CN113661207A - Styrene resin composition, molded article, and light guide plate - Google Patents
Styrene resin composition, molded article, and light guide plate Download PDFInfo
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- CN113661207A CN113661207A CN202080027564.8A CN202080027564A CN113661207A CN 113661207 A CN113661207 A CN 113661207A CN 202080027564 A CN202080027564 A CN 202080027564A CN 113661207 A CN113661207 A CN 113661207A
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- 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
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- 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
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- 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
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- C08L25/04—Homopolymers or copolymers of styrene
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- 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
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- 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
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Abstract
A styrene resin composition having excellent wet heat resistance, a molded article thereof, and a light guide plate are provided. According to the present invention, there is provided a styrene resin composition having an oxidation induction time t1 measured in an oxygen atmosphere at 200 ℃ and an oxidation induction time t2 measured in an oxygen atmosphere at 200 ℃ after a wet heat treatment for 500 hours in an air atmosphere at 80 ℃ and 90% humidity, wherein t1-t2 is 20 minutes or less.
Description
Technical Field
The present invention relates to a styrene resin composition, a molded article thereof, and a light guide plate.
Background
The backlight of the liquid crystal display device includes a direct type in which a light source is disposed on a front surface of the display device and an edge light type in which the light source is disposed on a side surface. In the edge light type, a member called a light guide plate is used which guides light from a light source disposed on a side surface to a front surface of a display device.
As a material of the light guide plate, acrylic resin typified by polymethyl methacrylate (PMMA) is used. However, since PMMA has high water absorption, the light guide plate may be warped or changed in size due to water absorption. Further, since thermal decomposition is likely to occur during molding, a problem of poor appearance of a molded article is likely to occur during molding at high temperature.
In order to improve these problems, a styrene-methyl (meth) acrylate copolymer has been proposed as a material for a light guide plate (see, for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2003-075648
Disclosure of Invention
Problems to be solved by the invention
The invention provides a styrene resin composition with excellent humidity resistance, a molded product thereof and a light guide plate.
Means for solving the problems
Namely, the present invention is as follows:
(1) a styrene resin composition, wherein the oxidation induction time measured in an oxygen atmosphere at 200 ℃ is t1, the oxidation induction time measured in an oxygen atmosphere at 200 ℃ is t2, and t1-t2 is 20 minutes or less after subjecting the composition to a moist heat treatment for 500 hours in an air atmosphere at 80 ℃ and 90% humidity.
(2) A styrene resin composition according to item (1), wherein t1 is 50 minutes or longer.
(3) A styrene resin composition as described in (1) or (2), which contains a hindered phenol antioxidant (B) and a phosphorus antioxidant (C2) having no phenolic hydroxyl group.
(4) A styrene resin composition according to any one of (1) to (3), which contains a styrene resin (A) having a styrene monomer unit and a (meth) acrylate monomer unit.
(5) A styrene resin composition as described in any one of (1) to (4), which contains a phosphorus antioxidant (C1) having a phenolic hydroxyl group.
(6) A styrene resin composition according to item (3), wherein said hindered phenol antioxidant (B) is at least one compound selected from octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
(7) A styrene resin composition as described in (3), wherein said phosphorus antioxidant (C2) is at least one compound selected from 2, 2' -methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite and tris (2, 4-di-tert-butylphenyl) phosphite.
(8) A styrene resin composition as described in (5), wherein said phosphorus antioxidant (C1) is 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2, 4, 8, 10-tetra-tert-butyldibenzo [ d, f ] [1, 3, 2] dioxaphosphorinane heptacyclic (dioxaphosphohepin).
(9) A styrene resin composition as described in any one of (1) to (8), wherein the YI value at an initial optical path length of 115mm is 2.5 or less.
(10) A molded article comprising the styrene-based resin composition according to any one of (1) to (9).
(11) A light guide plate using the molded article of (10).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a styrene resin composition having excellent moist heat resistance, a molded article thereof, and a light guide plate are obtained.
Drawings
FIG. 1 is a conceptual diagram of a method for measuring oxidation induction time by a Chemiluminescence method (Chemiluminescence method).
Detailed Description
In the present specification, "a to B" means a to B.
The styrene resin composition of the present invention has an oxidation induction time of t1 measured in an oxygen atmosphere at 200 ℃ and a t1-t2 of 20 minutes or less, preferably 15 minutes or less, more preferably 10 minutes or less, when the composition is subjected to a wet heat treatment at 80 ℃ and 90% humidity in an air atmosphere for 500 hours and then subjected to an oxidation induction time of t2 measured in an oxygen atmosphere at 200 ℃. When t1-t2 is in this range, deterioration in color when stored under a high-temperature and high-humidity environment can be suppressed. In addition, since increasing the amount of the antioxidant added contributes to maintaining the oxidation induction time, on the other hand, adversely affects the color phase, t1-t2 is preferably 1 minute or more, more preferably 2 minutes or more, and still more preferably 4 minutes or more in consideration of the balance. Specific examples of t1-t2 include 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 minutes, and may be a range between 2 of the numerical values exemplified here.
t1 is preferably 50 minutes or longer, more preferably 70 minutes or longer, and still more preferably 90 minutes or longer. When t1 is within this range, yellowing in a high-temperature environment can be suppressed. Although increasing the amount of the antioxidant added can prolong the oxidation induction time, on the other hand, it adversely affects the color phase, and therefore, in view of the balance, t1 is preferably 500 minutes or less, more preferably 200 minutes or less.
The oxidation induction time is a value measured by a chemiluminescence method. The time change of the light emission amount of the styrene resin composition was measured under the following conditions, and the time of focus between the straight line before the light emission amount was changed and the one after the light emission amount was increased as shown in fig. 1 was calculated from the relationship between the measurement time and the light emission amount. Styrenic resin compositions are gradually oxidized after heating in the presence of oxygen. When an antioxidant is present in the sample, the antioxidant is gradually consumed due to oxidation, and a certain amount of luminescence is exhibited in the presence of the antioxidant. When the antioxidant is absent, the resin itself is oxidized, and the light emission may increase once. That is, the oxidation induction time is a time when the antioxidant is consumed and the oxidation of the resin composition rapidly proceeds.
Chemiluminescence determinator: CLA-FS4 (manufactured by northeast electronics industry Co., Ltd.)
Measuring temperature: 200 deg.C
Oxygen flow rate: 100 mL/min
The styrene resin composition of the present invention preferably contains a styrene resin (a) which is a copolymer of a styrene monomer and a (meth) acrylate monomer.
The styrene monomer is an aromatic vinyl monomer, and is styrene, α -methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, p-tert-butylstyrene, or a mixture of 2 or more thereof. Among these monomers, styrene is preferably used from the viewpoint of good hue.
The (meth) acrylate monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, alone or in a mixture of 2 or more. Methyl (meth) acrylate is preferably used from the viewpoint of excellent hue and heat resistance.
The styrene resin (A) preferably contains 20 to 80 mass% of styrene monomer units, 80 to 20 mass% of (meth) acrylate monomer units, 30 to 60 mass% of styrene monomer units, and 70 to 40 mass% of (meth) acrylate monomer units. When the content of the monomer unit is within this range, the water absorption rate and the deformation rate (water absorption) are low, and the warpage and the increase in dimensional change due to moisture absorption can be suppressed, and the scratches caused by the deterioration of the color and the reduction in the surface hardness can be suppressed.
The styrene resin (a) may be copolymerized with a monomer other than the (meth) acrylate monomer in an amount of 5% by mass or less. The monomer to be copolymerized is a vinyl monomer copolymerizable with a styrene monomer and a (meth) acrylate monomer, and is acrylonitrile, methacrylic acid, acrylic acid, maleic anhydride, or the like.
The contents of the styrene-based monomer unit and the (meth) acrylate-based monomer unit of the styrene-based resin can be measured by thermal decomposition gas chromatography under the following conditions.
A pyrolysis furnace: PYR-2A (manufactured by Shimadzu corporation)
Setting the temperature of the pyrolysis furnace: 525 deg.C
Gas chromatograph: GC-14A (manufactured by Shimadzu Kaisha)
Column: the diameter of the glass is 3mm multiplied by 3m
Filling agent: FFAP Chromsorb WAW
Column temperature: 120 deg.C
Carrier gas: nitrogen gas
The styrene resin can be produced by known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Any of a continuous type, a batch type (batch type), and a semi-batch type can be applied as the operation method of the reaction apparatus. From the viewpoint of quality such as transparency and productivity, bulk polymerization or solution polymerization is preferable, and a continuous type is preferable. The solvent for bulk polymerization or solution polymerization is an alkylbenzene such as benzene, toluene, ethylbenzene or xylene, a ketone such as acetone or methyl ethyl ketone, an aliphatic hydrocarbon such as hexane or cyclohexane, or the like.
The polymerization method of the styrene resin may be a known method. The radical polymerization method is preferable because of its simple process and excellent productivity.
In the bulk polymerization or solution polymerization of the styrenic resin, a polymerization initiator and a chain transfer agent may be used, and the polymerization temperature is preferably in the range of 110 to 170 ℃. When the bulk polymerization or the solution polymerization is carried out in a continuous manner, it is preferable that the conversion of the styrene monomer and the (meth) acrylate monomer is 60% or more at the outlet of the polymerization step from the viewpoint of productivity.
The polymerization initiator is an organic peroxide such as benzoyl peroxide, t-butyl peroxybenzoate, 1-di (t-butylperoxy) cyclohexane, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, 2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, t-butyl peroxyisopropyl carbonate, dicumyl peroxide, t-butylcumyl peroxide, t-butyl peroxyacetate, t-butylperoxy-2-ethylhexanoate, polyether tetrakis (t-butyl peroxycarbonate), ethyl 3, 3-di (t-butylperoxy) butyrate, and t-butyl peroxyisobutyrate.
The amount of the polymerization initiator added is preferably 0.001 to 0.2% by mass, more preferably 0.001 to 0.05% by mass, based on 100% by mass of the total monomers. When the amount of the polymerization initiator added is too large, the hue deteriorates.
The chain transfer agent is aliphatic mercaptan, aromatic mercaptan, pentaphenylethane, alpha-methylstyrene dimer, terpinolene, or the like.
The amount of the chain transfer agent to be added is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.2% by mass, based on 100% by mass of the total monomers. When the amount of the chain transfer agent added is 0.001 to 0.5% by mass, thermal stability is improved.
The devolatilization method for removing unreacted monomers and volatile components such as a solvent suitable for solution polymerization from a solution after completion of polymerization of a styrene resin may be a known method, and for example, a vacuum devolatilization vessel equipped with a preheater or a devolatilization extruder with an exhaust port may be used. The temperature of the styrene resin in the devolatilization step is preferably 200 to 300 ℃, more preferably 220 to 260 ℃. When the temperature of the styrene-based resin in the devolatilization step is too high, the hue may be deteriorated. The devolatilized styrene-based resin in a molten state is transferred to a pelletizing step, extruded into a strand form using a porous die, and processed into pellets by a cold cutting method, an air-to-hot cutting method, or an underwater hot cutting method.
It is preferable that the unreacted monomer removed in the devolatilization step and the solvent used in the solution polymerization are recovered, purified to remove impurities such as a polymerization inhibitor, and then mixed with fresh raw materials as recovered raw materials. By using the recovered raw material in combination with a fresh raw material containing no polymerization inhibitor, the content of the polymerization inhibitor in the raw material supplied to the polymerization step can be reduced. The content of the polymerization inhibitor in the raw material fed to the polymerization step is preferably less than 12ppm, more preferably less than 9ppm, still more preferably less than 6ppm, and most preferably less than 4 ppm. When the content of the polymerization inhibitor in the raw material supplied to the polymerization step is less than 12ppm, the light transmittance and transparency become good. It is difficult to remove all the polymerization inhibitor, and usually 0.01ppm or more is contained. In order to distinguish from the recovered raw material, the raw material newly supplied to the production process of the styrene- (meth) acrylate copolymer is referred to as a fresh raw material.
The method for recovering and purifying the solvent used in the solution polymerization and removing the unreacted monomer in the devolatilization step may be a known method, and for example, the method may be a method of compressing and liquefying the unreacted monomer and the solvent gas removed in the devolatilization step by a condenser, and purifying and separating the high boiling point component by a flash column. Further, the method may be such that only the high boiling point component is condensed and separated from the unreacted monomer and solvent gas removed in the devolatilization step by a condenser or a spray tower, and the remaining gas is condensed by the condenser as a whole. 4-Tert-butylbenzenediol as a polymerization inhibitor has a boiling point of 285 ℃ and a boiling point of 249 ℃ for 6-t-butyl-2, 4-xylenol, and can be separated and removed from a monomer and a solvent as high-boiling components (the boiling point of styrene is 145 ℃, the boiling point of methyl (meth) acrylate is 101 ℃ and the boiling point of ethylbenzene is 136 ℃).
The weight average molecular weight (Mw) of the styrene resin is preferably 5 to 45 ten thousand, more preferably 7 to 30 ten thousand, and still more preferably 7 to 20 ten thousand. When the weight average molecular weight (Mw) is less than 5 ten thousand, the strength of the light guide plate may be reduced. When the weight average molecular weight (Mw) exceeds 20 ten thousand, the flowability is lowered and the moldability is deteriorated. The weight average molecular weight (Mw) can be controlled depending on the reaction temperature, residence time, the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, and the type and amount of the solvent used in the polymerization.
The weight average molecular weight (Mw) can be measured using Gel Permeation Chromatography (GPC) under the following conditions.
GPC type: shodex GPC-101 manufactured by Showa Denko K.K
Column: PLgel 10 μm MIXED-B manufactured by Polymer Laboratories
Mobile phase: tetrahydrofuran (THF)
Sample concentration: 0.2% by mass
Temperature: oven 40 deg.C, injection port 35 deg.C, detector 35 deg.C
A detector: differential refractometer
The molecular weight of the present invention is calculated by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene, and is calculated as the molecular weight in terms of polystyrene.
The total amount of the residual monomer and the polymerization solvent in the styrene resin is preferably 0.5% by mass or less, and more preferably 0.2% by mass. When the total amount of the residual monomer and the polymerization solvent exceeds 0.5% by mass, the heat resistance is insufficient.
The residual monomer and polymerization solvent are amounts of the monomer and polymerization solvent remaining in the styrenic resin, and are styrene, methyl (meth) acrylate, ethylbenzene, and the like. The amounts of the residual monomer and the polymerization solvent can be adjusted by the constitution of the devolatilization step or the conditions of the devolatilization step.
The amounts of the residual monomer and the polymerization solvent were measured by accurately weighing 0.2g of a styrene-based resin, dissolving it in 10mL of tetrahydrofuran containing p-diethylbenzene as an internal standard substance, and then measuring by capillary gas chromatography under the following conditions.
Capillary gas chromatograph: GC-4000 (manufactured by GL Sciences Inc.)
Column: InertCap WAX manufactured by GL Sciences Inc. and having an inner diameter of 0.25mm, a length of 30m and a film thickness of 50 μm
Injection temperature: 180 deg.C
Column temperature: 60-170 deg.C
Temperature of the probe: 210 deg.C
The split ratio is as follows: 5/1
The total amount of the styrene monomer and the dimer or trimer of the (meth) acrylate monomer (hereinafter referred to as oligomer) of the styrene resin is preferably 2 mass% or less, and more preferably 1 mass% or less. If the total amount of the oligomer exceeds 1 mass%, the heat resistance as a light guide plate is insufficient.
The oligomer was measured by dissolving 200mg of a styrene resin in 2mL of 1, 2-dichloromethane, adding 2mL of methanol to precipitate a copolymer, standing, and measuring the supernatant by gas chromatography under the following conditions.
Gas chromatograph: HP-5890 (made by Hewlett packard Co., Ltd.)
Column: DB-1(ht)0.25mm × 30m thick 0.1 μm
Injection temperature: 250 deg.C
Column temperature: 100 ℃ and 300 DEG C
Detector temperature: 300 deg.C
The split ratio is as follows: 50/1
Internal standard substance: n-eicosane
Carrier gas: nitrogen gas
The styrene resin composition of the present invention preferably contains a hindered phenol antioxidant (B). The hindered phenol antioxidant (B) contained in the styrene resin composition is an antioxidant having a phenolic hydroxyl group in the basic skeleton. The hindered phenol-based antioxidant is octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ], 3, 9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl ] -2, 4, 8, 10-tetraoxaspiro [5.5] undecane, pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 4, 6-bis (octylthiomethyl) -o-cresol, 4, 6-bis [ (dodecylthio) methyl ] -o-cresol, pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2, 4-dimethyl-6- (1-methylpentadecyl) phenol, tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, 4 '-thiobis (6-tert-butyl-3-methylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4' -butylidenebis (3-methyl-6-tert-butylphenol), bis- [3, 3-bis- (4 '-hydroxy-3' -tert-butylphenol) -butyric acid ] -ethylene glycol ester, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate And 2- [ 1- (2-hydroxy-3, 5-di-tert-butylphenyl) ethyl ] -4, 6-di-tert-pentylphenyl acrylate. The hindered phenol antioxidant may be used alone or in combination of 2 or more.
The content of the hindered phenol antioxidant (B) is preferably 0.001 to 0.3 parts by mass, more preferably 0.03 to 0.09 parts by mass, per 100 parts by mass of the styrene resin (a). By adjusting the content of the hindered phenol antioxidant (B) within this range, a styrene resin composition having excellent hue can be obtained.
The styrene resin composition of the present invention preferably contains a phosphorus antioxidant (C1) having a phenolic hydroxyl group. The phosphorus antioxidant (C1) contained in the styrene resin composition is a trivalent phosphorus compound having a phenolic hydroxyl group in the basic skeleton. Since the phosphorus-based antioxidant (C1) has a property of being easily hydrolyzed compared with other phosphorus-based antioxidants, the styrene resin composition obtained has a high hue-improving effect. The phosphorus-containing antioxidant (C1) is 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2, 4, 8, 10-tetra-tert-butyldibenzo [ d, f ] [1, 3, 2] dioxaphosphorinane, etc.
The content of the phosphorus-based antioxidant (C1) is preferably 0.001 to 0.3 parts by mass, more preferably 0.03 to 0.09 parts by mass, and still more preferably 0.05 to 0.08 parts by mass, based on 100 parts by mass of the styrene-based resin (a). When the content of the phosphorus antioxidant (C1) is adjusted to the above range, a styrene resin composition having excellent hue can be obtained.
The styrene resin composition of the present invention preferably contains a phosphorus antioxidant (C2) other than the phosphorus antioxidant (C1) having phenolic hydroxyl groups. The phosphorus antioxidant (C2) contained in the styrene resin composition is a trivalent phosphorus compound having no phenolic hydroxyl group in the basic skeleton. The phosphorus-based antioxidant (C2) is less likely to be hydrolyzed than the phosphorus-based antioxidant (C1), but can maintain the effect of improving the hue of the styrene resin composition for a long period of time. That is, it particularly contributes to moist heat resistance. The phosphorus-based antioxidant (C2) is 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2, 4, 8, 10-tetraoxazole-3, 9-diphosphaspiro [5.5] undecane, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, 2' -methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis [2, 4-bis (1, 1-dimethylethyl) -6-methylphenyl ] ethyl phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, cyclopentanetetra-ylbis (octadecyl phosphite), bis (nonylphenyl) pentaerythritol diphosphite, cyclopentanethiylbis (octadecyl) phosphite, 4, 4 ' -Biphenyldiphosphite tetrakis (2, 4-di-t-butylphenyl), 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2, 4-di-t-butyl-5-methylphenyl) -4, 4 ' -Biphenyldiphosphonite and the like, 2 ' -methylenebis (4, 6-di-t-butylphenyl) 2-phosphite and tris (2, 4-di-t-butylphenyl) phosphite are preferably used from the viewpoint of the effect of continuously improving the hue. The phosphorus-based antioxidant (C2) may be used alone or in combination of 2 or more.
The content of the phosphorus-based antioxidant (C2) is preferably 0.001 to 0.3 parts by mass, more preferably 0.03 to 0.09 parts by mass, and still more preferably 0.05 to 0.08 parts by mass, based on 100 parts by mass of the styrene-based resin (a). When the content of the phosphorus antioxidant (C2) is adjusted to the above range, a styrene resin composition having an excellent hue over a long period of time from the initial stage can be obtained.
The mixing ratio of the phosphorus antioxidant (C1) to the phosphorus antioxidant (C2) is preferably 3: 1-1: 3, more preferably 2: 1-1: 2. by adjusting the amount to the above range, the obtained styrene resin composition has a good balance between hue and durability.
A known method can be used for producing the styrene resin composition. The hindered phenol antioxidant (B), the phosphorus antioxidant (C1), and the phosphorus antioxidant (C2) are added in the production steps of the styrene resin, such as the polymerization step, the devolatilization step, and the granulation step, and preferably, the unreacted monomers and the solvent are removed in the devolatilization step and then added. When a vacuum devolatilization vessel was used, the hindered phenol antioxidant (B), the phosphorus antioxidant (C1), and the phosphorus antioxidant (C2) were added to the styrene resin extracted from the devolatilization vessel in a molten state and mixed by a static mixer, and when a devolatilization extruder with an exhaust port was used, the hindered phenol antioxidant (B), the phosphorus antioxidant (C1), and the phosphorus antioxidant (C2) were added and mixed after the exhaust port. The hindered phenol antioxidant (B), the phosphorus antioxidant (C), and the phosphorus antioxidant (C2) can be melt-mixed with the pelletized styrene resin (a) using an extruder.
The styrene resin composition may contain a mineral oil as long as transparency is not impaired. In addition, internal lubricants such as stearic acid and ethylene bis-stearamide; sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, hindered amine-based stabilizers, antistatic agents, and external lubricants such as ethylene bisstearamide.
The ultraviolet absorber is an additive having a function of suppressing deterioration or coloring due to ultraviolet rays, and is an ultraviolet absorber such as a benzophenone-based, benzotriazole-based, triazine-based, benzoate-based, salicylate-based, cyanoacrylate-based, malonate-based, or formamidine-based one. These can be used alone or in combination of 2 or more, and can also be used with hindered amine and other light stabilizer.
The vicat softening point of the styrene resin is preferably 95 ℃ or higher, and more preferably 98 ℃ or higher. When the Vicat softening point is less than 95 ℃, the heat resistance is insufficient and the molded article may be deformed depending on the use environment. (Vicat softening temperature was measured according to JIS K7206 at a temperature rise rate of 50 ℃/hr and a test load of 50N.)
The styrene resin composition can be used by preparing a plate-shaped molded article by a known method such as extrusion molding, injection molding, compression molding, blow molding, etc., and processing the molded article into a light guide plate.
The styrenic resin composition of the present invention is excellent in thermal stability, and thus non-product parts such as chips at the time of extrusion molding, bobbins and runners at the time of injection molding can be collected and pulverized and then mixed with virgin materials for use.
The light guide plate is a member that guides light incident from an end surface of a plate-shaped molded article to a surface side of the plate-shaped molded article by forming a reflection pattern on one side surface of the plate-shaped molded article and has a light emitting property. The reflective pattern can be formed by a screen printing method, a laser processing method, an ink jet method, or the like. Further, a prism pattern or the like may be provided on the surface (light-emitting surface) opposite to the surface on which the reflection pattern is formed. The reflection pattern and the prism pattern of the plate-shaped molded article may be formed during molding of the plate-shaped molded article, or may be formed by a mold shape during injection molding or by roll transfer during extrusion molding.
The YI value of the styrene resin composition measured at an optical path length of 115mm at the initial stage is preferably 2.5 or less, more preferably 2.0 or less. The term "initial stage" as used herein means a state before the wet heat treatment is performed for 500 hours in an air atmosphere of 80 ℃ and 90% humidity. The measurement is carried out by measuring the spectral transmittance at a wavelength of 350nm to 800nm at an optical path length of 115mm, and is a value calculated according to JIS K7373 as the YI value in a field of view of 2 DEG from a C light source. When the YI value measured by the optical path length of 115mm is higher than 2.5, the color varies depending on the optical path length, and therefore, when the liquid crystal display device is used as a backlight, color unevenness may occur on the surface of the liquid crystal display device. The average value of the spectral transmittance at a wavelength of 350 to 800nm measured at an optical path length of 115mm is preferably 87% or more, more preferably 88% or more, and still more preferably 89% or more.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
< preparation example of styrene resin A-1 >
Styrenic resins are produced by a free radical process and by continuous solution polymerization. A complete mixing tank type agitation tank was used as the 1 st reactor, a plug flow type reactor equipped with a static mixer was used as the 2 nd reactor, and they were connected in series to constitute a polymerization process. The capacity of the 1 st reactor was 30L, and the capacity of the 2 nd reactor was 12L. When styrene (hereinafter referred to as "fresh Sty") used in industry was prepared as a styrene monomer, the concentration of 4-t-butylcatechol (hereinafter referred to as "TBC") was 10.2 ppm. When methyl (meth) acrylate (hereinafter referred to as fresh MMA) used industrially was prepared as the (meth) acrylate-based monomer, the concentration of 6-tert-butyl-2, 4-xylenol (hereinafter referred to as TBX) was 4.9 ppm. As a polymerization solvent, industrially used ethylbenzene (hereinafter referred to as fresh EB) was prepared. Further, a gas such as a monomer and a polymerization solvent separated from a vacuum devolatilizer to be described later is condensed by a condenser, and is purified by a flash column or the like to be used as a recovered raw material. The concentration of TBX and TBC in the recovered feed was below the lower detection limit. Fresh Sty, fresh MMA and recovered feedstock were used and the ratio of Sty: 49 mass%, MMA: 41 mass%, EB: a raw material solution having a composition of 10% by mass was prepared and supplied to the polymerization step at a flow rate of 8.0 kg/h. The usage ratio of the recovered raw material in the raw material solution was 33 mass%. The raw material solution was continuously fed to the raw material solution supply line so that the concentration of t-butylperoxyisopropyl monocarbonate as a polymerization initiator was 150ppm and the concentration of n-dodecylmercaptan as a chain transfer agent was 500 ppm. The temperature in the 1 st reactor was adjusted to 135 ℃, a temperature gradient was formed in the flow direction in the 2 nd reactor, and the intermediate portion was adjusted to 130 ℃ and the outlet portion was adjusted to 145 ℃. The polymer concentration at the outlet of the polymerization process was 65% and the conversion of styrene to methyl (meth) acrylate was 72%. The polymer solution continuously withdrawn from the reactor was supplied to a vacuum devolatilization vessel equipped with a preheater, and unreacted styrene, methyl (meth) acrylate, ethylbenzene, and the like were separated. The temperature of the preheater was adjusted so that the polymer temperature in the devolatilization vessel was 240 ℃ and the pressure in the devolatilization vessel was 1 kPa. The polymer was extracted from the vacuum devolatilization vessel by a gear pump, extruded into a strand, cooled with cooling water, and then cut into pellets of styrene resin A-1. The composition of A-1 is Sty: 50 mass%, MMA: 50% by mass. Further, the weight average molecular weight of A-1 was 14.5 ten thousand, the total amount of the residual monomer and the polymerization solvent was 0.07 mass%, and the total amount of the residual oligomer was 0.35 mass%.
< preparation example of styrene resin A-2 >
The raw material composition is changed into Sty: 77 mass%, MMA: 13 mass%, EB: 10% by mass, the addition of n-dodecylmercaptan was stopped, and the temperature in the 1 st reactor was set to 140 ℃, the temperature in the middle part of the 2 nd reactor was set to 140 ℃, and the temperature in the outlet part was set to 160 ℃, and the operation was carried out in the same manner as in A-1. The usage ratio of the recovered raw material in the raw material solution was 33 mass%. The composition of A-2 is Sty: 82 mass%, MMA: 18% by mass. Further, A-2 had a weight average molecular weight of 24 ten thousand, and the total amount of the residual monomer and the polymerization solvent was 0.06 mass%, and the total amount of the residual oligomer was 0.33 mass%.
< preparation example of styrene resin A-3 >
The raw material composition is changed into Sty: 8 mass%, MMA: 79 mass%, EB: 13% by mass, the temperature of the middle portion of the 1 st reactor was 140 ℃ and the temperature of the outlet portion was 150 ℃ with the exception that the feed rate was set to 5.7kg/h, the concentration of t-butyl peroxyisopropyl monocarbonate was set to 100ppm, the concentration of n-dodecylmercaptan was set to 3000ppm, the temperature of the 1 st reactor was set to 122 ℃, and the temperature of the outlet portion was set to 150 ℃. The usage ratio of the recovered raw material in the raw material solution was 34 mass%. The composition of A-3 is Sty: 10 mass%, MMA: 90% by mass. Further, A-3 had a weight average molecular weight of 8 ten thousand, and the total amount of the residual monomer and the polymerization solvent was 0.06 mass%, and the total amount of the residual oligomer was 0.34 mass%.
< examples 1 to 10, comparative example 1 and reference examples 1 to 2>
The styrene resins A-1 to A-3 obtained in the production examples were reduced in the amounts shown in Table 1 of the hindered phenol antioxidant (B), the phosphorus antioxidant (C1), the phosphorus antioxidants (C2-1) and (C2-2) shown below, and the antioxidants were melt-kneaded by a sheet extruder manufactured by LEADER to obtain sheet-shaped moldings of 450 mm. times.500 mm. times.2 mm. The sheet extruder is composed of
A single-screw extruder, a T-die, and 3 mirror rolls, and sheet extrusion was performed under conditions in which the barrel temperature of the single-screw extruder was 225 ℃ and the number of screw revolutions was 120 rpm. The width of the T-die is 450mm and the opening is 3 mm.
(B) Octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan)
(C1)6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2, 4, 8, 10-tetra-tert-butyldibenzo [ d, f ] [1, 3, 2] dioxaphosphorinane (Sumilizer GP, Sumitomo chemical Co., Ltd.)
(C2-1)2, 2' -methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite (Adekastab HP-10, manufactured by ADEKA K.K.)
(C2-2) (2, 4-di-tert-butylphenyl) phosphite (Irgafos 168, manufactured by BASF Japan K.K.)
(Oxidation induction time)
A test piece of 30 mm. times.30 mm. times.2 mm in thickness was cut out from the obtained sheet-like molded article, and the amount of luminescence was measured at 200 ℃ and an oxygen flow rate of 100 mL/min by using a chemiluminescence analyzer CLA-FS4 manufactured by northeast electronics industries, and the oxidation induction time was determined from the relationship between the measurement time and the amount of luminescence by the method shown in FIG. 1. The results of measurement of the oxidation induction time (t1) of the sheet-like molded article immediately after extrusion and the oxidation induction time (t2) of the sheet-like molded article after wet heat treatment for 500 hours in an air atmosphere at 80 ℃ and 90% humidity are shown in Table 1. In reference example 1 and reference example 2, the amount of luminescence continuously increased immediately after the start of measurement, and therefore the oxidation induction time could not be measured.
(optical characteristics at an optical path length of 115 mm)
A test piece having a thickness of 115mm X85 mm X2 mm was cut out from the obtained sheet-like molded article, and the end face was polished to obtain a plate-like molded article having a mirror surface on the end face. The spectral transmittance of the plate-shaped molded article after polishing was measured in a range of 20X 1.6mm in size, 0 ℃ in the angle of diffusion of incident light and from 350 to 800nm in wavelength at 115mm in the optical path length using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO corporation, and the YI value was calculated in accordance with JIS K7373 in a range of 2 ℃ in view at a C light source. The light transmittance shown in Table 1 represents the average light transmittance at a wavelength of 380nm to 780 nm. The measurement results of the sheet-like molded article immediately after extrusion (initial stage), the sheet-like molded article subjected to the moist heat treatment for 500 hours in an air atmosphere of 80 ℃ and 90% humidity, and the sheet-like molded article after storage for 1000 hours in an environment of 80 ℃ are shown in Table 1.
(Water-absorbing Property)
The obtained sheet-like molded article was cut to obtain a molded article having a size of 200mm × 300 mm. The molded article was stored at 60 ℃ and 90% humidity for 500 hours, and the mass and the change in the dimension of the long side before and after storage were measured to calculate the water absorption and deformation ratio as an index of water absorption by the following formulas.
(water absorption rate) ((mass after storage) - (mass before storage))/(mass before storage) × 100 (%)
(deformation ratio) ((long side length after storage) - (long side length before storage))/(long side length before storage) × 100 (%)
The evaluation results are shown in table 1. The water absorption was found to be good when the water absorption was 1.0 or less, and the deformation was found to be good when the deformation was 0.30 or less.
[ Table 1]
Industrial applicability of the invention
The styrene resin composition and the molded product thereof of the present invention have excellent moisture and heat resistance and are less likely to deteriorate in hue and transparency, and therefore, can be suitably used for televisions, desktop computers, notebook computers, cellular phones, car navigation systems, and light guide plates for indoor illumination lamps.
Claims (11)
1. A styrene resin composition, wherein,
assuming that the oxidation induction time measured in an oxygen atmosphere at 200 ℃ is t1,
the wet heat treatment was carried out for 500 hours in an air atmosphere of 80 ℃ and 90% humidity, and the oxidation induction time measured in an oxygen atmosphere of 200 ℃ was t2,
t1-t2 is 20 minutes or less.
2. A styrenic resin composition according to claim 1, wherein,
t1 is 50 minutes or more.
3. A styrene-based resin composition according to claim 1 or 2,
the styrene resin composition contains a hindered phenol antioxidant (B) and a phosphorus antioxidant (C2) having no phenolic hydroxyl group.
4. A styrene-based resin composition according to any one of claims 1 to 3,
the styrene resin composition contains a styrene resin (A) having a styrene monomer unit and a (meth) acrylate monomer unit.
5. A styrene-based resin composition according to any one of claims 1 to 4,
the styrene resin composition contains a phosphorus antioxidant (C1) having a phenolic hydroxyl group.
6. A styrene-based resin composition according to claim 3,
the hindered phenol antioxidant (B) is at least one compound selected from the group consisting of octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
7. A styrene-based resin composition according to claim 3,
the phosphorus-based antioxidant (C2) is at least one compound selected from 2, 2' -methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite and tris (2, 4-di-tert-butylphenyl) phosphite.
8. A styrenic resin composition according to claim 5, wherein,
the phosphorus antioxidant (C1) is 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2, 4, 8, 10-tetra-tert-butyldibenzo [ d, f ] [1, 3, 2] dioxaphosphorinane.
9. A styrene-based resin composition according to any one of claims 1 to 8,
the styrene resin composition has a YI value of 2.5 or less at an initial optical path length of 115 mm.
10. A molded article comprising the styrene resin composition according to any one of claims 1 to 9.
11. A light guide plate using the molded article according to claim 10.
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| JP2019081859 | 2019-04-23 | ||
| JP2019-081859 | 2019-04-23 | ||
| PCT/JP2020/008979 WO2020217718A1 (en) | 2019-04-23 | 2020-03-03 | Styrene resin composition, molded article, and light guide plate |
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| KR (1) | KR20220005032A (en) |
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| CN103998514A (en) * | 2011-12-20 | 2014-08-20 | 东洋苯乙烯股份有限公司 | Styrene-based optical resin composition |
| JP2015067650A (en) * | 2013-09-27 | 2015-04-13 | 東洋スチレン株式会社 | Styrene resin composition for optical use |
| CN107250255A (en) * | 2015-02-12 | 2017-10-13 | 电化株式会社 | Optics styrene resin composite |
| JP2018145309A (en) * | 2017-03-06 | 2018-09-20 | 東洋スチレン株式会社 | Styrene-based resin composition for optical use, molded article and light guide body |
| CN111133050A (en) * | 2018-01-09 | 2020-05-08 | 电化株式会社 | Styrene resin composition, molded article, and light guide plate |
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| JP2003075648A (en) | 2001-09-07 | 2003-03-12 | Denki Kagaku Kogyo Kk | Light guide plate |
| JP5248094B2 (en) * | 2007-01-10 | 2013-07-31 | 旭化成イーマテリアルズ株式会社 | Resin composition for optical materials |
| JP6038497B2 (en) * | 2012-06-18 | 2016-12-07 | Ｐｓジャパン株式会社 | Polystyrene resin composition and light guide plate |
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| CN103998514A (en) * | 2011-12-20 | 2014-08-20 | 东洋苯乙烯股份有限公司 | Styrene-based optical resin composition |
| JP2015067650A (en) * | 2013-09-27 | 2015-04-13 | 東洋スチレン株式会社 | Styrene resin composition for optical use |
| CN107250255A (en) * | 2015-02-12 | 2017-10-13 | 电化株式会社 | Optics styrene resin composite |
| JP2018145309A (en) * | 2017-03-06 | 2018-09-20 | 東洋スチレン株式会社 | Styrene-based resin composition for optical use, molded article and light guide body |
| CN111133050A (en) * | 2018-01-09 | 2020-05-08 | 电化株式会社 | Styrene resin composition, molded article, and light guide plate |
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