of the liquid film can be adjusted by changing the amount of doping supplied, the speed of the endless belt (support), and the like. Since the solid film is obtained on the support by removing the organic solvent, the solid film is peeled off from the support.
  • the solid film can be dried.
  • the time from 20% by mass to 0.1% by mass of the organic solvent remaining on the solid film is preferably less than 40 minutes, more preferably 30 minutes or less, still more preferably 25 minutes or less. It can be done under the condition of.
  • the film after the drying treatment may be subjected to heat treatment, stretching treatment or the like.
  • the description of paragraphs [0617] to [0889] of JP-A-2005-104148 is cited here.
  • the physical properties of the methacrylic polymer and the like, as well as the methacrylic resin, the methacrylic resin composition and the doping were evaluated as follows.
  • the chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and the values (Mw, Mn, MPt ) converted into the molecular weight of standard polystyrene were calculated.
  • the baseline is that the slope of the peak on the high molecular weight side of the GPC chart changes from zero to plus when viewed from the earliest retention time, and the slope of the peak on the low molecular weight side changes from minus to zero when viewed from the earliest retention time. It is a line connecting the points that change to.
  • GPC device manufactured by Tosoh Corporation, HLC-8320 Detector: Differential refractive index detector Column: Two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 connected in series were used. Eluent: Tetrahydrofuran Eluent flow rate: 0.35 ml / min Column temperature: 40 ° C Calibration curve: Created using data of 10 standard polystyrene points
  • melt viscosity ⁇ After the resin sample was dried at 80 ° C. for 12 hours, the melt viscosity ⁇ was measured using “Capirograph 1D” manufactured by Toyo Seiki Co., Ltd. under the conditions of a temperature of 260 ° C. and a shear rate of 122 sec -1 .
  • the rubber particle dispersion sample was measured by a light scattering method (volume conversion) using a laser diffraction / scattering particle size distribution measuring device LA-910 manufactured by Horiba Seisakusho. A median diameter was adopted as the particle diameter.
  • Glass transition temperature Tg Glass transition temperature Tg
  • DSC-50 product number
  • the resin sample was subjected to hot press molding at 260 ° C. to obtain a molded product sample of 80 mm ⁇ 10 mm ⁇ 4 mm.
  • the notched Charpy impact strength of the molded product sample was measured using a digital impact tester manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7111 1eU. The measurement was performed 10 times, and the average value was taken as the Charpy impact strength.
  • the Rockwell hardness of the molded product sample was measured using a Rockwell hardness tester (Rockwell hardness tester manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K7202.
  • the haze of the molded product sample was measured using a haze meter (HM-150, manufactured by Murakami Color Research Institute) in accordance with JIS K7136, and the transparency I was judged according to the following criteria.
  • ⁇ Haze is less than 5%.
  • X Haze is 5% or more.
  • Residual solvent amount (mass%) [(XY) / Y] ⁇ 100
  • X is the mass of the solid film during drying
  • Y is the mass of the solid film when drying is in equilibrium. The measurement was performed twice and the average value was calculated.
  • a drying characteristic curve was created by plotting the drying time on the horizontal axis and the residual amount of organic solvent on the vertical axis. From the drying characteristic curve, the drying time when the residual amount of the organic solvent was 0.1% by mass was determined.
  • Transparency II For a solid film sample in which the residual amount of the organic solvent is 0.1% by mass, the haze is measured using a haze meter (HM-150, manufactured by Murakami Color Research Institute) in accordance with JIS K7136, and the haze is measured according to the following criteria. Transparency II was judged. ⁇ : Haze is less than 1%. X: Haze is 1% or more.
  • the methacrylic polymer (A-1) has a Mw of 70,000, a component having a molecular weight of 15,000 or less (M ⁇ 15,000) in an amount of 0.17% by mass, a melt viscosity ⁇ of 1200 Pa ⁇ s, and a Mw / Mn of 1.
  • the triadosyndio tacticity (rr) was 75%
  • the Tg was 131 ° C.
  • the amount of structural units derived from methyl methacrylate was 100% by mass.
  • Table 1 shows the physical characteristics of the methacrylic polymer (A-1).
  • the methacrylic polymer (A-2) has a Mw of 40,000, a component having a molecular weight of 15,000 or less (M ⁇ 15,000) in an amount of 1.52% by mass, a melt viscosity ⁇ of 450 Pa ⁇ s, and a Mw / Mn of 1.
  • the triadosyndio tacticity (rr) was 75%
  • the Tg was 130 ° C.
  • the amount of structural units derived from methyl methacrylate was 100% by mass.
  • Table 1 shows the physical characteristics of the methacrylic polymer (A-2).
  • the methacrylic polymer (A-3) has a Mw of 25,000, a component having a molecular weight of 15,000 or less (M ⁇ 15,000) in an amount of 7.06% by mass, a melt viscosity ⁇ of 150 Pa ⁇ s, and a Mw / Mn of 1.
  • the triadosyndio tacticity (rr) was 76%
  • the Tg was 130 ° C.
  • the amount of structural units derived from methyl methacrylate was 100% by mass.
  • Table 1 shows the physical characteristics of the methacrylic polymer (A-3).
  • Production Example 4 (Production of methacrylic polymer (A-4))
  • the inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen.
  • 100 parts by mass of purified methyl methacrylate, 0.0065 parts by mass of 2,2'-azobis (2-methylpropionitrile (hydrogen extraction capacity: 1%, 1-hour half-life temperature: 83 ° C.)), and 0.290 parts by mass of n-octyl mercaptan was added and stirred to obtain a raw material solution. Nitrogen was sent into this raw material solution to remove dissolved oxygen.
  • the raw material solution was put into a tank reactor connected to the autoclave by piping up to 2/3 of the capacity.
  • the polymerization reaction was first started by a batch method.
  • the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate with an average residence time of 120 minutes while maintaining the temperature at 140 ° C., and at the same time, it corresponds to the supply flow rate of the raw material liquid.
  • the reaction solution was withdrawn from the tank reactor at the desired flow rate, and the polymerization reaction was switched to the continuous flow method. After switching, the polymerization conversion rate in the steady state was 45% by mass.
  • the reaction solution extracted from the tank-type reactor in a steady state was supplied to a multi-tube heat exchanger having an internal temperature of 230 ° C.
  • the heated reaction solution was introduced into a flash evaporator to remove volatile components containing unreacted monomers as a main component to obtain a molten resin.
  • the molten resin from which the volatile matter had been removed was supplied to a twin-screw extruder having an internal temperature of 230 ° C., discharged in a strand shape, and cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (A-4).
  • the methacrylic polymer (A-4) has an Mw of 80,000, a component having a molecular weight of 15,000 or less (M ⁇ 15,000) in an amount of 6.92% by mass, a melt viscosity ⁇ of 700 Pa ⁇ s, and a Mw / Mn of 1.
  • the triadosyndio tacticity (rr) was 52%
  • the Tg was 120 ° C.
  • the amount of structural units derived from methyl methacrylate was 100% by weight.
  • Table 1 shows the physical characteristics of the methacrylic polymer (A-4).
  • Production Example 5 (Production of methacrylic polymer (A-5)) Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 120 rpm and a temperature of 250 ° C.
  • a twin-screw extruder manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600
  • the methacrylic polymer (A-4) was supplied at 2 kg / hr, and monomethylamine was injected into the melt-kneaded portion of the twin-screw extruder at 0.08 kg / hr, and the methacrylic polymer (A-4) and monomethylamine were injected. And reacted.
  • a kneading block was installed in the melt-kneading section, and a reverse flight was installed in the screw at the end of the reaction zone. In the volatilization section set to 20 Torr (about 2.7 kPa), by-products and excess monomethylamine were volatilized and discharged through the vent.
  • the strand-shaped molten resin extruded from the die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (A-5a). It was.
  • Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 230 ° C.
  • a methacrylic polymer (A-5a) was supplied at 1 kg / hr, and a liquid consisting of 1.6 parts by mass of carbon dimethyl and 0.2 parts by mass of triethylamine was added to the melt-kneaded portion of the twin-screw extruder at 0.01 kg / hr.
  • the carboxy group in the methacrylic polymer (A-5a) was reacted with carbon dimethyl.
  • a kneading block was installed in the melt-kneading section, and a reverse flight was installed in the screw at the end of the reaction zone.
  • the by-product and excess dimethyl carbonate were volatilized and discharged through the vent in the volatilization section set to 20 Torr (about 2.7 kPa).
  • the strand-shaped molten resin extruded from the die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic polymer [A-5b]. It was.
  • Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 230 ° C.
  • a methacrylic resin (A-5b) was supplied at 1 kg / hr.
  • volatile components such as unreactant were volatilized and discharged through the vent.
  • the strand-shaped molten resin extruded from the die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (A-5). It was.
  • the methacrylic polymer (A-5) has an Mw of 80,000, a Mw / Mn of 1.8, a molecular weight of 15,000 or less (M ⁇ 15,000) in an proportion of 6.60% by mass, and an imidization ratio of 7. At 0.0 mol%, the glass transition temperature was 130 ° C. Table 1 shows the physical characteristics of the methacrylic polymer (A-5).
  • Production Example 7 (Production of methacrylic polymer (B-2)) 89 parts by mass of purified methyl methacrylate and 11 parts by mass of methyl acrylate were placed in an autoclave with a stirrer and a sampling tube to obtain a monomer mixture. Polymerization initiator (2,2'-azobis (2-methylpropionitrile (AIBN), hydrogen extraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) 0.0026 parts by mass and chain transfer to the monomer mixture 0.09 part by mass of the agent (n-octyl mercaptan) was added and dissolved to obtain a raw material solution. Oxygen in the production apparatus was expelled with nitrogen.
  • the raw material solution was discharged from the autoclave in a constant amount, and the temperature was 140. It was supplied to a continuous flow tank type reactor controlled at ° C. at a flow rate having an average residence time of 150 minutes for massive polymerization. The reaction solution was separated from the sampling tube of the reactor and measured by gas chromatography. As a result, the polymerization conversion rate was 43% by mass.
  • the liquid discharged from the reactor was heated to 240 ° C. and supplied to a twin-screw extruder controlled at 260 ° C. at a constant flow rate.
  • the twin-screw extruder the volatile matter containing the unreacted monomer as a main component was removed, and the resin component was extruded into a strand shape.
  • the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (B-2).
  • Table 1 shows the physical characteristics of the methacrylic polymer (B-2).
  • Production Example 8 (Production of methacrylic polymer (B-3)) The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this, 98.9 parts by mass of purified methyl methacrylate, 1.1 parts by mass of methyl acrylate, 2,2'-azobis (2-methylpropionitrile (hydrogen extraction capacity: 1%, 1 hour half-life temperature). : 83 ° C.) 0.0050 parts by mass and 0.26 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material solution. Nitrogen was sent into the raw material solution to remove dissolved oxygen in the raw material solution. did.
  • the raw material liquid was put into the tank-type reactor connected to the autoclave by piping up to 2/3 of the reactor capacity.
  • the raw material liquid supply port to the tank reactor and the reaction liquid discharge port from the tank reactor were closed, and the temperature was maintained at 140 ° C. to start the batch-type polymerization reaction.
  • the polymerization conversion rate reaches 55% by mass, open the raw material liquid supply port to the tank reactor and the reaction liquid discharge port from the tank reactor, and open the raw material liquid at a flow rate with an average residence time of 150 minutes.
  • the reaction solution was withdrawn from the tank reactor at a flow rate corresponding to the supply flow rate of the raw material liquid and supplied from the autoclave to the tank reactor, maintained at a temperature of 140 ° C., and switched to a continuous flow type polymerization reaction. After switching, the polymerization conversion rate in the steady state was 55% by mass.
  • the liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C. at a constant flow rate.
  • the twin-screw extruder the volatile matter containing the unreacted monomer as a main component was removed, and the resin component was extruded into a strand shape.
  • the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic polymer (B-3).
  • the physical characteristics of the methacrylic polymer (B-3) are shown in Table 1.
  • MMA methyl methacrylate
  • MA methyl acrylate
  • AMA allyl methacrylate
  • 0.05 parts by mass of a 3% aqueous potassium persulfate solution was added to the reactor, and the mixture was stirred for 5 minutes.
  • the frozen emulsion was placed in warm water at 80 ° C., which was twice the amount of the frozen emulsion, and thawed to obtain a slurry.
  • the slurry was kept at 80 ° C. for 20 minutes. Then, it was dehydrated and dried at 70 ° C. to obtain a powder composed of a coagulated product of crosslinked rubber particles (C-1).
  • Production Example 10 (Production of Block Copolymer (D-1)) After degassing the inside of a 20-liter reaction vessel and replacing it with nitrogen, dried toluene at room temperature 10.29 kg, hexamethyltriethylenetetramine 0.019 kg, isobutylbis (2,6-di-t-butyl-4-) 0.35 kg of a toluene solution containing 0.17 mol of (methylphenoxy) aluminum was added, and 0.077 mol of sec-butyllithium was further added. To this, 0.50 kg of methyl methacrylate was added, and the mixture was reacted at room temperature for 1 hour.
  • the polymerization solution was cooled to ⁇ 25 ° C., and a mixed solution of 1.21 kg of n-butyl acrylate and 0.48 kg of benzyl acrylate was added dropwise over 1 hour. Subsequently, 1.23 kg of methyl methacrylate was added, the reaction solution was returned to room temperature, and the mixture was stirred for 8 hours. Then, 0.30 kg of methanol was added to the reaction solution to terminate the polymerization. The reaction solution is poured into a large amount of methanol, and the precipitated precipitate is recovered.
  • a block copolymer (D-1) having a triblock structure composed of a coalesced block (a1-2) was obtained.
  • the mass ratio of (a1-1): (a2): (a1-2) was 14.6: 49.5: 35.9.
  • Block co polymer (D-1) is, Mw is 62600, Mw / Mn is 1.11, the refractive index n d 1.493, tensile modulus 612MPa, plotting the relationship between the storage modulus G 'and temperature In the graph shown above, the temperature at which G'decreased sharply (order-disorder transition temperature (ODTT); JISB0103-5113)) was 207 ° C.
  • ODTT order-disorder transition temperature
  • Examples 2 to 3, Comparative Examples 1 to 7 and Reference Example 1 The methacrylic resin by the same method as in Example 1 except that the methacrylic polymers (A-1) to (A-5) and the methacrylic polymers (B-1) to (B-3) were changed to the mass ratios shown in Table 2. [2] to [11] were obtained. Table 2 shows the evaluation results of the methacrylic resins [2] to [11].
  • Example 4 100 parts by mass of methacrylic resin [1], 483 parts by mass of dichloromethane, and 42 parts by mass of methanol were put into a mixing tank and stirred at 25 ° C. to dissolve the methacrylic resin [1], and the solid content concentration was 16% by mass. Dope [1] was obtained. The evaluation results of the doping [1] are shown in Table 3.
  • Examples 5-6, Comparative Examples 8-15 and Reference Example 2 Dopings [2] to [11] having a solid content concentration of 16% by mass were obtained in the same manner as in Example 4 except that the methacrylic resin [1] was changed to the methacrylic resins [2] to [11]. The evaluation results of the dopings [2] to [11] are shown in Table 3.
  • the evaluation results of the methacrylic resin composition [12] are shown in Table 4.
  • Example 8 Comparative Example 16 and Reference Example 3
  • the mass ratios of methacrylic polymers (A-1) and (A-3), methacrylic polymers (B-1), crosslinked rubber particles (C-1) and block copolymers (D-1) are shown in Table 4.
  • Polymer resin compositions [13] to [15] were obtained in the same manner as in Example 7 except that they were changed.
  • Table 4 shows the evaluation results of the methacrylic resin compositions [13] to [15].
  • Example 9 100 parts by mass of methacrylic resin composition [12], 483 parts by mass of dichloromethane, and 42 parts by mass of methanol were put into a mixing tank and stirred at 25 ° C. to dissolve the methacrylic resin composition [12] and solid content. A dope [12] having a concentration of 16% by mass was obtained. The evaluation results of the doping [12] are shown in Table 5.
  • Example 10 Comparative Example 17 and Reference Example 4 Dopings [13] to [15] having a solid content concentration of 16% by mass were obtained in the same manner as in Example 9 except that the methacrylic resin composition [12] was changed to the methacrylic resin compositions [13] to [15], respectively. It was. The evaluation results of the dopings [13] to [15] are shown in Table 5.
  • the methacrylic resin or the methacrylic resin composition of the present invention can provide a molded product having high transparency, high strength, excellent surface smoothness, and excellent heat resistance.
  • the dope of the present invention has a high drying rate and is excellent in manufacturing suitability by the casting method.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une résine méthacrylique qui comprend : un polymère méthacrylique (A) de masse moléculaire moyenne en poids (ＭｗA) supérieure ou égale à ３００００, de rapport de masse moléculaire moyenne en poids (ＭｗA) pour la masse moléculaire moyenne en nombre (ＭｎA) compris entre １,０ et １,４, et de température de transition vitreuse supérieure ou égale à １２５℃ ; et un polymère méthacrylique (B) de masse moléculaire moyenne en poids (ＭｗB) comprise entre ８００００ et ３００００００ et supérieure ou égale à 2,5 fois la masse moléculaire moyenne en poids (ＭｗA). La viscosité à l'état fondu (ηB) pour une vitesse de cisaillement de １２２ secondes -1 et une température de ２６０℃ du polymère méthacrylique (B), est supérieure à la viscosité à l'état fondu (ηA) pour une vitesse de cisaillement de １２２ secondes -1 et une température de ２６０℃ du polymère méthacrylique (A). Le rapport massique du polymère méthacrylique (A) vis-à-vis du polymère méthacrylique (B), est compris entre ２／９８ et ３９／６１. La masse moléculaire de sommet de pic (ＭPt) de dérivé de fraction de poids le plus élevé, sur une courbe de distribution de poids moléculaire différentielle en termes de poids, est comprise entre １０００００ et ２００００００.
PCT/JP2020/028996 2019-07-30 2020-07-29 Composition de résine méthacrylique, modificateur de résine, corps moulé, et film ainsi que procédé de fabrication de celui-ci WO2021020426A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017200032A1 (fr) * 2016-05-19 2017-11-23 株式会社クラレ Composition de résine méthacrylique, et corps moulé
WO2018021449A1 (fr) * 2016-07-29 2018-02-01 株式会社クラレ Composition de résine de méthacrylate, son procédé de production, corps moulé, film, film stratifié et corps moulé stratifié
WO2018147234A1 (fr) * 2017-02-07 2018-08-16 株式会社クラレ Film à orientation biaxiale de résine acrylique et son procédé de production
WO2018155467A1 (fr) * 2017-02-22 2018-08-30 株式会社クラレ Composition de résine méthacrylique et utilisation correspondante

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017200032A1 (fr) * 2016-05-19 2017-11-23 株式会社クラレ Composition de résine méthacrylique, et corps moulé
WO2018021449A1 (fr) * 2016-07-29 2018-02-01 株式会社クラレ Composition de résine de méthacrylate, son procédé de production, corps moulé, film, film stratifié et corps moulé stratifié
WO2018147234A1 (fr) * 2017-02-07 2018-08-16 株式会社クラレ Film à orientation biaxiale de résine acrylique et son procédé de production
WO2018155467A1 (fr) * 2017-02-22 2018-08-30 株式会社クラレ Composition de résine méthacrylique et utilisation correspondante

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