WO2016129675A1 - Composition de résine optique à base de styrène - Google Patents

Composition de résine optique à base de styrène Download PDF

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Publication number
WO2016129675A1
WO2016129675A1 PCT/JP2016/054138 JP2016054138W WO2016129675A1 WO 2016129675 A1 WO2016129675 A1 WO 2016129675A1 JP 2016054138 W JP2016054138 W JP 2016054138W WO 2016129675 A1 WO2016129675 A1 WO 2016129675A1
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Prior art keywords
styrene
meth
mass
tert
content
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PCT/JP2016/054138
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English (en)
Japanese (ja)
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桂輔 井上
智輝 小林
広平 西野
黒川　欽也
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デンカ株式会社
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Priority to KR1020177024901A priority Critical patent/KR102457996B1/ko
Priority to JP2016574860A priority patent/JP6725431B2/ja
Priority to CN201680010023.8A priority patent/CN107250255B/zh
Publication of WO2016129675A1 publication Critical patent/WO2016129675A1/fr

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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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • 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
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/78—Stabilisers against oxidation, heat, light or ozone

Definitions

  • the present invention relates to an optical styrenic resin composition excellent in hue and transparency, a molded product thereof, and a light guide plate.
  • backlights for liquid crystal display devices: a direct type in which a light source is disposed in front of the display device and an edge light type in which a light source is disposed on a side surface.
  • the light guide plate is used for an edge light type backlight and plays a role of guiding light from a light source disposed on a side surface to the front.
  • Edge-light type backlights are used in TVs, personal computer monitors, mobile phones, car navigation systems, and other applications where thinness is required. Even in televisions (for example, 32 inches or more), the rate at which edge-light type backlights are used is increasing.
  • An acrylic resin typified by PMMA (polymethyl methacrylate) is used for the light guide plate.
  • Patent Document 1 has been proposed as a technique for improving water absorption of a styrene-methyl (meth) acrylate copolymer.
  • the styrene-methyl (meth) acrylate copolymer has a molded article having a poor hue (yellowish) as compared with PMMA, and when used as a backlight, color unevenness may occur on the surface of the liquid crystal display device. . Therefore, Patent Document 2 has been proposed as a technique for improving the hue of styrene-methyl (meth) acrylate copolymer.
  • An object of the present invention is to provide a novel optical styrenic resin composition having good transparency and hue and low water absorption, and a molded product thereof.
  • the molded products it can be suitably used particularly for a light guide plate used in a liquid crystal display device or the like.
  • the present invention is as follows. (1) a styrene- (meth) acrylate copolymer (A) having 20 to 80% by mass of a styrene monomer unit and 80 to 20% by mass of a (meth) acrylate monomer unit; It consists of a hindered phenol antioxidant (B) and a phosphorus antioxidant (C), and the content of (B) is 0.01 to 0. 0 relative to the total amount of (A) to (C). 3% by mass, the content of (C) is 0.001 to 0.3% by mass, and the styrene- (meth) acrylic acid ester copolymer (A) has a residual polymerization inhibitor content of 10 ppm.
  • a styrenic resin composition for optical use wherein (2) The optical styrene resin composition according to (1), wherein the styrene (meth) acrylic acid ester copolymer has a weight average molecular weight of 50,000 to 200,000. (3) The styrene- (meth) acrylic acid ester copolymer (A) contains a styrene monomer containing 0.1 to 20 ppm of 4-tert-butylcatechol, and 6-tert-butyl-2,4.
  • optical styrenic resin composition and molded article of the present invention are excellent in transparency and hue, low in water absorption and excellent in warpage resistance and dimensional stability due to moisture absorption, and are therefore suitably used for optical applications such as light guide plates. I can do it.
  • a to B means not less than A but not more than B.
  • the styrene resin composition of the present invention comprises a styrene- (meth) acrylic acid ester copolymer (A), a hindered phenol antioxidant (B), and a phosphorus antioxidant (C). It is a composition.
  • the styrene- (meth) acrylate copolymer (A) is a copolymer having a styrene monomer unit and a (meth) acrylate monomer unit.
  • the styrene monomer is an aromatic vinyl monomer. Styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, ethyl styrene, pt-butyl styrene and the like are used alone or as a mixture of two or more thereof, and styrene is preferred.
  • (Meth) acrylic acid ester monomers are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methacrylic acid ester of 2-ethylhexyl (meth) acrylate, methyl acrylate, ethyl acrylate, n -Butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate or the like alone or a mixture of two or more thereof, preferably methyl (meth) acrylate.
  • the content of the styrene monomer unit in the styrene- (meth) acrylic acid ester copolymer is 20 to 80% by mass, and the content of the (meth) acrylic acid ester monomer unit is 80 to 20% by mass. is there. More preferably, the content of styrene monomer units is 30 to 60% by mass, and the content of (meth) acrylic acid ester monomer units is 70 to 40% by mass. More preferably, the content of the styrene monomer unit is 45 to 55% by mass, and the content of the (meth) acrylate monomer unit is 55 to 45% by mass.
  • the content of the styrene monomer unit is small, warpage and dimensional deformation may increase due to moisture absorption.
  • the deterioration of a hue or surface hardness may fall, and it may become easy to be damaged.
  • styrene- (meth) acrylic acid ester copolymer those having a small amount of other unit structures can be used.
  • the other unit structure is preferably 5% by mass or less.
  • Other unit structures include a unit structure derived from a vinyl monomer copolymerizable with a styrene monomer and a (meth) acrylate monomer. Examples of the copolymerizable monomer include acrylonitrile, methacrylic acid, acrylic acid, and maleic anhydride.
  • a method for producing a styrene- (meth) acrylic ester copolymer a known method can be employed. For example, it can be produced by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like.
  • a method for operating the reactor any of a continuous type, a batch type (batch type), and a semibatch type can be applied. In view of quality such as transparency and productivity, bulk polymerization or solution polymerization is preferable, and continuous polymerization is preferable.
  • Examples of the bulk polymerization or solution polymerization solvent include alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane.
  • alkylbenzenes such as benzene, toluene, ethylbenzene and xylene
  • ketones such as acetone and methyl ethyl ketone
  • aliphatic hydrocarbons such as hexane and cyclohexane.
  • styrene- (meth) acrylic acid ester copolymer As a polymerization method of the styrene- (meth) acrylic acid ester copolymer, a known method can be adopted.
  • the radical polymerization method is preferable because it is a simple process and excellent in productivity.
  • a polymerization initiator and a chain transfer agent can be used, and the polymerization temperature is preferably in the range of 110 to 170 ° C.
  • the conversion rate of the styrene monomer and the (meth) acrylate monomer is 60% or more at the exit of the polymerization step from the viewpoint of productivity. It is preferable to perform polymerization.
  • polymerization initiator examples include benzoyl peroxide, t-butylperoxybenzoate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5.
  • the addition amount of the polymerization initiator is preferably 0.001 to 0.2% by mass with respect to 100% by mass of the total amount of monomers. More preferably, the content is 0.001 to 0.05% by mass. If the addition amount of the polymerization initiator is too large, the hue may deteriorate.
  • chain transfer agent examples include aliphatic mercaptans, aromatic mercaptans, pentaphenylethane, ⁇ -methylstyrene dimer, and terpinolene.
  • the addition amount of the chain transfer agent is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.2% by mass with respect to 100% by mass in total of the monomers.
  • the thermal stability becomes good.
  • a devolatilization method for removing volatile components such as unreacted monomers and a solvent used for solution polymerization from the solution after the completion of polymerization of the styrene- (meth) acrylate copolymer a known method can be adopted.
  • a vacuum devolatilization tank with a preheater or a vented devolatilization extruder can be used.
  • the temperature of the styrene- (meth) acrylic ester copolymer in the devolatilization step is preferably 200 ° C. to 300 ° C., more preferably 220 ° C. to 260 ° C.
  • the devolatilized molten styrene- (meth) acrylic acid ester copolymer is transferred to the granulation process and extruded into a strand shape from a porous die for cold cut method, air hot cut method, and underwater hot cut method. Can be processed into a pellet shape.
  • Unreacted monomers removed in the devolatilization process and the solvent used for solution polymerization are recovered and purified to remove impurities such as polymerization inhibitors, and then mixed with fresh raw materials for recovery. It is preferable. Since the recovered raw material does not contain a polymerization inhibitor, it is possible to reduce the content of the polymerization inhibitor in the raw material supplied to the polymerization step by using it by mixing it with a fresh raw material.
  • the content of the polymerization inhibitor in the raw material supplied to the polymerization step is preferably less than 12 ppm, more preferably less than 9 ppm, even more preferably less than 6 ppm, and most preferably less than 4 ppm.
  • the fresh raw material is a raw material newly supplied to the production process of the styrene- (meth) acrylic acid ester copolymer, and is referred to as such in order to distinguish it from the recovered raw material.
  • a known method can be adopted as a method for recovering and purifying the unreacted monomer removed in the devolatilization step and the solvent used in the solution polymerization.
  • a method in which unreacted monomer and solvent gas removed in the devolatilization step is condensed and liquefied by a condenser and purified by a flash distillation column to separate and remove high-boiling components.
  • the high-boiling components are first condensed using a condenser or spray tower, etc., and the remaining gas is completely removed by the condenser.
  • the method of condensing is mentioned.
  • 4-tert-butylcatechol has a boiling point of 285 ° C.
  • 6-tert-butyl-2,4-xylenol has a boiling point of 249 ° C., and is separated and removed from the monomer and solvent as a high-boiling component.
  • Boiling point of styrene is 145 ° C
  • boiling point of methyl (meth) acrylate is 101 ° C
  • boiling point of ethylbenzene is 136 ° C).
  • the weight average molecular weight (Mw) of the styrene (meth) acrylic acid ester copolymer is preferably 50,000 to 200,000. More preferably, it is 70,000 to 180,000, more preferably 75,000 to 160,000, and most preferably 80 to 150,000.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is less than 50,000, the strength of the light guide plate may decrease.
  • Mw exceeds 200,000, the fluidity may be lowered and the molding processability may be deteriorated.
  • the weight average molecular weight (Mw) can be controlled by the reaction temperature of the polymerization process, the residence time, the type and addition amount of the polymerization initiator, the type and addition amount of the chain transfer agent, the type and amount of the solvent used during the polymerization, and the like. it can.
  • the weight average molecular weight (Mw) was measured under the following conditions using gel permeation chromatography (GPC).
  • GPC model Shodex GPC-101 manufactured by Showa Denko KK Column: PLgel 10 ⁇ m MIXED-B manufactured by Polymer Laboratories
  • Mobile phase Tetrahydrofuran Sample concentration: 0.2% by mass
  • Temperature 40 ° C oven, 35 ° C inlet, 35 ° C detector
  • Detector Differential refractometer
  • the molecular weight of the present invention is calculated as the molecular weight in terms of polystyrene by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene.
  • the total amount of the residual monomer and the polymerization solvent in the styrene- (meth) acrylic acid ester copolymer is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less. When the total amount of the residual monomer and the polymerization solvent exceeds 0.5% by mass, the heat resistance may be insufficient.
  • the residual monomer and polymerization solvent are the amount of monomer and polymerization solvent remaining in the styrene- (meth) acrylic acid ester copolymer, and examples thereof include styrene, methyl (meth) acrylate, and ethylbenzene. .
  • the amount of the residual monomer and the polymerization solvent can be adjusted by the constitution of the devolatilization process and the conditions of the devolatilization process.
  • the amount of the residual monomer and the polymerization solvent was determined by accurately weighing 0.2 g of a styrene- (meth) acrylate copolymer and dissolving it in 10 ml of tetrahydrofuran containing p-hour ethylbenzene as an internal standard substance.
  • Capillary gas chromatograph GC-4000 (manufactured by GL Sciences Inc.) Column: GS Science Co., Ltd.
  • InertCap WAX inner diameter 0.25 mm, length 30 m, film thickness 50 ⁇ m
  • Injection temperature 180 ° C
  • Detector temperature 210 ° C Split ratio: 5/1
  • the total amount of dimer or trimer (hereinafter referred to as oligomer) of styrene monomer and (meth) acrylate monomer in the styrene- (meth) acrylate copolymer is 2% by mass. The following is preferable. More preferably, it is 1 mass% or less. When the total amount of oligomers exceeds 1% by mass, heat resistance as a light guide plate may be insufficient.
  • the oligomer was measured by dissolving 200 mg of a styrene- (meth) acrylic acid ester copolymer in 2 mL of 1,2-dichloromethane, adding 2 mL of methanol to precipitate the copolymer, allowing it to stand, The liquid was measured under the following conditions using a gas chromatograph.
  • Gas chromatograph HP-5890 (manufactured by Hewlett-Packard Company) Column: DB-1 (ht) 0.25 mm ⁇ 30 m, film thickness 0.1 ⁇ m
  • Injection temperature 250 ° C
  • Detector temperature 300 ° C
  • Split ratio 50/1
  • Internal reference material n-eicosane Carrier gas: Nitrogen
  • the Vicat softening point of the styrene- (meth) acrylic acid ester copolymer is preferably 95 ° C. or higher, and more preferably 98 ° C. or higher. If the Vicat softening point is less than 95 ° C., the heat resistance is insufficient, and the molded product may be deformed depending on the use environment. (The Vicat softening temperature was tested in accordance with JIS K 7206 at a heating rate of 50 ° C./hr and a test load of 50 N.)
  • the content of the hindered phenol antioxidant (B) in the styrene resin composition is 0.01 to 0.3% by mass with respect to the total amount of (A) to (C).
  • the amount is preferably 0.02 to 0.2% by mass, more preferably 0.03 to 0.15% by mass, and still more preferably 0.04 to 0.1% by mass. If the content of the hindered phenol-based antioxidant (B) is too small, the hue improving effect is not obtained, and if it is too much, the hue may be deteriorated.
  • the hindered phenol antioxidant (B) is an antioxidant having a phenolic hydroxyl group in the basic skeleton.
  • examples of the hindered phenol antioxidant include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, ethylene bis (oxyethylene) bis [3- (5-tert-butyl- 4-hydroxy-m-tolyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro [5.5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,6-bis (octyl) Thiomethyl) -o-cresol, 4,6-bis [(dodecylthi
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) Propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. More preferred is octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.
  • Hindered phenolic antioxidants may be used alone or in combination of two or more.
  • the content of the phosphorus-based antioxidant (C) in the styrene-based resin composition is 0.001 to 0.3% by mass with respect to the total amount of (A) to (C).
  • the content is preferably 0.001 to 0.1% by mass, more preferably 0.001 to 0.05% by mass, and still more preferably 0.001 to 0.02% by mass.
  • a hue may deteriorate.
  • mold contamination may occur during injection molding or roll contamination may occur during extrusion of a plate-shaped molded product.
  • Phosphorous antioxidant (C) is a phosphite that is a trivalent phosphorus compound.
  • Phosphorous antioxidants include, for example, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butylbenz [d, f ] [1,3,2] dioxaphosphine, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5.5] undecane, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyl) Oxy) phosphorus, tris (2,4-di-tert-butylphenyl) phosphite
  • the total ⁇ (B) + (C) ⁇ of the content of the hindered phenolic antioxidant (B) and the content of the phosphorus antioxidant (C) in the styrene resin composition is (A) to ( It is 0.011 to 0.6% by mass relative to the total amount of C).
  • the content is preferably 0.021 to 0.25% by mass, more preferably 0.031 to 0.2% by mass, and still more preferably 0.041 to 0.12% by mass. If the total amount of the content of the hindered phenolic antioxidant (B) and the content of the phosphorus antioxidant (C) ⁇ (B) + (C) ⁇ is too small, there will be no effect of improving the hue. Hue may deteriorate.
  • a method for producing a styrene resin composition from a styrene- (meth) acrylic acid ester copolymer (A), a hindered phenol antioxidant (B) and a phosphorus antioxidant (C) is known.
  • the method can be adopted.
  • a styrene- (meth) acrylic acid ester copolymer is used in the production step (A) such as polymerization step, devolatilization step, granulation step, etc. in the hindered phenolic antioxidant (B) and phosphorus antioxidant ( There is a method of adding C), which is preferably added after the unreacted monomer and solvent are removed in the devolatilization step.
  • a hindered phenol antioxidant (B) and a phosphorus antioxidant (C) in a molten state are added to a styrene- (meth) acrylate ester copolymer extracted from the devolatilization tank.
  • a static mixer or when using a vented devolatilizing extruder, add a hindered phenolic antioxidant (B) and a phosphorus antioxidant (C) after the venting zone.
  • it can be added directly at the time of molding the styrene- (meth) acrylic acid ester copolymer (A), or it can be added by preparing a master batch.
  • the styrene resin composition may contain mineral oil as long as the transparency is not impaired. Also includes additives such as internal lubricants such as stearic acid and ethylene bisstearylamide, sulfur antioxidants, lactone antioxidants, UV absorbers, hindered amine stabilizers, antistatic agents, external lubricants, etc. It may be. As the external lubricant, ethylene bisstearylamide is suitable.
  • the ultraviolet absorber has a function of suppressing deterioration and coloring due to ultraviolet rays.
  • benzophenone, benzotriazole, triazine, benzoate, salicylate, cyanoacrylate, malonic ester, formamidine UV absorbers such as those of the system.
  • a light stabilizer such as a hindered amine may be used in combination.
  • the polymerization inhibitor is added to the monomer in order to prevent unintended polymerization from occurring during storage of the monomer.
  • the polymerization inhibitor include catechols such as 4-tert-butylcatechol, phenols such as 6-tert-butyl-2,4-xylenol and paramethoxyphenol, hydroquinone, 2,2,6,6, and the like. -Tetramethylpiperidinyl-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl and the like.
  • the content of the polymerization inhibitor remaining in the styrene- (meth) acrylic acid ester copolymer is preferably less than 10 ppm, more preferably less than 5 ppm, and even more preferably less than 3 ppm.
  • the polymerization inhibitor includes a styrene monomer used for copolymerization of a styrene- (meth) acrylate ester copolymer, 4-tert-butylcatechol derived from a (meth) acrylate ester monomer, and 6- tert-butyl-2,4-xylenol and the like.
  • the content of 6-tert-butyl-2,4-xylenol remaining in the styrene- (meth) acrylic acid ester copolymer is preferably less than 4 ppm, more preferably less than 2 ppm. If the content of the polymerization inhibitor is too large, the polymerization inhibitor itself may be modified during the polymerization reaction or molding process, becoming a colored substance and deteriorating transparency and hue.
  • the content of the polymerization inhibitor remaining in the copolymer can be controlled by the content of the polymerization inhibitor in the monomer used for the copolymerization. Also, in continuous bulk polymerization or solution polymerization, the content of the polymerization inhibitor remaining in the copolymer is efficiently reduced by reusing the recovered and purified unreacted monomer. can do.
  • the 4-tert-butylcatechol concentration and 6-tert-butyl-2,4-xylenol concentration in the styrene- (meth) acrylic acid ester copolymer were first dissolved in tetrahydrofuran (adjusted to 50 mg / ml). ) After that, trimethylsilyl derivatization treatment was performed using BSTFA (N, O-bis (trimethylsilyl) trifluoroacetamide), and the supernatant separated by centrifugation was analyzed by gas chromatography mass spectrometry (GC / MS). The measurement was performed under the following conditions. A calibration curve prepared in advance was used to determine the concentration.
  • GC / MS measurement conditions GC device: Agilent 6890 Column: DB-1 (0.25 mm id x 30 m) Liquid phase thickness 0.25mm Column temperature: 40 ° C. (5 min hold) ⁇ (20 ° C./min temperature increase) ⁇ 320 ° C (6 min hold) 25 min total Inlet temperature: 320 ° C Injection method: Split method (split ratio 1: 5) Sample volume: 2 ⁇ l MS equipment: Agilent MSD5973 Ion source temperature: 230 ° C Interface temperature: 320 ° C Ionization method: Electron ionization (EI) method Measurement method: SCAN method (scan range m / z 10 to 800)
  • the styrenic monomer preferably contains 0.1 to 20 ppm of 4-tert-butylcatechol as a polymerization inhibitor, more preferably 0.1 to 12 ppm, and even more preferably 0.1 to 7 ppm. It is.
  • concentration of 4-tert-butylcatechol in the styrene monomer exceeds 20 ppm, the 4-tert-butylcatechol itself is modified and becomes a colored substance. Therefore, a styrene- (meth) acrylate ester copolymer Transparency and hue may deteriorate.
  • the (meth) acrylic acid ester monomer preferably contains 0.1 to 20 ppm, more preferably 0.1 to 12 ppm of 6-tert-butyl-2,4-xylenol as a polymerization inhibitor. More preferably, it is 0.1 to 7 ppm.
  • concentration of 6-tert-butyl-2,4-xylenol in the (meth) acrylic acid ester monomer exceeds 20 ppm, 6-tert-butyl-2,4-xylenol itself is denatured, Therefore, the transparency and hue of the styrene- (meth) acrylic acid ester copolymer may be deteriorated.
  • the polymerization inhibitor of styrene monomer or (meth) acrylic acid ester monomer can be removed or reduced by adsorption removal with activated alumina.
  • the 4-tert-butylcatechol in the styrene monomer and the 6-tert-butyl-2,4-xylenol concentration in the (meth) acrylic acid ester monomer were first set to 50 mg / ml for each monomer. After being mixed with tetrahydrofuran so as to be, trimethylsilyl derivatization treatment was performed using BSTFA (N, O-bis (trimethylsilyl) trifluoroacetamide), and gas chromatography / mass spectrometry (GC / MS) was used. It measured on the same conditions as the measurement of a (meth) acrylic acid ester-type copolymer. A calibration curve prepared in advance was used to determine the concentration.
  • the styrene resin composition can be formed into a molded product by a known method such as extrusion molding, injection molding, compression molding, or blow molding.
  • a plate-shaped molded product can be produced by extrusion molding and processed into a light guide plate or the like.
  • the styrenic resin composition of the present invention is excellent in thermal stability, it collects and grinds unfinished parts such as sheet end materials during extrusion molding and spools and runners during injection molding, and mixes them with virgin raw materials. Can be used.
  • the light guide plate is a member having a function of guiding light incident from the end face of the plate-shaped molded product to the surface side of the plate-shaped molded product by a reflection pattern formed on one surface of the plate-shaped molded product and emitting light.
  • the reflection pattern can be formed by a method such as a screen printing method, a laser processing method, or an ink jet method.
  • a prism pattern or the like can be provided on the opposite surface (light emitting surface) of the surface on which the reflection pattern is formed.
  • the reflection pattern and prism pattern of the plate-shaped molded product can be formed when the plate-shaped molded product is molded. For example, it can be formed by a mold shape in injection molding, or by roll transfer in extrusion molding.
  • Optical use refers to use in products in which components include light sources such as LEDs, fluorescent lamps, and incandescent lamps.
  • components include light sources such as LEDs, fluorescent lamps, and incandescent lamps.
  • Examples of the product include a television, a desktop personal computer, a notebook personal computer, a mobile phone, a car navigation, indoor lighting, and the like.
  • the optical styrene resin composition preferably has an average value of spectral transmittance at a wavelength of 350 nm to 800 nm measured at an optical path length of 115 mm of 87.0% or more, more preferably 87.5% or more, More preferably, it is 88.0% or more, and most preferably 88.5% or more.
  • the YI value measured in accordance with JIS K7105 at a visual field of 2 ° with a C light source is 3.5 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. And most preferably 2.0 or less.
  • styrene- (meth) acrylic ester copolymer A-1 The styrene- (meth) acrylic acid ester copolymer was produced by continuous solution polymerization by a radical polymerization method. A complete mixing tank type stirring tank was used as the first reactor, a plug flow type reactor with a static mixer was used as the second reactor, and the polymerization process was configured by connecting in series. The capacity of the first reactor was 30L, and the capacity of the second reactor was 12L.
  • fresh MMA 6-tert-butyl-2,4-xylenol
  • fresh MMA 6-tert-butyl-2,4-xylenol
  • TBX concentration of (referred to as TBX) was 4.9 ppm.
  • Resh Sty concentration of 4-tert-butylcatechol (hereinafter referred to as “TBC”) was 10.2 ppm.
  • fresh EB industrially used ethylbenzene
  • gases such as a monomer and a polymerization solvent separated from a vacuum devolatilizer described later were condensed by a condenser and purified by a flash distillation column as a recovered raw material.
  • concentrations of TBX and TBC in the recovered raw material were below the lower limit of detection.
  • fresh MMA, fresh Sty and the recovered raw material a raw material solution was prepared so as to have the raw material composition shown in Table 1, and continuously supplied to the polymerization step at a feed flow rate shown in Table 1.
  • the use ratio of the recovered raw materials is as shown in Table 1, and is balanced with the amount separated and purified in the devolatilization tank.
  • t-butylperoxyisopropyl monocarbonate as a polymerization initiator was continuously added to the raw material solution supply line to a concentration of 150 ppm and n-dodecyl mercaptan as a chain transfer agent to a concentration of 500 ppm. .
  • the temperature of the first reactor was adjusted to 135 ° C.
  • the second reactor was adjusted to have a temperature gradient along the flow direction and adjusted to 130 ° C. at the middle portion and 145 ° C. at the outlet portion.
  • the polymer concentration at the outlet of the polymerization process was 65%, and the conversion ratio of methyl (meth) acrylate and styrene was 72%.
  • the polymer solution continuously taken out from the reactor was supplied to a vacuum devolatilization tank equipped with a preheater to separate unreacted methyl (meth) acrylate, styrene, ethylbenzene and the like.
  • the temperature of the preheater was adjusted so that the polymer temperature in the devolatilization tank was 240 ° C., and the pressure in the devolatilization tank was 1 kPa.
  • the polymer was extracted from the vacuum devolatilization tank using a gear pump, extruded into a strand, cooled with cooling water, and then cut to obtain a pellet-shaped styrene- (meth) acrylate copolymer A-1.
  • Table 1 shows the composition of A-1 and the content of the polymerization inhibitor.
  • Sty is an abbreviation for styrene, MMA for methyl (meth) acrylate, and EB for ethylbenzene.
  • the weight average molecular weight of A-1 was 145,000, the total amount of residual monomer and polymerization solvent was 0.07% by mass, and the total amount of residual oligomer was 0.35% by mass.
  • Examples 1 to 22 and Comparative Examples 1 to 7> The hindered phenolic antioxidants (B-1) to (B-3) and phosphorus antioxidants (C-1) shown below are added to the styrene-methyl (meth) acrylate copolymers obtained in the production examples.
  • (C-6) was mixed at the content shown in Table 2, and a sheet molded product of 450 mm ⁇ 500 mm ⁇ 2 mm was obtained while melt-kneading the antioxidant using a sheet extruder manufactured by LEADER.
  • the sheet extruder was composed of a 50 mm ⁇ single-screw extruder, a T die, and three mirror rolls, and sheet extrusion was performed at a cylinder temperature of 225 ° C.
  • Spectral transmittances from 350 nm to 800 nm were measured, and the YI value at a visual field of 2 ° with a C light source was calculated according to JIS K7105.
  • the transmittance shown in Table 1 indicates an average transmittance at a wavelength of 380 nm to 780 nm.
  • Table 2 shows the evaluation results.
  • the styrene- (meth) acrylic acid ester copolymer and the styrene resin composition of the present invention and the molded product thereof have low water absorption and excellent transparency and hue in a long optical path.
  • televisions, desktop personal computers It can be suitably used for light guide plate applications such as notebook personal computers, mobile phones, car navigation systems, and indoor lighting.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'objectif de la présente invention est de fournir un copolymère de styrène-ester (méth)acrylique ayant une excellente transparence et une excellente teinte, une faible absorption d'eau et une excellente stabilité dimensionnelle ou une excellente résistance à la déformation due à l'absorption d'humidité. L'invention concerne une composition de résine optique à base de styrène comprenant (A) un copolymère de styrène-ester (méth)acrylique ayant 20 à 80 % en masse de motifs monomères à base de styrène et 80 à 20 % en masse de motifs monomères à base d'ester (méth)acrylique, (B) un antioxydant à base de phénol encombré et (C) un antioxydant à base de phosphore, la teneur en composant (B) par rapport à la teneur totale en composants (A) à (C) étant de 0,01 à 0,3 % en masse, et la teneur en composant (C) par rapport à la teneur totale en composants (A) à (C) étant de 0,001 à 0,3 % en masse.
PCT/JP2016/054138 2015-02-12 2016-02-12 Composition de résine optique à base de styrène WO2016129675A1 (fr)

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WO2019138997A1 (fr) * 2018-01-09 2019-07-18 デンカ株式会社 Composition de résine à base de styrène, article moulé et plaque de guidage de lumière
WO2020217718A1 (fr) * 2019-04-23 2020-10-29 デンカ株式会社 Composition de résine de styrène, article moulé et plaque de guidage de lumière
WO2021132001A1 (fr) * 2019-12-24 2021-07-01 デンカ株式会社 Plaque de diffusion de lumière et unité de source de lumière de surface directe
WO2021199501A1 (fr) * 2020-04-01 2021-10-07 デンカ株式会社 Composition de résine optique à base de styrène, plaque de guidage de lumière, et unité de source de lumière plane de type lumière latérale
WO2023190540A1 (fr) * 2022-03-30 2023-10-05 デンカ株式会社 Composition de résine contenant un copolymère, procédé de production associé et corps moulé la comprenant
WO2023218994A1 (fr) * 2022-05-13 2023-11-16 デンカ株式会社 Composition de résine à base de styrène à usage optique, plaque de guidage de lumière, unité de source de lumière de surface de type à émission latérale, plaque de diffusion de lumière, et unité de source de lumière de surface de type directement sous-jacent

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CN109575174A (zh) * 2018-12-20 2019-04-05 重庆颖锋兴瑞光电科技有限公司 一种改性聚苯乙烯树脂
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WO2019138997A1 (fr) * 2018-01-09 2019-07-18 デンカ株式会社 Composition de résine à base de styrène, article moulé et plaque de guidage de lumière
KR20200103639A (ko) 2018-01-09 2020-09-02 덴카 주식회사 스티렌계 수지 조성물, 성형품 및 도광판
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WO2021132001A1 (fr) * 2019-12-24 2021-07-01 デンカ株式会社 Plaque de diffusion de lumière et unité de source de lumière de surface directe
WO2021199501A1 (fr) * 2020-04-01 2021-10-07 デンカ株式会社 Composition de résine optique à base de styrène, plaque de guidage de lumière, et unité de source de lumière plane de type lumière latérale
WO2023190540A1 (fr) * 2022-03-30 2023-10-05 デンカ株式会社 Composition de résine contenant un copolymère, procédé de production associé et corps moulé la comprenant
WO2023218994A1 (fr) * 2022-05-13 2023-11-16 デンカ株式会社 Composition de résine à base de styrène à usage optique, plaque de guidage de lumière, unité de source de lumière de surface de type à émission latérale, plaque de diffusion de lumière, et unité de source de lumière de surface de type directement sous-jacent

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