WO2021199501A1 - Composition de résine optique à base de styrène, plaque de guidage de lumière, et unité de source de lumière plane de type lumière latérale - Google Patents

Composition de résine optique à base de styrène, plaque de guidage de lumière, et unité de source de lumière plane de type lumière latérale Download PDF

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Publication number
WO2021199501A1
WO2021199501A1 PCT/JP2020/045195 JP2020045195W WO2021199501A1 WO 2021199501 A1 WO2021199501 A1 WO 2021199501A1 JP 2020045195 W JP2020045195 W JP 2020045195W WO 2021199501 A1 WO2021199501 A1 WO 2021199501A1
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Prior art keywords
styrene
resin composition
tert
antioxidant
phosphorus
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PCT/JP2020/045195
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English (en)
Japanese (ja)
Inventor
山口　泰生
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デンカ株式会社
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Priority to KR1020227037676A priority Critical patent/KR20220162743A/ko
Priority to CN202080099327.2A priority patent/CN115397913A/zh
Priority to MX2022011738A priority patent/MX2022011738A/es
Priority to JP2022511521A priority patent/JPWO2021199501A1/ja
Publication of WO2021199501A1 publication Critical patent/WO2021199501A1/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
    • 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
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • 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
    • 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
    • G02B6/0065—Manufacturing aspects; Material aspects
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133615—Edge-illuminating devices, i.e. illuminating from the side

Definitions

  • the present invention relates to an optical styrene resin composition, a light guide plate, and an edge light type surface light source unit.
  • the backlight of the liquid crystal display device includes a direct type in which the light source is arranged on the back surface of the display device and an edge light type in which the light source is arranged on the side surface.
  • the edge light type backlight uses a part called a light guide plate that guides the light of the light source placed on the side to the entire surface of the display device, and uses a TV, a monitor of a desktop personal computer, a notebook personal computer, a mobile phone, and a car. It is used in a wide range of applications such as navigation monitors.
  • a backlight using a light guide plate is also used as a lighting device, a signboard, or the like.
  • the light guide plate Since the light guide plate has a relatively long light transmission distance and a large light loss at the optical path length, it is required to have a particularly high light transmittance. Therefore, as the material of the light guide plate, an acrylic resin typified by polymethyl methacrylate (PMMA) is used. However, since PMMA has high water absorption, the light guide plate may warp or change in size due to water absorption. In addition, since it is easily thermally decomposed during molding, there is a problem that the molded product tends to have a poor appearance when molded at a high temperature. In order to improve these problems, it has been proposed to use a styrene-methyl acrylate copolymer as a material for a light guide plate (see, for example, Patent Document 1).
  • a styrene resin made from a styrene monomer is excellent in low water absorption, but has a problem that the molded product becomes cloudy due to environmental changes such as temperature and humidity. Specifically, when a molded product is exposed to a high temperature and high humidity environment to a room temperature environment or a room temperature environment to a low temperature environment, the moisture uniformly present in the molded product becomes unstable and undergoes phase separation. , Small defects occur in the molded product, and as a result, cloudiness occurs.
  • optical styrene resin composition constituting the light guide plate it was difficult for the optical styrene resin composition constituting the light guide plate to simultaneously satisfy transparency, hue, hue stability, extrusion stability, dimensional stability, moisture-heat whitening resistance, and strength.
  • the present invention has been made in view of such problems, and provides a styrene-based resin composition for a light guide plate that simultaneously satisfies hue, hue stability, extrusion stability, dimensional stability, moisture-heat whitening resistance, and strength. It is a thing.
  • a styrene resin (A) which is a copolymer containing 51 to 99% by mass of a styrene-based monomer unit and 1 to 49% by mass of a (meth) acrylic acid ester-based monomer unit is oxidized.
  • An optical styrene resin composition containing an inhibitor (B), wherein the antioxidant (B) is a phosphorus-based antioxidant (B-1), a phenol-based antioxidant (B-2), and the like.
  • phosphorus-phenolic antioxidants B-3
  • the present inventors have found that the contents of the styrene-based monomer unit and the (meth) acrylic acid ester-based monomer unit in the styrene-based resin and the content of the antioxidant are within a predetermined range.
  • the present invention was completed by finding that the styrene-based resin composition for optics simultaneously satisfies hue, hue stability, extrusion stability, dimensional stability, moisture-heat whitening resistance, and strength. ..
  • the phosphorus-based antioxidant (B-1) is 2,2'-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, tris (2,).
  • the phenolic antioxidant (B-2) is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [3- (5). -Tert-Butyl-4-hydroxy-m-trill) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2-[ Selected from 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane It is at least one kind of styrene-based resin composition for optics.
  • the phosphorus-phenolic antioxidant (B-3) is 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-.
  • a styrene-based resin composition for optics which is tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepine.
  • the optical styrene resin composition is an optical styrene resin composition containing 0.1 to 20 ppm of 6-tert-butyl-2,4-xylenol.
  • the optical styrene resin composition is an optical styrene resin composition containing 0.1 to 500 ppm of sulfur.
  • the weight average molecular weight (Mw) of the styrene resin (A) is 50,000 to 400,000, and the ratio of the weight average molecular weight (Mw) of the styrene resin (A) to the number average molecular weight (Mn).
  • Mw / Mn is an optical styrene resin composition having a molecular weight of 1.0 to 3.0.
  • it is an optical styrene resin composition having an average transmittance of 85% or more at a wavelength of 380 to 780 nm at an initial optical path length of 115 mm.
  • a light guide plate obtained by molding the above-mentioned optical styrene resin composition.
  • a light guide plate having a thickness of 1.0 to 3.0 mm is preferable.
  • an edge light type surface light source unit having the light guide plate and a light source for supplying light to an end surface of the light guide plate.
  • the styrene-based resin composition according to the embodiment of the present invention is an optical styrene-based resin composition containing a styrene-based resin (A) and an antioxidant (B).
  • the styrene-based resin (A) is a resin obtained by copolymerizing a styrene-based monomer and a monomer containing a (meth) acrylic acid ester-based monomer.
  • the styrene-based resin (A) is a copolymer containing 51 to 99% by mass of the styrene-based monomer unit and 1 to 49% by mass of the (meth) acrylic acid ester-based monomer unit, and is preferably a styrene-based single amount.
  • the content of the (meth) acrylic acid ester-based monomer unit of the styrene resin (A) is, for example, 1,5,10,15,16,17,18,19,20,25,30. , 35, 40, 45, 50% by mass, and may be within the range between any two of the numerical values exemplified here.
  • styrene-based monomer examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • the styrene-based monomer is preferably styrene.
  • Examples of the (meth) acrylic acid ester-based monomer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid.
  • -Alkylate (meth) acrylic acid such as butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.
  • (Meta) Acrylic acid aryl ester such as (meth) phenyl acrylate, (meth) benzyl acrylate; (meth) acrylate cyclohexyl, (meth) acrylate 4-t-butylcyclohexyl, (meth) acrylate tricyclo Cycloalkyl esters of (meth) acrylic acid such as decanyl and adamantyl (meth) acrylate; glycidyl (meth) acrylate; dicyclopentadienyl (meth) acrylate and the like can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
  • the (meth) acrylic acid ester-based monomer is preferably a (meth) acrylic acid alkyl ester, and more preferably methyl methacrylate.
  • the styrene resin (A) may be a copolymer obtained by copolymerizing with a styrene monomer and a monomer copolymerizable with the (meth) acrylic acid ester monomer.
  • the copolymerizable monomer include (meth) acrylic acid such as acrylic acid and methacrylic acid; vinyl cyanide such as acrylonitrile and methacrylic acid; ⁇ , ⁇ -ethylene unsaturated such as maleic anhydride and fumaric acid.
  • Saturated carboxylic acids; imides such as phenylmaleimide and cyclohexylmaleimide can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
  • the weight average molecular weight (Mw) of the styrene resin (A) is preferably 50,000 to 400,000, more preferably 100,000 to 140,000.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the styrene resin (A) is preferably 1.0 to 3.0, more preferably 1.5 to. It is 2.5. By setting it in such a range, both moldability and strength of the light guide plate can be achieved. If the weight average molecular weight (Mw) is less than 50,000, the strength of the molded product may be insufficient, and if it exceeds 400,000, the moldability may decrease. Further, if the ratio (Mw / Mn) of the number average molecular weight (Mn) is less than 1.0, the moldability may decrease, and if it exceeds 3.0, the strength of the molded product may decrease.
  • the antioxidant (B) contains at least one of a phosphorus-based antioxidant (B-1), a phenol-based antioxidant (B-2), and a phosphorus-phenolic antioxidant (B-3). ..
  • a phosphorus-based antioxidant (B-1) and a phosphorus-phenolic antioxidant (B-3) are added to 100 parts by mass of the styrene-based resin (A) in total. Contains 1 to 0.5 parts by mass. Within such a range, transparency, hue, hue stability, extrusion stability, dimensional stability, moisture heat whitening resistance and strength can be satisfied at the same time.
  • the total content of the phosphorus-based antioxidant (B-1) and the phosphorus-phenol-based antioxidant (B-3) is, specifically, for example, 0. It is 1, 0.2, 0.3, 0.4, 0.5 parts by mass, and may be within the range between any two of the numerical values exemplified here.
  • a phenol-based antioxidant (B-2) and a phosphorus-phenolic antioxidant (B-3) are added to 100 parts by mass of the styrene-based resin (A) in total. It contains 0.01 to 0.5 parts by mass, preferably 0.05 to 0.3 parts by mass. Within such a range, transparency, hue, hue stability, extrusion stability, dimensional stability, moisture heat whitening resistance and strength can be satisfied at the same time.
  • the total content of the phenol-based antioxidant (B-2) and the phosphorus / phenol-based antioxidant (B-3) is, specifically, for example, 0.
  • the phosphorus-based antioxidant (B-1) is a (sub) phosphate ester that does not have a phenolic hydroxyl group in the basic skeleton, and is preferably a phosphite ester that is a trivalent phosphorus compound.
  • Phenyl antioxidants (B-1) include, for example, 2,2'-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, tris (2,4-).
  • Di-tert-butylphenyl) phosphite 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5, 5]
  • Undecane tetrakis (2,4-di-tert-butylphenyl) [1,1 biphenyl] -4,4 diylbisphosphonite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl
  • Phenolic antioxidant (B-2) is an antioxidant that has a phenolic hydroxyl group in its basic skeleton and is not a (sub) phosphate ester.
  • Phenolic antioxidants (B-2) include, for example, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and ethylenebis (oxyethylene) bis [3- (5-tert).
  • the phosphorus-phenolic antioxidant (B-3) is a (sub) phosphoric acid ester having a phenolic hydroxyl group in the basic skeleton, and preferably a trivalent phosphorus compound having a phenolic hydroxyl group in the basic skeleton.
  • Phosphorus-phenolic antioxidants (B-3) include, for example, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-.
  • the optical styrene resin composition preferably contains 6-tert-butyl-2,4-xylenol (TBX) at 0.1 to 20 ppm, more preferably 1 to 5 ppm. Within such a range, a light guide plate having excellent hue and transmittance can be obtained.
  • the TBX content is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, It is 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20ppm, and any two of the numerical values exemplified here. It may be within the range between.
  • the optical styrene resin composition preferably contains t-butylcatechol (TBC) at 0.1 to 100 ppm, more preferably 1 to 20 ppm. Within such a range, a light guide plate having excellent hue and transmittance can be obtained.
  • TBC content is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,30,40,50,60,70,80, It is 90,100 ppm, and may be in the range between any two of the numerical values exemplified here.
  • the optical styrene resin composition preferably contains 0.1 to 500 ppm of sulfur, more preferably 1 to 400 ppm, and further preferably 5 to 350 ppm. Within such a range, a light guide plate having a particularly excellent hue can be obtained.
  • the sulfur content is, for example, 0.1,0.5,1,2,3,4,5,6,7,8,9,10,100,200,300,400,500 ppm. It may be within the range between any two of the numerical values exemplified here.
  • the optical styrene resin composition includes a sulfur-based antioxidant, a lactone-based antioxidant, an ultraviolet absorber, a hindered amine-based stabilizer, an antioxidant, a hydrophilic additive, as long as the characteristics of the present invention are not impaired.
  • Higher fatty acids such as liquid paraffin (mineral oil), polyethylene wax, microcrystallin wax, brewing agent, lauric acid, myristic acid, palmitic acid, stearic acid, higher grades such as stearic acid amide, erucic acid amide, ethylene bisstearic acid amide, etc. It may contain a release agent such as a higher alcohol such as fatty acid amide, myristyl alcohol, cetyl alcohol and stearyl alcohol.
  • the styrene-based resin composition has an average transmittance of 380 to 780 nm at an initial optical path length of 115 mm, preferably 85% or more, and more preferably 86% or more.
  • the styrene resin composition has an average transmittance of preferably 80% or more, more preferably 83% or more, still more preferably 85% or more at a wavelength of 380 to 780 nm at an optical path length of 115 mm after a long-term durability test. ..
  • the styrene-based resin composition has a YI value of preferably 6.0 or less, and more preferably 4.0 or less at the initial optical path length of 115 mm.
  • the styrene resin composition has a YI value of preferably 7.0 or less, more preferably 5.0 or less, at an optical path length of 115 mm after a long-term durability test.
  • the difference ( ⁇ YI) between the YI value at the initial optical path length of 115 mm and the YI value at the optical path length of 115 mm after the long-term durability test is preferably 3.0 or less. It is more preferably 1.5 or less, still more preferably 1.0 or less.
  • the Vicat softening temperature of the styrene resin composition is preferably 95 to 104 ° C, more preferably 100 to 104 ° C. If the Vicat softening temperature is less than 95 ° C., the heat resistance is insufficient, and the light guide plate may be deformed depending on the usage environment.
  • Examples of the polymerization method of the styrene resin (A) include known styrene polymerization methods such as a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. From the viewpoint of quality and productivity, the bulk polymerization method and the solution polymerization method are preferable, and continuous polymerization is preferable.
  • alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane can be used.
  • a polymerization initiator When the styrene resin (A) is polymerized, a polymerization initiator, a chain transfer agent, a cross-linking agent and other polymerization aids, and other polymerization aids can be used, if necessary.
  • a radical polymerization initiator is preferable, and for example, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 2,2-di (t-butylperoxy) butane, which are known and commonly used, are preferable.
  • Peroxyketals such as di (4,5-di-t-butylperoxycyclohexyl) propane, 1,1-di (t-amylperoxy) cyclohexane, cumenehydroperoxide, t-butylhydroperoxide and the like.
  • alkyl peroxides such as t-butylperoxyacetate, t-amylperoxyisononanoate, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t -Dialkyl peroxides such as hexyl peroxide, peroxyesters such as t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxyisopropylcarbonate, polyether Peroxycarbonates such as tetrakis (t-butylperoxycarbonate), N, N'-azobis (cyclohexane-1-carbonitrile), N, N'-azobis (2-methylbutyronitrile), N, N' -Azobis (2,4-dimethylvaleronitrile), N, N'-azobis [2- (hydroxymethyl)
  • chain transfer agent examples include aliphatic mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, thiocarboxylic acids such as aromatic mercaptan, thioglycolic acid and mercaptopropionic acid, ethylene glycol, tetraethylene glycol, neopentyl glycol and trimethylol.
  • Polyfunctional mercaptan, pentaphenylethane, ⁇ -methylstyrene dimer, terpinolene and the like obtained by esterifying polyhydric alcohol hydroxyl groups such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol with thioglycolic acid or mercaptopropionic acid.
  • polyhydric alcohol hydroxyl groups such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol with thioglycolic acid or mercaptopropionic acid.
  • aliphatic mercaptans, aromatic mercaptans, thiocarboxylic acids, and polyfunctional mercaptans are preferable from the viewpoint of being able to adjust the sulfur content.
  • the styrene resin (A) can be produced by a method including a polymerization step, a volatilization step, and a granulation step.
  • a known complete mixing tank type stirring tank, a tower reactor, or the like is used, and the polymerization reaction is controlled by adjusting the polymerization temperature or the like so as to obtain the target molecular weight, molecular weight distribution, and reaction conversion rate.
  • the polymerization solution containing the polymer that has left the polymerization step is transferred to the devolatile step, and the unreacted monomer and the polymerization solvent are removed.
  • the devolatilization process consists of a vacuum devolatilization tank with a heater and a devolatilization extruder with a vent.
  • the molten polymer that has left the devolatile step is transferred to the granulation step.
  • the molten resin is extruded into a strand shape from a porous die and processed into a pellet shape by a cold cut method, an aerial hot cut method, or an underwater hot cut method.
  • the styrene-based resin composition can be produced by adding an antioxidant (B) to the styrene-based resin (A).
  • the antioxidant (B) may be added at the time of polymerization of the styrene resin (A), or after the styrene resin (A) is polymerized, the antioxidant (B) is dry-blended and melt-kneaded to produce the product. You may. Further, a pellet-shaped masterbatch obtained by previously melt-kneading the antioxidant (B) with a small amount of styrene-based resin is prepared, and the styrene-based resin (A) and the masterbatch are dry-blended and then melt-kneaded. You may adjust.
  • the content and sulfur content of t-butylcatechol or 6-tert-butyl-2,4-xylenol in the styrene resin composition are adjusted at the start of polymerization of the styrene resin (A) and subsequently removed.
  • the content can be adjusted in the volatilization process and the like. Further, it may be added and adjusted at an arbitrary timing.
  • the light guide plate according to the embodiment of the present invention is a molded product obtained by molding the above-mentioned optical styrene resin composition.
  • the light guide plate is a light guide plate that can be used in an edge light type surface light source unit.
  • the light guide plate may have an uneven shape on the surface of the light guide plate. More specifically, the surface of the light guide plate may have a plurality of lenticular-shaped and / or prism-shaped protrusions.
  • the convex portion is preferably provided on at least one surface of the light guide plate, and particularly on one surface which is the front surface (light emitting surface) of the light guide plate. Other surfaces may be provided if necessary, but it is more preferable that the other surfaces are provided only on the front surface (light emitting surface) of the light guide plate.
  • the lenticular-shaped convex portion is an arc-shaped convex portion
  • the edge shape of the cross section is an arc-shaped ridge.
  • the prism shape is an arcuate convex portion
  • the edge shape of the cross section is a triangular chevron shape.
  • the convex portions may be formed so as to have a plurality of rows and a parallel relationship with each other. Further, the convex portion can be integrally formed on the light guide plate.
  • the thickness of the light guide plate is 1.0 to 3.0 mm, preferably 1.5 to 2.5 mm, and more preferably 1.6 to 2.4 mm. Within such a range, it is easy to manufacture a light guide plate having excellent moldability such as excellent extrusion stability and strength in molding of a styrene resin composition to which an antioxidant is added.
  • the light guide plate according to an embodiment of the present invention is obtained by molding the above-mentioned styrene resin composition, and as a molding method, known methods such as sheet extrusion molding, injection molding, and compression molding can be used. However, continuous sheet extrusion molding provided with a surface shape transfer mold is preferable in terms of productivity and easy enlargement of the molded product.
  • the sheet extrusion molding include an extrusion step of supplying a resin in a heat-melted state to a feed block to continuously produce an extrusion sheet from a die, and a pressing step of sandwiching the resin sheet between a pressure-bonding roll and a cooling roll.
  • the light guide plate may have an uneven shape on the front surface (light emitting surface), and the back surface may be subjected to a reflection process for diffusely reflecting light.
  • the reflection processing include silk printing, inkjet printing, and a method of imparting dot-shaped irregularities by laser irradiation.
  • dot pattern printing ink having fine particles that diffuse light can be used. can.
  • the edge light type surface light source unit according to the embodiment of the present invention is an edge light type surface light source unit having the light guide plate and a light source for supplying light to the end surface of the light guide plate.
  • the edge light type surface light source unit is suitably used as a surface light source device for a liquid crystal display device.
  • a polymerization process is configured by connecting the first reactor, which is a complete mixing type stirring tank, and the second reactor, which is a plug-flow type reactor with a static mixer, in series. Then, the styrene-based resin was produced under the conditions shown in Table 1. The capacity of each reactor was 30 liters for the first reactor and 12 liters for the second reactor. A raw material solution was prepared with the raw material composition shown in Table 1, and the raw material solution was continuously supplied to the first reactor at the flow rate shown in Table 1.
  • the polymerization initiator was added to the raw material solution at the inlet of the first reactor so as to have the addition concentration (concentration based on the mass with respect to the raw material styrene) shown in Table 1, and uniformly mixed.
  • the raw materials listed in Table 1 are as follows.
  • Polymerization Initiator t-Butyl Peroxyisopropyl Monocarbonate (manufactured by NOF CORPORATION: Perbutyl I)
  • Chain transfer agent n-dodecyl mercaptan (manufactured by Arkema Co., Ltd.)
  • a temperature gradient was applied along the flow direction of the reaction solution, and the temperature was adjusted so as to be the temperature shown in Table 1 at the intermediate portion and the outlet portion.
  • a solution containing the polymer continuously taken out from the second reactor was introduced into a vacuum devolatilization tank with a preheater composed of two stages in series, and the preheater was adjusted to the resin temperature shown in Table 1.
  • the strands are extruded into strands from a porous die, and the strands are cooled and cut by a cold cut method to pellet. It became.
  • melt mass flow rate was measured according to JIS K 7210 under the conditions of a temperature of 200 ° C. and a load of 49 N.
  • GC device Agilent 7890A
  • Column Agilent DB-5ms (0.25mm id x 30m) liquid phase film thickness 0.25 ⁇ m
  • Injection port 300 ° C, 1.5 mL / min, (split ratio 1: 5)
  • MS device Agilent 5975C Interface temperature: 320 ° C
  • MS detection conditions SIM measurement TBC (quantitative m / z 295, confirmation m / z 310)
  • the weight average molecular weight (Mw), Z average molecular weight (Mz), and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC model Showa Denko Corporation Shodex GPC-101 Column: Polymer Laboratories PLgel 10 ⁇ m MIXED-B Mobile phase: tetrahydrofuran Sample concentration: 0.2% by mass Temperature: Oven 40 ° C, inlet 35 ° C, detector 35 ° C Detector: Differential refractometer
  • the molecular weight is calculated as the polystyrene-equivalent molecular weight by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene.
  • Example 1 0.2 parts by mass of phosphorus-based antioxidant (HP-10) and 0.1 parts by mass of phosphorus-phenolic antioxidant (GP) with respect to 100 parts by mass of pelletized styrene resin (A-1).
  • the mixture was mixed with a blender and mixed at a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm using a uniaxial extruder having a screw diameter of 40 mm to obtain a styrene resin composition.
  • Examples 2 to 18 and Comparative Examples 1 to 8 A styrene-based resin composition and a light guide plate were produced in the same manner as in Example 1 except that the formulations were changed as shown in Tables 2 to 4. The results of various measurements and evaluations are shown in Tables 2 to 4.
  • the phosphorus-based antioxidants (B-1), phenol-based antioxidants (B-2), and phosphorus-phenolic antioxidants (B-3) in Tables 2 to 4 are as follows. Is.
  • Phosphorus Antioxidant (B-1)) HP-10 2,2'-Methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) Phosphorus (ADEKA CORPORATION ADEKA STAB HP-10) 168: Tris (2,4-di-tert-butylphenyl) phosfite (Irgafos 168 manufactured by BASF Japan Ltd.)
  • PEP-36 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane (Co., Ltd.) ADEKA ADEKA STAB PEP-36)
  • P-EPQ Tetrakis (2,4-di-tert-butylphenyl) [1,1 biphenyl] -4,4 diylbiphosphonite (Hostanox P-EPQ manufactured by Clariant
  • (Phenolic antioxidant (B-2)) 1076 Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan Ltd.) 245: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245, manufactured by BASF Japan Ltd.) 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by BASF Japan Ltd.) AO80: 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetra Oxaspiro [5.5] Undecane (ADEKA STAB AO
  • TBC, TBX and sulfur in the evaluation tables 2 to 4 are values calculated based on the contents in the styrene resin used.
  • ⁇ Average transmittance and YI value of styrene resin composition The average transmittance and the YI value were measured by the following procedure. Using pellets of the styrene resin composition, injection molding was performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to form a plate-shaped molded product (initial sample) having a thickness of 127 ⁇ 127 ⁇ 3 mm.
  • the sample for which the long-term durability is evaluated was stored in an oven at 80 ° C. for 1000 hours.
  • a test piece having a thickness of 115 ⁇ 85 ⁇ 3 mm was cut out from the plate-shaped molded product of the initial sample and the sample after the long-term durability test, and the end face was polished by buffing to prepare a plate-shaped molded product having a mirror surface on the end face. ..
  • the polished plate-shaped molded product has a wavelength at an optical path length of 115 mm in an incident light having a size of 20 ⁇ 1.6 mm and a spreading angle of 0 ° using an ultraviolet visible spectrophotometer V-670 manufactured by JASCO Corporation.
  • the spectral transmittance of 350 nm to 800 nm was measured, and the YI value at a field of view of 2 ° in the C light source was calculated according to JIS K7105.
  • the average transmittance (total light transmittance) was calculated as the average of the spectral transmittances at wavelengths of 380 to 780 nm.
  • the die was discharged at a T-die temperature of 245 to 250 ° C., cooled and solidified with three vertical cooling rolls, and then the end face was trimmed to obtain a light guide plate having a width of 800 mm and a thickness of 2.0 mm.
  • Deformation rate ((length of long side after storage)-(length of long side before storage)) ⁇ (length of long side before storage) x 100 (%)
  • the dimensional stability (moisture absorption change) of the light guide plate was evaluated with a deformation rate of 0.10% or less as ⁇ , a deformation rate of 0.10 to 0.15% as ⁇ , and a deformation rate of 0.15% or more as ⁇ . ..

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Abstract

L'invention concerne une composition de résine à base de styrène pour plaques de guidage de lumière qui satisfait simultanément la teinte, la stabilité de teinte, la stabilité d'extrusion, la stabilité dimensionnelle, la résistance à l'opacification par la chaleur humide, et la solidité.　La présente invention concerne une composition de résine optique à base de styrène comprenant : une résine à base de styrène (A) qui est un copolymère contenant de 51 à 99 % en masse d'unités monomères à base de styrène et de 1 à 49 % en masse d'unités monomères à base de (méth)acrylate ; et un antioxydant (B). L'antioxydant (B) contient au moins un type d'antioxydant parmi un antioxydant à base de phosphore (B-1), un antioxydant à base de phénol (B-2), et un antioxydant à base de phosphore-phénol (B-3), et la composition de résine optique à base de styrène contient, par rapport à 100 parties en masse de la résine à base de styrène (A), de 0,1 à 0,5 parties en masse au total de l'antioxydant à base de phosphore (B-1) et de l'antioxydant à base de phosphore-phénol (B-3) et de 0,01 à 0,5 parties en masse au total de l'antioxydant à base de phénol (B-2) et de l'antioxydant à base de phosphore-phénol (B-3).
PCT/JP2020/045195 2020-04-01 2020-12-04 Composition de résine optique à base de styrène, plaque de guidage de lumière, et unité de source de lumière plane de type lumière latérale WO2021199501A1 (fr)

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KR1020227037676A KR20220162743A (ko) 2020-04-01 2020-12-04 광학용 스티렌계 수지 조성물, 도광판 및 에지라이트형 면 광원 유닛
CN202080099327.2A CN115397913A (zh) 2020-04-01 2020-12-04 光学用苯乙烯系树脂组合物、导光板以及侧光型面光源单元
MX2022011738A MX2022011738A (es) 2020-04-01 2020-12-04 Composicion optica de resina a base de estireno, placa de guia de luz y unidad de fuente de luz plana tipo luz de borde.
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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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WO2010071152A1 (fr) * 2008-12-17 2010-06-24 電気化学工業株式会社 Objet moulé pour applications optiques, et plaque guide de lumière et diffuseur comprenant l'objet
JP2013154546A (ja) * 2012-01-30 2013-08-15 Mitsubishi Gas Chemical Co Inc 積層体およびそれを備えた保護部材
WO2014010137A1 (fr) * 2012-07-13 2014-01-16 東洋スチレン株式会社 Composition de résine à base de styrène pour applications optiques, produit moulé et plaque guide de lumière
WO2016129675A1 (fr) * 2015-02-12 2016-08-18 デンカ株式会社 Composition de résine optique à base de styrène

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JP2003075648A (ja) 2001-09-07 2003-03-12 Denki Kagaku Kogyo Kk 導光板
WO2013094642A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition optique à base de styrène, produit moulé et plaque guide de lumière
JP6039907B2 (ja) 2012-02-17 2016-12-07 東洋スチレン株式会社 スチレン系樹脂板状成形品および導光板

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Publication number Priority date Publication date Assignee Title
WO2010071152A1 (fr) * 2008-12-17 2010-06-24 電気化学工業株式会社 Objet moulé pour applications optiques, et plaque guide de lumière et diffuseur comprenant l'objet
JP2013154546A (ja) * 2012-01-30 2013-08-15 Mitsubishi Gas Chemical Co Inc 積層体およびそれを備えた保護部材
WO2014010137A1 (fr) * 2012-07-13 2014-01-16 東洋スチレン株式会社 Composition de résine à base de styrène pour applications optiques, produit moulé et plaque guide de lumière
WO2016129675A1 (fr) * 2015-02-12 2016-08-18 デンカ株式会社 Composition de résine optique à base de styrène

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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