WO2014010137A1 - Styrene-based resin composition for optical applications, molded product, and light guide plate - Google Patents
Styrene-based resin composition for optical applications, molded product, and light guide plate Download PDFInfo
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- WO2014010137A1 WO2014010137A1 PCT/JP2012/082946 JP2012082946W WO2014010137A1 WO 2014010137 A1 WO2014010137 A1 WO 2014010137A1 JP 2012082946 W JP2012082946 W JP 2012082946W WO 2014010137 A1 WO2014010137 A1 WO 2014010137A1
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- 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
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- 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
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
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- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
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- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/045—Light guides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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 a styrenic resin composition, a molded product, and a light guide plate that are excellent in hue and transparency and excellent in long-term thermal stability.
- the light guide plate is incorporated in the edge-light type backlight and plays the role of guiding the light from the side to the liquid crystal panel, and is used in a wide range of applications such as televisions, desktop personal computer monitors, notebook personal computers, mobile phones, car navigation systems.
- the A backlight using a light guide plate is also used for illumination.
- An acrylic resin typified by PMMA (polymethyl methacrylate) is used for the light guide plate.
- PMMA polymethyl methacrylate
- Patent Document 1 has been proposed as an improvement technique of MS resin such as water absorption and reduction of discoloration during molding.
- Patent Document 1 discloses a light guide plate in which the weight average molecular weight (Mw) of a styrene- (meth) acrylic ester copolymer resin is 60 to 170,000, the residual monomer amount is 3000 ppm or less, and the oligomer amount is 2% or less.
- Mw weight average molecular weight
- the water absorption is high and the dimensional stability tends to be worse than that of a styrene resin using a styrene monomer as a raw material.
- An object of the present invention is to provide a styrenic resin composition, a molded article, and a light guide plate that are excellent in hue and transparency, and have small changes in hue and transmittance even after long-term use.
- a styrene resin having a weight average molecular weight of 150,000 to 700,000 and at least one (b) phosphorus-based oxidation selected from (B-1) to (B-4)
- a styrene resin composition comprising an inhibitor and at least one (c) hindered phenol antioxidant selected from (C-1) to (C-4),
- the optical styrene resin characterized in that the content of (b) in 100% by mass is 0.03 to 0.40% by mass and the content of (c) is 0.02 to 0.30% by mass.
- a composition is provided.
- B-1 Tris (2,4-di-tert-butylphenyl) phosphite (B-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (C-1) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (C -2) 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,
- the present inventors have intensively studied to suppress discoloration that occurs during long-term use, and it has been found that the combined use of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is effective in suppressing discoloration. It was. However, further investigations have shown that it may not be successful if these two types of antioxidants are used in combination. Then, when further examination was advanced, (1) phosphorus antioxidant has a specific structure, (2) the content is the quantity of a specific range, (3) hindered phenolic oxidation It has been found that when the inhibitor has a specific configuration and (4) the content is in a specific range, the discoloration suppressing effect of the styrene-based resin composition becomes extremely high. Although the operational effect for obtaining such an effect is not necessarily clarified, it is considered to be due to the synergistic effect of these four conditions because it is exhibited effectively only when the above four conditions are met.
- the combination of (b) phosphorus antioxidant and (c) hindered phenol antioxidant is (B-1) and (C-1), (B-1) and (C-2), (B-1) and (C-3), (B-1) and (C-4), (B-2) and (C-1), (B-2) and (C-4), (B -3) and (C-1), (B-3) and (C-2), (B-3) and (C-3), (B-3) and (C-4), (B-4) ) And (C-1), (B-4) and (C-2), (B-4) and (C-3), (B-4) and (C-4) At least one set, more preferably (B-1) and (C-1), (B-1) and (C-2), (B-1) and (C-3), (B-1 ) And (C-4), (B-2) and (C-1), or (B-2) and (C-4).
- the styrene resin is a styrene- (meth) acrylic acid copolymer resin obtained by copolymerizing a styrene monomer and (meth) acrylic acid, and the styrene monomer unit of the styrene resin. Is 90.0 to 99.9% by mass, and (meth) acrylic acid unit content is 0.1 to 10.0% by mass. However, the total content of styrene monomer units and (meth) acrylic acid units in the styrene resin is 100% by mass.
- the styrene resin is a styrene- (meth) acrylate copolymer resin obtained by copolymerizing a styrene monomer and a (meth) acrylate ester
- the content of body units is 40.0 to 99.0% by mass
- the content of (meth) acrylic acid ester units is 1.0 to 60.0% by mass.
- the total content of styrene monomer units and (meth) acrylic acid ester units in the styrene resin is 100% by mass. Further, it contains 0.4 to 2.0% by mass of a hydrophilic additive having a polyether chain.
- it is a molded article which consists of said styrene resin composition for optics.
- it is a light-guide plate which consists of said molded article.
- the styrenic resin composition and molded article of the present invention have low water absorption and are inexpensive compared to PMMA and MS resin, have small changes in hue and transmittance during long-term use, and are excellent in colorless transparency. Therefore, it can be suitably used for optical applications such as a light guide plate. Moreover, the coloring prevention effect with respect to high temperature heat history, such as a shaping
- the styrene resin of the present invention can be obtained by polymerizing a styrene monomer.
- Styrene monomers are aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene, etc. Or it is a mixture of two or more, preferably styrene.
- acrylic acid monomers such as acrylic acid and methacrylic acid
- vinyl cyanide monomers such as acrylonitrile and methacrylonitrile
- butyl acrylate Acrylic monomers such as ethyl acrylate, methyl acrylate, and methyl methacrylate
- ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as maleic anhydride and fumaric acid
- imide monomers such as phenyl maleimide and cyclohexyl maleimide.
- the styrene resin composition is preferably composed of a styrene resin and various additives, and the ratio of the styrene resin in 100% by mass of the styrene resin composition is, for example, 90 to 99.95% by mass. 95 to 99.95% by mass is preferable. Specifically, the ratio of the styrenic resin is, for example, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.95% by mass, and any one of the numerical values exemplified here is 2 It may be within a range between the two.
- the styrene resin is a styrene- (meth) acrylic acid copolymer resin obtained by copolymerizing a styrene monomer and (meth) acrylic acid
- the content of the styrene resin unit of the styrene resin It was experimentally confirmed that the object of the present application can be achieved even when the amount is 90.0 to 99.9% by mass and the content of the (meth) acrylic acid unit is 0.1 to 10.0% by mass.
- the total content of styrene monomer units and (meth) acrylic acid units is 100% by mass.
- (Meth) acrylic acid is acrylic acid, methacrylic acid or the like, with methacrylic acid being preferred.
- the content of the (meth) acrylic acid unit in the styrenic resin can be adjusted by the composition ratio of the raw styrene monomer and the (meth) acrylic acid monomer during the polymerization of the styrene resin.
- a styrene resin containing a (meth) acrylic acid unit and a styrene resin not containing a (meth) acrylic acid unit can be blended and adjusted.
- the styrene resin is a styrene- (meth) acrylate copolymer resin obtained by copolymerizing a styrene monomer and a (meth) acrylate ester
- a styrene monomer unit of the styrene resin It has been experimentally confirmed that the object of the present invention can be achieved even when the content of is 40.0 to 99.0% by mass and the content of the (meth) acrylate unit is 1.0 to 60.0% by mass. It was. However, the total content of the styrene monomer unit and the (meth) acrylate unit is 100% by mass.
- the (meth) acrylic acid ester is a methacrylic acid ester such as methyl methacrylate or ethyl methacrylate, or an acrylic acid ester such as methyl acrylate or ethyl acrylate.
- the content of the (meth) acrylic acid ester unit in the styrene resin can be measured under the following conditions by pyrolysis gas chromatography.
- Pyrolysis furnace PYR-2A (manufactured by Shimadzu Corporation) Pyrolysis furnace temperature setting: 525 ° C
- Gas chromatograph GC-14A (manufactured by Shimadzu Corporation) Column: Glass 3mm diameter x 3m Filler: FFAP Chromsorb WAW 10% Injection, detector temperature: 250 ° C Column temperature: 120 ° C Carrier gas: Nitrogen
- Examples of the polymerization method of the styrene resin include known styrene polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. In terms of quality and productivity, bulk polymerization and solution polymerization are preferable, and continuous polymerization is preferable.
- Examples of the 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.
- a polymerization initiator and a chain transfer agent can be used as needed during the polymerization of the styrene resin.
- a radical polymerization initiator is preferable.
- 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 2,2- Peroxyketals such as di (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-di (t-amylperoxy) cyclohexane, cumene hydroperoxide, t-butyl hydroperoxide, etc.
- Alkyl peroxides such as hydroperoxides, t-butylperoxyacetate, t-amylperoxyisononanoate, t-butylcumyl peroxide, di-t-butylperoxide, dicumylperoxide, di-t -Dialkyl peroxides such as hexyl peroxide, t-butylperoxyacetate Peroxyesters such as t-butyl peroxybenzoate and t-butylperoxyisopropyl monocarbonate, peroxycarbonates such as t-butyl peroxyisopropyl carbonate and polyether tetrakis (t-butyl peroxycarbonate) N, N′-azobis (cyclohexane-1-carbonitrile), N, N′-azobis (2-methylbutyronitrile), N, N′-azobis (2,4-dimethylvaleronitrile), N, N '-Azobis [2- (hydroxymethyl
- the polymerization reaction is first controlled by adjusting the polymerization temperature to achieve the target molecular weight, molecular weight distribution, and reaction conversion rate using a well-known complete mixing tank type stirring tank or tower reactor in the polymerization process. Is done.
- the polymerization solution containing the polymer exiting the polymerization step is transferred to the devolatilization step, and unreacted monomers and polymerization solvent are removed.
- the devolatilization process includes a vacuum devolatilization tank with a heater, a vented devolatilization extruder, and the like.
- the polymer in the molten state that has exited the devolatilization step is transferred to the granulation step.
- the molten resin is extruded in a strand form from a porous die and processed into a pellet shape by a cold cut method, an air hot cut method, or an underwater hot cut method.
- the weight average molecular weight of the styrene resin is 150,000 to 700,000, preferably 160,000 to 700,000, more preferably 160,000 to 400,000 or 180,000 to 500,000. If it is less than 150,000, the strength of the molded product becomes insufficient.
- the weight average molecular weight of the styrenic resin should be controlled by the reaction temperature of the polymerization process, the residence time, the type and amount of polymerization initiator, the type and amount of chain transfer agent, the type and amount of solvent used during polymerization, etc. Can do.
- the weight average molecular weight (Mw), the Z average molecular weight (Mz), and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions.
- 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 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 styrene resin composition contains (b) a phosphorus antioxidant and / or (c) a hindered phenol antioxidant, and the content of (b) in 100% by mass of the styrene resin composition is 0. 0.03 to 0.40 mass%, and the content of (c) is 0.02 to 0.30 mass%.
- the content of (b) is 0.05 to 0.30% by mass, and the content of (c) is 0.02 to 0.20% by mass. More preferably, the content of (b) is 0.10 to 0.25% by mass, and the content of (c) is 0.05 to 0.15% by mass.
- the long-term thermal stability When the contents of (b) and (c) are outside the above ranges, the long-term thermal stability is poor.
- Long-term thermal stability represents changes in hue and transmittance due to heat in long-term use, and those having excellent thermal stability have small changes in hue and transmittance.
- the long-term thermal stability can be evaluated as an accelerated test by storing the molded product under a high temperature condition (60 to 90 ° C.) that does not cause deformation of the resin, and changing the hue and transmittance over time.
- the content of the phosphorus antioxidant in 100% by mass of the styrene resin composition is, for example, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40 mass%, and within the range between any two of the numerical values exemplified here It may be.
- the content of the hindered phenol-based antioxidant in 100% by mass of the styrene-based resin composition is, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.0. 07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30 mass%, and within the range between any two of the numerical values exemplified here. May be.
- Phosphorous antioxidants are phosphites which are trivalent phosphorus compounds
- hindered phenolic antioxidants are antioxidants having a phenolic hydroxyl group in the basic skeleton.
- the present inventors have at least selected from the following (B-1) to (B-4): A combination of one phosphorus antioxidant and at least one hindered phenol antioxidant selected from (C-1) to (C-4) is extremely effective in preventing discoloration of the styrene resin composition. It was experimentally found to be effective.
- B-1 Tris (2,4-di-tert-butylphenyl) phosphite (B-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (C-1) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (C -2) 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,
- Methods for adding phosphorus antioxidants and hindered phenol antioxidants include addition and mixing in the polymerization process, devolatilization process, and granulation process of styrene resins, and extruders and injection molding machines during molding. And a method of diluting and mixing a resin composition prepared by adding a hydrophilic additive to a high concentration with a non-added styrenic resin to a desired content, and the like.
- the styrenic resin composition may contain mineral oil as long as the colorless transparency of the present invention is not impaired. Also includes additives such as internal lubricants such as stearic acid and ethylenebisstearylamide, 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, and the content is preferably 30 to 200 ppm in the resin composition.
- the ultraviolet absorber has a function of suppressing deterioration and coloring caused by ultraviolet rays.
- benzophenone, benzotriazole, triazine, benzoate, salicylate, cyanoacrylate, oxalic anilide, malonic ester UV absorbers such as those of formaldehyde and formamidine. These can be used alone or in combination of two or more thereof, and a light stabilizer such as hindered amine may be used in combination.
- the styrenic resin that can be obtained by polymerizing styrenic monomers may cause the molded product to become cloudy due to environmental changes such as temperature, humidity, and hot water immersion.
- Styrene- (meth) acrylic acid copolymer resin obtained by copolymerization with acrylic acid, or styrene- (meth) acrylic acid obtained by copolymerization of styrene monomer and (meth) acrylic acid ester Cloudiness can be prevented by using an ester copolymer resin. Further, white turbidity can be prevented even when a hydrophilic additive having a polyether chain is contained in the styrene resin composition.
- the method of changing the kind of styrene resin and the method of adding a hydrophilic additive can also be used together.
- Styrenic resins have the problem that the molded product becomes cloudy (whitening phenomenon) due to environmental changes such as temperature, humidity, and hot water immersion (Journal of the Fiber Science Society, Vol. 34, No. 6, pp. 245-253, 1978).
- the transparency which is an advantage, may be impaired.
- a molded product was exposed to an environmental change from a high-temperature and high-humidity environment to a room temperature environment or an environment change from a room temperature environment to a low-temperature environment, it was uniformly present in the styrene resin. This is a phenomenon in which moisture becomes unstable and phase separation occurs to form a disk-like defect, and as a result, the inside of the molded product becomes cloudy.
- a molded product of a styrene resin is immersed in warm water for a certain period of time or more and then the molded product is taken out, whitening may occur.
- the styrene resin is a styrene- (meth) acrylic acid copolymer resin obtained by copolymerizing a styrene monomer and (meth) acrylic acid
- the content of styrene monomer units in the styrene resin is preferably 90.0 to 99.2% by mass, and the content of (meth) acrylic acid units is preferably 0.8 to 10.0% by mass,
- the content of the (meth) acrylic acid unit is more preferably 0.8 to 4.5% by mass, and further preferably 1.8 to 3.0% by mass.
- the total content of styrene monomer units and (meth) acrylic acid units is 100% by mass.
- (Meth) acrylic acid is acrylic acid, methacrylic acid or the like, with methacrylic acid being preferred.
- content of the (meth) acrylic acid unit is less than 0.8% by mass, the whitening suppression effect tends to be insufficient.
- a styrene- (meth) acrylate copolymer resin obtained by copolymerizing a styrene resin with a styrene monomer and a (meth) acrylate ester
- the content of the styrene monomer unit in the styrene resin is preferably 40 to 96% by mass
- the content of the (meth) acrylic acid ester unit is preferably 4 to 60% by mass.
- the content of the ester unit is more preferably 4 to 15% by mass, further preferably 6 to 12% by mass, and further preferably 7 to 9% by mass.
- the total content of the styrene monomer unit and the (meth) acrylate unit is 100% by mass.
- the (meth) acrylic acid ester is a methacrylic acid ester such as methyl methacrylate or ethyl methacrylate, or an acrylic acid ester such as methyl acrylate or ethyl acrylate.
- the content of the (meth) acrylic acid ester unit is less than 4% by mass, the whitening suppression effect tends to be insufficient. Moreover, when it exceeds 60.0 mass%, water absorption will deteriorate easily. Further, when the content of the (meth) acrylic acid ester unit increases, the fluidity tends to decrease, and the moldability tends to decrease in applications where high fluidity is required such as injection molding.
- the hydrophilic additive is a compound having a hydrophilic group capable of interacting with water (hydrogen bonding).
- the hydrophilic group is preferably a polyether chain.
- the polyether chain is a skeleton structure in which ether bonds are linked.
- Polyglycerol chains synthesized by dehydration condensation of glycerin and the like can be mentioned, and polyoxyethylene chains are preferable.
- the polyether chain may have not only one set per molecule but also a plurality of sets.
- Polyoxyethylene type nonionic surfactant polyoxyethylene type anionic surfactant, polyoxyethylene type cationic surfactant, polyoxyethylene type amphoteric as hydrophilic additive having polyoxyethylene chain
- examples thereof include polyoxyethylene type surfactants such as surfactants and polyethylene glycol.
- polyoxyethylene type surfactants polyoxyethylene type nonionic surfactants are preferred.
- Polyoxyethylene type nonionic surfactants include polyoxyethylene alkyl ether represented by the following general formula (1), polyoxyethylene fatty acid ester represented by the following general formula (2), polyoxyethylene hydrogenated castor oil, polyoxy Ethylene sorbitan fatty acid ester and polyoxyethylene sorbitol fatty acid ester are exemplified, but one or more selected from the group of polyoxyethylene alkyl ether and / or polyoxyethylene fatty acid ester are preferable.
- polyvalent polyoxyethylene alkyl ethers having a plurality of polyoxyethylene alkyl ether skeletons in one molecule and polyvalent polyoxyethylene fatty acid esters having a plurality of polyoxyethylene fatty acid ester skeletons in one molecule are used.
- the valence of polyoxyethylene alkyl ether or polyoxyethylene fatty acid ester means the number of polyoxyethylene alkyl ether skeleton or polyoxyethylene fatty acid ester skeleton present in one molecule.
- R represents an alkyl group having 8 to 20 carbon atoms.
- a polyvalent polyoxyethylene alkyl ether up to hexavalent having a plurality of polyoxyethylene alkyl ether skeletons, and a plurality of polyoxyethylene fatty acid ester skeletons.
- It may be a polyvalent polyoxyethylene fatty acid ester having up to 6 valences, where n is an integer and represents the number of added moles of ethylene oxide units.
- Polyoxyethylene alkyl ether is made by adding ethylene oxide to alcohol
- polyoxyethylene fatty acid ester is made by adding ethylene oxide to fatty acid or directly esterifying fatty acid and polyethylene glycol.
- the number is preferably 7 to 100, more preferably 10 to 50.
- the average molecular weight of polyethylene glycol is preferably 200 to 10,000. It is more preferably 200 to 4000, and further preferably 300 to 1000. If the average molecular weight of polyethylene glycol is less than 200, gas is generated during the molding process, and the mold and roll are soiled, which is not preferable. In addition, if it exceeds 10,000, the effect of preventing the whitening phenomenon tends to be reduced, and the compatibility with the styrene resin is reduced, and the styrene resin composition and the molded product thereof may become cloudy.
- the average molecular weight is calculated from the hydroxyl group concentration (based on JIS K1557) measured by the pyridine phthalic anhydride method.
- hydrophilic additive having a polyether chain examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl decyl ether, polyoxyethylene myristyl ether, polyoxyethylene 2 -Polyoxyethylene alkyl ethers such as ethylhexyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate , Polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol di Polyoxyethylene fatty acid esters such as tearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyethylene glycol, polyoxyethylene monomethyl ether, polyoxyethylene dimethyl ether, polyoxyethylene glyceryl ether, polyoxy
- the HLB value of the hydrophilic additive having a polyether chain is preferably 8 or more, more preferably 10-20.
- HLB Hydrophilic-lipophilic balance
- HLB Hydrophilic-lipophilic balance
- the heat loss of the hydrophilic additive having a polyether chain at a temperature of 200 ° C. in a nitrogen atmosphere is 10% by mass or less.
- Heat loss in a nitrogen atmosphere at a temperature of 200 ° C. can be determined by thermogravimetric analysis (TGA). Heating is performed at a temperature increase rate of 10 ° C./min from a room temperature in a nitrogen atmosphere, and the weight loss at a temperature of 200 ° C. It can be determined from the quantity.
- An additive having a temperature loss of 200 ° C. and a heating loss of more than 10% by mass in a nitrogen atmosphere has high volatility, and gas is generated during the molding process of the styrene-based resin, which may cause mold or roll contamination.
- the hydrophilic additive having a polyether chain has a content in 100% by mass of the styrene resin composition of 0.4 to 2.0% by mass, and preferably 0.7 to 1.6% by mass. . If the content of the hydrophilic additive having a polyether chain is less than 0.4% by mass, it is difficult to prevent the whitening phenomenon due to environmental changes, and if it exceeds 2.0% by mass, the heat resistance of the styrene-based resin composition decreases. To do.
- hydrophilicity As a method of adding a hydrophilic additive having a polyether chain, a method of adding and mixing in a polymerization step, a devolatilization step and a granulation step of a styrenic resin, a method of adding and mixing with an extruder during molding processing, etc., hydrophilicity A method of diluting and mixing the resin composition with the additive adjusted to a high concentration with an additive-free styrenic resin to the desired content can be mentioned, and is not particularly limited.
- a styrene resin composition containing 0.5 to 50.0% by mass of a hydrophilic additive and an additive-free styrene resin are mixed using an extruder or an injection molding machine to obtain a styrene resin having a desired concentration.
- the method include obtaining a resin composition, a molded product, and a light guide plate.
- the Vicat softening temperature of the styrene resin composition of the present invention is preferably 95 to 104 ° C, more preferably 97 to 104 ° C. When the Vicat softening temperature is less than 95 ° C., the heat resistance is insufficient, and the molded product may be deformed depending on the use environment.
- the haze of the styrenic resin composition of the present invention is a molded product having a thickness of 4 mm, preferably 5% or less, and more preferably 1% or less.
- the styrenic resin composition of the present invention can be molded by a molding method according to the purpose such as injection molding, extrusion molding, compression molding, blow molding, and the shape thereof is not limited.
- a molding method such as injection molding, extrusion molding, compression molding, blow molding, and the shape thereof is not limited.
- it is a plate-shaped molded product, it can be processed into a light guide plate or the like.
- the obtained molded product is used as an optical member that functions by transmitting light into the molded product such as a light guide plate.
- An optical member such as a light guide plate is preferably a material having a high transmittance and an excellent hue because of a long light transmission distance (optical path length).
- the initial transmittance at an optical path length of 115 mm is preferably 84% or more and the YI value is 7.0 or less.
- the YI difference after storage for 1000 hours at 80 ° C. is preferably 3.0 or less, and more preferably 1.5 or less.
- the transmittance and YI value for an optical path length of 115 mm were measured by the following procedure. Using pellets of the styrene-based 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 article having a thickness of 127 ⁇ 127 ⁇ 3 mm.
- the sample to be evaluated for long-term thermal stability 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, and the end surface was polished by buffing to produce a plate-shaped molded product having a mirror surface on the end surface.
- the polished plate-like molded product was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation, with an incident light having a size of 20 ⁇ 1.6 mm and a spread angle of 0 °, and a wavelength at an optical path length of 115 mm Spectral transmittances from 350 nm to 800 nm were measured, and the YI value with a C light source at a visual field of 2 ° was calculated according to JIS K7105.
- the transmittance is an average transmittance at a wavelength of 380 nm to 780 nm.
- the light guide plate receives light from the end surface (side surface) of the plate-shaped molded product, and guides light to the front surface (light emitting surface) of the molded product by a reflection pattern formed on the rear surface (non-light emitting surface) of the molded product. It is a member that has the function of emitting surface light.
- the reflective pattern can be formed by a method such as a screen printing method, an injection molding method, a laser method, or an ink jet method. When processing the plate-shaped molded product into the light guide plate, it is preferable to polish the light incident surface or the entire end surface to a mirror surface.
- a prism pattern or the like can be provided on the front surface (light emitting surface) of the plate-shaped molded product.
- the pattern on the front surface or the rear surface of the plate-shaped molded product can be formed at the time of molding the plate-shaped molded product.
- the pattern can be formed by a mold shape in injection molding or roll transfer in extrusion molding.
- the polymerization reactor is configured by connecting a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer.
- the styrene resin was manufactured by the above.
- the capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor.
- a raw material solution was prepared with the raw material composition described in Table 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1.
- the polymerization initiator was added to the raw material solution at the inlet of the first reactor so that the addition concentration shown in Table 1 (concentration based on mass with respect to the total amount of raw styrene and methacrylic acid) was mixed.
- the polymerization initiators listed in Table 1 are as follows: Polymerization initiator-1: 2,2-di (4,4-t-butylperoxycyclohexyl) propane (Pertetra A manufactured by NOF Corporation was used).
- Polymerization initiator-2 1,1-di (t-butylperoxy) cyclohexane (Perhexa C manufactured by NOF Corporation was used.)
- a temperature gradient was provided along the flow direction, and the temperature in Table 1 was adjusted at the intermediate part and the outlet part. Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted by two stages in series, and the preheater was adjusted to the resin temperature shown in Table 1.
- Examples 1-1 to 1-30, Comparative Examples 1-1 to 1-10) Using the content shown in Table 2, styrene resins PS-1, PS-2, PS-3 and B and C as additives and a single screw extruder with a screw diameter of 40 mm, cylinder temperature 230 ° C., screw rotation Pellets were obtained by melting and kneading at several hundred rpm.
- Additives B and C used in Table 2 are shown below.
- Additive B represents (b) a phosphorus-based antioxidant
- additive C represents (c) a hindered phenol-based antioxidant.
- B-1 Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168 manufactured by BASF Japan Ltd.)
- B-2 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus (ADEKA STAB HP-10 manufactured by ADEKA Corporation)
- B-3 Bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228 manufactured by Dober Chemical Corporation)
- B-4 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane ADEKA ADK STAB PEP-36)
- B-5 Tetrakis (2,4-di-tert-butylphenyl) [1,1biphenyl]
- B-6 Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Irgafos 38 manufactured by BASF Japan Ltd.)
- B-7 Diphenyl-2-ethylhexyl phosphite (ADEKA STAB C manufactured by ADEKA Corporation)
- B-8 Triisodecyl phosphite (Adeka Corporation Adeka Stub 3010)
- B-9 Cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl phosphite) (Adeka Stab PEP-8 manufactured by ADEKA Corporation)
- C-1 Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan Ltd.)
- C-2 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl
- injection molding was performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to form a plate-shaped molded article having a thickness of 127 ⁇ 127 ⁇ 3 mm.
- the obtained molded product was stored in an oven at 80 ° C. for 1000 hours.
- a 115 ⁇ 85 ⁇ 3 mm thickness test piece was cut out from the plate-shaped molded product, the end surface was polished by buffing, and a mirror surface was formed on the end surface.
- a plate-shaped molded article having the same was prepared.
- the polished plate-like molded product was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation, with an incident light having a size of 20 ⁇ 1.6 mm and a spread angle of 0 °, and a wavelength at an optical path length of 115 mm.
- Spectral transmittances from 350 nm to 800 nm were measured, and the YI value at 2 ° for the C light source was calculated according to JIS K7105.
- the transmittance shown in Table 2 represents an average transmittance at a wavelength of 380 nm to 780 nm.
- YI value after ⁇ heating was calculated based on the following formula.
- “without additive” means that neither additive B nor additive C is added, and “with additive” means at least one of additive B and additive C. Is added.
- examples, comparative examples, and reference examples are collectively referred to as “test examples”.
- YI value after heating (“YI value after 80 ° C. ⁇ 1000 hours” of test example with additive) ⁇ (“YI value after 80 ° C. ⁇ 1000 hour” of test example without additive))
- Example 1-1 For example, in Example 1-1 with an additive, the YI value after 7.0 hours at 80 ° C. is 7.0, and in Reference Example 1-1 in which the same kind of styrenic resin is used, 80 ° C. ⁇ 1000 Since the YI value after time is 11.6, the “YI value after ⁇ heating” in Example 1-1 is ⁇ 4.6. This value indicates the degree of the discoloration preventing effect due to the addition of the additives B and C, and the smaller the value, the greater the effect.
- the molded product of the example was excellent in the initial transmittance and YI value, had a small amount of YI change during storage at 80 ° C. ⁇ 1000 hours, and was excellent in long-term thermal stability.
- the phosphorus-based antioxidant has a specific configuration
- the content is in a specific range
- the hindered phenol-based antioxidant has a specific configuration.
- Examples 1-13 and 1-14 the same effect can be obtained even if the type of the styrene resin is a styrene- (meth) acrylic acid copolymer resin or a styrene- (meth) acrylic acid ester copolymer resin. It turns out that it is obtained.
- a polymerization process is configured by connecting in series a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer.
- the styrene resin was manufactured by the above.
- the capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor.
- a raw material solution was prepared with the raw material composition described in Condition 1 of 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1.
- hydrophilic additive D which has a polyether chain
- the types of additives and polyethylene glycol used are as follows.
- D-1 Polyethylene glycol having an average molecular weight of 400 (PEG # 400 manufactured by NOF Corporation)
- D-2 Polyethylene glycol having an average molecular weight of 1000 (PEG # 1000 manufactured by NOF Corporation)
- D-3 Polyethylene glycol having an average molecular weight of 2000 (PEG # 2000 manufactured by NOF Corporation)
- D-8 Polyethylene glycol monolaurate Average addition mole number of ethylene oxide
- the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted of two stages in series, and after separating unreacted styrene and ethylbenzene, a strand shape After being extruded and cooled, it was cut into pellets.
- the resin temperature in the first stage devolatilization tank is set to 160 ° C.
- the pressure in the vacuum devolatilization tank is set to 65 kPa
- the resin temperature in the second stage devolatilization layer is set to 235 ° C.
- the pressure in the volatilization tank was 0.8 kPa. All of the obtained styrene resins had a weight average molecular weight (Mw) of 370,000.
- melt mass flow rate conforms to JIS K-7210, under conditions of 200 ° C. and 49 N load, the Vicat softening temperature conforms to JIS K 7206, the heating rate is 50 ° C./hr, and the test load is 50 N.
- the transmittance and YI value were measured in the same manner as in Test 1.
- a plate-like molded article having a mirror surface on the end face is exposed to an environment of 60 ° C. and 90% relative humidity for 150 hours, and the test piece is placed in an environment of 23 ° C. and 50% relative humidity Taking out and observing the whitening phenomenon occurring inside the molded product, the following judgment was made as a whitening suppression effect.
- ⁇ Whitening occurs after 1 hour, but almost disappears after 24 hours.
- X Remarkably whitening after 1 hour. Table 3 shows the characteristics and evaluation results of each resin composition.
- the molded products of Examples 2-1 to 2-23 are excellent in whitening suppression effect, excellent in initial transmittance and YI value, have a small amount of YI change during storage at 80 ° C. ⁇ 1000 hours, and have long-term heat. Excellent stability.
- the hydrophilic additive D was not added, or the addition amount was too small, and the whitening phenomenon occurred.
- Example 2-26 since the amount of the hydrophilic additive D added was too large, the heat resistance was lowered.
- the polymerization reactor is configured by connecting a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer, to form a polymerization process, and the conditions shown in Table 4
- the styrene resin was manufactured by the above.
- the capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor.
- a raw material solution was prepared with the raw material composition described in Table 4, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 4.
- the polymerization initiator was added to the raw material solution at the inlet of the first reactor so as to have the addition concentration shown in Table 4 (concentration based on mass relative to the total amount of raw material styrene and methyl methacrylate), and was uniformly mixed.
- the polymerization initiators listed in Table 4 were as follows: Polymerization initiator-1: 1,1-di (t-butylperoxy) cyclohexane (Perhexa C manufactured by NOF Corporation was used.)
- a temperature gradient was provided along the flow direction, and the temperature in Table 4 was adjusted at the intermediate part and the outlet part.
- the solution containing the polymer continuously taken out from the third 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 4.
- the preheater was adjusted to the resin temperature shown in Table 4.
- the content of methyl methacrylate units (PMMA amount) in the styrene resin was measured by pyrolysis gas chromatography under the following conditions.
- Pyrolysis furnace PYR-2A (manufactured by Shimadzu Corporation) Pyrolysis furnace temperature setting: 525 ° C
- Gas chromatograph GC-14A (manufactured by Shimadzu Corporation)
- Column Glass 3mm diameter x 3m
- Filler FFAP Chromsorb WAW 10% Injection, detector temperature: 250 ° C
- Carrier gas Nitrogen Melt mass flow rate (MFR) conforms to JIS K 7210, temperature 200 ° C, 49N load, Vicat softening temperature conforms to JIS K 7206, heating rate 50 ° C / hr, test Measurement was performed at a load of 50N.
- MFR Nitrogen Melt mass flow rate
- the molded products of Examples 3-1 to 3-16 having a relatively high content of (meth) acrylic acid ester units are excellent in whitening suppression effect, excellent in initial transmittance and YI value, and are 80 ° C. ⁇ 1000.
- the amount of change in YI during storage over time was small, and long-term thermal stability was also excellent.
- the (meth) acrylic acid ester unit was not contained or the content thereof was relatively small, the whitening suppressing effect was not sufficient.
- the optical styrenic resin composition and molded article of the present invention are excellent in hue and transparency and excellent in long-term thermal stability.
- transparency which is an advantage of styrenic resins, can be maintained even in applications where the whitening phenomenon has conventionally occurred due to environmental changes.
- light guide plate applications such as a television, a desktop personal computer, a notebook personal computer, a mobile phone, and a car navigation can be used.
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Abstract
Description
そのため、これら特性を改善したスチレンと(メタ)アクリル酸メチルとの共重合体であるMS樹脂を用いることが提案されている。MS樹脂の、吸水性や成形時の変色低減等の改良技術としては特許文献1が提案されている。
特許文献1では、スチレン-(メタ)アクリル酸エステル系共重合体樹脂の重量平均分子量(Mw)6~17万、残存モノマー量3000ppm以下、更にオリゴマー量が2%以下の導光板が開示されているが、吸水性が高く寸法安定性がスチレン系単量体を原料とするスチレン系樹脂よりも悪い傾向にある。
一方、スチレン系単量体を原料とするスチレン系樹脂は吸水性が低いものの、長期間の使用において熱による変色が発生し、成形品が黄変して透過率が低下することがある。その結果、バックライトの輝度が低下し、色度が変化することがある。 There are two types of backlights for liquid crystal displays: a direct type backlight in which a light source is disposed in front of the display device and an edge light type backlight in which a light source is disposed on a side surface. The light guide plate is incorporated in the edge-light type backlight and plays the role of guiding the light from the side to the liquid crystal panel, and is used in a wide range of applications such as televisions, desktop personal computer monitors, notebook personal computers, mobile phones, car navigation systems. The A backlight using a light guide plate is also used for illumination. An acrylic resin typified by PMMA (polymethyl methacrylate) is used for the light guide plate. However, since the water absorption is high, the molded product may be warped or dimensional changes may occur.
Therefore, it has been proposed to use MS resin which is a copolymer of styrene and methyl (meth) acrylate with improved properties. Patent Document 1 has been proposed as an improvement technique of MS resin such as water absorption and reduction of discoloration during molding.
Patent Document 1 discloses a light guide plate in which the weight average molecular weight (Mw) of a styrene- (meth) acrylic ester copolymer resin is 60 to 170,000, the residual monomer amount is 3000 ppm or less, and the oligomer amount is 2% or less. However, the water absorption is high and the dimensional stability tends to be worse than that of a styrene resin using a styrene monomer as a raw material.
On the other hand, although a styrene resin using a styrene monomer as a raw material has low water absorption, discoloration due to heat may occur during long-term use, and the molded product may turn yellow to lower the transmittance. As a result, the luminance of the backlight may decrease and the chromaticity may change.
(B-1)トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト
(B-2)2,2'-メチレンビス(4,6-ジ-tert-ブチル-1-フェニルオキシ)(2-エチルヘキシルオキシ)ホスホラス
(B-3)ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト
(B-4)3,9-ビス(2,6-ジ-tert-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ〔5.5〕ウンデカン
(C-1)オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート
(C-2)3,9-ビス[2-〔3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン
(C-3)エチレンビス(オキシエチレン)ビス〔3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート〕
(C-4)ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート] According to the present invention, (a) a styrene resin having a weight average molecular weight of 150,000 to 700,000 and at least one (b) phosphorus-based oxidation selected from (B-1) to (B-4) A styrene resin composition comprising an inhibitor and at least one (c) hindered phenol antioxidant selected from (C-1) to (C-4), The optical styrene resin characterized in that the content of (b) in 100% by mass is 0.03 to 0.40% by mass and the content of (c) is 0.02 to 0.30% by mass. A composition is provided.
(B-1) Tris (2,4-di-tert-butylphenyl) phosphite (B-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (C-1) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (C -2) 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,1 - tetraoxaspiro [5.5] undecane (C-3) ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -m- tolyl) propionate]
(C-4) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
そこで、さらに検討を進めたところ、(1)リン系酸化防止剤が特定の構成を有するものであり、(2)その含有量が特定の範囲の量であり、(3)ヒンダードフェノール系酸化防止剤が特定の構成を有するものであり、且つ(4)その含有量が特定の範囲の量である場合に、スチレン系樹脂組成物の変色抑制効果が極めて高くなることが分かった。このような効果が得られる作用効果は必ずしも明らかになっていないが、上記4条件が揃った場合にのみ効果的に発揮されることから、これら4条件による相乗効果によるものであると考えられる。 The present inventors have intensively studied to suppress discoloration that occurs during long-term use, and it has been found that the combined use of a phosphorus-based antioxidant and a hindered phenol-based antioxidant is effective in suppressing discoloration. It was. However, further investigations have shown that it may not be successful if these two types of antioxidants are used in combination.
Then, when further examination was advanced, (1) phosphorus antioxidant has a specific structure, (2) the content is the quantity of a specific range, (3) hindered phenolic oxidation It has been found that when the inhibitor has a specific configuration and (4) the content is in a specific range, the discoloration suppressing effect of the styrene-based resin composition becomes extremely high. Although the operational effect for obtaining such an effect is not necessarily clarified, it is considered to be due to the synergistic effect of these four conditions because it is exhibited effectively only when the above four conditions are met.
好ましくは、(b)リン系酸化防止剤と(c)ヒンダードフェノール系酸化防止剤の組合せが、(B-1)と(C-1)、(B-1)と(C-2)、(B-1)と(C-3)、(B-1)と(C-4)、(B-2)と(C-1)、(B-2)と(C-4)、(B-3)と(C-1)、(B-3)と(C-2)、(B-3)と(C-3)、(B-3)と(C-4)、(B-4)と(C-1)、(B-4)と(C-2)、(B-4)と(C-3)、(B-4)と(C-4)の組合せの中から選ばれる少なくとも1組であり、さらに好ましくは、(B-1)と(C-1)、(B-1)と(C-2)、(B-1)と(C-3)、(B-1)と(C-4)、(B-2)と(C-1)、(B-2)と(C-4)の組合せの中から選ばれる少なくとも1組である。
また、スチレン系樹脂が、スチレン系単量体と(メタ)アクリル酸とを共重合して得られるスチレン-(メタ)アクリル酸共重合樹脂であって、スチレン系樹脂のスチレン系単量体単位の含有量が90.0~99.9質量%、(メタ)アクリル酸単位の含有量が0.1~10.0質量%である。ただし、スチレン系樹脂のスチレン系単量体単位と(メタ)アクリル酸単位の含有量の合計を100質量%とする。
また、スチレン系樹脂が、スチレン系単量体と(メタ)アクリル酸エステルとを共重合して得られるスチレン-(メタ)アクリル酸エステル共重合樹脂であって、スチレン系樹脂のスチレン系単量体単位の含有量が40.0~99.0質量%、(メタ)アクリル酸エステル単位の含有量が1.0~60.0質量%である。ただし、スチレン系樹脂のスチレン系単量体単位と(メタ)アクリル酸エステル単位の含有量の合計を100質量%とする。
また、ポリエーテル鎖を有する親水性添加剤を0.4~2.0質量%含有する。
また、上記の光学用スチレン系樹脂組成物からなる成形品である。
また、上記の成形品からなる導光板である。 Hereinafter, various embodiments of the present invention will be exemplified. The various embodiments described below can be combined with each other.
Preferably, the combination of (b) phosphorus antioxidant and (c) hindered phenol antioxidant is (B-1) and (C-1), (B-1) and (C-2), (B-1) and (C-3), (B-1) and (C-4), (B-2) and (C-1), (B-2) and (C-4), (B -3) and (C-1), (B-3) and (C-2), (B-3) and (C-3), (B-3) and (C-4), (B-4) ) And (C-1), (B-4) and (C-2), (B-4) and (C-3), (B-4) and (C-4) At least one set, more preferably (B-1) and (C-1), (B-1) and (C-2), (B-1) and (C-3), (B-1 ) And (C-4), (B-2) and (C-1), or (B-2) and (C-4). That.
The styrene resin is a styrene- (meth) acrylic acid copolymer resin obtained by copolymerizing a styrene monomer and (meth) acrylic acid, and the styrene monomer unit of the styrene resin. Is 90.0 to 99.9% by mass, and (meth) acrylic acid unit content is 0.1 to 10.0% by mass. However, the total content of styrene monomer units and (meth) acrylic acid units in the styrene resin is 100% by mass.
Further, the styrene resin is a styrene- (meth) acrylate copolymer resin obtained by copolymerizing a styrene monomer and a (meth) acrylate ester, The content of body units is 40.0 to 99.0% by mass, and the content of (meth) acrylic acid ester units is 1.0 to 60.0% by mass. However, the total content of styrene monomer units and (meth) acrylic acid ester units in the styrene resin is 100% by mass.
Further, it contains 0.4 to 2.0% by mass of a hydrophilic additive having a polyether chain.
Moreover, it is a molded article which consists of said styrene resin composition for optics.
Moreover, it is a light-guide plate which consists of said molded article.
本発明のスチレン系樹脂は、スチレン系単量体を重合して得ることができる。スチレン系単量体とは、芳香族ビニル系モノマーである、スチレン、α-メチルスチレン、o-メチルスチレン、p-メチルスチレン、m-メチルスチレン、エチルスチレン、p-t-ブチルスチレン等の単独または2種以上の混合物であり、好ましくはスチレンである。また、本発明の特徴を損ねない範囲でスチレン系単量体と共重合してもよく、アクリル酸、メタクリル酸等のアクリル酸モノマー、アクリロニトリル、メタクリロニトリル等のシアン化ビニルモノマー、アクリル酸ブチル、アクリル酸エチル、アクリル酸メチル、メタクリル酸メチル等のアクリル系モノマーや無水マレイン酸、フマル酸等のα,β-エチレン不飽和カルボン酸類、フェニルマレイミド、シクロヘキシルマレイミド等のイミド系モノマー類が挙げられる。
スチレン系樹脂組成物は、スチレン系樹脂と、各種添加剤とで構成されていることが好ましく、スチレン系樹脂組成物100質量%中のスチレン系樹脂の割合は、例えば90~99.95質量%であり、95~99.95質量%が好ましい。スチレン系樹脂の割合は、具体的には例えば、90、91、92、93、94、95、96、97、98、99、99.95質量%であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。 << Styrenic resin >>
The styrene resin of the present invention can be obtained by polymerizing a styrene monomer. Styrene monomers are aromatic vinyl monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene, etc. Or it is a mixture of two or more, preferably styrene. Further, it may be copolymerized with a styrene monomer within the range not impairing the characteristics of the present invention, acrylic acid monomers such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and butyl acrylate. , Acrylic monomers such as ethyl acrylate, methyl acrylate, and methyl methacrylate; α, β-ethylenically unsaturated carboxylic acids such as maleic anhydride and fumaric acid; and imide monomers such as phenyl maleimide and cyclohexyl maleimide. .
The styrene resin composition is preferably composed of a styrene resin and various additives, and the ratio of the styrene resin in 100% by mass of the styrene resin composition is, for example, 90 to 99.95% by mass. 95 to 99.95% by mass is preferable. Specifically, the ratio of the styrenic resin is, for example, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.95% by mass, and any one of the numerical values exemplified here is 2 It may be within a range between the two.
熱分解炉:PYR-2A(株式会社島津製作所製)
熱分解炉温度設定:525℃
ガスクロマトグラフ:GC-14A(株式会社島津製作所製)
カラム:ガラス製3mm径×3m
充填剤:FFAP Chromsorb WAW 10%
インジェクション、ディテクター温度:250℃
カラム温度:120℃
キャリアーガス:窒素 The content of the (meth) acrylic acid ester unit in the styrene resin can be measured under the following conditions by pyrolysis gas chromatography.
Pyrolysis furnace: PYR-2A (manufactured by Shimadzu Corporation)
Pyrolysis furnace temperature setting: 525 ° C
Gas chromatograph: GC-14A (manufactured by Shimadzu Corporation)
Column: Glass 3mm diameter x 3m
Filler: FFAP Chromsorb WAW 10%
Injection, detector temperature: 250 ° C
Column temperature: 120 ° C
Carrier gas: Nitrogen
重量平均分子量(Mw)及びZ平均分子量(Mz)、数平均分子量(Mn)は、ゲルパーミエイションクロマトグラフィー(GPC)を用いて、次の条件で測定した。
GPC機種:昭和電工株式会社製Shodex GPC-101
カラム:ポリマーラボラトリーズ社製 PLgel 10μm MIXED-B
移動相:テトラヒドロフラン
試料濃度:0.2質量%
温度:オーブン40℃、注入口35℃、検出器35℃
検出器:示差屈折計
分子量は単分散ポリスチレンの溶出曲線より各溶出時間における分子量を算出し、ポリスチレン換算の分子量として算出したものである。 The weight average molecular weight of the styrene resin is 150,000 to 700,000, preferably 160,000 to 700,000, more preferably 160,000 to 400,000 or 180,000 to 500,000. If it is less than 150,000, the strength of the molded product becomes insufficient. The weight average molecular weight of the styrenic resin should be controlled by the reaction temperature of the polymerization process, the residence time, the type and amount of polymerization initiator, the type and amount of chain transfer agent, the type and amount of solvent used during polymerization, etc. Can do.
The weight average molecular weight (Mw), the Z average molecular weight (Mz), and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions.
GPC model: Shodex GPC-101 manufactured by Showa Denko KK
Column: PLgel 10 μm 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 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.
スチレン系樹脂組成物は、(b)リン系酸化防止剤および/または(c)ヒンダードフェノール系酸化防止剤を含有し、スチレン系樹脂組成物100質量%中の(b)の含有量が0.03~0.40質量%、(c)の含有量が0.02~0.30質量%である。好ましくは、(b)の含有量が0.05~0.30質量%、(c)の含有量が0.02~0.20質量%である。さらに好ましくは、(b)の含有量が0.10~0.25質量%、(c)の含有量が0.05~0.15質量%である。(b)および(c)の含有量が上記の範囲外では、長期の熱安定性に劣る。長期の熱安定性は、長期間の使用における熱による色相および透過率の変化を表し、熱安定性に優れるものは色相および透過率の変化が小さい。長期の熱安定性は、加速試験として、樹脂が変形しない程度の高温度条件(60~90℃)に成形品を保管し、色相および透過率の経時変化によって評価することができる。スチレン系樹脂組成物100質量%中のリン系酸化防止剤の含有量は、具体的には例えば、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.10、0.15、0.20、0.25、0.30、0.35、0.40質量%であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。スチレン系樹脂組成物100質量%中のヒンダードフェノール系酸化防止剤の含有量は、具体的には例えば、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.10、0.15、0.20、0.25、0.30質量%であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。 << Phosphorus antioxidants and hindered phenol antioxidants >>
The styrene resin composition contains (b) a phosphorus antioxidant and / or (c) a hindered phenol antioxidant, and the content of (b) in 100% by mass of the styrene resin composition is 0. 0.03 to 0.40 mass%, and the content of (c) is 0.02 to 0.30 mass%. Preferably, the content of (b) is 0.05 to 0.30% by mass, and the content of (c) is 0.02 to 0.20% by mass. More preferably, the content of (b) is 0.10 to 0.25% by mass, and the content of (c) is 0.05 to 0.15% by mass. When the contents of (b) and (c) are outside the above ranges, the long-term thermal stability is poor. Long-term thermal stability represents changes in hue and transmittance due to heat in long-term use, and those having excellent thermal stability have small changes in hue and transmittance. The long-term thermal stability can be evaluated as an accelerated test by storing the molded product under a high temperature condition (60 to 90 ° C.) that does not cause deformation of the resin, and changing the hue and transmittance over time. Specifically, the content of the phosphorus antioxidant in 100% by mass of the styrene resin composition is, for example, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40 mass%, and within the range between any two of the numerical values exemplified here It may be. Specifically, the content of the hindered phenol-based antioxidant in 100% by mass of the styrene-based resin composition is, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.0. 07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30 mass%, and within the range between any two of the numerical values exemplified here. May be.
(B-1)トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト
(B-2)2,2'-メチレンビス(4,6-ジ-tert-ブチル-1-フェニルオキシ)(2-エチルヘキシルオキシ)ホスホラス
(B-3)ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト
(B-4)3,9-ビス(2,6-ジ-tert-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ〔5.5〕ウンデカン
(C-1)オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート
(C-2)3,9-ビス[2-〔3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン
(C-3)エチレンビス(オキシエチレン)ビス〔3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート〕
(C-4)ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート] Phosphorous antioxidants are phosphites which are trivalent phosphorus compounds, and hindered phenolic antioxidants are antioxidants having a phenolic hydroxyl group in the basic skeleton. There are a large number of compounds that can be used as phosphorus-based or hindered phenol-based antioxidants. The present inventors have at least selected from the following (B-1) to (B-4): A combination of one phosphorus antioxidant and at least one hindered phenol antioxidant selected from (C-1) to (C-4) is extremely effective in preventing discoloration of the styrene resin composition. It was experimentally found to be effective.
(B-1) Tris (2,4-di-tert-butylphenyl) phosphite (B-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (C-1) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (C -2) 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,1 - tetraoxaspiro [5.5] undecane (C-3) ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -m- tolyl) propionate]
(C-4) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
スチレン系樹脂組成物には、本発明の無色透明性を損なわない範囲でミネラルオイルを含有しても良い。また、ステアリン酸、エチレンビスステアリルアミド等の内部潤滑剤や、イオウ系酸化防止剤、ラクトン系酸化防止剤、紫外線吸収剤、ヒンダードアミン系安定剤、帯電防止剤、外部潤滑剤等の添加剤が含まれていても良い。また、外部潤滑剤としては、エチレンビスステアリルアミドが好適であり、含有量としては樹脂組成物中に30~200ppmであることが好ましい。 << Other additives >>
The styrenic resin composition may contain mineral oil as long as the colorless transparency of the present invention is not impaired. Also includes additives such as internal lubricants such as stearic acid and ethylenebisstearylamide, 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, and the content is preferably 30 to 200 ppm in the resin composition.
(式中、Rは炭素数8~20のアルキル基を示す。また、ポリオキシエチレンアルキルエーテル骨格を複数個有する6価までの多価ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル骨格を複数個有する6価までの多価ポリオキシエチレン脂肪酸エステルであっても良い。nは整数でエチレンオキサイド単位の付加モル数を表す。) Polyoxyethylene type nonionic surfactants include polyoxyethylene alkyl ether represented by the following general formula (1), polyoxyethylene fatty acid ester represented by the following general formula (2), polyoxyethylene hydrogenated castor oil, polyoxy Ethylene sorbitan fatty acid ester and polyoxyethylene sorbitol fatty acid ester are exemplified, but one or more selected from the group of polyoxyethylene alkyl ether and / or polyoxyethylene fatty acid ester are preferable. In addition, polyvalent polyoxyethylene alkyl ethers having a plurality of polyoxyethylene alkyl ether skeletons in one molecule and polyvalent polyoxyethylene fatty acid esters having a plurality of polyoxyethylene fatty acid ester skeletons in one molecule are used. Can also achieve the object of the present invention. The valence of polyoxyethylene alkyl ether or polyoxyethylene fatty acid ester means the number of polyoxyethylene alkyl ether skeleton or polyoxyethylene fatty acid ester skeleton present in one molecule.
(In the formula, R represents an alkyl group having 8 to 20 carbon atoms. In addition, a polyvalent polyoxyethylene alkyl ether up to hexavalent having a plurality of polyoxyethylene alkyl ether skeletons, and a plurality of polyoxyethylene fatty acid ester skeletons. (It may be a polyvalent polyoxyethylene fatty acid ester having up to 6 valences, where n is an integer and represents the number of added moles of ethylene oxide units.)
光路長115mmの透過率及びYI値は、次の手順にて測定を行った。スチレン系樹脂組成物のペレットを用い、シリンダー温度230℃、金型温度50℃にて射出成形を行い、127×127×3mm厚みの板状成形品を成形した。ここで長期の熱安定性を評価するサンプルは、80℃のオーブン内に1000時間保管した。次に、板状成形品から115×85×3mm厚みの試験片を切り出し、端面をバフ研磨によって研磨し、端面に鏡面を有する板状成形品を作成した。研磨後の板状成形品について、日本分光株式会社製の紫外線可視分光光度計V-670を用いて、大きさ20×1.6mm、広がり角度0°の入射光において、光路長115mmでの波長350nm~800nmの分光透過率を測定し、C光源における、視野2°でのYI値をJIS K7105に倣い算出した。また、透過率とは、波長380nm~780nmの平均透過率である。 The styrenic resin composition of the present invention can be molded by a molding method according to the purpose such as injection molding, extrusion molding, compression molding, blow molding, and the shape thereof is not limited. For example, if it is a plate-shaped molded product, it can be processed into a light guide plate or the like. The obtained molded product is used as an optical member that functions by transmitting light into the molded product such as a light guide plate. An optical member such as a light guide plate is preferably a material having a high transmittance and an excellent hue because of a long light transmission distance (optical path length). The initial transmittance at an optical path length of 115 mm is preferably 84% or more and the YI value is 7.0 or less. Further, the YI difference after storage for 1000 hours at 80 ° C. is preferably 3.0 or less, and more preferably 1.5 or less.
The transmittance and YI value for an optical path length of 115 mm were measured by the following procedure. Using pellets of the styrene-based 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 article having a thickness of 127 × 127 × 3 mm. Here, the sample to be evaluated for long-term thermal stability was stored in an oven at 80 ° C. for 1000 hours. Next, a test piece having a thickness of 115 × 85 × 3 mm was cut out from the plate-shaped molded product, and the end surface was polished by buffing to produce a plate-shaped molded product having a mirror surface on the end surface. The polished plate-like molded product was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation, with an incident light having a size of 20 × 1.6 mm and a spread angle of 0 °, and a wavelength at an optical path length of 115 mm Spectral transmittances from 350 nm to 800 nm were measured, and the YI value with a C light source at a visual field of 2 ° was calculated according to JIS K7105. The transmittance is an average transmittance at a wavelength of 380 nm to 780 nm.
(スチレン系樹脂PS-1~PS-3の製造)
完全混合型撹拌槽である第1反応器と第2反応器及び静的混合器付プラグフロー型反応器である第3反応器を直列に接続して重合工程を構成し、表1に示す条件によりスチレン系樹脂の製造を実施した。各反応器の容量は、第1反応器を39リットル、第2反応器を39リットル、第3反応器を16リットルとした。表1に記載の原料組成にて、原料溶液を作成し、第1反応器に原料溶液を表1に記載の流量にて連続的に供給した。重合開始剤は、第1反応器の入口で表1に記載の添加濃度(原料スチレン及びメタクリル酸の合計量に対する質量基準の濃度)となるように原料溶液に添加し、均一混合した。表1に記載の重合開始剤は次の通り
重合開始剤-1 :2,2-ジ(4,4-t-ブチルパーオキシシクロヘキシル)プロパン(日油株式会社製パーテトラAを使用した。)
重合開始剤-2 :1,1-ジ(t-ブチルパーオキシ)シクロヘキサン(日油株式会社製パーヘキサCを使用した。)
なお、第3反応器では、流れの方向に沿って温度勾配をつけ、中間部分、出口部分で表1の温度となるよう調整した。
続いて、第3反応器より連続的に取り出した重合体を含む溶液を直列に2段より構成される予熱器付き真空脱揮槽に導入し、表1に記載の樹脂温度となるよう予熱器の温度を調整し、表1に記載の圧力に調整することで、未反応スチレン及びエチルベンゼンを分離した後、多孔ダイよりストランド状に押し出しして、コールドカット方式にて、ストランドを冷却および切断しペレット化した。 << Test 1 >>
(Manufacture of styrene resins PS-1 to PS-3)
The polymerization reactor is configured by connecting a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer. The styrene resin was manufactured by the above. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. A raw material solution was prepared with the raw material composition described in Table 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1. The polymerization initiator was added to the raw material solution at the inlet of the first reactor so that the addition concentration shown in Table 1 (concentration based on mass with respect to the total amount of raw styrene and methacrylic acid) was mixed. The polymerization initiators listed in Table 1 are as follows: Polymerization initiator-1: 2,2-di (4,4-t-butylperoxycyclohexyl) propane (Pertetra A manufactured by NOF Corporation was used).
Polymerization initiator-2: 1,1-di (t-butylperoxy) cyclohexane (Perhexa C manufactured by NOF Corporation was used.)
In the third reactor, a temperature gradient was provided along the flow direction, and the temperature in Table 1 was adjusted at the intermediate part and the outlet part.
Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted by two stages in series, and the preheater was adjusted to the resin temperature shown in Table 1. By adjusting the temperature and adjusting to the pressure shown in Table 1, unreacted styrene and ethylbenzene are separated and then extruded into a strand form from a perforated die, and the strand is cooled and cut by a cold cut method. Pelletized.
表2に示す含有量にて、スチレン系樹脂PS-1、PS-2、PS-3と添加剤としてBおよびCをスクリュー径40mmの単軸押出機を用いて、シリンダー温度230℃、スクリュー回転数100rpmで溶融混錬してペレットを得た。表2で用いた添加剤BおよびCを次に示す。なお、添加剤Bは(b)リン系酸化防止剤、添加剤Cは(c)ヒンダードフェノール系酸化防止剤を表す。
B-1:トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト(BASFジャパン株式会社製 Irgafos 168)
B-2:2,2'-メチレンビス(4,6-ジ-tert-ブチル-1-フェニルオキシ)(2-エチルヘキシルオキシ)ホスホラス(株式会社ADEKA製 アデカスタブHP-10)
B-3:ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト(Dover Chemical Corporation製 Doverphos S-9228)
B-4:3,9-ビス(2,6-ジ-tert-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ〔5.5〕ウンデカン(株式会社ADEKA製 アデカスタブ PEP-36)
B-5:テトラキス(2,4-ジ-tert-ブチルフェニル)[1,1ビフェニル]-4,4ジイルビホスホナイト(クラリアントCo.Ltd.製 Hostanox P-EPQ)
B-6:ビス(2,4-ジ-tert-ブチル-6-メチルフェニル)エチル亜りん酸エステル(BASFジャパン株式会社製 Irgafos 38)
B-7:亜りん酸ジフェニル-2-エチルヘキシル(株式会社ADEKA製 アデカスタブ C)
B-8:亜りん酸トリイソデシル(株式会社ADEKA製 アデカスタブ 3010)
B-9:サイクリックネオペンタンテトライルビス(2,4-ジ-t-ブチルフェニルフォスファイト)(株式会社ADEKA製 アデカスタブ PEP-8)
C-1:オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート(BASFジャパン株式会社製 Irganox 1076)
C-2:3,9-ビス[2-〔3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(株式会社ADEKA製 アデカスタブAO-80)
C-3:エチレンビス(オキシエチレン)ビス〔3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート〕(BASFジャパン株式会社製 Irganox 245)
C-4:ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](BASFジャパン株式会社製 Irganox 1010)
C-5:1,1,3-トリス(2-メチル-4-ヒドロキシ-5-tert-ブチルフェニル)ブタン(株式会社ADEKA製 アデカスタブAO-30)
C-6:4,4'-ブチリデンビス(3-メチル-6-t-ブチルフェノール)(株式会社ADEKA製 アデカスタブAO-40)
C-7:2-メチル-4,6-ビス(ドデシルチオメチル)フェノール(BASFジャパン株式会社製 Irganox 1726) (Examples 1-1 to 1-30, Comparative Examples 1-1 to 1-10)
Using the content shown in Table 2, styrene resins PS-1, PS-2, PS-3 and B and C as additives and a single screw extruder with a screw diameter of 40 mm, cylinder temperature 230 ° C., screw rotation Pellets were obtained by melting and kneading at several hundred rpm. Additives B and C used in Table 2 are shown below. Additive B represents (b) a phosphorus-based antioxidant, and additive C represents (c) a hindered phenol-based antioxidant.
B-1: Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168 manufactured by BASF Japan Ltd.)
B-2: 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus (ADEKA STAB HP-10 manufactured by ADEKA Corporation)
B-3: Bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228 manufactured by Dober Chemical Corporation)
B-4: 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane ADEKA ADK STAB PEP-36)
B-5: Tetrakis (2,4-di-tert-butylphenyl) [1,1biphenyl] -4,4 diylbiphosphonite (Hostanox P-EPQ manufactured by Clariant Co. Ltd.)
B-6: Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Irgafos 38 manufactured by BASF Japan Ltd.)
B-7: Diphenyl-2-ethylhexyl phosphite (ADEKA STAB C manufactured by ADEKA Corporation)
B-8: Triisodecyl phosphite (Adeka Corporation Adeka Stub 3010)
B-9: Cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl phosphite) (Adeka Stab PEP-8 manufactured by ADEKA Corporation)
C-1: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076 manufactured by BASF Japan Ltd.)
C-2: 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5.5] undecane (Adeka Corporation Adeka Stub AO-80)
C-3: Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245 manufactured by BASF Japan Ltd.)
C-4: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by BASF Japan Ltd.)
C-5: 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (ADEKA STAB AO-30 manufactured by ADEKA Corporation)
C-6: 4,4′-butylidenebis (3-methyl-6-t-butylphenol) (Adeka Corporation Adeka Stub AO-40)
C-7: 2-methyl-4,6-bis (dodecylthiomethyl) phenol (Irganox 1726, manufactured by BASF Japan Ltd.)
Δ加熱後YI値=(添加剤ありの試験例の「80℃×1000時間後のYI値」)-(添加剤なしの試験例の「80℃×1000時間後のYI値」) Next, the YI value after Δ heating was calculated based on the following formula. In the following formula, “without additive” means that neither additive B nor additive C is added, and “with additive” means at least one of additive B and additive C. Is added. In addition, examples, comparative examples, and reference examples are collectively referred to as “test examples”.
YI value after heating = (“YI value after 80 ° C. × 1000 hours” of test example with additive) − (“YI value after 80 ° C. × 1000 hour” of test example without additive))
S:Δ加熱後YI値<-4.0
A:-4.0≦Δ加熱後YI値<-3.5
B:-3.5≦Δ加熱後YI値<-2.5
C:-2.5≦Δ加熱後YI値
表2に各樹脂組成物の特性及び評価結果を示す。 Furthermore, based on the YI value after Δ heating, the examples and comparative examples were ranked according to the following criteria.
S: YI value after Δ heating <−4.0
A: −4.0 ≦ ΔYI value after heating <−3.5
B: −3.5 ≦ ΔYI value after heating <−2.5
C: −2.5 ≦ ΔYI value after heating Table 2 shows the characteristics and evaluation results of each resin composition.
(実施例2-1~2-26)
完全混合型撹拌槽である第1反応器と第2反応器及び静的混合器付プラグフロー型反応器である第3反応器を直列に接続して重合工程を構成し、表1の条件1によりスチレン系樹脂の製造を実施した。各反応器の容量は、第1反応器を39リットル、第2反応器を39リットル、第3反応器を16リットルとした。1の条件1に記載の原料組成にて、原料溶液を作成し、第1反応器に原料溶液を表1に記載の流量にて連続的に供給した。
また、第3反応器の入口に、ポリエーテル鎖を有する親水性添加剤Dを表3に示す種類と含有量になるよう添加した。使用した添加剤及びポリエチレングリコールの種類は次の通り。
D-1:平均分子量が400のポリエチレングリコール(日油株式会社製PEG#400)
D-2:平均分子量が1000のポリエチレングリコール(日油株式会社製PEG#1000)
D-3:平均分子量が2000のポリエチレングリコール(日油株式会社製PEG#2000)
D-4:ポリオキシエチレンエチレンラウリルエーテル エチレンオキサイド平均付加モル数=25(花王株式会社製エマルゲン123P)
D-5:ポリオキシエチレンエチレンラウリルエーテル エチレンオキサイド平均付加モル数=12(花王株式会社製エマルゲン320P)
D-6:ポリオキシエチレンエチレンラウリルエーテル エチレンオキサイド平均付加モル数=9(花王株式会社製エマルゲン109P)
D-7:ポリオキシエチレンエチレンラウリルエーテル エチレンオキサイド平均付加モル数=30(花王株式会社製エマルゲン130K)
D-8:ポリエチレングリコールモノラウレート エチレンオキサイド平均付加モル数=12(花王株式会社製エマノーン1112) << Test 2 >>
(Examples 2-1 to 2-26)
A polymerization process is configured by connecting in series a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer. The styrene resin was manufactured by the above. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. A raw material solution was prepared with the raw material composition described in Condition 1 of 1, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 1.
Moreover, the hydrophilic additive D which has a polyether chain | strand was added to the inlet_port | entrance of a 3rd reactor so that it might become a kind and content shown in Table 3. The types of additives and polyethylene glycol used are as follows.
D-1: Polyethylene glycol having an average molecular weight of 400 (PEG # 400 manufactured by NOF Corporation)
D-2: Polyethylene glycol having an average molecular weight of 1000 (PEG # 1000 manufactured by NOF Corporation)
D-3: Polyethylene glycol having an average molecular weight of 2000 (PEG # 2000 manufactured by NOF Corporation)
D-4: polyoxyethylene ethylene lauryl ether average addition mole number of ethylene oxide = 25 (Emalgen 123P manufactured by Kao Corporation)
D-5: Polyoxyethylene ethylene lauryl ether Average addition mole number of ethylene oxide = 12 (Emulgen 320P manufactured by Kao Corporation)
D-6: Polyoxyethylene ethylene lauryl ether Average addition mole number of ethylene oxide = 9 (Emulgen 109P manufactured by Kao Corporation)
D-7: Polyoxyethylene ethylene lauryl ether Average addition mole number of ethylene oxide = 30 (Emulgen 130K manufactured by Kao Corporation)
D-8: Polyethylene glycol monolaurate Average addition mole number of ethylene oxide = 12 (Emanon 1112 manufactured by Kao Corporation)
得られたスチレン系樹脂の重量平均分子量(Mw)はすべて37万であった。 Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted of two stages in series, and after separating unreacted styrene and ethylbenzene, a strand shape After being extruded and cooled, it was cut into pellets. The resin temperature in the first stage devolatilization tank is set to 160 ° C., the pressure in the vacuum devolatilization tank is set to 65 kPa, the resin temperature in the second stage devolatilization layer is set to 235 ° C. The pressure in the volatilization tank was 0.8 kPa.
All of the obtained styrene resins had a weight average molecular weight (Mw) of 370,000.
◎:全く白化が発生しない
○:取出し1時間後にやや白化するが、24時間後には消失する
△:取出し1時間後に白化するが、24時間後にはほとんど消失する
×:取出し1時間後に著しく白化し、24時間経っても消失しない
表3に各樹脂組成物の特性及び評価結果を示す。 Furthermore, in order to confirm the whitening phenomenon due to environmental changes, a plate-like molded article having a mirror surface on the end face is exposed to an environment of 60 ° C. and 90% relative humidity for 150 hours, and the test piece is placed in an environment of 23 ° C. and 50% relative humidity Taking out and observing the whitening phenomenon occurring inside the molded product, the following judgment was made as a whitening suppression effect.
A: No whitening occurs. O: Whitening occurs slightly after 1 hour, but disappears after 24 hours. Δ: Whitening occurs after 1 hour, but almost disappears after 24 hours. X: Remarkably whitening after 1 hour. Table 3 shows the characteristics and evaluation results of each resin composition.
(スチレン系樹脂A-1~7の製造例)
完全混合型撹拌槽である第1反応器と第2反応器及び静的混合器付プラグフロー型反応器である第3反応器を直列に接続して重合工程を構成し、表4に示す条件によりスチレン系樹脂の製造を実施した。各反応器の容量は、第1反応器を39リットル、第2反応器を39リットル、第3反応器を16リットルとした。表4に記載の原料組成にて、原料溶液を作成し、第1反応器に原料溶液を表4に記載の流量にて連続的に供給した。重合開始剤は、第1反応器の入口で表4に記載の添加濃度(原料スチレン及びメタクリル酸メチルの合計量に対する質量基準の濃度)となるように原料溶液に添加し、均一混合した。表4に記載の重合開始剤は次の通り
重合開始剤-1 :1,1-ジ(t-ブチルパーオキシ)シクロヘキサン(日油株式会社製パーヘキサCを使用した。)
なお、第3反応器では、流れの方向に沿って温度勾配をつけ、中間部分、出口部分で表4の温度となるよう調整した。 << Test 3 >>
(Production example of styrene resins A-1 to A-7)
The polymerization reactor is configured by connecting a first reactor, which is a complete mixing tank, a second reactor, and a third reactor, which is a plug flow reactor with a static mixer, to form a polymerization process, and the conditions shown in Table 4 The styrene resin was manufactured by the above. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. A raw material solution was prepared with the raw material composition described in Table 4, and the raw material solution was continuously supplied to the first reactor at a flow rate described in Table 4. The polymerization initiator was added to the raw material solution at the inlet of the first reactor so as to have the addition concentration shown in Table 4 (concentration based on mass relative to the total amount of raw material styrene and methyl methacrylate), and was uniformly mixed. The polymerization initiators listed in Table 4 were as follows: Polymerization initiator-1: 1,1-di (t-butylperoxy) cyclohexane (Perhexa C manufactured by NOF Corporation was used.)
In the third reactor, a temperature gradient was provided along the flow direction, and the temperature in Table 4 was adjusted at the intermediate part and the outlet part.
熱分解炉:PYR-2A(株式会社島津製作所製)
熱分解炉温度設定:525℃
ガスクロマトグラフ:GC-14A(株式会社島津製作所製)
カラム:ガラス製3mm径×3m
充填剤:FFAP Chromsorb WAW 10%
インジェクション、ディテクター温度:250℃
カラム温度:120℃
キャリアーガス:窒素
メルトマスフローレート(MFR)は、JIS K 7210に準拠し、温度200℃、49N荷重の条件で、ビカット軟化温度は、JIS K 7206に準拠し、昇温速度50℃/hr、試験荷重50Nで測定した。
吸水量は上記の板状成形品を用い、温度80℃で24時間乾燥後の質量W1を測定した後、温度40℃で80%相対湿度の環境下に板状成形品を保管し、一定時間毎に取出し直後の重量を測定し、重量変化がなくなったところ(飽和状態)の質量W2より、吸水量=(W2-W1)/W2×1000000(ppm)として求めた。表4に各スチレン系樹脂の特性を示す。 The content of methyl methacrylate units (PMMA amount) in the styrene resin was measured by pyrolysis gas chromatography under the following conditions.
Pyrolysis furnace: PYR-2A (manufactured by Shimadzu Corporation)
Pyrolysis furnace temperature setting: 525 ° C
Gas chromatograph: GC-14A (manufactured by Shimadzu Corporation)
Column: Glass 3mm diameter x 3m
Filler: FFAP Chromsorb WAW 10%
Injection, detector temperature: 250 ° C
Column temperature: 120 ° C
Carrier gas: Nitrogen Melt mass flow rate (MFR) conforms to JIS K 7210, temperature 200 ° C, 49N load, Vicat softening temperature conforms to JIS K 7206, heating rate 50 ° C / hr, test Measurement was performed at a load of 50N.
The amount of water absorption was measured using the above-mentioned plate-shaped molded product, and after measuring the mass W1 after drying for 24 hours at a temperature of 80 ° C., the plate-shaped molded product was stored in an environment of 80% relative humidity at a temperature of 40 ° C. for a certain period of time. The weight immediately after removal was measured for each time, and the water absorption amount = (W2−W1) / W2 × 1000000 (ppm) was determined from the mass W2 when the weight change disappeared (saturated state). Table 4 shows the characteristics of each styrene resin.
次に、表5に示す含有量にて、スチレン系樹脂Aと添加剤としてB及びCをスクリュー径40mmの単軸押出機を用いて、シリンダー温度230℃、スクリュー回転数100rpmで溶融混錬してペレットを得た。表5で用いた添加剤B、Cの記号は試験1に示す記号と同じである。
透過率、YI値、白化抑制効果は、試験2と同様の方法で測定又は評価した。
表5に各樹脂組成物の特性及び評価結果を示す。 (Examples 3-1 to 3-18)
Next, with the contents shown in Table 5, styrene resin A and B and C as additives were melt kneaded at a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm using a single screw extruder with a screw diameter of 40 mm. To obtain a pellet. The symbols for Additives B and C used in Table 5 are the same as those shown in Test 1.
The transmittance, YI value, and whitening suppression effect were measured or evaluated in the same manner as in Test 2.
Table 5 shows the characteristics and evaluation results of each resin composition.
Claims (8)
- (a)重量平均分子量が15万~70万のスチレン系樹脂と、(B-1)~(B-4)の中から選ばれる少なくとも1種の(b)リン系酸化防止剤と、(C-1)~(C-4)の中から選ばれる少なくとも1種の(c)ヒンダードフェノール系酸化防止剤からなるスチレン系樹脂組成物であって、スチレン系樹脂組成物100質量%中の(b)の含有量が0.03~0.40質量%、(c)の含有量が0.02~0.30質量%であることを特徴とする光学用スチレン系樹脂組成物。
(B-1)トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト
(B-2)2,2'-メチレンビス(4,6-ジ-tert-ブチル-1-フェニルオキシ)(2-エチルヘキシルオキシ)ホスホラス
(B-3)ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト
(B-4)3,9-ビス(2,6-ジ-tert-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ〔5.5〕ウンデカン
(C-1)オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート
(C-2)3,9-ビス[2-〔3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン
(C-3)エチレンビス(オキシエチレン)ビス〔3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート〕
(C-4)ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート] (A) a styrene resin having a weight average molecular weight of 150,000 to 700,000, at least one (b) a phosphorus antioxidant selected from (B-1) to (B-4), and (C -1) to (C-4), a styrenic resin composition comprising at least one (c) hindered phenolic antioxidant selected from 100% by mass of the styrenic resin composition ( A styrenic resin composition for optical use, wherein the content of b) is 0.03 to 0.40% by mass and the content of (c) is 0.02 to 0.30% by mass.
(B-1) Tris (2,4-di-tert-butylphenyl) phosphite (B-2) 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2- Ethylhexyloxy) phosphorus (B-3) bis (2,4-dicumylphenyl) pentaerythritol diphosphite (B-4) 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (C-1) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (C -2) 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,1 - tetraoxaspiro [5.5] undecane (C-3) ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -m- tolyl) propionate]
(C-4) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] - (b)リン系酸化防止剤と(c)ヒンダードフェノール系酸化防止剤の組合せが、(B-1)と(C-1)、(B-1)と(C-2)、(B-1)と(C-3)、(B-1)と(C-4)、(B-2)と(C-1)、(B-2)と(C-4)、(B-3)と(C-1)、(B-3)と(C-2)、(B-3)と(C-3)、(B-3)と(C-4)、(B-4)と(C-1)、(B-4)と(C-2)、(B-4)と(C-3)、(B-4)と(C-4)の組合せの中から選ばれる少なくとも1組であることを特徴とする請求項1に記載の光学用スチレン系樹脂組成物。 The combinations of (b) phosphorus antioxidant and (c) hindered phenol antioxidant are (B-1) and (C-1), (B-1) and (C-2), (B- 1) and (C-3), (B-1) and (C-4), (B-2) and (C-1), (B-2) and (C-4), (B-3) And (C-1), (B-3) and (C-2), (B-3) and (C-3), (B-3) and (C-4), (B-4) and ( C-1), (B-4) and (C-2), (B-4) and (C-3), and (B-4) and (C-4). The styrenic resin composition for optics according to claim 1, wherein
- (b)リン系酸化防止剤と(c)ヒンダードフェノール系酸化防止剤の組合せが、(B-1)と(C-1)、(B-1)と(C-2)、(B-1)と(C-3)、(B-1)と(C-4)、(B-2)と(C-1)、(B-2)と(C-4)の組合せの中から選ばれる少なくとも1組であることを特徴とする請求項1または請求項2に記載の光学用スチレン系樹脂組成物。 The combinations of (b) phosphorus antioxidant and (c) hindered phenol antioxidant are (B-1) and (C-1), (B-1) and (C-2), (B- 1) and (C-3), (B-1) and (C-4), (B-2) and (C-1), or (B-2) and (C-4) The styrenic resin composition for optics according to claim 1 or 2, wherein at least one set is selected.
- スチレン系樹脂が、スチレン系単量体と(メタ)アクリル酸とを共重合して得られるスチレン-(メタ)アクリル酸共重合樹脂であって、スチレン系樹脂のスチレン系単量体単位の含有量が90.0~99.9質量%、(メタ)アクリル酸単位の含有量が0.1~10.0質量%であることを特徴とする請求項1~請求項3のいずれか1つに記載の光学用スチレン系樹脂組成物。ただし、スチレン系樹脂のスチレン系単量体単位と(メタ)アクリル酸単位の含有量の合計を100質量%とする。 The styrene resin is a styrene- (meth) acrylic acid copolymer resin obtained by copolymerizing a styrene monomer and (meth) acrylic acid, and contains a styrene monomer unit of the styrene resin. 4. The method according to claim 1, wherein the amount is 90.0 to 99.9% by mass, and the content of (meth) acrylic acid units is 0.1 to 10.0% by mass. The styrenic resin composition for optics described in 1. However, the total content of styrene monomer units and (meth) acrylic acid units in the styrene resin is 100% by mass.
- スチレン系樹脂が、スチレン系単量体と(メタ)アクリル酸エステルとを共重合して得られるスチレン-(メタ)アクリル酸エステル共重合樹脂であって、スチレン系樹脂のスチレン系単量体単位の含有量が40.0~99.0質量%、(メタ)アクリル酸エステル単位の含有量が1.0~60.0質量%であることを特徴とする請求項1~請求項3のいずれか1つに記載の光学用スチレン系樹脂組成物。ただし、スチレン系樹脂のスチレン系単量体単位と(メタ)アクリル酸エステル単位の含有量の合計を100質量%とする。 A styrene resin is a styrene- (meth) acrylate copolymer resin obtained by copolymerizing a styrene monomer and a (meth) acrylate ester, and a styrene monomer unit of the styrene resin. 4. The content of claim 1 is 40.0 to 99.0% by mass, and the content of (meth) acrylate unit is 1.0 to 60.0% by mass. The optical styrene resin composition according to any one of the above. However, the total content of styrene monomer units and (meth) acrylic acid ester units in the styrene resin is 100% by mass.
- ポリエーテル鎖を有する親水性添加剤を0.4~2.0質量%含有することを特徴とする請求項1~請求項5のいずれか1つに記載の光学用スチレン系樹脂組成物。 The optical styrenic resin composition according to any one of claims 1 to 5, wherein the hydrophilic additive having a polyether chain is contained in an amount of 0.4 to 2.0 mass%.
- 請求項1~請求項6のいずれか1つに記載の光学用スチレン系樹脂組成物からなる成形品。 A molded article comprising the optical styrenic resin composition according to any one of claims 1 to 6.
- 請求項7に記載の成形品からなる導光板。 A light guide plate comprising the molded product according to claim 7.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280061422.9A CN104245823B (en) | 2012-07-13 | 2012-12-19 | Styrene resin composition for optical use, molded article and light guide plate |
JP2014524589A JPWO2014010137A1 (en) | 2012-07-13 | 2012-12-19 | Styrenic resin composition for optics, molded product and light guide plate |
KR1020197027144A KR20190108658A (en) | 2012-07-13 | 2012-12-19 | Styrene-based resin composition for optical applications, molded product, and light guide plate |
KR1020147021117A KR102165456B1 (en) | 2012-07-13 | 2012-12-19 | Styrene-based resin composition for optical applications, molded product, and light guide plate |
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PCT/JP2012/082946 WO2014010137A1 (en) | 2012-07-13 | 2012-12-19 | Styrene-based resin composition for optical applications, molded product, and light guide plate |
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JP (2) | JPWO2014010137A1 (en) |
KR (2) | KR102165456B1 (en) |
CN (2) | CN104245823B (en) |
TW (1) | TWI597316B (en) |
WO (1) | WO2014010137A1 (en) |
Cited By (5)
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KR20170117105A (en) * | 2015-02-12 | 2017-10-20 | 덴카 주식회사 | Styrenic resin composition for optical use |
CN113087827A (en) * | 2021-04-02 | 2021-07-09 | 惠州仁信新材料股份有限公司 | Transparent polystyrene with ultraviolet aging resistance and good yellowing resistance and preparation method thereof |
WO2021199501A1 (en) * | 2020-04-01 | 2021-10-07 | デンカ株式会社 | Optical styrene-based resin composition, light guide plate, and edge-light-type planar light-source unit |
WO2023190540A1 (en) * | 2022-03-30 | 2023-10-05 | デンカ株式会社 | Resin composition containing copolymer, method for producing same and molded body of same |
WO2024204040A1 (en) * | 2023-03-29 | 2024-10-03 | デンカ株式会社 | Styrene-based resin composition for optical use, molded body, light guide plate, and edge-light type planar light source unit |
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TWI535772B (en) * | 2015-03-31 | 2016-06-01 | 長興材料工業股份有限公司 | Composition for optical materials and their use thereof |
JP7129430B2 (en) * | 2018-01-09 | 2022-09-01 | デンカ株式会社 | Styrene resin composition, molded article and light guide plate |
CN111655784B (en) * | 2018-03-06 | 2023-04-28 | 东洋苯乙烯股份有限公司 | Optical styrene resin composition and optical member |
KR20220002423A (en) * | 2019-04-26 | 2022-01-06 | 덴카 주식회사 | Edge light type light guide plate and edge light type surface light source unit |
KR102660598B1 (en) * | 2023-09-18 | 2024-04-26 | 에이치디씨현대이피 주식회사 | A thermoplastic resin composition with high ultraviolet stability |
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Also Published As
Publication number | Publication date |
---|---|
JPWO2014010137A1 (en) | 2016-06-20 |
JP6496339B2 (en) | 2019-04-03 |
KR102165456B1 (en) | 2020-10-14 |
CN110408133A (en) | 2019-11-05 |
TWI597316B (en) | 2017-09-01 |
CN104245823A (en) | 2014-12-24 |
CN104245823B (en) | 2020-06-09 |
TW201402680A (en) | 2014-01-16 |
KR20190108658A (en) | 2019-09-24 |
KR20150035482A (en) | 2015-04-06 |
JP2017141459A (en) | 2017-08-17 |
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