WO2023218994A1 - 光学用スチレン系樹脂組成物、導光板、エッジライト型面光源ユニット、光拡散版、及び直下型面光源ユニット - Google Patents
光学用スチレン系樹脂組成物、導光板、エッジライト型面光源ユニット、光拡散版、及び直下型面光源ユニット Download PDFInfo
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- WO2023218994A1 WO2023218994A1 PCT/JP2023/016702 JP2023016702W WO2023218994A1 WO 2023218994 A1 WO2023218994 A1 WO 2023218994A1 JP 2023016702 W JP2023016702 W JP 2023016702W WO 2023218994 A1 WO2023218994 A1 WO 2023218994A1
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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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
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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
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V3/00—Globes; Bowls; Cover glasses
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V3/00—Globes; Bowls; Cover glasses
- F21V3/04—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
- F21V3/06—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V3/00—Globes; Bowls; Cover glasses
- F21V3/04—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
- F21V3/06—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material
- F21V3/062—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material the material being plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0065—Manufacturing aspects; Material aspects
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2105/00—Planar light sources
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2105/00—Planar light sources
- F21Y2105/10—Planar light sources comprising a two-dimensional [2D] array of point-like light-generating elements
- F21Y2105/14—Planar light sources comprising a two-dimensional [2D] array of point-like light-generating elements characterised by the overall shape of the two-dimensional [2D] array
- F21Y2105/16—Planar light sources comprising a two-dimensional [2D] array of point-like light-generating elements characterised by the overall shape of the two-dimensional [2D] array square or rectangular, e.g. for light panels
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2115/00—Light-generating elements of semiconductor light sources
- F21Y2115/10—Light-emitting diodes [LED]
Definitions
- the present invention relates to an optical styrene resin composition, a light guide plate, an edge-light type surface light source unit, a light diffusion plate, and a direct type surface light source unit.
- backlights for liquid crystal display devices: a direct type in which the light source is placed in front of the display device, and an edge light type in which the light source is placed on the side.
- Edge-lit backlights use a component called a light guide plate that guides light from a light source placed on the side to the front of the display device. It is used in a wide range of applications, including televisions, desktop personal computer monitors, notebook personal computers, mobile phones, and car navigation monitors. Furthermore, backlights using light guide plates are also used as lighting devices, signboards, and the like.
- the light guide plate is required to have a particularly high light transmittance because the light transmission distance is relatively long and the light loss due to the optical path length is large.
- the material used for the light guide plate is an acrylic resin such as polymethyl methacrylate (PMMA).
- PMMA polymethyl methacrylate
- the light guide plate may warp or change dimensions due to water absorption.
- Patent Document 1 proposes using a styrene-methyl (meth)acrylate copolymer as a material for a light guide plate.
- Patent Document 2 has been proposed as a technology for improving the hue of styrene-methyl (meth)acrylate.
- the present invention was made in view of these problems, and provides an optical styrenic resin composition that has excellent transparency, hue, and dimensional stability, and also has excellent light stability for long-term use of LED light sources. It is something to do.
- an optical material containing a styrenic resin (A) which is a copolymer containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit and a hindered amine light stabilizer (B)
- a styrenic resin composition wherein the copolymer contains 95 to 20% by mass of the styrene monomer unit and the (meth)acrylic acid ester monomer unit in 100% by mass of the copolymer.
- a composition is provided.
- the present inventors conducted extensive studies and found that styrenic resins in which the content of styrene monomer units and (meth)acrylic acid ester monomer units are within a specific range, and It was discovered that an optical styrenic resin composition containing a hindered amine light stabilizer simultaneously satisfies transparency, hue, dimensional stability, and light stability for long-term use of LED light sources, leading to the completion of the present invention. Ta.
- A Optical styrenic resin containing styrenic resin
- B a hindered amine light stabilizer
- the composition, wherein the copolymer contains 95 to 20 mass % of the styrene monomer units and 5 to 80 mass % of the (meth)acrylate monomer units in 100 mass % of the copolymer.
- the NH type hindered amine light stabilizer is bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethyl-4-piperidylhexadecanoate, 2,2,6,6-tetramethyl-4-piperidyloctadecanoate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, A polycondensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino2,6-dichloro-1,3,5-triazine, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino) and 1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4 - polycondensate with piperidyl)hexamethylene diamine,
- the NR type hindered amine light stabilizer is Methyl (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl 4-hydroxybenzylmalonate, Polycondensate of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and dimethyl succinate, 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazine- 2-yl]-1,5,8,12-tetraazadodecane, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and ⁇ ,
- the phosphorus antioxidant (C-1) is tris(2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butyl-1) -phenyloxy)(2-ethylhexyloxy)phosphorus, bis-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, 3,9-bis(2,6-di-tert-butyl-4- methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, tetrakis(2,4-di-tert-butylphenyl)[1,1 biphenyl]-4,4' -
- the optical styrenic resin composition according to [5] which is at least one selected from diylbisphosphonite and bis(2,4-di-tert-butyl-6-methylphen
- a light guide plate formed by molding the optical styrenic resin composition according to any one of [1] to [6].
- An edge-light surface light source unit comprising the light guide plate according to [7] and a light source that supplies LED light to an end surface of the light guide plate.
- a light diffusing plate formed by molding the optical styrenic resin composition according to any one of [1] to [6].
- a direct type surface light source unit comprising the light diffusing plate according to [9] and a light source that supplies LED light to the light diffusing plate.
- the styrenic resin composition for optics is a styrenic resin composition for optics containing a styrenic resin (A) and a hindered amine light stabilizer (B). be.
- the styrenic resin (A) is a resin obtained by copolymerizing a monomer containing a styrene monomer and a (meth)acrylic acid ester monomer.
- the styrenic resin (A) is a copolymer containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit.
- the copolymer contains 95 to 20 mass % of styrene monomer units and 5 to 80 mass % of (meth)acrylate monomer units in 100 mass % of the copolymer, preferably styrene monomer units.
- the content of (meth)acrylic acid ester monomer units in the styrene resin (A) is, for example, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35 , 40, 45, 50, 55, 60, 65, 70, 75, 80% by mass, and may be within a range between any two of the numerical values exemplified here.
- styrenic monomer examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, and pt-butylstyrene. These can be used alone or in combination of two or more.
- the styrenic monomer is preferably styrene.
- Examples of (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate.
- - (Meth)acrylic acid alkyl esters such as butyl, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.
- (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 2-(meth)acrylate norbornyl, isobornyl (meth)acrylate, adamantan-1-yl (meth)acrylate, 2-methyladamantan-2-yl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylate
- Examples include cycloalkyl (meth)acrylates such as tricyclodecanyl acrylate; glycidyl (meth)acrylate; dicyclopentanyl (meth)acrylate; and the like. These can be used alone or in combination of two or more.
- the (meth)acrylic acid ester monomer is preferably an alkyl (meth)acrylate, more
- the styrene resin (A) may be a copolymer obtained by copolymerizing with a monomer copolymerizable with a styrene monomer and a (meth)acrylic acid ester monomer.
- copolymerizable monomers include (meth)acrylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; and ⁇ , ⁇ -ethylene monomers such as maleic anhydride and fumaric acid.
- Saturated carboxylic acids; Imides such as phenylmaleimide and cyclohexylmaleimide can be mentioned. These can be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the styrenic resin (A) is preferably 50,000 to 400,000, more preferably 100,000 to 350,000. Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the styrene resin (A) is preferably 1.0 to 3.5, more preferably 1.5 to It is 3.0. By setting it within such a range, it is possible to achieve both moldability and strength of the light guide plate. If the weight average molecular weight (Mw) is less than 50,000, the strength of the molded article will be insufficient, and if it exceeds 400,000, moldability may deteriorate. Further, when the ratio of number average molecular weight (Mn) (Mw/Mn) is less than 1.0, moldability is reduced, and when it exceeds 3.5, the strength of the molded article may be reduced.
- the optical styrenic resin composition contains 0.001 to 1.0 parts by mass of the hindered amine light stabilizer (B), preferably 0.01 to 0.0 parts by mass, per 100 parts by mass of the styrene resin (A). Contains 3 parts by mass. By setting it as such a range, transparency, hue, and light stability with respect to an LED light source can be improved. Specifically, the content of the hindered amine light stabilizer (B) is, for example, 0.001, 0.005, 0.01, 0.02, 0.03, 0.
- the amount may be 0.8, 0.9, or 1.0 part by mass, and may be within a range between any two of the numerical values exemplified here.
- the hindered amine light stabilizer (B) may be used alone or in combination of two or more.
- the hindered amine light stabilizer (B) is a compound having a structural unit represented by the following general formula (1).
- R is a hydrogen atom, it is an N-H type hindered amine light stabilizer, and when R is a linear or branched alkyl group having 1 to 10 carbon atoms, or a methylene group, it is an N-R type hindered amine.
- a light stabilizer in which R is an alkoxy group is referred to as an N-OR hindered amine light stabilizer.
- N-H type hindered amine light stabilizer examples include bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate (TINUVIN770DF manufactured by BASF), 2,2,6,6-tetramethyl -4-piperidylhexadecanoate, 2,2,6,6-tetramethyl-4-piperidyl octadecanoate (SABOSTAB UV91 manufactured by SONGWON), tetrakis (2,2,6,6-tetramethyl-4- piperidyl)-1,2,3,4-butanetetracarboxylate (ADK STAB LA-57 manufactured by ADEKA), N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexa Polycondensate of methylene diamine and 4-morpholino 2,6-dichloro-1,3,5-triazine (SABOSTAB UV79 manufactured by SONGWON), 2,4-dichloro-6-(1,1,3,3-te
- Henicosan-20-yl)propionate tetradecyl 3-(2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazadispiro(5.1.11.2)henicosan -20-yl) propionate (manufactured by CLARIANT HOSTAVIN3030), 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro-(5.1.11.2) henicosan-21-one and epi Examples include polycondensates with chlorohydrin (HOSTAVIN N30P manufactured by CLARIANT).
- NR type hindered amine light stabilizers include methyl (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethyl piperidin-4-yl) sebacate (manufactured by BASF, TINUVIN292, TINUVIN765), bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl 4- Hydroxybenzyl malonate (TINUVIN144 manufactured by BASF), polycondensate of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and dimethyl succinate (TINUVIN622SF manufactured by BASF), 1,5 ,8,12-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl ]-1,5,8,12-tetraazad
- N-OR type hindered amine light stabilizers include bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate (TINUVIN123 manufactured by BASF), bis(1-undecanoxy-2,2 , 6,6-tetramethylpiperidin-4-yl) carbonate (ADKSTAB LA-81 manufactured by ADEKA).
- the hindered amine light stabilizer (B) is preferred as the NH type hindered amine light stabilizer and/or the NR type hindered amine light stabilizer in that it has little influence on the transparency and hue of the optical styrenic resin composition.
- a light stabilizer is preferable, and an NR type hindered amine light stabilizer is more preferable.
- the hindered amine light stabilizer (B) is generally oxidized by oxygen, ultraviolet light, and peroxide to generate nitroxy radicals.
- the mechanism by which the hindered amine light stabilizer (B) can improve the photostability of LED light sources for long-term use is still being elucidated, the effectiveness of the hindered amine light stabilizer (B) has been discovered by the present invention. It is something that
- the optical styrenic resin composition preferably contains 0.001 to 0.5 parts by mass of the phosphorus antioxidant (C-1), more preferably, based on 100 parts by mass of the styrenic resin (A). is 0.002 to 0.4 parts by weight, particularly preferably 0.005 to 0.3 parts by weight. By setting it as such a range, transparency and hue can be improved.
- the content of the phosphorus antioxidant (C-1) is, for example, 0.001, 0.002, 0.003, 0.004, based on 100 parts by mass of the styrene resin (A). 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5 parts by mass, and any two of the numerical values exemplified here. It may be within the range between.
- the phosphorous antioxidant (C-1) is a ()phosphorous ester that does not have a phenolic hydroxyl group in its basic skeleton, preferably a phosphorous ester that is a trivalent phosphorus compound.
- Specific examples of the phosphorus antioxidant (C-1) include 2,2'-methylenebis(4,6-di-tert-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, bis-(2 , 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, 3,9-bis(2,6-di-tert-butyl-4- methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, tetrakis(2,4-di-tert-butylphenyl)
- the optical styrenic resin composition may contain 0 to 0.5 parts by mass of a phenolic antioxidant (C-2) based on 100 parts by mass of the styrenic resin (A). If the content of the phenolic antioxidant (C-2) exceeds 0.5 parts by mass, the hue deteriorates, which is not preferable.
- the content of the phenolic antioxidant (C-2) is, for example, 0, 0.001, 0.002, 0.003, 0.000%, based on 100 parts by mass of the styrene resin (A).
- the phenolic antioxidant (C-2) is an antioxidant that has a phenolic hydroxyl group in its basic skeleton and is not a ()phosphate ester.
- Specific examples of the phenolic antioxidant (C-2) include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, ethylenebis(oxyethylene)bis[3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and these are one type. These can be used alone or in combination of two or more.
- Antioxidants include 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][ 1,3,2]
- phosphorus-phenol compounds such as dioxaphosphepine that have both a phosphite structure and a phenol structure in the same molecule.
- the optical styrenic resin composition is considered to contain each of a phosphorus antioxidant and a phenolic antioxidant, and for example, based on 100 parts by mass of the styrenic resin (A), When containing 0.1 part by mass of the phosphorus-phenol compound, it is considered that 0.1 part by mass of the phosphorus antioxidant and 0.1 part by mass of the phenolic antioxidant are contained.
- the content of t-butylcatechol (TBC) in the optical styrenic resin composition is preferably 10 ppm or less, more preferably 5 ppm or less. By setting it as such a range, a light guide plate with excellent hue and transmittance can be obtained.
- the content of TBC is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 ppm, and may be within the range between any two of the numerical values exemplified here.
- the content of 6-tert-butyl-2,4-xylenol (TBX) in the optical styrenic resin composition is preferably 10 ppm or less, more preferably 5 ppm or less. By setting it as such a range, a light guide plate with excellent hue and transmittance can be obtained.
- the content of TBX is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 ppm, and any two of the numerical values exemplified here. It may be within the range between.
- the optical styrenic resin composition may contain sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, antistatic agents, hydrophilic additives, liquid paraffin (mineral oil), within a range that does not impair the characteristics of the present invention. ), polyethylene wax, microcrystalline wax, bluing agent, higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, higher fatty acid amides such as stearic acid amide, erucic acid amide, ethylene bisstearic acid amide, lauric acid It may contain a mold release agent such as higher fatty acid glycerides such as monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, and behenic acid monoglyceride, higher alcohols such as myristyl alcohol, cetyl alcohol, and stearyl alcohol.
- a mold release agent such as higher fatty acid glycerides such as monoglyceride, palm
- the melt mass flow rate (MFR) of the optical styrenic resin composition at a temperature of 200° C. and a load of 49 N is preferably 0.5 to 5.0 g/10 minutes, more preferably 1.0 to It is 4.0g/10 minutes. If the MFR is less than 0.5 g/10 minutes, the molding stability will decrease, and if the MFR exceeds 5.0 g/10 minutes, the strength will be insufficient.
- the Vicat softening temperature of the optical styrenic resin composition is preferably 95 to 104°C, more preferably 100 to 104°C. If the Vicat softening temperature is less than 95° C., heat resistance will be insufficient, and the light guide plate may be deformed depending on the usage environment.
- Examples of the polymerization method for the styrene resin (A) include known styrene polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In terms of quality and productivity, bulk polymerization and solution polymerization are preferred, and continuous polymerization is preferred.
- Examples of solvents that can be used 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.
- polymerization auxiliaries such as a polymerization initiator, chain transfer agent, crosslinking agent, and other polymerization auxiliaries can be used as necessary.
- the polymerization initiator is preferably a radical polymerization initiator, such as known and commonly used ones such as 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, and 2,2-di(t-butylperoxy)butane.
- Peroxy ketals such as di(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di(t-amylperoxy)cyclohexane, cumene hydroperoxide, t-butyl hydroperoxide, etc.
- Hydroperoxides alkyl peroxides such as t-amylperoxyisononanoate, dialkyl such as t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, etc.
- Peroxides peroxy esters such as t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl carbonate, polyether tetrakis (t-butylperoxy) carbonate), N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azobis(2,4- dimethylvaleronitrile), N,N'-azobis[2-(hydroxymethyl)propionitrile], and the like, and one or more of these can be used in combination.
- peroxy esters such as t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl carbonate, polyether tetrakis (t-butylper
- chain transfer agents examples include aliphatic mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, aromatic mercaptans, thiocarboxylic acids such as thioglycolic acid and mercaptopropionic acid, ethylene glycol, tetraethylene glycol, neopentyl glycol, and trimethylol.
- Polyfunctional mercaptans obtained by esterifying the hydroxyl groups of polyhydric alcohols such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid or mercaptopropionic acid, pentaphenylethane, ⁇ -methylstyrene dimer, and terpinolene.
- polyhydric alcohols such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid or mercaptopropionic acid, pentaphenylethane, ⁇ -methylstyrene dimer, and terpinolene.
- aliphatic mercaptans, aromatic mercaptans, thiocarboxylic acids, and polyfunctional mercaptans are preferred from the viewpoint of easy molecular weight adjustment.
- the styrenic resin (A) can be produced by a method including a polymerization step, a devolatilization step, and a granulation step.
- the polymerization reaction is controlled by adjusting the polymerization temperature, etc. so that the target molecular weight, molecular weight distribution, and reaction conversion rate are achieved.
- the polymerization solution containing the polymer that has exited the polymerization step is transferred to a devolatilization step, where unreacted monomers and polymerization solvent are removed.
- the devolatilization process consists of a vacuum devolatilization tank with a heater and a devolatilization extruder with a vent.
- the molten polymer that has exited the devolatilization step is transferred to the granulation step.
- the molten resin is extruded into strands through a perforated die and processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method.
- the optical styrenic resin composition is produced by adding a hindered amine light stabilizer (B), a phosphorus antioxidant (C-1), and a phenolic antioxidant (C-2) to the styrenic resin (A).
- a hindered amine light stabilizer (B), phosphorus antioxidant (C-1), and a phenolic antioxidant (C-2) may be added to the raw material solution before polymerization of the styrenic resin (A).
- the styrenic resin (A) may be mixed in an extruder installed after polymerization and before granulation, or in a static mixing device.
- pellets after granulating the styrene resin (A), the hindered amine light stabilizer (B), the phosphorus antioxidant (C-1), and the phenolic antioxidant (C-2) are dry blended and melted. It may be manufactured by kneading.
- a pellet-shaped masterbatch obtained by melt-kneading a hindered amine light stabilizer (B), a phosphorus antioxidant (C-1), and a phenolic antioxidant (C-2) with a small amount of styrene resin in advance. may be prepared, dry-blended the styrenic resin (A) and the masterbatch, and then melt-kneaded and adjusted.
- the content of t-butylcatechol or 6-tert-butyl-2,4-xylenol in the optical styrene resin composition is determined by adjusting the content at the start of polymerization of the styrenic resin (A) and by devolatilizing it thereafter. It is possible to adjust the content in the process etc.
- a light guide plate according to one embodiment of the present invention is a molded product formed by molding the optical styrenic resin composition.
- the light guide plate is a light guide plate that can be used in an edge-light type surface light source unit.
- the light guide plate may have an uneven shape on the surface of the light guide plate. More specifically, the light guide plate may have a plurality of lenticular and/or prism-shaped protrusions on its surface.
- the convex portion is preferably provided on at least one surface of the light guide plate, and particularly on one surface that is the front surface (light emitting surface) of the light guide plate. Although it may be provided on other surfaces if necessary, it is more preferable that it is provided only on the front surface (light emitting surface) of the light guide plate.
- the lenticular-shaped convex portion is an arc-shaped convex portion, and is a protrusion whose cross-sectional edge shape is circular.
- the prism shape is an arcuate convex portion, and a protrusion whose cross-sectional edge shape is a triangular mountain shape.
- a plurality of convex portions may be formed in parallel relationship with each other.
- the convex portion may be integrally formed with the light guide plate.
- the thickness of the light guide plate is 0.2 to 3.0 mm, preferably 0.3 to 2.5 mm, and more preferably 0.4 to 2.4 mm. Within this range, it is easy to produce a light guide plate with excellent moldability such as excellent extrusion stability and strength when molding an optical styrenic resin composition.
- the average transmittance of the light guide plate in the wavelength range of 380 to 780 nm at an optical path length of 115 mm is preferably 85% or more, more preferably 86% or more.
- the YI value of the light guide plate at an optical path length of 115 mm is preferably 6.0 or less, more preferably 4.0 or less.
- a light guide plate according to an embodiment of the present invention is obtained by molding the optical styrenic resin composition described above, and a known method such as sheet extrusion molding, injection molding, or compression molding is used as the molding method.
- a known method such as sheet extrusion molding, injection molding, or compression molding is used as the molding method.
- continuous sheet extrusion molding equipped with a surface shape transfer mold is preferable in terms of productivity and ease of increasing the size of the molded product.
- Examples of sheet extrusion molding include an extrusion process in which a resin is supplied in a heated molten state to a feed block and continuously extruded from a die to create a sheet; a pressing process in which the resin sheet is sandwiched between a pressure roll and a cooling roll; After the pressing step, there is a continuous sheet extrusion molding method that has a conveyance step of conveying the resin sheet while keeping it in close contact with a cooling roll, and has a transfer mold on the surface of the cooling roll, and by changing the shape of the transfer mold, Any uneven shape can be transferred onto the sheet surface.
- the light guide plate may have an uneven shape on the front surface (light-emitting surface), and the back surface may be subjected to reflective processing to diffusely reflect light.
- reflective processing include silk printing, inkjet printing, and methods of applying dot-shaped irregularities by laser irradiation. For printing dot patterns, it is possible to use ink with fine particles that diffuse light. can.
- Edge-light type surface light source unit is an edge-light type surface light source unit having the above-mentioned light guide plate and a light source that supplies LED light to the end face of the light guide plate. .
- the edge-light type surface light source unit is suitably used as a surface light source device for a liquid crystal display device.
- a light diffusing plate according to one embodiment of the present invention is a molded article formed by molding the optical styrenic resin composition.
- the light diffusing plate is a light diffusing plate that can be used in a direct type surface light source unit.
- the thickness of the light diffusing plate according to an embodiment of the present invention is, for example, 1 to 3 mm, although it is not limited.
- An antistatic agent may be applied to the surface of the light diffusion plate. By applying the antistatic agent, the attachment of dust and the like due to static electricity is suppressed after the light diffusion plate is attached to the backlight device, so that it can be used for a long period of time without deterioration in brightness.
- the light diffusing plate of the present invention may have a fine uneven shape such as embossing on both sides or one side, or may have a lenticular shape or a prism shape on both sides or one side. .
- the light diffusing plate may contain 0.1 to 1.0 parts by mass of a light diffusing agent based on 100 parts by weight of the optical styrene resin composition.
- the light diffusing agent can be particles having a refractive index different from that of the optical styrene resin composition and can be used as long as it has the effect of diffusing incident light.
- styrene polymer particles acrylic Organic particles such as polymer particles and siloxane polymer particles, and inorganic particles such as glass beads, silica particles, aluminum hydroxide particles, calcium carbonate particles, barium sulfate particles, titanium oxide particles, and talc can be used.
- at least one selected from acrylic polymer particles, styrene polymer particles, and siloxane polymer particles is preferable.
- the light diffusing plate according to one embodiment of the present invention can be manufactured by molding the optical styrene resin composition described above by various methods such as extrusion molding and injection molding, but preferably by extrusion molding. do.
- extrusion molding is a method in which an optical styrene resin composition is melt-kneaded using a single-screw extruder or a twin-screw extruder, continuously extruded from a T die, and then cooled and solidified using a cooling roll unit. It can be raised.
- a transfer mold is provided on the surface of the cooling roll, and by changing the shape of the transfer mold, an arbitrary uneven shape can be formed.
- methods such as a coextrusion method, an adhesion method, a thermal adhesion method, a solvent adhesion method, a casting method, and a surface coating method can be employed.
- a direct type surface light source unit is a direct type surface light source unit that includes the above-mentioned light diffusion plate and a light source that supplies LED light to the light diffusion plate.
- the direct type surface light source unit is suitably used as a surface light source device for a liquid crystal display device.
- Example 1 Production of optical styrenic resin composition
- a first reactor which is a complete mixing type stirring tank
- a second reactor which is a plug flow type reactor with a static mixer, are connected in series to constitute a polymerization process, and a styrenic resin is produced.
- the capacity of each reactor was 30 liters for the first reactor and 12 liters for the second reactor.
- the polymerization rate of the monomer at this time was 70%.
- a temperature gradient was created along the flow direction, and the temperature was adjusted to 130° C. at the middle portion and 145° C. at the outlet portion.
- the solution containing the polymer continuously taken out from the second reactor is introduced into a vacuum devolatilization tank with a preheater, which consists of two stages in series, and the temperature of the preheater is adjusted so that the resin temperature is 220°C. was adjusted to separate unreacted styrene and ethylbenzene at a pressure of 0.8 kPa.
- the obtained molten polymer was continuously fed to the extruder, and 0.1 parts by mass of hindered amine light stabilizer (770) was added to 100 parts by mass of the polymer from the additive feed port, and the settings were made. After mixing at a temperature of 220° C., the mixture was extruded into a strand through a multi-hole die, and the strand was cooled and cut using a cold cut method to form pellets.
- the TBC concentration in the obtained optical styrenic resin composition was 1.5 ⁇ g/g, and the TBX concentration was 0.2 ⁇ g/g. Further, the weight average molecular weight (Mw) was 170,000, and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) was 2.0.
- Examples 2 to 17 and Comparative Examples 1 to 6 The composition of the raw material solution and polymerization conditions were changed as shown in Table 1, and a hindered amine light stabilizer (B), a phosphorus antioxidant (C-1), a phenolic antioxidant (C-2), and an ultraviolet absorber were added.
- An optical styrenic resin composition and a light guide plate were produced in the same manner as in Example 1, except that the formulation of agent (D) was changed as shown in Tables 2 (Tables 2-1 and 2-2) to Table 3.
- Tables 2 Table 2-1 and Table 2-2
- the ultraviolet absorbers (D) are as follows.
- (Hindered amine light stabilizer (B)) 770 Bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate (BASF TINUVIN770DF) 944: 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino) and 1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl Polycondensate of -4-piperidyl)hexamethylenediamine (Chimass®rb944FDL, manufactured by BASF) 292: Methyl (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate: 25% and bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate: 75 % mixture (BASF TINUVIN292) 123: Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate (BASF TINUVIN123)
- Phosphorous antioxidant (C-1)) 168 Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168 manufactured by BASF) HP-10: 2,2'-methylenebis(4,6-di-tert-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus (ADKSTAB HP-10 manufactured by ADEKA) 126: Bis-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (Irgafos 126 manufactured by BASF)
- melt mass flow rate (MFR)> The melt mass flow rate was measured according to JIS K 7210 at a temperature of 200°C and a load of 49N.
- the Vicat softening temperature was measured according to JIS K 7206 at a heating rate of 50°C/hr and a test load of 50N.
- ⁇ Content of TBC and TBX in optical styrenic resin composition After dissolving 0.2 g of the optical styrene resin composition in a small amount of THF, 200 ⁇ L of BSTFA (M,O-bis(trimethylsilyl)trifluoroacetamide) was added, trimethylsilyl derivatization treatment was performed, and 10 mL of THF was added. After adjusting the volume, the supernatant liquid was separated by centrifugation, and the supernatant liquid was measured by gas chromatography/mass spectrometry (GC/MS) under the following conditions. Note that a previously prepared calibration curve was used to determine the concentration.
- BSTFA M,O-bis(trimethylsilyl)trifluoroacetamide
- GC device Agilent 7890A
- Column Agilent DB-5ms (0.25mm i.d. x 30m) Liquid phase film thickness 0.25 ⁇ m
- Inlet 300°C, 1.5mL/min, (split ratio 1:5)
- MS device Agilent 5975C Interface temperature: 320°C MS detection conditions: SIM measurement TBC (m/z 295 for quantification, m/z 310 for confirmation)
- GC device GC2010 Plus manufactured by Shimadzu Corporation
- Column: DB-1 (30m x 0.25mm i.d., df 0.10 ⁇ m)
- ⁇ Weight average molecular weight (Mw)> The weight average molecular weight (Mw), Z average molecular weight (Mz), and number average molecular weight (Mn) were measured using gel permeation chromatography (GPC) under the following conditions.
- ⁇ Average transmittance and YI value of light guide plate> The average transmittance and YI value were measured using the following procedure.
- a test piece of 115 mm x 85 mm was cut out from the light guide plate obtained above, and the end surface was polished by buffing to create a plate-shaped molded product having a mirror surface on the end surface.
- the plate-shaped molded product after polishing was measured using an ultraviolet-visible spectrophotometer V-670 manufactured by JASCO Corporation to measure the wavelength at an optical path length of 115 mm for incident light with a size of 20 x 1.6 mm and a spread angle of 0°.
- the spectral transmittance from 350 nm to 800 nm was measured, and the YI value at a field of view of 2° using a C light source was calculated according to JIS K7105.
- the average transmittance (total light transmittance) was calculated as the average of the spectral transmittances in the wavelength range of 380 to 780 nm.
- ⁇ Dimensional stability (moisture absorption deformation)> Cut out a 200 mm x 300 mm test piece from the light guide plate obtained above, store the test piece at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours, and measure the dimensional change of the long side before and after storage.
- the deformation rate was calculated using the following formula.
- Deformation rate ((Long side length after storage) - (Long side length before storage)) ⁇ (Long side length before storage) x 100 (%)
- the dimensional stability (moisture absorption change) of the light guide plate was evaluated by rating a change rate of less than 0.10% as ⁇ , a rate of change of 0.10 to 0.15% as ⁇ , and a rate of change of more than 0.15% as ⁇ . .
- a test piece of 115 mm x 85 mm was cut from the light guide plate obtained above, and the end face was polished at 2.0 m/min with a diamond blade rotating at 8000 rpm using an end face polisher (GCPB-500 manufactured by Megalo Technica Co., Ltd.). Polishing was performed at a feed rate of 0.2 mm to create a plate-shaped molded product with mirror surfaces on the end faces.
- a flat blue LED light source for TV peak wavelength 445 nm
- an input current of 0.05 W/mm 2 was applied in an environment of 80°C. , 500h, LED light was irradiated.
- the wavelength at an optical path length of 115 mm was measured for incident light with a size of 20 x 1.6 mm and a spread angle of 0°.
- the spectral transmittance from 350 nm to 800 nm was measured, and the YI value at a field of view of 2° using a C light source was calculated according to JIS K7105.
- the value obtained by subtracting the YI value before the test from the YI value after the test was defined as ⁇ YI.
- the LED light entrance part of the plate-shaped molded product after the test was visually checked, and the LED durability was evaluated by rating ⁇ if there was no change and rating ⁇ if carbonization occurred.
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Abstract
Description
[1] スチレン系単量体単位と(メタ)アクリル酸エステル系単量体単位を含む共重合体であるスチレン系樹脂(A)とヒンダードアミン光安定剤(B)を含有する光学用スチレン系樹脂組成物であって、 前記共重合体は、前記共重合体100質量%中に、前記スチレン系単量体単位95~20質量%と前記(メタ)アクリル酸エステル系単量体単位5~80質量%を含有し、前記スチレン系樹脂(A)100質量部に対して、前記ヒンダードアミン光安定剤(B)を0.001~1.0質量部、含有する、光学用スチレン系樹脂組成物。
[2] 前記ヒンダードアミン光安定剤(B)が、N-H型ヒンダードアミン光安定剤、及び/または、N-R型ヒンダードアミン光安定剤である、[1]に記載の光学用スチレン系樹脂組成物。
[3] 前記N-H型ヒンダードアミン光安定剤が、
ビス(2,2,6,6-テトラメチルピペリジン-4-イル)セバケート、
2,2,6,6-テトラメチル-4-ピペリジルヘキサデカノエート、2,2,6,6-テトラメチル-4-ピペリジルオクタデカノエート、
テトラキス(2,2,6,6-テトラメチル-4-ピペリジル)-1,2,3,4-ブタンテトラカルボキシレート、
N,N′-ビス(2,2,6,6-テトラメチルピペリジン-4-イル)ヘキサメチレンジアミンと4-モルホリノ2,6-ジクロロ-1,3,5-トリアジンとの重縮合物、
2,4-ジクロロ-6-(1,1,3,3-テトラメチルブチルアミノ)と1,3,5-トリアジン・N,N′-ビス(2,2,6,6-テトラメチル-4-ピペリジル)ヘキサメチレンジアミンとの重縮合物、
N,N′-ビス(2,2,6,6-テトラメチルピペリジン-4-イル)ヘキサメチレンジアミンと2,4,6-トリクロロ-1,3,5-トリアジンとN-ブチル-1ーブタンアミンとN-ブチル-2,2,6,6-テトラメチル-4-ピペリジンアミンとの重縮合物、
1,6,11-トリス〔2,4-ビス(N-ブチル-N-(2,2,6,6-テトラメチル-4-ピペリジル)アミノ)-s-トリアジン-6-イル〕アミノウンデカン、
1,2,3,4-ブタンテトラカルボン酸と2,2,6,6-テトラメチル-4-ピペリジノールとβ,β,β′,β′-テトラメチル-2,4,8,10-テトラオキサスピロ[5,5]ウンデンカン―3,9-ジエタノールとの重縮合物、
から選ばれる少なくとも1種である、[2]に記載の光学用スチレン系樹脂組成物。
[4] 前記N-R型ヒンダードアミン光安定剤が、
メチル(1,2,2,6,6-ペンタメチルピペリジン-4-イル)セバケート、
ビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)セバケート、
ビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)n-ブチル3,5-ジ-tert-ブチル4-ヒドロキシベンジルマロネート、
4-ヒドロキシ-2,2,6,6-テトラメチル-1-ピペリジンエタノールとコハク酸ジメチルエステルとの重縮合物、
1,5,8,12-テトラキス〔4,6-ビス(N-ブチル-N-(1,2,2,6,6-ペンタメチル-4-ピペリジル)アミノ)-1,3,5-トリアジン-2-イル〕-1,5,8,12-テトラアザドデカン、
1,2,3,4-ブタンテトラカルボン酸と1,2,2,6,6-ペンタメチル-4-ピペリジノールとβ,β,β′,β′-テトラメチル-2,4,8,10-テトラオキサスピロ[5,5]ウンデンカン―3,9-ジエタノールとの重縮合物、
コハク酸と(4-ヒドロキシ―2,2,6,6-テトラメチルピペリジン―1-イル)エタノールとの重縮合物及びN,N′,N′′,N′′′-テトラキス-(4,6-ビス-(ブチル-(N-メチル-2,2,6,6-テトラメチルピペリジン-4-イル)アミノ)-トリアジン-2-イル)-4,7-ジアザデカン-1,10-ジアミンの混合物、
から選ばれる少なくとも1種である、[2]または[3]に記載の光学用スチレン系樹脂組成物。
[5] 前記スチレン系樹脂(A)100質量部に対して、リン系酸化防止剤(C-1)を0.001~0.5質量部、含有する、[1]~[4]の何れか1つに記載の光学用スチレン系樹脂組成物。
[6] 前記リン系酸化防止剤(C-1)は、トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト、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、ビス-(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジフォスファイト、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、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′-ジイルビスホスホナイト、ビス(2,4-ジ-tert-ブチル-6-メチルフェニル)エチル亜リン酸エステルから選ばれる少なくとも1種である、[5]に記載の光学用スチレン系樹脂組成物。
[7] [1]~[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を成形してなる導光板。
[8] [7]に記載の導光板と、該導光板の端面にLED光を供給する光源を有する、エッジライト型面光源ユニット。
[9] [1]~[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を成形してなる光拡散板。
[10] [9]に記載の光拡散板と、該光拡散板にLED光を供給する光源を有する、直下型面光源ユニット。
本発明の一実施形態に係る光学用スチレン系樹脂組成物は、スチレン系樹脂(A)と、ヒンダードアミン光安定剤(B)を含有する光学用スチレン系樹脂組成物である。
スチレン系樹脂(A)は、スチレン系単量体と(メタ)アクリル酸エステル系単量体を含む単量体を共重合して得られる樹脂である。スチレン系樹脂(A)は、スチレン系単量体単位と(メタ)アクリル酸エステル系単量体単位を含む共重合体である。共重合体は、共重合体100質量%中に、スチレン系単量体単位95~20質量%と(メタ)アクリル酸エステル系単量体単位5~80質量%を含有し、好ましくはスチレン系単量体単位90~25質量%と(メタ)アクリル酸エステル系単量体単位10~75質量%を含有し、より好ましくはスチレン系単量体単位80~30質量%と(メタ)アクリル酸エステル系単量体単位20~70質量%を含有し、さらに好ましくはスチレン系単量体単位60~40質量%と(メタ)アクリル酸エステル系単量体単位40~60質量%を含有する。このような範囲とすることで、透明性、色相、寸法安定性を同時に満たすことができる。スチレン系単量体を90質量%以下とすることで、透明性、色相に優れる導光板が得られ、スチレン単量体を20%以上とすることで、寸法安定性に優れる導光板を得ることができる。スチレン系樹脂(A)の(メタ)アクリル酸エステル系単量体単位の含有量は、具体的には例えば、5,6,7,8,9,10,15,20,25,30,35,40,45,50,55,60,65,70,75,80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。
光学用スチレン系樹脂組成物は、スチレン系樹脂(A)100質量部に対して、ヒンダードアミン光安定剤(B)を0.001~1.0質量部含有し、好ましくは0.01~0.3質量部含有する。このような範囲とすることで、透明性、色相、LED光源に対する光安定性を改善することができる。ヒンダードアミン光安定剤(B)の含有量は、スチレン系樹脂(A)に対して、具体的には例えば、0.001,0.005,0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.1,0.2,0.3,0.4,0.5、0.6、0.7、0.8、0.9、1.0質量部であり、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。また、ヒンダードアミン光安定剤(B)は、1種を単独又は2種以上を組み合わせて使用してもよい。
光学用スチレン系樹脂組成物は、スチレン系樹脂(A)100質量部に対して、リン系酸化防止剤(C-1)を0.001~0.5質量部含有することが好ましく、さらに好ましくは0.002~0.4質量部、特に好ましくは0.005~0.3質量部である。このような範囲とすることで、透明性、色相を改善することができる。リン系酸化防止剤(C-1)の含有量は、スチレン系樹脂(A)100質量部に対して、具体的には例えば、0.001,0.002,0.003,0.004,0.005,0.01,0.02,0.05,0.1,0.2,0.3,0.4,0.5質量部であり、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。
光学用スチレン系樹脂組成物中のt-ブチルカテコール(TBC)は、10ppm以下であることが好ましく、より好ましくは、5ppm以下である。このような範囲とすることで、色相と透過率に優れる導光板が得られる。TBCの含有量は、具体的には例えば、0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,2,3,4,5,6,7,8,9,10ppm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(A)の重合方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等公知のスチレン重合方法が挙げられる。品質面や生産性の面では、塊状重合法、溶液重合法が好ましく、連続重合であることが好ましい。溶媒として例えばベンゼン、トルエン、エチルベンゼン及びキシレン等のアルキルベンゼン類やアセトンやメチルエチルケトン等のケトン類、ヘキサンやシクロヘキサン等の脂肪族炭化水素等が使用できる。
本発明の一実施形態に係る導光板は、上記光学用スチレン系樹脂組成物を成形してなる成形品である。導光板は、エッジライト型面光源ユニットに用いることが可能な導光板である。
導光板は、導光板の表面に凹凸形状を有していてよい。より詳細には、導光板の表面に複数のレンチキュラー形状及び/又はプリズム形状の凸部を有していてよい。凸部は、導光板の少なくとも一つの面に設けられていることが好ましく、特に導光板の前面(発光面)である一つの面に設けられる。他の面についても必要であれば設けてもよいが、導光板の前面(発光面)にのみ設けられていることがより好ましい。
導光板の光路長115mmでの波長380~780nmの平均透過率は、好ましくは85%以上であり、より好ましくは86%以上である。
本発明の一実施形態に係る導光板は、上記の光学用スチレン系樹脂組成物を成形して得られ、成形方法としては、シート押出成形や、射出成形、圧縮成形等の公知の方法を用いることができるが、生産性、成形品の大型化が容易という点で、表面形状転写型を備えた連続シート押出成形であることが好ましい。該シート押出成形の例としては、樹脂を加熱溶融状態でフィードブロックに供給し、ダイから連続的に押し出しシートを作成する押出工程と、前記樹脂シートを、圧着ロールと冷却ロールで挟み込む押圧工程、押圧工程後、樹脂シートを冷却ロールに密着させながら搬送する搬送工程を有し、冷却ロールの表面に転写型を備える連続シート押出成形法が挙げられ、該転写型の形状を変更することで、シート表面に任意の凹凸形状を転写することができる。
本発明の一実施形態に係るエッジライト型面光源ユニットは、上記導光板と、該導光板の端面にLED光を供給する光源を有する、エッジライト型面光源ユニットである。エッジライト型面光源ユニットは、液晶表示装置用の面光源装置として好適に用いられる。
本発明の一実施形態に係る光拡散板は、上記光学用スチレン系樹脂組成物を成形してなる成形品である。光拡散板は、直下型面光源ユニットに用いることが可能な光拡散板である。
本発明の一実施形態に係る光拡散板の厚みは、制限されないが、例えば1~3mmである。光拡散板には、その表面に帯電防止剤が塗布されていてもよい。帯電防止剤が塗布されていることによって、光拡散板をバックライト装置に取り付け後、静電気による埃等の付着が抑えられるため、長期間にわたって輝度の低下なく使用することができる。また、本発明の光拡散板には、その両面もしくは方面にエンボス加工等の細かな凹凸形状が形成されていてもよいし、両面もしくは片面にレンチキュラー形状、もしくはプリズム形状が形成されていてもよい。
本発明の一実施形態に係る光拡散板は、上記の光学スチレン系樹脂組成物を、押出成形、射出成形等、種々の方法により成形することにより製造可能であるが、好ましくは押出成形によって製造する。押出成形の例としては、光学スチレン系樹脂組成物を単軸押出機、または二軸押出機を用いて溶融混錬し、Tダイスより連続的に押出し後、冷却ロールユニットにより冷却固化する方法が上げられる。光拡散板の表面に凹凸形状を形成させる場合には、冷却ロールの表面に転写型を備え、該転写型の形状を変更することで、任意の凹凸形状を形成させることができる。また、光拡散板の両面、片面に表面層を積層する場合には、共押出法、貼付法、熱接着法、溶剤接着法、キャスト法、表面塗布法等の方法を採用することができる。
本発明の一実施形態に係る直下型面光源ユニットは、上記光拡散板と、該光拡散板にLED光を供給する光源を有する、直下型面光源ユニットである。直下型面光源ユニットは、液晶表示装置用の面光源装置として好適に用いられる。
[実施例1]
完全混合型撹拌槽である第1反応器と静的混合器付プラグフロー型反応器である第2反応器を直列に接続して重合工程を構成し、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30リットル、第2反応器を12リットルとした。スチレン(TBC濃度11μg/g)51質量%、メタクリル酸メチル(TBX濃度7μg/g)39質量%、エチルベンゼン10質量%の原料組成に対して、第1反応器の入口で、重合開始剤として、t-ブチルパーオキシイソプロピルモノカーボネート(日油株式会社製:パーブチルI)150ppm、連鎖移動剤として、n-ドデシルメルカプタン(アルケマ株式会社製)500ppmの添加濃度(いずれも単量体全体に対する質量基準の濃度)となるように調整した後、原料溶液を128℃に設定した第1反応器に、8.0kg/hにて連続的に供給した。さらに、得られた重合溶液を第2反応器に連続的に供給し、重合を完結させた。このときの単量体の重合率は70%であった。なお、第2反応器では、流れの方向に沿って温度勾配をつけ、中間部分を130℃、出口部分で145℃となるよう調整した。
続いて、第2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、樹脂温度が220℃となるよう予熱器の温度を調整し、0.8kPaの圧力にて、未反応スチレン及びエチルベンゼンを分離した。得られた溶融ポリマーを押出機に連続的に供給し、添加剤のフィード口から、重合体100質量部に対して、ヒンダードアミン光安定剤(770)を0.1質量部にて添加し、設定温度220℃にて混合した後、多孔ダイよりストランド状に押出して、コールドカット方式にて、ストランドを冷却及び切断しペレット化した。得られた光学用スチレン系樹脂組成物中のTBC濃度は1.5μg/g、TBX濃度は0.2μg/gであった。また、重量平均分子量(Mw)は、17万であり、重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)は2.0であった。
原料溶液の組成、及び重合条件を表1に示すように変更し、ヒンダードアミン光安定剤(B)、リン系酸化防止剤(C-1)、フェノール系酸化防止剤(C-2)、紫外線吸収剤(D)の配合を表2(表2-1及び表2-2)~表3のように変更した以外は実施例1と同様に光学用スチレン系樹脂組成物及び導光板を製造した。各種測定及び評価結果を表2(表2-1及び表2-2)~表3に示す。
770:ビス(2,2,6,6-テトラメチルピペリジン-4-イル)セバケート(BASF社製 TINUVIN770DF)
944:2,4-ジクロロ-6-(1,1,3,3-テトラメチルブチルアミノ)と1,3,5-トリアジン・N,N′-ビス(2,2,6,6-テトラメチル-4-ピペリジル)ヘキサメチレンジアミンの重縮合物(BASF社製 Chimassоrb944FDL)
292:メチル(1,2,2,6,6-ペンタメチルピペリジン-4-イル)セバケート:25%とビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)セバケート:75%の混合物(BASF社製 TINUVIN292)
123:ビス(1-オクチルオキシ-2,2,6,6-テトラメチルピペリジル)セバケート(BASF社製 TINUVIN123)
168:トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト(BASF社製 Irgafos 168)
HP-10:2,2′-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(ADEKA社製 ADKSTAB HP-10)
126:ビス-(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジフォスファイト(BASF社製 Irgafos 126)
1076: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社製 Irganox 1076)
P:2-(2-ヒドロキシ―5-メチルフェニル)ベンゾトリアゾール(BASF社製 TINUVIN P)
表2(表2-1及び表2-2)~3に記載の光学用スチレン系樹脂組成物の評価は、下記の方法により行った。
メルトマスフローレートは、JIS K 7210に従って、温度200℃、49N荷重の条件で測定した。
ビカット軟化温度は、JIS K 7206に従って、昇温速度50℃/hr、試験荷重50Nで測定した。
光学用スチレン系樹脂組成物0.2gを少量のTHFに溶解した後、BSTFA(M,O-ビス(トリメチルシリル)トリフルオロアセトアミド)200μLを添加し、トリメチルシリル誘導体化処理を実施し、THFにて10mL定容した後、遠心分離によって分離した上澄み液について、ガスクロマトグラフ質量分析(GC/MS)にて、以下の条件で測定した。なお、濃度の決定には、予め作成した検量線を用いた。
GC装置 :Agilent社製 7890A
カラム :Agilent社製 DB-5ms(0.25mm i.d.×30m)液相膜厚0.25μm
カラム温度:50℃(1min)→(20℃/min昇温)→320℃(6.5min)計20min
注入口 :300℃、1.5mL/min、(スプリット比1:5)
注入量 :1μL
MS装置 :Agilent社製 5975C
インターフェイス温度:320℃
MS検出条件:SIM測定 TBC(定量用m/z 295、確認用m/z 310)
光学用スチレン系樹脂組成物1.0gを20mLのTHFに完全に溶解した後、メタノールを5mL滴下し、20分間攪拌した。4000rpmで10分間、遠心分離を行い、分離した上澄み液について、ガスクロマトグラフィー(GC)にて、以下の条件で測定した。なお、濃度の決定には、予め作成した検量線を用いた。
GC装置 : 島津製作所社製 GC2010 Plus
カラム : DB-1(30m×0.25mm i.d.、df=0.10μm)
カラム温度 :240℃(1min)→(10℃/min昇温)→320℃(15min)
注入口 :320℃、1.02mL/min(スプリット比1:5)
注入量 :1μL
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。
<導光板の製造>
前記光学用スチレン系樹脂組成物を、スクリュー径90mm、L/D=32の単軸ベント付き押出機に供給し、200~235℃で溶融混練した後、リップ幅1000mm、リップ開度3.0mmのTダイにて、Tダイ温度245~250℃で吐出し、縦型3本冷却ロールで冷却固化後、端面をトリミングし、幅800mm、厚み2.0mmの導光板を得た。
表2~表3における導光板の平均透過率、YI値、寸法安定性(吸湿変形)、LED耐久性について下記のように評価した。
平均透過率及びYI値は、次の手順にて測定を行った。
前記で得られた導光板から115mm×85mm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。平均透過率(全光線透過率)は、波長380~780nmにおける分光透過率の平均として算出した。
前記で得られた導光板から、200mm×300mmの試験片を切り出し、試験片を温度60℃、相対湿度90%の条件で500時間保管し、保管前後での長辺の寸法変化を測定し、以下の式により変形率を計算した。
変形率=((保管後の長辺長さ)-(保管前の長辺長さ))÷(保管前の長辺の長さ)×100(%)
変化率が0.10%未満のものを〇、0.10~0.15%のものを△、0.15%超のものを×として、導光板の寸法安定性(吸湿変化)を評価した。
前記で得られた導光板から115mm×85mmの試験片を切り出し、端面を端面研磨機(メガロテクニカ株式会社製GCPB-500)を用い、8000rpmの速度で回転するダイヤモンド刃で2.0m/minの送り速度で0.2mm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、端面より0.5mmの位置にTV用フラット型青色LED光源(ピーク波長445nm)を配置し、80℃の環境下、0.05W/mm2の入力電流にて、500h、LED光を照射した。試験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。試験後のYI値から試験前のYI値を差し引いた値をΔYIとした。また、試験後の板状成形品のLED入光部を目視で確認し、変化がないものを〇、炭化が発生したものを×として、LED耐久性を評価した。
Claims (10)
- スチレン系単量体単位と(メタ)アクリル酸エステル系単量体単位を含む共重合体であるスチレン系樹脂(A)と、ヒンダードアミン光安定剤(B)とを含有する光学用スチレン系樹脂組成物であって、
前記共重合体は、前記共重合体100質量%中に、前記スチレン系単量体単位95~20質量%と前記(メタ)アクリル酸エステル系単量体単位5~80質量%を含有し、
前記スチレン系樹脂(A)100質量部に対して、前記ヒンダードアミン光安定剤(B)を0.001~1.0質量部、含有する、光学用スチレン系樹脂組成物。 - 前記ヒンダードアミン光安定剤(B)が、N-H型ヒンダードアミン光安定剤、及び/または、N-R型ヒンダードアミン光安定剤である、請求項1に記載の光学用スチレン系樹脂組成物。
- 前記N-H型ヒンダードアミン光安定剤が、
ビス(2,2,6,6-テトラメチルピペリジン-4-イル)セバケート、
2,2,6,6-テトラメチル-4-ピペリジルヘキサデカノエート、2,2,6,6-テトラメチル-4-ピペリジルオクタデカノエート、
テトラキス(2,2,6,6-テトラメチル-4-ピペリジル)-1,2,3,4-ブタンテトラカルボキシレート、
N,N′-ビス(2,2,6,6-テトラメチルピペリジン-4-イル)ヘキサメチレンジアミンと4-モルホリノ2,6-ジクロロ-1,3,5-トリアジンとの重縮合物、
2,4-ジクロロ-6-(1,1,3,3-テトラメチルブチルアミノ)と1,3,5-トリアジン・N,N′-ビス(2,2,6,6-テトラメチル-4-ピペリジル)ヘキサメチレンジアミンとの重縮合物、
N,N′-ビス(2,2,6,6-テトラメチルピペリジン-4-イル)ヘキサメチレンジアミンと2,4,6-トリクロロ-1,3,5-トリアジンとN-ブチル-1ーブタンアミンとN-ブチル-2,2,6,6-テトラメチル-4-ピペリジンアミンとの重縮合物、
1,6,11-トリス〔2,4-ビス(N-ブチル-N-(2,2,6,6-テトラメチル-4-ピペリジル)アミノ)-s-トリアジン-6-イル〕アミノウンデカン、
1,2,3,4-ブタンテトラカルボン酸と2,2,6,6-テトラメチル-4-ピペリジノールとβ,β,β′,β′-テトラメチル-2,4,8,10-テトラオキサスピロ[5,5]ウンデンカン―3,9-ジエタノールとの重縮合物、
から選ばれる少なくとも1種である、請求項2に記載の光学用スチレン系樹脂組成物。 - 前記N-R型ヒンダードアミン光安定剤が、
メチル(1,2,2,6,6-ペンタメチルピペリジン-4-イル)セバケート、
ビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)セバケート、
ビス(1,2,2,6,6-ペンタメチルピペリジン-4-イル)n-ブチル3,5-ジ-tert-ブチル4-ヒドロキシベンジルマロネート、
4-ヒドロキシ-2,2,6,6-テトラメチル-1-ピペリジンエタノールとコハク酸ジメチルエステルとの重縮合物、
1,5,8,12-テトラキス〔4,6-ビス(N-ブチル-N-(1,2,2,6,6-ペンタメチル-4-ピペリジル)アミノ)-1,3,5-トリアジン-2-イル〕-1,5,8,12-テトラアザドデカン、
1,2,3,4-ブタンテトラカルボン酸と1,2,2,6,6-ペンタメチル-4-ピペリジノールとβ,β,β′,β′-テトラメチル-2,4,8,10-テトラオキサスピロ[5,5]ウンデンカン―3,9-ジエタノールとの重縮合物、
コハク酸と(4-ヒドロキシ―2,2,6,6-テトラメチルピペリジン―1-イル)エタノールとの重縮合物及びN,N′,N′′,N′′′-テトラキス-(4,6-ビス-(ブチル-(N-メチル-2,2,6,6-テトラメチルピペリジン-4-イル)アミノ)-トリアジン-2-イル)-4,7-ジアザデカン-1,10-ジアミンの混合物、
から選ばれる少なくとも1種である、請求項2または請求項3に記載の光学用スチレン系樹脂組成物。 - 前記スチレン系樹脂(A)100質量部に対して、リン系酸化防止剤(C-1)を0.001~0.5質量部、含有する、請求項1~請求項3の何れか1項に記載の光学用スチレン系樹脂組成物。
- 前記リン系酸化防止剤(C-1)は、トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト、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、ビス-(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジフォスファイト、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、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′-ジイルビスホスホナイト、ビス(2,4-ジ-tert-ブチル-6-メチルフェニル)エチル亜リン酸エステルから選ばれる少なくとも1種である、請求項5に記載の光学用スチレン系樹脂組成物。
- 請求項1~請求項3のいずれか1項に記載の光学用スチレン系樹脂組成物を成形してなる導光板。
- 請求項7に記載の導光板と、該導光板の端面にLED光を供給する光源を有する、エッジライト型面光源ユニット。
- 請求項1~請求項3のいずれか1項に記載の光学用スチレン系樹脂組成物を成形してなる光拡散板。
- 請求項9に記載の光拡散板と、該光拡散板にLED光を供給する光源を有する、直下型面光源ユニット。
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