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WO2015064576A1 - Procédé de production d'une composition de résine méthacrylique - Google Patents

Procédé de production d'une composition de résine méthacrylique Download PDF

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Publication number
WO2015064576A1
WO2015064576A1 PCT/JP2014/078638 JP2014078638W WO2015064576A1 WO 2015064576 A1 WO2015064576 A1 WO 2015064576A1 JP 2014078638 W JP2014078638 W JP 2014078638W WO 2015064576 A1 WO2015064576 A1 WO 2015064576A1
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WO
WIPO (PCT)
Prior art keywords
methacrylic resin
polymerizable monomer
mass
resin composition
methacrylic
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/JP2014/078638
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English (en)
Japanese (ja)
Inventor
卓郎 新村
淳裕 中原
敦 松村
宙 小澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
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Kuraray Co Ltd
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Filing date
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Priority to KR1020167005429A priority Critical patent/KR20160079767A/ko
Priority to JP2015545008A priority patent/JP6228225B2/ja
Publication of WO2015064576A1 publication Critical patent/WO2015064576A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/35—Extrusion nozzles or dies with rollers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/005—Removal of residual monomers by physical means from solid polymers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings

Definitions

  • the present invention relates to a method for producing a methacrylic resin composition. More specifically, the present invention is a thin-walled and wide-area plate-shaped molded article having little coloring, high transparency, low haze, high impact, low saturated water absorption, small dimensional change, good appearance, etc.
  • the present invention relates to a method for producing a methacrylic resin composition or a methacrylic resin pellet suitable for producing the above.
  • Methacrylic resin is excellent in transparency, light resistance and surface hardness.
  • various optical members such as a light guide plate and a lens can be obtained.
  • a methacrylic resin composition that is a raw material for optical members is strongly required to have high transparency, low hygroscopicity, high heat resistance, small dimensional change, high impact property, good moldability, and the like.
  • a resin material for optical members for example, an optical resin material obtained by polymerizing a polymerizable composition containing 5% by weight or more of tricyclodecanyl (meth) acrylate is known (see Patent Document 1). .
  • this optical resin material is molded at a high molding temperature, a colored molded body is easily obtained.
  • this optical resin material is injection-molded at a low temperature of 230 to 260 ° C., the molded product is not colored.
  • the productivity of the molded body is low, and stress is likely to remain in the obtained molded body, so that a dimensional change is likely to occur due to heat.
  • a polymerizable monomer, a polymerization initiator, and a chain transfer agent are continuously supplied to a reactor, (II) In the reactor, a part of the polymerizable monomer is radically bulk-polymerized to form 60 to 90% by mass of a structural unit derived from methyl methacrylate and a structure derived from a methacrylic acid alicyclic hydrocarbon ester.
  • a dimer or trimer comprising 10 to 40% by mass of a unit and a methacrylic resin having 0 to 10% by mass of a structural unit derived from an acrylate ester, an unreacted polymerizable monomer, and a polymerizable monomer
  • a resin mixture containing the body (III) The resin mixture is continuously transferred from the reactor to a twin-screw extruder equipped with a vent, (IV) removing unreacted polymerizable monomer and dimer or trimer comprising the polymerizable monomer from the resin mixture in the twin-screw extruder, A method for producing a methacrylic resin composition having a total content of a dimer and a trimer comprising a polymerizable monomer of 0.3% by mass or less.
  • a polymerizable monomer, a polymerization initiator, and a chain transfer agent are continuously supplied to the reactor, (II) In the reactor, a part of the polymerizable monomer is radically bulk-polymerized to form 60 to 90% by mass of a structural unit derived from methyl methacrylate and a structure derived from a methacrylic acid alicyclic hydrocarbon ester.
  • a dimer or trimer comprising 10 to 40% by mass of a unit and a methacrylic resin having 0 to 10% by mass of a structural unit derived from an acrylate ester, an unreacted polymerizable monomer, and a polymerizable monomer
  • a resin mixture containing the body (III) The resin mixture is continuously transferred from the reactor to a twin-screw extruder equipped with a vent, (IV) In the twin-screw extruder, the unreacted polymerizable monomer and the dimer or trimer composed of the polymerizable monomer are removed from the resin mixture to obtain a methacrylic resin composition, Extruding the methacrylic resin composition into a strand, (V) having a methacrylic resin composition extruded in a strand shape by cutting with a pelletizer, A method for producing a methacrylic resin pellet having a total content of a dimer and a trimer composed of a polymerizable monomer of 0.3% by mass or less.
  • [6] Carry out the production method according to [5] to obtain methacrylic resin pellets, (VI) A method for producing a molded body, comprising heating and melting the methacrylic resin pellets to form a desired shape.
  • a methacrylic resin composition is obtained by carrying out the production method according to any one of [1] to [4], Having the methacrylic resin composition heated and melted to form a plate, A method for producing a plate-like molded body having an optical path length of 200 mm and a yellow index of 10 or less.
  • the method for producing a plate-shaped body according to [7] wherein the ratio of the resin flow length to the thickness of the plate-shaped body is 380 or more.
  • a methacrylic resin composition or a methacrylic resin pellet suitable for the above can be produced with high efficiency.
  • the method for producing a methacrylic resin composition of the present invention includes: (I) a polymerizable monomer, a polymerization initiator, and a chain transfer agent are continuously supplied to a reactor; and (II) the polymerizable in the reactor.
  • a part of the monomer is radically bulk polymerized to give 60 to 90% by mass of structural units derived from methyl methacrylate, 10 to 40% by mass of structural units derived from methacrylic acid alicyclic hydrocarbon ester, and acrylic acid ester
  • a resin mixture containing a methacrylic resin having a structural unit derived from 0 to 10% by mass, an unreacted polymerizable monomer, and a dimer or trimer composed of the polymerizable monomer is obtained.
  • the method for producing methacrylic resin pellets of the present invention comprises (I) continuously supplying a polymerizable monomer, a polymerization initiator and a chain transfer agent to a reactor, and (II) performing polymerization in the reactor.
  • a part of the polymerizable monomer is radically bulk-polymerized to form 60 to 90% by mass of structural units derived from methyl methacrylate, 10 to 40% by mass of structural units derived from methacrylic acid alicyclic hydrocarbon ester, and acrylic acid Obtaining a resin mixture containing a methacrylic resin having a structural unit derived from an ester of 0 to 10% by mass, an unreacted polymerizable monomer, and a dimer or trimer comprising the polymerizable monomer, (III) The resin mixture is continuously transferred from the reactor to a twin screw extruder equipped with a vent. (IV) In the twin screw extruder, unreacted polymerizable monomer from the resin mixture.
  • Dimer or trimer consisting of a monomer and a polymerizable monomer Are removed to obtain a methacrylic resin composition, the methacrylic resin composition is extruded in a strand shape, and (V) the methacrylic resin composition extruded in a strand shape is cut with a pelletizer.
  • methyl methacrylate hereinafter sometimes referred to as monomer (I)
  • methacrylic acid alicyclic hydrocarbon esters (hereinafter sometimes referred to as monomers (II)), and acrylic esters (hereinafter sometimes referred to as monomers (III)) and other monomers are used as necessary.
  • Examples of the monomer (II) include methacrylic acid monocyclic aliphatic hydrocarbon esters such as cyclohexyl methacrylate, cyclopentyl methacrylate, and cycloheptyl methacrylate; 2-norbornyl methacrylate, 2-methyl-2-methacrylate Norbornyl, 2-ethyl-2-norbornyl methacrylate, 2-isobornyl methacrylate, 2-methyl-2-isobornyl methacrylate, 2-ethyl-2-isobornyl methacrylate, 8-tricyclomethacrylate [5.2.1.
  • decanyl 8-methyl-8-tricyclo [5.2.1.0 2,6 ] decanyl methacrylate, 8-ethyl-8-tricyclomethacrylate [5.2.1.0 2,6 ] Decanyl, 2-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, methacrylic acid Methacrylic acid polycyclic aliphatic hydrocarbon esters such as ethyl-2-adamantyl, 1-adamantyl methacrylate, 2-fenkyl methacrylate, 2-methyl-2-fenkyl methacrylate, 2-ethyl-2-fenkyl methacrylate; Etc.
  • polycyclic aliphatic hydrocarbon esters of methacrylic acid are preferred, and tricyclo [5.2.1.0 2,6 ] decanyl methacrylate (also known as dicyclopentanyl methacrylate) or 2-isobornyl methacrylate (methacrylic acid). Isobornyl acid) is more preferred.
  • Monomers (III) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic Amyl acid, Isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate, benzyl acrylate, acrylic acid Examples include phenoxyethyl, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, and phenyl acrylate. Of these, alkyl acrylates having 1 to 6 carbon atoms are preferred
  • monomers other than the monomers (I), (II) and (III) can be used.
  • monomer (IV) ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, methacrylic acid Methyl methacrylate other than methyl methacrylate such as isoamyl acid, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, etc .; acrylic acid, methacrylic acid, maleic anhydride , Unsaturated carboxylic acids such as maleic acid and itac
  • the amount of monomer (I) to be used is generally 60 to 90% by mass, preferably 60 to 88% by mass, more preferably 70 to 86% by mass, and still more preferably 74%, based on the total polymerizable monomers. It is -86 mass%.
  • the amount of monomer (II) used is usually 10 to 40% by mass, preferably 11 to 35% by mass, more preferably 12 to 20% by mass, based on the total polymerizable monomer.
  • the amount of monomer (III) used is usually 10% by mass or less, preferably 0.5 to 8% by mass, more preferably 1 to 6% by mass, based on the total polymerizable monomer.
  • the amount of monomer (IV) to be used is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less with respect to the total polymerizable monomer.
  • the polymerizable monomer used in the present invention that is, the monomer (I), the monomer (II), and the optional monomers (III) and (IV) have a yellow index of 2 Or less, more preferably 1 or less. If the yellow index of the polymerizable monomer is small, when the resulting methacrylic resin composition or methacrylic resin pellet is molded, a molded product with little coloration is easily obtained with high production efficiency.
  • the yellow index is a yellowness value calculated in accordance with JIS K 7373 based on a value measured in accordance with JIS 87 Z8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. .
  • the amount of dissolved oxygen in the polymerizable monomer is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, and particularly preferably 3 ppm or less.
  • the amount of dissolved oxygen is in such a range, the polymerization reaction proceeds smoothly, and it becomes easy to obtain a molded body without silver or coloring.
  • the polymerization initiator used in the present invention is not particularly limited as long as it generates a reactive radical.
  • t-hexyl peroxyisopropyl monocarbonate t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate T-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 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), di
  • the polymerization initiator preferably has a one-hour half-life temperature of 60 to 140 ° C, more preferably 80 to 120 ° C.
  • the polymerization initiator preferably has a hydrogen abstraction ability of 20% or less, more preferably 10% or less, and even more preferably 5% or less.
  • t-hexylperoxy 2-ethylhexanoate, 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2'-azobis (2-methylpropionate) are preferable.
  • These polymerization initiators may be used alone or in combination of two or more. Moreover, the usage-amount of a polymerization initiator, the addition method, etc.
  • the amount of the polymerization initiator used in the bulk polymerization method is preferably 0.0001 to 0.02 parts by mass, more preferably 0.001 to 0.0. 01 parts by mass.
  • the hydrogen abstraction ability can be known from technical data (for example, Non-Patent Document 1) of the polymerization initiator manufacturer. Further, it can be measured by a radical trapping method using ⁇ -methylstyrene dimer, that is, ⁇ -methylstyrene dimer trapping method. The measurement is generally performed as follows. First, the polymerization initiator is cleaved in the presence of ⁇ -methylstyrene dimer as a radical trapping agent and cyclohexane to generate radical fragments. Among the generated radical fragments, radical fragments having a low hydrogen abstraction ability are added to and trapped by the double bond of ⁇ -methylstyrene dimer.
  • a radical fragment having a high hydrogen abstraction capacity abstracts hydrogen from cyclohexane to generate a cyclohexyl radical, and the cyclohexyl radical is added to and trapped by a double bond of ⁇ -methylstyrene dimer to generate a cyclohexane trapping product. Therefore, the ratio (mole fraction) of radical fragments having a high hydrogen abstraction capacity with respect to the theoretical radical fragment generation amount, which is obtained by quantifying cyclohexane or cyclohexane supplement product, is defined as the hydrogen abstraction capacity.
  • chain transfer agent used in the present invention examples include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol.
  • These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably 0.1 to 1 part by mass, more preferably 0.2 to 0.8 part by mass, and still more preferably 0.3 to 100 parts by mass of the total polymerizable monomer. ⁇ 0.6 parts by mass.
  • the reaction raw material is supplied to the reactor at a constant flow rate, the liquid containing the reaction product obtained in the reactor is withdrawn at a constant flow rate, the reaction raw material is supplied and the liquid containing the reaction product is withdrawn It is a method of proceeding the reaction continuously with the balance.
  • Typical examples of the reactor used for the continuous flow reaction include a continuous flow tank reactor and a continuous flow tube reactor.
  • the continuous flow tank reactor can be reacted in a mixed state in which the reaction liquid is almost completely mixed.
  • the continuous flow tubular reactor can react in a mixed state in which the reaction solution is close to plug flow.
  • the initial stage to the middle stage of the reaction can be performed with a continuous flow tank reactor, and the final stage of the reaction can be performed with a continuous flow tubular reactor.
  • the reactor may have a stirrer, and the stirrer can be selected according to the type of the reactor.
  • a max blend type stirrer a lattice rotating around a vertical rotation shaft arranged in the center Examples include a stirrer having a blade, a propeller stirrer, a screw stirrer, a static mixer, etc.
  • a Max blend stirrer from the viewpoint of uniform mixing.
  • a suitable reaction apparatus used in the present invention has at least one continuous flow tank reactor.
  • a plurality of continuous flow tank reactors may be connected in series or in parallel.
  • the amount supplied to the tank reactor and the amount withdrawn from the tank reactor are balanced so that the amount of liquid in the tank reactor is substantially constant.
  • the amount of liquid in the tank reactor is preferably 1/4 to 3/4, more preferably 1/3 to 2/3 with respect to the volume of the tank reactor.
  • the polymerizable monomer, the polymerization initiator, and the chain transfer agent may be mixed together, and the mixture may be continuously supplied to the reactor, or they may be separately supplied to the reactor and continuously reacted. You may mix in a container.
  • a method in which all of the polymerizable monomer, the polymerization initiator and the chain transfer agent are mixed and the mixture is continuously fed to the reactor is preferred.
  • the mixing of the polymerizable monomer, the polymerization initiator and the chain transfer agent is preferably performed in an inert atmosphere such as nitrogen gas. Further, in order to smoothly operate the continuous flow reaction, the monomer (I), the monomer (II), the polymerization initiator, the chain transfer agent, and optional monomers (III) and (IV It is preferable to continuously supply and mix from the tank storing the water) to the mixer provided in the front stage of the reactor through the pipes, and continuously supply the mixture to the reactor.
  • the mixer is preferably equipped with a stirrer such as a static mixer.
  • the suspension polymerization method can reduce the amount of residual monomers in the resin, but the yellow index increases due to the influence of impurities such as stabilizers and dispersants.
  • impurities such as stabilizers and dispersants.
  • it is not only difficult to obtain a plate-like molded product with a small amount of residual monomer, but it is also difficult to obtain a thin-walled and large-area plate-like molded product.
  • the quality is low and it is difficult to use for optical members such as a light guide plate.
  • the temperature in the polymerization reactor is preferably 100 to 160 ° C, more preferably 110 to 150 ° C. When the temperature in the polymerization reactor is within such a range, it is easy to lower the yellow index of the obtained molded article.
  • the average residence time in the polymerization reactor varies depending on the scale of the reactor, but is preferably 0.5 to 4 hours, more preferably 1 to 3 hours. If the average residence time is too short, the required amount of the polymerization initiator tends to increase. Further, increasing the amount of the polymerization initiator makes it difficult to control the polymerization reaction, and tends to make it difficult to control the molecular weight. On the other hand, if the average residence 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 performed in an inert gas atmosphere such as nitrogen gas.
  • the polymerization conversion rate of the polymerizable monomer is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. . If the polymerization conversion rate is too high, a large stirring power tends to be required for increasing the viscosity. If the polymerization conversion rate is too low, devolatilization tends to be insufficient, and when the obtained methacrylic resin composition or methacrylic resin pellet is molded, there is a tendency to cause appearance defects such as silver in the molded product.
  • the methacrylic resin contained in the resin mixture contains 60 to 90% by mass of structural units derived from monomer (I), 10 to 40% by mass of structural units derived from monomer (II), and monomer ( Those having 0 to 10% by mass of structural units derived from III), preferably 74 to 86% by mass of structural units derived from monomer (I), and 12 to 20% by mass of structural units derived from monomer (II) %, And 2 to 6% by mass of structural units derived from the monomer (III).
  • the methacrylic resin contained in the resin mixture preferably has a weight average molecular weight of 35,000 to 100,000, more preferably 40,000 to 90,000, still more preferably 45,000 to 80,000, Preferably, it is 60,000 to 80,000. If the weight average molecular weight is less than 35,000, the impact resistance and toughness of the molded product made of the methacrylic resin composition tend to be insufficient, and if it is greater than 100,000, the moldability of the methacrylic resin composition is insufficient. It becomes the tendency to become.
  • the ratio of the weight average molecular weight to the number average molecular weight of the methacrylic resin contained in the resin mixture is preferably 1. 0.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0. If the molecular weight distribution of the methacrylic resin is small, the moldability of the methacrylic resin composition tends to decrease. When the molecular weight distribution is large, the impact resistance of the molded product obtained from the resin composition tends to be reduced and tends to be brittle.
  • a weight average molecular weight and a number average molecular weight are molecular weights of standard polystyrene conversion measured by GPC (gel permeation chromatography). Further, the weight average molecular weight, number average molecular weight and molecular weight distribution of the methacrylic resin can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.
  • the methacrylic resin contained in the resin mixture has a glass transition temperature of preferably 100 to 140 ° C., more preferably 105 to 135 ° C., and further preferably 110 to 130 ° C.
  • a glass transition temperature preferably 100 to 140 ° C., more preferably 105 to 135 ° C., and further preferably 110 to 130 ° C.
  • the glass transition temperature is low, the heat resistance and the like tend to decrease.
  • the glass transition temperature is high, moldability and the like tend to decrease.
  • the dimer or trimer contained in the resin mixture is a structure derived from the same or different two or three polymerizable monomers produced by a polymerization step and / or a heating step after polymerization. It is a compound consisting of units. Specific examples of the dimer or trimer include a dimer or trimer composed of methyl methacrylate, a dimer or trimer composed of acrylic acid ester, and a dimer or trimer composed of methacrylic acid alicyclic hydrocarbon ester.
  • Dimer or trimer dimer consisting of methyl methacrylate and acrylate ester, dimer consisting of methyl methacrylate and methacrylic acid alicyclic hydrocarbon ester, acrylic acid ester and methacrylic acid alicyclic carbonization Dimer consisting of hydrogen ester, trimer consisting of two methyl methacrylates and one acrylate ester, trimer consisting of one methyl methacrylate and two acrylate esters, two methyl methacrylates And a methacrylic alicyclic hydrocarbon ester, one methyl methacrylate and two methacrylic alicyclics A trimer consisting of a hydrocarbon ester, a trimer consisting of two acrylic esters and one methacrylic alicyclic hydrocarbon ester, one acrylic ester and two methacrylic alicyclic hydrocarbon esters, And a trimer consisting of methyl methacrylate, acrylic acid ester and methacrylic acid alicyclic hydrocarbon ester.
  • the resin mixture is continuously transferred from the polymerization reactor to a twin screw extruder equipped with a vent.
  • the transferred resin mixture is preferably equilibrated flash or adiabatic flash, preferably adiabatic flash, at the twin screw extruder inlet.
  • the adiabatic flash is preferably performed at a temperature of 210 to 300 ° C, more preferably 220 to 280 ° C, and even more preferably 230 to 260 ° C.
  • the pressure of the resin mixture immediately before the flash is preferably 1.5 to 3.0 MPa, more preferably 2.0 to 2.5 MPa. If it is less than 1.5 MPa, the flash is insufficient and the residual monomer tends to increase. Conversely, if it exceeds 3.0 MPa, it tends to be difficult to obtain stable production.
  • Volatile components (dimer or trimer consisting of unreacted polymerizable monomer and polymerizable monomer) evaporated by flash are usually discharged from the rear vent, but may be discharged from other vents. .
  • the vent provided in the twin-screw extruder used in the present invention is preferably a vacuum vent or an open vent. At least one vent is provided downstream from the polymer inflow portion.
  • the pressure in the vacuum vent is preferably 30 Torr or less, more preferably 15 Torr or less, further preferably 9 Torr or less, and most preferably 6 Torr or less. If the pressure in the vacuum vent is within the above range, the devolatilization efficiency is good and the residual monomer can be reduced.
  • the screw of the twin screw extruder is preferably a twin screw in the same direction.
  • the shear energy given to the resin is large, and the degree of surface renewal is large, so that devolatilization can be performed efficiently, so that the residual monomer can be reduced.
  • the screw structure has a kneading segment part of 5% or more with respect to the total length of the screw. Examples of the kneading segment include a rotor segment, a forward feed kneading disc, a reverse feed kneading disc, and a mixing gear.
  • the cylinder heating temperature of the twin-screw extruder is preferably 210 to 300 ° C, more preferably 220 to 280 ° C, and further preferably 230 to 260 ° C. If it is less than 210 degreeC, time will be required for devolatilization, and devolatilization will be insufficient. When devolatilization is insufficient, the molded product may have poor appearance such as silver. On the other hand, when the temperature exceeds 300 ° C., not only the production of the dimer and trimer described above increases, but also the amount of terminal double bonds increases, making it difficult to ensure thermal stability.
  • a methacrylic resin composition can be obtained by flash evaporation, which is an optional process, and devolatilization by a twin screw extruder with a vent, which is a subsequent process.
  • the obtained methacrylic resin composition can be made into pellets or powders by a known method.
  • the obtained methacrylic resin composition into a methacrylic resin pellet by extruding it from the twin screw extruder into a strand shape and cutting it with a pelletizer.
  • a die plate is usually used at the tip of the extruder to form a strand.
  • the strand can have a circular, oval, quadrangular, etc. cross section.
  • the thickness of the strand is not particularly limited as long as it can be a desired resin pellet size.
  • the polymer filter has a filtration accuracy of preferably 1 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m, and still more preferably 2 ⁇ m to 3 ⁇ m.
  • the shape of the methacrylic resin pellet obtained by the method of the present invention is not particularly limited. For example, a cylindrical shape, a prismatic shape, etc. are mentioned.
  • the size of the methacrylic resin pellet varies depending on the application, and examples thereof include a width of 4 mm or less, a thickness of 4 mm or less and a length of 5 mm or less, a width of 3 mm or less, a thickness of 3 mm or less and a length of 4 mm or less. It is done.
  • the strand is preferably cut at a temperature at which cut defects (long resin pieces), chips (resin powder) and the like are not generated as much as possible. The temperature is appropriately set in consideration of the glass transition temperature of the methacrylic resin. Examples of the method for cooling the strand include an air cooling method, a water cooling method, a refrigerant cooling method, and a mist cooling method.
  • the amount of the methacrylic resin contained in the methacrylic resin composition or methacrylic resin pellet obtained by the method of the present invention is preferably 97% by mass or more, more preferably 98% by mass with respect to the entire methacrylic resin composition or methacrylic resin pellet. As mentioned above, More preferably, it is 99 mass% or more.
  • the methacrylic resin contained in the methacrylic resin composition or the methacrylic resin pellets obtained by the method of the present invention comprises 60 to 90% by mass of structural units derived from monomer (I) and structural units derived from monomer (II). Those having 10 to 40% by mass and structural units derived from monomer (III) of 0 to 10% by mass, preferably 74 to 86% by mass of structural units derived from monomer (I), monomer ( It has 12 to 20% by mass of structural units derived from II) and 2 to 6% by mass of structural units derived from monomer (III).
  • the methacrylic resin contained in the methacrylic resin composition or methacrylic resin pellet obtained by the method of the present invention has a weight average molecular weight of preferably 35,000 to 100,000, more preferably 40,000 to 90,000, Preferably it is 45,000-80,000, most preferably 60,000-80,000. If the weight average molecular weight is less than 35,000, the impact resistance and toughness of the molded product made of the methacrylic resin composition tend to be insufficient, and if it is greater than 100,000, the moldability of the methacrylic resin composition is insufficient. It becomes the tendency to become.
  • the methacrylic resin contained in the methacrylic resin composition or the methacrylic resin pellets obtained by the method of the present invention has a weight average molecular weight / number average molecular weight ratio (weight average molecular weight / number average molecular weight: hereinafter, this ratio is expressed as molecular weight distribution). However, it is preferably 1.7 to 2.6, more preferably 1.7 to 2.3, and still more preferably 1.7 to 2.0. If the molecular weight distribution of the methacrylic resin is small, the moldability of the methacrylic resin composition tends to decrease. When the molecular weight distribution is large, the impact resistance of the molded product obtained from the resin composition tends to be reduced and tends to be brittle.
  • a weight average molecular weight and a number average molecular weight are molecular weights of standard polystyrene conversion measured by GPC (gel permeation chromatography). Further, the weight average molecular weight, number average molecular weight and molecular weight distribution of the methacrylic resin can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.
  • the methacrylic resin contained in the methacrylic resin composition or methacrylic resin pellet obtained by the method of the present invention has a glass transition temperature of preferably 100 to 140 ° C, more preferably 105 to 135 ° C, and further preferably 110 to 130 ° C. It is. When the glass transition temperature is low, the heat resistance and the like tend to decrease. When the glass transition temperature is high, moldability and the like tend to decrease.
  • the total content of the aforementioned dimer and trimer is 0.3% by mass or less, preferably 0.25% by mass or less, more preferably Is 0.2 mass% or less.
  • dimers and trimers can be quantified by gas chromatography.
  • the methacrylic resin composition or methacrylic resin pellet obtained by the method of the present invention has a melt flow rate of preferably 5 to 35 g / 10 minutes, more preferably 8 to 30 g / min at 230 ° C. and a load of 3.8 kg. 10 minutes, more preferably 10 to 25 g / 10 minutes.
  • the melt flow rate is a value of the melt mass flow rate measured in accordance with JIS K7210.
  • the methacrylic resin composition or methacrylic resin pellet obtained by the method of the present invention preferably has a methacrylic acid alicyclic hydrocarbon ester content of 1.0% by mass or less, more preferably 0.8% by mass or less, Preferably it is 0.6 mass% or less, Most preferably, it is 0.4 mass% or less.
  • a methacrylic acid alicyclic hydrocarbon ester content of 1.0% by mass or less, more preferably 0.8% by mass or less, Preferably it is 0.6 mass% or less, Most preferably, it is 0.4 mass% or less.
  • the content of methacrylic acid alicyclic hydrocarbon ester can be quantified by gas chromatography.
  • the methacrylic resin composition or methacrylic resin pellet obtained by the method of the present invention preferably has a saturated water absorption of 1.6% by mass or less from the viewpoint of suppressing dimensional change of a molded product obtained therefrom. It is more preferable that the amount is not more than mass%.
  • the saturated water absorption is the rate of mass increase between the mass of the molded product vacuum-dried for 3 days or more and the mass after leaving the molded product for 300 hours at 60 ° C. and 90% humidity. As measured.
  • additives can be blended in the methacrylic resin composition or the methacrylic resin pellets obtained by the method of the present invention, if necessary.
  • the amount of the additive is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less with respect to the methacrylic resin. If the amount of the additive is too large, appearance defects such as silver may occur in the molded product.
  • Additives include heat stabilizers, antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, inorganic fillers, inorganic or organic fibers, mineral oil softeners, polymer processing Auxiliaries, antistatic agents, flame retardants, dyes and pigments, colorants, matting agents, light diffusing agents, impact resistance modifiers, phosphors, adhesives, tackifiers, plasticizers, foaming agents, etc. .
  • An antioxidant is effective in preventing oxidative degradation of a resin alone in the presence of oxygen.
  • examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants can be used alone or in combination of two or more.
  • the combined use of a phosphorus-based antioxidant and a hindered phenol-based antioxidant or the combined use of a thioether-based antioxidant and a hindered phenol-based antioxidant More preferred.
  • the ratio is not particularly limited, but a phosphorus antioxidant (or thioether antioxidant) / hindered phenol antioxidant.
  • the mass ratio of the dophenol antioxidant is preferably 1/5 to 2/1, more preferably 1/2 to 1/1.
  • Examples of phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: ADK STAB HP-10), tris (2,4-di-t- (Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRUGAFOS168), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10- And tetraoxa-3,9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADK STAB PEP-36).
  • thioether-based antioxidant 2,2-bis ⁇ (3-dodecylthio-1-oxopropoxy) methyl ⁇ propane-1,3-diylbis (3-dodecylthiopropionate) (manufactured by ADEKA; trade name: Adekastab AO-412S), ditridecyl 3,3′-thiodipropionate (manufactured by ADEKA; trade name: Adekastab AO-503) and the like.
  • the thermal degradation inhibitor is a compound that can prevent thermal degradation of the resin by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
  • 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM)
  • 2,4-di- Examples thereof include t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilyzer GS).
  • the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays.
  • examples include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. These can be used alone or in combination of two or more. Among these, benzotriazoles and anilides are preferable.
  • benzotriazoles examples include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN329), 2 -(2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN234) and the like.
  • anilides examples include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, trade name: Sundebore VSU).
  • benzotriazoles are particularly preferable from the viewpoint that resin deterioration due to ultraviolet irradiation can be suppressed.
  • the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
  • examples thereof include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
  • the mold release agent is a compound having a function of easily releasing the molded body from the mold.
  • examples thereof include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
  • higher alcohols and glycerin fatty acid monoester are preferably used in combination.
  • the ratio is not particularly limited, but the mass ratio of higher alcohols / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1.
  • the preferred range is 2.8 / 1 to 3.2 / 1.
  • the polymer processing aid is a compound that exhibits an effect on thickness accuracy and thinning when a methacrylic resin composition or a methacrylic resin pellet is formed.
  • the polymer processing aid can usually be produced by an emulsion polymerization method.
  • the polymer processing aid is preferably polymer particles having a particle size of 0.05 to 0.5 ⁇ m.
  • the polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be.
  • particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.
  • the polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g. If the intrinsic viscosity is too small, the effect of improving moldability is low. If the intrinsic viscosity is too large, the melt fluidity of the methacrylic resin composition or methacrylic resin pellets tends to be lowered.
  • the impact modifier examples include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; a modifier containing a plurality of rubber particles, and the like.
  • the organic dye a compound having a function of converting ultraviolet rays that are harmful to the resin into visible light is preferably used.
  • the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
  • the phosphor examples include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent brighteners, and fluorescent bleaching agents.
  • Mineral oil softeners are used to improve fluidity during molding. Examples thereof include paraffinic oil and naphthenic oil.
  • the inorganic filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
  • the fibrous filler include glass fiber and carbon fiber.
  • the methacrylic resin composition or methacrylic resin pellet obtained by the production method of the present invention can be used by mixing with other polymers as long as the effects of the present invention are not impaired.
  • other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, and high impact polystyrene.
  • Styrene resin such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, Polyamide such as polyamide elastomer; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, Polyurethane, modified polyphenylene ether, polyphenylene sulfide, silicone-modified resins; acrylic rubber, silicone rubber; SEPS, SEBS, styrene-based thermoplastic elastomers such as SIS, IR, EPR, and olefin-based rubber such as EPDM and the like.
  • Injection molding insert method, two-color method, press method, core back method, sandwich method, etc.
  • compression molding extrusion molding
  • vacuum molding blow molding
  • Various molded products can be obtained by heat-melt molding by a method such as inflation molding or calendar molding.
  • the methacrylic resin composition or methacrylic resin pellet is preferably dried before molding.
  • the drying method include a hot air drying method, a dehumidifying drying method, a reduced pressure drying method, and a low oxygen drying method. If the moisture content is reduced by drying before molding, molding defects such as silver can be reduced.
  • the defective cut is a long resin piece obtained as a result of failing to cut the strand.
  • the resin powder is a powder that can be produced by rubbing chips and pellets generated when a strand is cut.
  • a method for removing defective products and resin powder is not particularly limited. Examples thereof include a centrifugal separation method and a sieving method.
  • the temperature of the methacrylic resin composition or the methacrylic resin pellet is preferably maintained at, for example, 70 ° C. or higher.
  • the transfer is performed at a high temperature, it may be possible to suppress the generation of resin powder due to moisture absorption during transfer or rubbing between pellets.
  • the plate-shaped molded body preferably has a resin flow length to thickness ratio of 380 or more. Moreover, it is preferable that this plate-shaped molded object is 1 mm or less in thickness.
  • the resin flow length is a distance between the gate of the injection mold and the inner wall of the mold farthest from the gate.
  • the resin flow length in the film gate is the distance between the vertical leg (intersection with the gate) drawn from the sprue attachment part of the injection mold and the inner wall of the mold farthest from the intersection. (See FIG. 1).
  • the gate of the mold for obtaining the plate-shaped molded body is preferably a film gate. The film gate is cut with a cutting machine and finished with a router or the like. In a mold for obtaining a light guide plate used in a liquid crystal display device, it is preferable to provide a gate on an end face on which no light source is scheduled.
  • the plate-like molded product obtained by the method of the present invention has a yellow index (YI) with an optical path length of 200 mm, preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the yellow index is a value calculated according to JIS K 7373 based on a value measured according to JIS Z8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the plate-like molded product obtained by the present invention has a transmittance at an optical path length of 3 mm at a wavelength of 435 nm of preferably 90% or more, more preferably 90.5% or more, and still more preferably 91% or more.
  • Examples of the use of the plate-shaped molded body include billboard parts such as advertising towers, stand signs, sleeve signs, bamboard signs, and rooftop signs; display parts such as showcases, partition boards, and store displays; fluorescent lamp covers and mood lighting covers.
  • Lighting parts such as lamp shades, light ceilings, light walls, and chandeliers; interior parts such as pendants and mirrors; for buildings such as doors, domes, safety window glass, partitions, stair waist plates, balcony waist plates, and roofs of leisure buildings Parts: Aircraft windshield, pilot visor, motorcycle, motorboat windshield, bus shading plate, automotive side visor, rear visor, head wing, headlight cover, and other transport related parts; audio visual nameplate, stereo cover, TV protection mask
  • Electronic device parts such as vending machine display covers Medical equipment parts such as incubators and X-ray parts; machine-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; LCD protective plates, light guide plates, light guide films, Fresnel lenses, lenticular lenses,
  • the unevenness for light guide is obtained by a known method such as fusion, adhesion, coating, printing, injection molding, or processing with laser light.
  • the shape may be formed on the back surface of the plate. Light incident from the end face of the plate can be reflected and refracted by the uneven shape and emitted to the front of the plate.
  • the concavo-convex shape include a perfect circle or elliptical dot pattern, a line pattern such as a rectangle or a V groove, a hemispherical lens concavo-convex pattern, a wrinkle pattern, and the like.
  • the width is 1 to 600 ⁇ m
  • the length is 2 to 1200 ⁇ m
  • the height or depth is 1 to 500 ⁇ m
  • the adjacent unevenness The interval between the shapes is preferably 2 to 10,000 ⁇ m. If the concavo-convex shape is too large, it is visually recognized and the quality of the display is lowered, and if it is too small, the processing is difficult and the productivity is lowered. Further, if the interval between adjacent uneven shapes is narrower than 2 ⁇ m, it becomes difficult to form adjacent uneven portions independently, and molding defects tend to occur. If the width is larger than 10,000 ⁇ m, the number of uneven portions cannot be increased.
  • the concavo-convex portion has a function of emitting light
  • the limitation on the number of the concavo-convex portions causes a utilization rate limitation that is a ratio of light that is effectively emitted from the light incident from the end face of the light guide plate.
  • These uneven shapes may be the same shape in one light guide plate, may be formed by combining different shapes, or patterns having the same shape and different sizes may be arranged. Furthermore, the interval and size of the unevenness may be modulated according to the distance from the light source arranged adjacent to the end face of the light guide plate.
  • a white reflective material may be printed on the back surface of the light guide plate instead of forming the uneven shape.
  • the size of the white reflector is preferably 500 ⁇ m to 5000 ⁇ m. If the thickness is smaller than 500 ⁇ m, it is difficult to print the white reflective material by the existing screen printing or the like. If it is larger than 5000 ⁇ m, the white reflective material is visually recognized even when viewed through a diffusion sheet or the like, and the quality of the display deteriorates.
  • the interval between the reflecting materials is preferably 1000 to 5000 ⁇ m. If the interval is smaller than 1000 ⁇ m, adjacent white reflectors overlap with each other by screen printing or the like, resulting in a defect.
  • the interval and size of the white reflecting material may be modulated in accordance with the distance from the light source arranged adjacent to the end face of the light guide plate.
  • prisms and arcuate line-shaped convex portions may be formed on the surface of the light guide plate from which light is emitted (front of the plate) by the same means.
  • a reflection sheet may be appropriately disposed on the back side of the light guide plate, and a diffusion sheet and / or a prism sheet may be appropriately disposed on the front side of the light guide plate.
  • the molded product of the present invention can be used as a front plate for various displays.
  • a front plate can be obtained by a general molding method such as extrusion molding or injection molding by heating and melting the resin composition.
  • the display device in which the front plate is used is not particularly limited, and examples thereof include large display devices such as large-screen televisions and advertising displays; small and medium display devices such as mobile phones and smartphones.
  • the front plate is not limited to a planar shape, and may have a curved shape.
  • the curved surface shape may be a shape curved in one direction or a shape curved in a plurality of directions.
  • the plate-like molded body may have a flexible characteristic, or may be previously molded into a desired curved shape.
  • a functional layer such as an antiglare layer, an antireflection layer, a layer that cuts electromagnetic waves, ultraviolet rays, near infrared rays, or the like may be provided.
  • the molded article of the present invention may be laminated with another functional film or functional sheet via an adhesive layer or an adhesive layer, or may be laminated by film insert molding. Examples of the functional film and functional sheet include a light guide plate, a diffusion plate, a scattering prevention film, and a transparent conductive film.
  • melt flow rate The melt flow rate of the methacrylic resin compositions obtained in Examples and Comparative Examples was measured under conditions of 230 ° C., 3.8 kg load, and 10 minutes in accordance with JIS K7210.
  • the yellow index of the monomer mixture used in Examples and Comparative Examples was determined based on JIS based on values measured according to JIS Z-8722 using a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. It calculated based on K7373. Test pieces having a length of 200 mm were cut out from the plate-shaped molded bodies produced in the examples and comparative examples, and a yellow index having an optical path length of 200 mm was used as a colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. Was calculated according to JIS K7373 based on the value measured according to JIS Z-8722.
  • Light transmittance A test piece with an optical path length of 200 mm and a test piece with an optical path length of 3 mm were cut out from the plate-shaped molded bodies produced in Examples and Comparative Examples, respectively, and the transmittances of light having a wavelength of 435 nm at optical path lengths of 200 mm and 3 mm were measured.
  • dicyclopentanyl methacrylate is TCDMA
  • isobornyl methacrylate is IBXMA
  • methyl methacrylate is MMA
  • methyl acrylate is MA
  • n-octyl mercaptan is n-OM
  • 2,2'-azobis (2-methylpropio) Nitrile is denoted AIBN.
  • Example 1 A monomer mixture was prepared by putting 78 parts by mass of purified MMA, 20 parts by mass of TCDMA, and 2 parts by mass of MA in an autoclave with a stirrer and a sampling tube. The yellow index of the monomer mixture was 0.9. To the monomer mixture, 0.006 parts by mass of a polymerization initiator (AIBN, hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) and 0.37 parts by mass of a chain transfer agent (n-OM) are added and dissolved. The raw material liquid was obtained. The oxygen gas in the production apparatus was purged with nitrogen gas. The raw material liquid was supplied from an autoclave to a continuous flow tank reactor controlled at a temperature of 140 ° C. at a constant flow rate so as to have an average residence time of 120 minutes, and bulk polymerization was performed. When the reaction solution was collected from the collection tube of the reactor and measured by gas chromatography, the polymerization conversion was 57% by mass.
  • AIBN hydrogen abstraction capacity: 1%
  • the liquid discharged from the reactor was heated to 250 ° C., supplied to a twin screw extruder controlled at 260 ° C. at a constant flow rate, and adiabatic flushed at the extruder inlet. Volatiles (monomer, dimer, trimer, etc.) evaporated by the adiabatic flash were discharged from the open vent.
  • the liquid introduced into the twin-screw extruder by the adiabatic flash was kneaded with a screw, thereby evaporating volatile components from the liquid and discharging the evaporated volatile components from the twin-screw extruder vent.
  • the molten methacrylic resin composition obtained by devolatilization with the heat insulating flash and the twin screw extruder vent was extruded in a strand form from the twin screw extruder outlet.
  • the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic resin composition.
  • the content of TCDMA was 0.4% by mass.
  • the physical property of the obtained pellet-like methacrylic resin composition was measured.
  • the pellet-shaped methacrylic resin composition is injection molded at a cylinder temperature of 280 ° C., a mold temperature of 75 ° C., and a molding cycle of 1 minute.
  • a plate-like molded body having a length of 205 mm, a width of 160 mm, and a thickness of 0.5 mm was produced.
  • the ratio of the resin flow length (190 mm) to the thickness is 380.
  • the properties of the obtained plate-like molded body were evaluated. The results are shown in Table 1.
  • Example 2 The amount of MMA was changed to 73 parts by mass, the amount of TCDMA was changed to 23 parts by mass, the amount of MA was changed to 4 parts by mass, and the amount of n-OM was changed to 0.33 parts by mass.
  • a pellet-like methacrylic resin composition was obtained in the same manner as in Example 1 except that the value was changed.
  • the physical properties of the obtained pellet-like methacrylic resin composition were measured by the same method as in Example 1. Moreover, the plate-shaped molded object was produced similarly to Example 1, and the characteristic was evaluated. These results are shown in Table 1.
  • Example 3 Except for changing the amount of MMA to 83 parts by mass, the amount of TCDMA to 15 parts by mass, the amount of MA to 2 parts by mass, and the amount of n-OM to 0.38 parts by mass, the same method as in Example 1 was used. A pellet-like methacrylic resin composition was obtained. The physical properties of the obtained pellet-like methacrylic resin composition were measured by the same method as in Example 1. Moreover, the plate-shaped molded object was produced similarly to Example 1, and the characteristic was evaluated. These results are shown in Table 1.
  • Example 4 A pellet-like methacrylic resin composition was obtained in the same manner as in Example 1 except that TCDMA was changed to IBXMA and the amount of n-OM was changed to 0.36 parts by mass. The physical properties of the obtained pellet-like methacrylic resin composition were measured by the same method as in Example 1. Moreover, the plate-shaped molded object was produced similarly to Example 1, and the characteristic was evaluated. These results are shown in Table 1.
  • Comparative Examples 1 to 4 A pellet-shaped methacrylic resin composition was obtained in the same manner as in Example 1 except that the synthesis conditions and the resin production conditions shown in Tables 1 and 2 were changed. The physical properties of these methacrylic resin compositions in the form of pellets were measured by the same method as in Example 1. Moreover, it shape
  • Comparative Example 5 A pellet-like methacrylic resin composition was obtained in the same manner as in Example 1 except that the synthesis conditions and the resin production conditions shown in Table 2 were changed.
  • This pellet-shaped methacrylic resin composition was supplied to a twin screw extruder controlled at 270 ° C. at a constant speed. In the twin-screw extruder, volatile components mainly composed of unreacted monomers were separated and removed, and the resin component was extruded in a strand shape. The strand was cut with a pelletizer to obtain a pellet-shaped methacrylic resin composition (repellet). The content of TCDMA was 0.7% by mass.
  • the physical properties of the re-pelletized methacrylic resin composition were measured in the same manner as in Example 1. Moreover, the plate-shaped molded object was produced similarly to Example 1, and the characteristic was measured. These results are shown in Table 2.
  • Comparative Example 6 A pellet-like methacrylic resin composition was obtained in the same manner as in Example 1 except that the synthesis conditions and the resin production conditions shown in Table 2 were changed. A solution of 20 parts by mass of the pellet-shaped methacrylic resin composition and 80 parts by mass of toluene was prepared, and the solution was poured into a large amount of methanol and reprecipitated to obtain a powdery methacrylic resin composition. The powdery methacrylic resin composition was supplied to a single screw extruder controlled at 230 ° C. at a constant speed, and the extruded strand was cut with a pelletizer to obtain a pellet-like methacrylic resin composition (repellet). The TCDMA content was 0.2% by mass. The physical properties of the re-pelletized methacrylic resin composition were measured in the same manner as in Example 1. Moreover, the plate-shaped molded object was produced similarly to Example 1, and the characteristic was measured. These results are shown in Table 2.
  • Comparative Example 7 A monomer mixture was prepared by adding 83 parts by mass of MMA, 15 parts by mass of TCDMA, and 2 parts by mass of MA. The yellow index of the monomer mixture was 0.9. 0.1 parts by mass of a polymerization initiator (AIBN, hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) and 0.4 parts by mass of a chain transfer agent (n-OM) are added to the monomer mixture. To obtain a raw material solution. 100 parts by mass of ion-exchanged water, 0.03 parts by mass of sodium sulfate, and 0.46 parts by mass of a suspension dispersant were mixed to obtain a mixed solution.
  • AIBN hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83 ° C.
  • n-OM chain transfer agent
  • the obtained copolymer was supplied to a single screw extruder controlled at 230 ° C. to separate and remove volatile components such as unreacted monomers, and then the resin component was extruded into a strand.
  • the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic resin composition.
  • the plate-shaped molded object was produced similarly to Example 1, and the characteristic was measured.
  • Comparative Example 8 A monomer mixture was prepared by adding 73 parts by mass of MMA, 25 parts by mass of TCDMA, and 2 parts by mass of MA. The yellow index of the monomer mixture was 0.9. 0.1 parts by mass of a polymerization initiator (AIBN, hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.) was added to the monomer mixture and dissolved to obtain a raw material solution. This raw material solution was poured into a glass cell composed of two glass plates (thickness 10 mm, 30 cm square) treated with water repellency and a vinyl chloride resin gasket, and deaerated at 760 mmHg for 3 minutes. The glass cell was polymerized at 70 ° C. for 2 hours and then at 120 ° C.
  • AIBN hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.
  • a plate-like molded body having a thickness of 2 mm and 4 mm was prepared under the same polymerization conditions as above, and a test piece having a length of 290 mm, a width of 100 mm, and a thickness of 2 mm was used for evaluating light transmittance from the obtained plate-shaped molded body. For the impact resistance evaluation, a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was cut out, and the physical properties of the resin composition and the properties of the plate-shaped molded body were evaluated.
  • the obtained plate-like molded body was a very high molecular weight body, so it did not dissolve in the solvent but only swollen. Therefore, the molecular weight could not be measured.
  • the estimated weight average molecular weight is 1 million g / mol or more.
  • the plate-like molded product according to the present invention has little coloring, high transparency, low haze, low saturated water absorption, small dimensional change, and good appearance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Planar Illumination Modules (AREA)
  • Polymerisation Methods In General (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

La présente invention concerne une composition de résine méthacrylique contenant un dimère et un trimère comportant chacun un monomère polymérisable à hauteur d'une quantité totale inférieure ou égale à 0,3 % en poids. Ladite composition est produite par un procédé comprenant les étapes consistant à introduire en continu dans un réacteur ledit monomère polymérisable, un initiateur de polymérisation et un agent de transfert de chaîne ; à mettre en œuvre, dans le réacteur, une polymérisation radicalaire en masse d'une partie du monomère polymérisable afin de produire un mélange de résine comprenant une résine méthacrylique comportant 60 à 90 % en poids d'un motif structural dérivé du méthacrylate de méthyle, 10 à 40 % en poids d'un motif structural dérivé d'un ester hydrocarboné alicyclique d'acide méthacrylique et 0 à 10 % en poids d'un motif structural dérivé d'un ester d'acide acrylique, une partie n'ayant pas réagi du monomère polymérisable et le dimère ou le trimère comprenant chacun le monomère polymérisable ; à transférer en continu le mélange de résine du réacteur jusqu'à une extrudeuse bi-vis comprenant un orifice d'évacuation ; puis à évacuer la partie n'ayant pas réagi du monomère polymérisable et le dimère ou le trimère comportant chacun le monomère polymérisable du mélange de résine se trouvant dans l'extrudeuse bi-vis.
PCT/JP2014/078638 2013-10-28 2014-10-28 Procédé de production d'une composition de résine méthacrylique Ceased WO2015064576A1 (fr)

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WO2016021694A1 (fr) * 2014-08-06 2016-02-11 株式会社クラレ Procédé de production de composition de résine (méth)acrylique
CN112979859A (zh) * 2019-12-16 2021-06-18 中国石油天然气股份有限公司 （甲基）丙烯酸酯类聚合物、其制备方法及导光板
CN113619054A (zh) * 2020-05-08 2021-11-09 科思创德国股份有限公司 曲面镜用热塑性树脂基板及其制备方法
WO2021223947A1 (fr) * 2020-05-08 2021-11-11 Covestro Deutschland Ag Substrat de résine thermoplastique pour miroir incurvé et procédé de préparation d'un tel substrat

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CN105111359B (zh) * 2015-09-13 2019-04-02 长春工业大学 一种聚甲基丙烯酸甲酯共聚物的制备方法
WO2017169931A1 (fr) * 2016-03-29 2017-10-05 旭化成株式会社 Composition de résine méthacrylique et corps moulé

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WO2016021694A1 (fr) * 2014-08-06 2016-02-11 株式会社クラレ Procédé de production de composition de résine (méth)acrylique
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CN113619054A (zh) * 2020-05-08 2021-11-09 科思创德国股份有限公司 曲面镜用热塑性树脂基板及其制备方法
WO2021223947A1 (fr) * 2020-05-08 2021-11-11 Covestro Deutschland Ag Substrat de résine thermoplastique pour miroir incurvé et procédé de préparation d'un tel substrat
CN113619054B (zh) * 2020-05-08 2025-08-19 科思创德国股份有限公司 曲面镜用热塑性树脂基板及其制备方法

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TW201527391A (zh) 2015-07-16

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