WO2019093385A1 - Copolymère méthacrylique et article moulé correspondant - Google Patents

Copolymère méthacrylique et article moulé correspondant Download PDF

Info

Publication number
WO2019093385A1
WO2019093385A1 PCT/JP2018/041382 JP2018041382W WO2019093385A1 WO 2019093385 A1 WO2019093385 A1 WO 2019093385A1 JP 2018041382 W JP2018041382 W JP 2018041382W WO 2019093385 A1 WO2019093385 A1 WO 2019093385A1
Authority
WO
WIPO (PCT)
Prior art keywords
methacrylic copolymer
mass
polymerization
molecular weight
chain transfer
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/JP2018/041382
Other languages
English (en)
Japanese (ja)
Inventor
伸崇 平岡
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 JP2019552352A priority Critical patent/JPWO2019093385A1/ja
Publication of WO2019093385A1 publication Critical patent/WO2019093385A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation

Definitions

  • the present invention relates to a methacrylic copolymer excellent in transparency, flowability and mechanical strength, and a molded article comprising the methacrylic copolymer.
  • the methacrylic copolymer produced by radical polymerization is used as a molded article in various applications such as OA equipment field, automobile field, electric / electronic field, and has high transparency, so it has a front plate of a display device and a light guide plate Are widely used in optical applications such as
  • the moldability of the methacrylic copolymer can be realized by reducing the weight-average molecular weight (Mw) of the methacrylic copolymer to improve the flowability, the problem arises that the strength of the resulting molded article decreases.
  • Mw weight-average molecular weight
  • Patent Document 1 discloses that when polymerizing a monomer mixture containing methyl methacrylate alone or methyl methacrylate in an amount of 50% by mass or more, 0.01 to 2% by weight of a peroxide or per monomer as a polymerization initiator There is a description of a process for producing a methacrylic copolymer characterized in that it is polymerized using an azo compound and 0.02 to 3% by weight of a polyfunctional mercaptan per monomer as a chain transfer agent.
  • the production method is a method for producing a methacrylic copolymer excellent in thermal decomposition resistance, and sufficient examination has not been made regarding flowability and impact resistance.
  • the present invention is [1] A methacrylic copolymer containing 90% by mass or more of a structural unit derived from methyl methacrylate, wherein the methacrylic copolymer is a mercaptan chain transfer having a molecular weight of 200 or less relative to a structural unit derived from methyl methacrylate Copolymer derived from a lubricant and having an amount of bound sulfur atoms of 0.4 mol% or more and a melt flow rate of 25 g / 10 minutes or more and 50 g / 10 minutes or less under conditions of 230 ° C.
  • the reaction product is continuously supplied, and bulk polymerization is carried out at a polymerization conversion rate of 40 to 70% by mass in the tank reactor to obtain a reaction product, and the reaction product is continuously withdrawn from the tank reactor, and the reaction is carried out.
  • a pellet-like molding material comprising the methacrylic copolymer according to any one of [1] to [4], [7] An optical member obtained by injection molding the molding material according to [6], wherein the optical length is 200 mm or less and the yellow index (YI) is 5 or less. [8] An optical member obtained by press-molding the methacrylic copolymer according to any one of [1] to [4].
  • the present invention it is possible to provide a methacrylic copolymer which has transparency suitable for optical applications and is excellent in fluidity and mechanical strength under slow deformation. Further, since the methacrylic copolymer has high moldability, a molded article excellent in appearance can be provided.
  • the methacrylic copolymer of the present invention is a methacrylic copolymer comprising 90% by mass or more, preferably 90.5 to 99% by mass, more preferably 91 to 97% by mass of structural units derived from methyl methacrylate,
  • the amount of bound sulfur atoms derived from a mercaptan-based chain transfer agent having a molecular weight of 200 or less is 0.4 mol% or more, preferably 0.45 mol% or more, based on the structural unit derived from methyl methacrylate .
  • the upper limit of the amount of bound sulfur atoms is 1.50 mol%, preferably 1.00 mol%.
  • the molecular weight of the mercaptan chain transfer agent is preferably 100 to 200, more preferably 120 to 200, and most preferably 130 to 200.
  • a mercaptan chain transfer agent having a molecular weight of 200 or less By using a mercaptan chain transfer agent having a molecular weight of 200 or less, the unreacted chain transfer agent can be easily volatilized in the pelletizing step, and the optical properties of the resulting resin become good. Mercaptan chain transfer agents having a molecular weight of less than 100 are highly volatile, and the odor at the time of production is a problem.
  • the mercaptan chain transfer agent is preferably bifunctional. By using a bifunctional chain transfer agent, the balance of strength, flowability and optical properties can be highly maintained. When a monofunctional chain transfer agent is used, the strength of the resulting methacrylic copolymer tends to be insufficient when the fluidity of the resin is enhanced. A trifunctional chain transfer agent having a molecular weight of 200 or less is difficult to obtain industrially, and the use of a polyfunctional chain transfer agent having a molecular weight of 200 or more tends to deteriorate the optical properties.
  • radical polymerization is carried out using a mercaptan chain transfer agent having a molecular weight of 200 or less (hereinafter sometimes referred to as mercaptan chain transfer agent (A)) to obtain a methacrylic copolymer derived from methyl methacrylate which is obtained.
  • mercaptan chain transfer agent (A) a mercaptan chain transfer agent having a molecular weight of 200 or less
  • the weight average molecular weight (Mw) / number average molecular weight (Mn) can be narrowed, and flowability and strength can be enhanced.
  • mercaptan chain transfer agent (A) for example, a difunctional compound such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 3,6-dioxa-1,8-octanedithiol and the like Mercaptan is mentioned.
  • These mercaptan chain transfer agents (A) may be used alone or in combination of two or more.
  • the amount of bound sulfur atoms of the methacrylic copolymer is a value determined as follows.
  • the methacrylic copolymer is dissolved in chloroform to obtain a solution.
  • This solution is added to n-hexane to obtain a precipitate.
  • the precipitate is dried at 80 ° C. for more than 12 hours under vacuum.
  • An appropriate amount of the obtained dried product is precisely weighed, set in a sulfur combustion apparatus, decomposed in a reactor at a temperature of 400 ° C., and generated gas is passed through a furnace at a temperature of 900 ° C., and then 0.3% hydrogen peroxide solution Absorb with The resulting solution (decomposed gas aqueous solution) is appropriately diluted with pure water, and the sulfate ion is quantified by ion chromatography (ICS-1500 manufactured by DIONEX, column: AS12A). The mass W p (mass%) of sulfur atoms per mass of the dried product is calculated.
  • the copolymer of the present invention contains 10% by mass of a structural unit derived from a radically polymerizable monomer (hereinafter sometimes referred to as a radically polymerizable monomer (B)) other than methyl methacrylate monomer
  • the content is preferably 1.0 to 9.5% by mass, more preferably 3.0 to 9.0% by mass.
  • methacrylic acid alkyl esters other than methyl methacrylate such as ethyl methacrylate and butyl methacrylate
  • aryl methacrylate esters such as phenyl methacrylate
  • methacrylic acid cyclohexyl 2-isobornyl methacrylic acid
  • Methacrylic acid cycloalkyl esters such as 8-tricyclo [5.2.1.0 2,6 ] decanyl methacrylate, 2-norbornyl methacrylate, 2-adamantyl methacrylate; 2-methylene-1,3-dioxepane etc.
  • Cyclic ketene acetals vinyl aromatic hydrocarbons such as styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, etc .; vinylcyclohexane, vinylcyclopentane, vinylcyclohexene, vinylcycloheptane, vinylcyclohepte Vinyl cycloaliphatic hydrocarbons such as styrene and vinyl norbornene; ethylenically unsaturated carboxylic acids such as maleic anhydride, maleic acid and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; butadiene, Isoprene, conjugated dienes such as myrcene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ketone, vinyl chloride, vinylidene chloride, vinyli
  • the methacrylic copolymer of the present invention has a weight-average molecular weight / number-average molecular weight ratio (hereinafter, this ratio may be referred to as a molecular weight distribution) is 1.85 or less, preferably 1.60 to 1.85. And more preferably 1.70 to 1.79. If the molecular weight distribution is small, the molding processability of the methacrylic copolymer tends to decrease. When the molecular weight distribution is large, the impact resistance of a molded article obtained from the methacrylic copolymer is lowered, and it tends to be brittle.
  • a weight average molecular weight and a number average molecular weight are the value of standard polystyrene conversion calculated based on the chromatogram obtained by gel permeation chromatography (GPC).
  • the weight average molecular weight and molecular weight distribution of the methacrylic copolymer can be controlled by adjusting the type and amount of the polymerization initiator and the mercaptan chain transfer agent having a molecular weight of 200 or less.
  • the weight average molecular weight of the methacrylic copolymer obtained by the present invention is preferably 35,000 to 90,000, more preferably 40,000 to 70,000, and particularly preferably 40,000 to 65,000. If the Mw is too small, the impact resistance and toughness of the molded article obtained from the methacrylic copolymer tend to decrease. If the Mw is too large, the flowability of the methacrylic copolymer will decrease, and the moldability tends to decrease accordingly.
  • Each monomer contained in the polymerization reaction raw material preferably has a measured length of 200 mm and a yellow index (YI) of 2 or less, more preferably 1 or less.
  • YI yellow index
  • the yellow index is a value measured according to JIS Z8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • the polymerization reaction of the polymerization reaction raw material is preferably carried out by bulk polymerization or solution polymerization, more preferably by bulk polymerization.
  • Bulk polymerization is preferably continuous bulk polymerization.
  • the polymerization reaction is initiated by adding a polymerization initiator and a mercaptan chain transfer agent having a molecular weight of 200 or less to the polymerization reaction raw material. By adding a chain transfer agent to the polymerization reaction raw material, the weight average molecular weight and the like of the resulting methacrylic copolymer can be adjusted.
  • the raw material for the polymerization reaction preferably has a dissolved oxygen content of 10 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, and most preferably 3 ppm or less.
  • a dissolved oxygen content 10 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, and most preferably 3 ppm or less.
  • the polymerization initiator 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'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azo
  • t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, dimethyl 2,2'-azobis (2-methylpropionate) and the like are preferable.
  • the polymerization initiator preferably has a one-hour half-life temperature of 60 to 140 ° C., and more preferably 80 to 120 ° C.
  • the polymerization initiator used for bulk polymerization preferably has a hydrogen extraction ability of 20% or less, more preferably 10% or less, and still more preferably 5% or less. These polymerization initiators can be used alone or in combination of two or more. Further, the addition amount, addition method, and the like of the polymerization initiator may be appropriately set according to the purpose, and are not particularly limited.
  • the amount of the polymerization initiator used for bulk polymerization is preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.01 parts by mass, and further 100 parts by mass of the polymerization reaction raw material. Preferably, it is 0.005 to 0.007 parts by mass.
  • the hydrogen extraction ability from the technical data of the polymerization initiator manufacturer for example, Nippon Oil and Fats Co., Ltd. technical data "Hydrogen extraction ability and initiator efficiency of organic peroxide” (created in April 2003) etc. Can.
  • 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.
  • the solvent used for the solution polymerization is not particularly limited as long as it has a dissolving ability to the polymerization reaction raw material and the methacrylic copolymer obtained therefrom, but aromatic hydrocarbons such as benzene, toluene and ethylbenzene are preferable. These solvents can be used singly or in combination of two or more.
  • the amount of the solvent used is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the polymerization reaction raw material. The greater the amount of solvent used, the lower the viscosity of the reaction solution and the better the handling, but the productivity tends to decrease.
  • the polymerization conversion ratio of the polymerization reaction raw material is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 35 to 65% by mass.
  • the polymerization conversion rate is too high, a large stirring power tends to be required to increase the viscosity. If the polymerization conversion rate is too low, removal of the remaining monomer tends to be insufficient, and the monomer content in the resulting methacrylic resin tends to be high. As a result, when a methacrylic resin is molded, the molded product tends to have an appearance defect such as silver. Unreacted monomers can be recovered from the polymerization reaction solution and used again for the polymerization reaction. The yellow index of the recovered monomer may be high due to the heat applied at the time of recovery and the like. The recovered monomer is preferably purified by an appropriate method to reduce the yellow index.
  • the apparatus for performing the bulk polymerization method or the solution polymerization method includes a tank reactor with a stirrer, a tubular reactor with a stirrer, and a tubular reactor with a static stirring ability.
  • a tank reactor with a stirrer a stirrer, a tubular reactor with a stirrer, and a tubular reactor with a static stirring ability.
  • One or more of these apparatuses may be used, or two or more different reactors may be used in combination.
  • the device may be either batch or continuous flow.
  • the stirrer used can be selected according to the type of reactor. Examples of the stirrer include a dynamic stirrer and a static stirrer.
  • An apparatus most suitable for obtaining the methacrylic copolymer used in the present invention is one having at least one continuous flow tank reactor.
  • the plurality of continuous flow tank reactors may be connected in series or in parallel.
  • a stirring means for stirring the liquid in the reaction tank usually, a stirring means for stirring the liquid in the reaction tank, a supply unit for supplying polymerization reaction raw materials, polymerization auxiliary materials and the like to the reaction tank, and a reaction product for extracting reaction products from the reaction tank Has an extraction part of
  • the amount supplied to the reaction vessel and the amount withdrawn from the reaction vessel are balanced so that the amount of liquid in the reaction vessel becomes substantially constant.
  • the amount of liquid in the reaction vessel relative to the volume of the reaction vessel is preferably at least 1/4, more preferably 1/4 to 3/4, and still more preferably 1/3 to 2/3.
  • the stirring means may, for example, be a Max-blend type stirring device, a stirring device having a grid-like blade rotating along with the 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 monomer containing at least methyl methacrylate, and the polymerization initiator and the chain transfer agent may be mixed and supplied to the reaction tank before they are all supplied to the reaction tank, or they may be separately supplied to the reaction tank It may be supplied.
  • a method in which all are mixed before being supplied to the reaction vessel and supplied to the reaction vessel is preferable.
  • the mixing of the monomers, the polymerization initiator and the chain transfer agent contained in the polymerization reaction raw material is preferably carried out in an inert atmosphere such as nitrogen gas.
  • an inert atmosphere such as nitrogen gas.
  • the mixture obtained by mixing while continuously supplying from the storage tank to the mixer provided in the previous stage of the reaction tank through the tube is reacted It is preferred to flow continuously into the tank.
  • the mixer can be equipped with a dynamic stirrer or a static stirrer.
  • the temperature during the polymerization reaction is preferably 100 to 150 ° C., more preferably 110 to 140 ° C.
  • the temperature at the time of the polymerization reaction is in such a range, it is easy to adjust the melt flow rate to the range described later.
  • the polymerization temperature is set to 100 ° C. or higher, the polymerization rate is increased, and the viscosity of the polymerization solution is lowered, so that the productivity tends to be improved.
  • coloring of the molded article obtained from the methacrylic copolymer obtained can be suppressed by setting superposition
  • the polymerization reaction time is preferably 0.5 to 4 hours, more preferably 1.5 to 3.5 hours, and still more preferably 1 to 3 hours.
  • the polymerization reaction time is the average residence time in the reactor. If the polymerization reaction time is too short, the necessary amount of polymerization initiator will increase. In addition, the control of the polymerization reaction becomes difficult by increasing the amount of the polymerization initiator, and not only the control of the molecular weight becomes difficult, but also the amount of chain transfer agent necessary to adjust with the melt flow rate of the obtained methacrylic copolymer decreases. The amount of bonded sulfur atoms to the structural unit derived from methyl methacrylate is decreased, and the thermal stability is deteriorated. On the other hand, when the polymerization reaction time is too long, it takes time for the reaction to reach a steady state, and the productivity tends to decrease.
  • the polymerization is preferably carried out in an inert gas atmosphere such as nitrogen gas.
  • the removal method is not particularly limited, but heat degassing is preferred.
  • the volatilization method may, for example, be an equilibrium flash method or an adiabatic flash method.
  • the degassing is performed at a temperature of preferably 200 to 300 ° C., more preferably 200 to 280 ° C., still more preferably 220 to 270 ° C., particularly preferably 220 to 260 ° C. If it is less than 200 ° C., it takes a long time to degas, and it tends to be insufficient. When the degassing is insufficient, appearance defects such as silver may occur in the molded product.
  • 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 particularly preferably 0.5 to 2 minutes. If the heating time is less than 0.3 minutes, the heating of the resin is insufficient and the amount of unreacted monomers is increased. Moreover, when it is made to retain for 5 minutes or more, the molded article obtained from the obtained methacrylic copolymer becomes easy to color.
  • the methacrylic copolymer of the present invention may further contain various additives in an amount of 0.5% by mass or less, preferably 0.2% by mass or less, as necessary. When the content of the additive is too large, appearance defects such as silver may occur in the molded article.
  • Additives include antioxidants, heat deterioration inhibitors, ultraviolet light absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes , Matting agents, impact modifiers, phosphors and the like.
  • 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. These antioxidants can be used singly or in combination of two or more. Among them, phosphorus antioxidants and hindered phenol antioxidants are preferred from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and the combination of phosphorus antioxidant and hindered phenol antioxidant is more preferable. preferable.
  • the ratio is not particularly limited, but the mass ratio of phosphorus-based antioxidant / hindered phenol-based antioxidant is preferably 1/5. It is preferably 2 to 1, more preferably 1/2 to 1/1.
  • phosphorus-based antioxidants examples include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (Asahi Denka Co., Ltd .; trade name: Adekastab HP-10), tris (2,4-di-t). -Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRGAFOS 168) and the like are preferable.
  • a hindered phenol-based antioxidant pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Chiba Specialty Chemicals; trade name IRGANOX1010), Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Chiba Specialty Chemicals; trade name IRGANOX 1076) is preferable.
  • 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.
  • the 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), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (Sumitomo Chemical; trade name: SMILIZER GS) etc. preferable.
  • the ultraviolet light absorber is a compound having the ability to absorb ultraviolet light.
  • UV absorbers are compounds that are said to mainly have the function of converting light energy into thermal energy.
  • benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic esters, formamidines and the like can be mentioned. These can be used singly or in combination of two or more.
  • benzotriazoles or UV absorbers having a maximum value ⁇ max of the molar absorption coefficient at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less are preferable.
  • an ultraviolet absorber used when the methacrylic copolymer of the present invention is applied to applications requiring the above-mentioned properties. As preferred.
  • the ultraviolet absorber having a maximum value ⁇ max of molar absorption coefficient at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less can suppress the yellowish taste of the obtained molded article.
  • maximum value (epsilon) max of the molar absorption coefficient of a ultraviolet absorber is measured as follows. Add 10.00 mg of a UV absorber to 1 L of cyclohexane, and dissolve it so that there is no undissolved matter by visual observation. This solution is injected into a 1 cm ⁇ 1 cm ⁇ 3 cm quartz glass cell, and the absorbance at a wavelength of 380 to 450 nm is measured using a Hitachi U-3410 spectrophotometer. The molar absorption coefficient maximum value ⁇ max is calculated from the molecular weight (Mw) of the ultraviolet absorber and the maximum value (A max ) of the measured absorbance according to the following equation.
  • a 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd.) as a UV absorber having a maximum value ⁇ max of molar extinction coefficient at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol -1 cm -1 or less (Trade name: Sanduiboa VSU) and the like.
  • ⁇ max of molar extinction coefficient at a wavelength of 380 to 450 nm of 1200 dm 3 ⁇ mol -1 cm -1 or less
  • benzotriazoles are preferably used from the viewpoint of suppressing resin deterioration due to ultraviolet irradiation.
  • 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 include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine backbone.
  • the lubricant 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 release agent is a compound having a function of facilitating the release of the molded article from the mold.
  • a mold release agent higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as monoglyceride stearate and diglyceride stearate are mentioned.
  • the ratio is not particularly limited, but the mass ratio of the higher alcohol / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1, Preferably, it is 2.8 / 1 to 3.2 / 1.
  • the polymer processing aid is a compound that exerts an effect on thickness accuracy and thinning when molding a methacrylic copolymer.
  • the polymer processing aid is usually a polymer particle having a particle size of 0.05 to 0.5 ⁇ m, which can be produced by an emulsion polymerization method.
  • 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.
  • 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 melt flowability of the methacrylic resin tends to be lowered.
  • 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.
  • the antistatic agent for example, stearoamidopropyl dimethyl- ⁇ -hydroxyethyl ammonium nitrate and the like can be mentioned.
  • dyes and pigments include titanium oxide and bengala.
  • An impact modifier may be used in the methacrylic copolymer of the present invention.
  • the impact modifier includes, for example, a core-shell modifier containing an acrylic rubber or a diene rubber as a core layer component; and a modifier containing a plurality of rubber particles.
  • the organic dye a compound having a function of converting ultraviolet light, which is harmful to the resin, into visible light is preferably used.
  • the light diffusing agent and the matting agent include glass particles, polysiloxane based crosslinked particles, crosslinked polymer particles, talc, calcium carbonate and barium sulfate.
  • the fluorescent substance fluorescent pigment, fluorescent dye, fluorescent white dye, fluorescent whitening agent, fluorescent bleach and the like can be mentioned.
  • additives may be added to the polymerization reaction solution for producing the methacrylic copolymer, or may be added to the methacrylic copolymer produced by the polymerization reaction.
  • the methacrylic copolymer of the present invention has a melt flow rate of 25 g / 10 min or more, preferably 25 to 50 g / 10 min, more preferably 27 to 45 g / 10 min, more preferably at 230 ° C. and a load of 3.8 kg. Is 28 to 42 g / 10 min.
  • the melt flow rate is a value measured under the conditions of 230 ° C., 3.8 kg load, and 10 minutes in accordance with JIS K 7210. When the melt flow rate is in this range, the effect of the present invention in which the strength of the methacrylic copolymer in a high flow region is excellent can be characteristically exhibited.
  • the yellow index (YI) of the optical path length of 200 mm of the injection molded article obtained by obtaining the methacrylic copolymer of the present invention at a cylinder temperature of 280 ° C. and a molding cycle of 1 minute is preferably 5 or less, more preferably 4 or less, more preferably Is less than 3.5.
  • the yellow index is a value measured according to JIS Z8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • the methacrylic copolymer of the present invention can be formed into a pellet-like molding material in accordance with a known method to facilitate handling.
  • the pellet-like molding material can be obtained, for example, by injecting the methacrylic copolymer of the present invention, which has been melted in an extruder, into a die plate, and cooling and cutting the resin extruded in the form of a strand.
  • methods such as underwater cutting, hot cutting, strand cutting and the like can be adopted.
  • the methacrylic copolymer of the present invention is excellent in transparency, moldability and mechanical strength, it is useful as various molded articles.
  • molded articles excellent in mechanical strength and appearance of various shapes are formed by molding (melting and heating molding) by a conventionally known molding method such as press molding, injection molding, compression molding, extrusion molding, vacuum molding and the like. You can get it.
  • the molded article of the present invention is preferably an optical member.
  • the optical member is preferably manufactured by injection molding, press molding. Examples of the optical member include a light guide, a diffuser, a prism, a lens, an optical filter, an optical disc, and an optical member having two or more functions among those described above. These optical members are suitably used as, for example, liquid crystal display devices, plasma display devices, light emitting diode display devices, field emission display devices, organic electroluminescent display devices, projection display devices, light receiving members of automatic toll systems for highways, etc. Used.
  • methacrylic copolymer of the present invention is excellent in transparency, moldability and mechanical strength, it is useful as various molded articles.
  • applications of molded articles obtained include billboard articles such as advertising towers, stand signs, sleeve signs, cross signs, roof signs and the like; display articles such as showcases, partition plates, store displays; fluorescent light covers, mood lighting covers, Lighting products such as lampshades, light ceilings, light walls and chandeliers; interior products such as pendants and mirrors; doors, domes, safety glass panes, partitions, stairwells, balcony waistboards, architectural parts such as leisure roofs Transportation parts such as aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shades for cars, side visors for cars, rear visors, head wings, headlight covers, meter covers, tail lamp covers etc.
  • nameplates for audio visuals, stereo Cover, TV protective mask, vending machine Which electronic equipment parts; medical equipment parts such as incubators, X-ray parts; machine related parts such as instrument covers, instrument covers, experimental equipment, rulers, dials, observation windows etc; LCD protective plates, light guide plates, light guide films, fresnels
  • Optical components such as lenses, lenticular lenses, front plates of various displays, diffusion plates, etc.
  • Traffic related components such as road signs, guide plates, curved mirrors, sound barriers, etc.
  • the present invention will be more specifically described with reference to examples and comparative examples.
  • the present invention is not limited by the following examples.
  • the present invention includes all aspects in which the above-described matters representing technical characteristics such as characteristic values, forms, manufacturing methods, applications and the like are arbitrarily combined.
  • compositional unit composition analysis of copolymer Device: Nuclear magnetic resonance device (Bruker ULTRA SHIELD 400 PLUS) Solvent: Heavy chloroform Measurement nuclide: 1 H Measurement temperature: Room temperature Integration number: 64 times (weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution) The chromatogram was measured by gel permeation chromatography (GPC) under the following conditions, and the value converted to the molecular weight of standard polystyrene was calculated.
  • GPC gel permeation chromatography
  • MFR Melt flow rate
  • the amount of bound sulfur atoms of the methacrylic copolymer is a value determined as follows.
  • the methacrylic copolymer is dissolved in chloroform to obtain a solution.
  • This solution is added to n-hexane to obtain a precipitate.
  • the precipitate is dried at 80 ° C. for more than 12 hours under vacuum.
  • An appropriate amount of the obtained dried product is precisely weighed, set in a sulfur combustion apparatus, decomposed in a reactor at a temperature of 400 ° C., and generated gas is passed through a furnace at a temperature of 900 ° C., and then 0.3% hydrogen peroxide solution Absorb with The resulting solution (decomposed gas aqueous solution) is appropriately diluted with pure water, and the sulfate ion is quantified by ion chromatography (ICS-1500 manufactured by DIONEX, column: AS12A). The mass W p (mass%) of sulfur atoms per mass of the dried product is calculated.
  • the methacrylic copolymer obtained in the examples is heated up to 250 ° C. once using a differential scanning calorimeter (DSC-50 (product number) manufactured by Shimadzu Corporation) in accordance with JIS K 7121 and then room temperature
  • DSC-50 product number
  • JIS K 7121 room temperature
  • the DSC curve was measured under the conditions of cooling to room temperature and then raising the temperature from room temperature to 200 ° C. at 10 ° C./min.
  • 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.
  • the methacrylic copolymer is heated from 25 ° C. to 500 ° C. at a flow rate of 50 ml / minute in an air atmosphere at a temperature of 10 ° C./minute using a thermogravimetric apparatus (manufactured by Shimadzu Corporation, TGA-50 (product number)) The thermal weight loss was measured under the conditions of temperature rise. Based on a weight (X1) of 200 ° C. (100%), the temperature at which a 1% weight loss was observed was evaluated.
  • Total light transmittance The total light transmittance at an optical path length of 3 mm of the flat plate was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) according to JIS K7361-1.
  • methyl methacrylate is MMA
  • methyl acrylate is MA
  • azobisisobutyronitrile is AIBN
  • n-octylmercaptan is n-OM
  • 1,4-butanedithiol is 1,4-BDT
  • 3,6-dioxax The 1,1,8-octanedithiol is denoted as DMDO, pentaerythritol tetrakisthiopropionate as PETP, and ethylene glycol thiobisglycolate as EGTG.
  • DMDO is manufactured by Tokyo Chemical Industry Co., Ltd., and all other reagents are manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 In a polymerization reactor equipped with a stirrer, a monomer mixture consisting of 93.3 parts by mass of MMA and 6.7 parts by mass of MA, 0.007 parts by mass of AIBN as a radical polymerization initiator, DMDO 0. 2 as a polyfunctional chain transfer agent. A mixed solution consisting of 435 parts by mass was continuously fed, bulk polymerization was carried out under conditions of a polymerization temperature of 140 ° C. and an average residence time of 2 hours, and the polymerization reaction solution was continuously withdrawn. Then, the reaction liquid coming out of the polymerization reactor was heated to 230 ° C., and was fed to a twin-screw extruder controlled to 260 ° C.
  • Example 2 A pellet-like methacrylic copolymer [2] was obtained in the same manner as in Example 1 except that the amount of DMDO in Example 1 was changed to 0.480 parts by mass. Molded articles were produced using the methacrylic copolymer [2] and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 3 In a polymerization reactor equipped with a stirrer, a monomer mixture comprising 88.0 parts by mass of MMA and 12.0 parts by mass of MA, 0.007 parts by mass of AIBN as a radical polymerization initiator, BDT 0. 2 as a polyfunctional chain transfer agent. A mixed solution consisting of 256 parts by mass was continuously supplied, bulk polymerization was carried out under conditions of a polymerization temperature of 140 ° C. and an average residence time of 2 hours, and the polymerization reaction solution was continuously withdrawn. Then, the reaction liquid coming out of the polymerization reactor was heated to 230 ° C., and was fed to a twin-screw extruder controlled to 260 ° C.
  • Example 4 A pellet-like methacrylic copolymer [4] was obtained in the same manner as in Example 3 except that the amount of BDT in Example 3 was changed to 0.285 parts by mass. A molded article was produced using the methacrylic copolymer [4] and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 5 A pellet-shaped methacrylic copolymer [5] was obtained in the same manner as in Example 3, except that 0.340 parts by mass of DMDO was used as a polyfunctional chain transfer agent in place of BDT in Example 3. A molded article was produced using the methacrylic copolymer [5] and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 1 A pellet-shaped methacrylic copolymer [6] was obtained in the same manner as in Example 1 except that 0.480 parts by mass of n-OM was used as a monofunctional chain transfer agent instead of DMDO in Example 1. Molded articles were produced using the methacrylic copolymer [6] and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 2 A pellet-shaped methacrylic copolymer [7] was obtained in the same manner as in Example 1 except that 0.525 parts by mass of n-OM was used as a monofunctional chain transfer agent instead of DMDO in Example 1. Molded articles were produced using the methacrylic copolymer [7], and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 3 A pellet-shaped methacrylic copolymer [8] was obtained in the same manner as in Example 3 except that 0.440 parts by mass of n-OM was used as a monofunctional chain transfer agent instead of BDT in Example 3. Molded articles were produced using the methacrylic copolymer [8], and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 4 A pellet-shaped methacrylic copolymer [9] was obtained in the same manner as in Example 3 except that 0.470 parts by mass of EGTG was used as a polyfunctional chain transfer agent instead of BDT in Example 3. A molded article was produced using the methacrylic copolymer [9], and used for the above evaluation. The evaluation results are shown in Table 1.
  • Example 5 A pellet-shaped methacrylic copolymer [10] was obtained in the same manner as in Example 3 except that 0.660 parts by mass of PETP as a polyfunctional chain transfer agent was used instead of BDT in Example 3. A molded article was produced using the methacrylic copolymer [10] and used for the above evaluation. The evaluation results are shown in Table 1.
  • the binding sulfur atom content is 0. It can be seen that the mechanical strength is excellent while having the same MFR value as compared with Comparative Examples 1 to 3 different from the present invention in that it is less than 4 mol%. Moreover, compared with Comparative Examples 4 and 5 which are different from the present invention in that they are methacrylic copolymers derived from mercaptan chain transfer agents having a molecular weight of 200 or more and having a binding sulfur atom amount of 0.4 mol% or more.
  • the color indicated by YI is excellent. Further, it is understood that the color indicated by YI is superior as compared with Comparative Example 6 which is different from the present invention in the content of the MMA structural unit.
  • the methacrylic copolymer of the present invention has transparency suitable for optical applications, and is excellent in both MFR and flexural strength. From this, by using the methacrylic copolymer of the present invention, a molded article excellent in mechanical strength and appearance can be obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un copolymère méthacrylique comprenant 90 % en masse ou plus de motifs de structure dérivés de méthacrylate de méthyle, le copolymère méthacrylique contenant des atomes de soufre combinés dérivés d'un agent de transfert de chaîne à base de mercaptan ayant une masse moléculaire inférieure ou égale à 200 en une quantité supérieure ou égale à 0,4 % en moles par rapport à la quantité des motifs de structure dérivés de méthacrylate de méthyle et ayant un indice de fluidité à chaud, mesuré dans les conditions de 230°C et une charge de 3,8 kg, de 25 à 50 g/10 min.
PCT/JP2018/041382 2017-11-09 2018-11-07 Copolymère méthacrylique et article moulé correspondant Ceased WO2019093385A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019552352A JPWO2019093385A1 (ja) 2017-11-09 2018-11-07 メタクリル共重合体およびその成形品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-216688 2017-11-09
JP2017216688 2017-11-09

Publications (1)

Publication Number Publication Date
WO2019093385A1 true WO2019093385A1 (fr) 2019-05-16

Family

ID=66437824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/041382 Ceased WO2019093385A1 (fr) 2017-11-09 2018-11-07 Copolymère méthacrylique et article moulé correspondant

Country Status (2)

Country Link
JP (1) JPWO2019093385A1 (fr)
WO (1) WO2019093385A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113336882A (zh) * 2021-05-24 2021-09-03 博立尔化工（扬州）有限公司 一种采用间歇式本体聚合法制备窄分子量分布的pmma树脂的工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6187748A (ja) * 1984-10-05 1986-05-06 Kyowa Gas Chem Ind Co Ltd 熱安定性メタクリル樹脂組成物
JPS61272206A (ja) * 1985-05-28 1986-12-02 Asahi Chem Ind Co Ltd 耐熱分解性に優れたメタクリル樹脂の製造法
KR20120068451A (ko) * 2010-12-17 2012-06-27 제일모직주식회사 메타크릴계 수지 및 그 제조방법
WO2013141106A1 (fr) * 2012-03-22 2013-09-26 株式会社クラレ Composé polymère, son procédé de fabrication et article moulé à base de celui-ci

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63162702A (ja) * 1986-12-26 1988-07-06 Toray Ind Inc 光学用樹脂
JP5613610B2 (ja) * 2011-03-31 2014-10-29 株式会社クラレ メタクリル系樹脂の製造方法および成形品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6187748A (ja) * 1984-10-05 1986-05-06 Kyowa Gas Chem Ind Co Ltd 熱安定性メタクリル樹脂組成物
JPS61272206A (ja) * 1985-05-28 1986-12-02 Asahi Chem Ind Co Ltd 耐熱分解性に優れたメタクリル樹脂の製造法
KR20120068451A (ko) * 2010-12-17 2012-06-27 제일모직주식회사 메타크릴계 수지 및 그 제조방법
WO2013141106A1 (fr) * 2012-03-22 2013-09-26 株式会社クラレ Composé polymère, son procédé de fabrication et article moulé à base de celui-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113336882A (zh) * 2021-05-24 2021-09-03 博立尔化工（扬州）有限公司 一种采用间歇式本体聚合法制备窄分子量分布的pmma树脂的工艺
CN113336882B (zh) * 2021-05-24 2022-11-04 博立尔化工（扬州）有限公司 一种采用间歇式本体聚合法制备窄分子量分布的pmma树脂的工艺

Also Published As

Publication number Publication date
JPWO2019093385A1 (ja) 2020-11-19

Similar Documents

Publication Publication Date Title
TWI568751B (zh) （甲基）丙烯酸樹脂組成物
CN104395360B (zh) 甲基丙烯酸类树脂组合物以及其成形品和制造方法
TWI595012B (zh) （甲基）丙烯酸樹脂組成物
EP2868673B1 (fr) Procédé de fabrication d'une composition de résine (méth)acrylique
JP6438882B2 (ja) 共重合体の製造方法
JP6259400B2 (ja) メタクリル樹脂組成物
US20170174802A1 (en) Copolymer and molded article
TWI568753B (zh) 甲基丙烯酸樹脂組成物
WO2019093385A1 (fr) Copolymère méthacrylique et article moulé correspondant
JP6908629B2 (ja) メタクリル共重合体および成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18876178

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019552352

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18876178

Country of ref document: EP

Kind code of ref document: A1