TW202346381A - Optical styrene-based resin composition, light guide plate, edge-light system flat-surface light source unit, light diffusion plate, and direct under-light system flat-surface light source unit - Google Patents
Optical styrene-based resin composition, light guide plate, edge-light system flat-surface light source unit, light diffusion plate, and direct under-light system flat-surface light source unit Download PDFInfo
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- TW202346381A TW202346381A TW112115668A TW112115668A TW202346381A TW 202346381 A TW202346381 A TW 202346381A TW 112115668 A TW112115668 A TW 112115668A TW 112115668 A TW112115668 A TW 112115668A TW 202346381 A TW202346381 A TW 202346381A
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- styrene
- light
- mass
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- resin composition
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 230000003287 optical effect Effects 0.000 title claims abstract description 71
- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- 238000009792 diffusion process Methods 0.000 title claims description 26
- 239000004611 light stabiliser Substances 0.000 claims abstract description 51
- -1 acrylic ester Chemical class 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 36
- 239000003963 antioxidant agent Substances 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 32
- 229920001890 Novodur Polymers 0.000 claims description 31
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 238000009833 condensation Methods 0.000 claims description 22
- 230000005494 condensation Effects 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 9
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 claims description 7
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical group C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 4
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical group COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 claims description 4
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 claims description 4
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 4
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 claims description 4
- JMUOXOJMXILBTE-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 JMUOXOJMXILBTE-UHFFFAOYSA-N 0.000 claims description 3
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 claims description 3
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 claims description 3
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 claims description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- YSSBODGKHOXDDC-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 YSSBODGKHOXDDC-UHFFFAOYSA-N 0.000 claims description 2
- JDLQSLMTBGPZLW-UHFFFAOYSA-N 1-(1-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC(O)N1C(C)(C)CC(O)CC1(C)C JDLQSLMTBGPZLW-UHFFFAOYSA-N 0.000 claims description 2
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
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- 239000002245 particle Substances 0.000 description 11
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Classifications
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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
-
- 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
-
- 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
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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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- 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 array of point-like light-generating elements
- F21Y2105/14—Planar light sources comprising a two-dimensional array of point-like light-generating elements characterised by the overall shape of the two-dimensional array
- F21Y2105/16—Planar light sources comprising a two-dimensional array of point-like light-generating elements characterised by the overall shape of the two-dimensional 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]
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Abstract
Description
本發明係關於一種光學用苯乙烯系樹脂組合物、導光板、邊緣光型面光源單元、光擴散板、及直下型面光源單元。The present invention relates to an optical styrene resin composition, a light guide plate, an edge light surface light source unit, a light diffusion plate, and a direct type surface light source unit.
液晶顯示裝置之背光源有將光源配置於顯示裝置之正面之直下型及配置於側面之邊緣光型。邊緣光型背光源使用將配置於側面之光源之光引導至顯示裝置之正面之稱為導光板之零件。用於電視、桌上型個人電腦之顯示器、筆記型個人電腦、行動電話機、汽車導航用顯示器等廣泛之用途中。又,使用導光板之背光源亦用作照明裝置或看板等。The backlight of the liquid crystal display device includes a direct type in which the light source is arranged on the front of the display device and an edge light type in which the light source is arranged on the side. Edge-light backlights use a component called a light guide plate that guides light from light sources arranged on the side to the front of the display device. It is used in a wide range of applications such as televisions, desktop PC monitors, notebook PCs, mobile phones, and car navigation monitors. In addition, backlights using light guide plates are also used as lighting devices or signage.
導光板之光透過距離相對較長,光程長度中之光損耗較大,因而要求具有特別高之光線透過率。因此,導光板之材料使用以聚甲基丙烯酸甲酯(PMMA)為代表之丙烯酸系樹脂。然而,PMMA之吸水性較高,因此存在因吸水而導致導光板產生翹曲或發生尺寸變化之情形。又,於成形時容易熱分解,因而若於高溫下成形,則存在成形體容易發生外觀不良之問題。為了改善該等問題,例如,於專利文獻1中,提出了將苯乙烯-(甲基)丙烯酸甲酯共聚物用作導光板之材料。The light transmission distance of the light guide plate is relatively long, and the light loss in the optical path length is large, so it requires a particularly high light transmittance. Therefore, acrylic resin represented by polymethylmethacrylate (PMMA) is used as the material of the light guide plate. However, PMMA has high water absorption, so water absorption may cause the light guide plate to warp or change dimensions. In addition, it is easily thermally decomposed during molding, so if molded at high temperatures, there is a problem that the appearance of the molded product is likely to be poor. In order to improve these problems, for example, in Patent Document 1, it is proposed to use a styrene-methyl (meth)acrylate copolymer as a material for a light guide plate.
另一方面,苯乙烯-(甲基)丙烯酸甲酯共聚物之成形體與PMMA相比,色相較差,於用作背光源之情形時,有時會發生色不均。為了改善該問題,作為苯乙烯-(甲基)丙烯酸甲酯之色相改善技術,提出專利文獻2。 [先前技術文獻] [專利文獻] On the other hand, the molded body of styrene-methyl (meth)acrylate copolymer has a poorer hue than PMMA, and when used as a backlight, color unevenness may occur. In order to improve this problem, Patent Document 2 is proposed as a hue improvement technology of styrene-methyl (meth)acrylate. [Prior technical literature] [Patent Document]
[專利文獻1]日本專利特開2003-075648號公報 [專利文獻2]國際公開第2016-129675號 [Patent Document 1] Japanese Patent Application Publication No. 2003-075648 [Patent Document 2] International Publication No. 2016-129675
[發明所欲解決之問題][Problem to be solved by the invention]
近年來,伴隨電視或顯示器等背光源單元之高解析度化,有時會使用高亮度型LED(light-emitting diode,發光二極體)作為邊緣光源,但先前之苯乙烯-(甲基)丙烯酸甲酯共聚物之導光板根據使用環境,有時於長時間點亮後,導光板之端面部會發生劣化(碳化)。In recent years, as the resolution of backlight units such as televisions and monitors has increased, high-brightness LEDs (light-emitting diodes) have sometimes been used as edge light sources. However, previously, styrene-(methyl) Depending on the usage environment, the end surface of the light guide plate made of methyl acrylate copolymer may deteriorate (carbonate) after being lit for a long time.
本發明係鑒於此種問題而成者,提供一種透明性、色相、尺寸穩定性優異,且針對LED光源之長期使用之光穩定性優異之光學用苯乙烯系樹脂組合物。 [解決問題之技術手段] The present invention was made in view of such problems, and provides an optical styrene-based resin composition that is excellent in transparency, hue, and dimensional stability, and has excellent light stability for long-term use of an LED light source. [Technical means to solve problems]
根據本發明,提供一種光學用苯乙烯系樹脂組合物,其含有作為包含苯乙烯系單體單元與(甲基)丙烯酸酯系單體單元之共聚物的苯乙烯系樹脂(A)、及受阻胺光穩定劑(B),且上述共聚物於上述共聚物100質量%中含有上述苯乙烯系單體單元95~20質量%及上述(甲基)丙烯酸酯系單體單元5~80質量%,上述光學用苯乙烯系樹脂組合物相對於上述苯乙烯系樹脂(A)100質量份含有上述受阻胺光穩定劑(B)0.001~1.0質量份。According to the present invention, there is provided an optical styrene-based resin composition containing a styrene-based resin (A) that is a copolymer containing a styrene-based monomer unit and a (meth)acrylate-based monomer unit, and a hindered Amine light stabilizer (B), and the above-mentioned copolymer contains 95 to 20 mass% of the above-mentioned styrene monomer units and 5 to 80 mass% of the above-mentioned (meth)acrylate monomer units in 100 mass% of the above-mentioned copolymer. The optical styrenic resin composition contains 0.001 to 1.0 parts by mass of the hindered amine light stabilizer (B) based on 100 parts by mass of the styrenic resin (A).
本發明人等進行銳意研究,結果發現包含苯乙烯系單體單元及(甲基)丙烯酸酯系單體單元之含量處於特定範圍內之苯乙烯系樹脂、以及特定範圍內之受阻胺光穩定劑的光學用苯乙烯系樹脂組合物同時滿足透明性、色相、尺寸穩定性、及針對LED光源之長期使用之光穩定性,從而完成本發明。The present inventors conducted intensive research and found that a styrene-based resin containing a styrene-based monomer unit and a (meth)acrylate-based monomer unit content within a specific range, and a hindered amine light stabilizer within a specific range The present invention was completed by developing an optical styrenic resin composition that simultaneously satisfies transparency, hue, dimensional stability, and light stability for long-term use of an LED light source.
以下,例示本發明之各種實施方式。以下所示之實施方式可相互組合。 [1]一種光學用苯乙烯系樹脂組合物,其含有作為包含苯乙烯系單體單元與(甲基)丙烯酸酯系單體單元之共聚物的苯乙烯系樹脂(A)、及受阻胺光穩定劑(B),且上述共聚物於上述共聚物100質量%中含有上述苯乙烯系單體單元95~20質量%及上述(甲基)丙烯酸酯系單體單元5~80質量%,上述光學用苯乙烯系樹脂組合物相對於上述苯乙烯系樹脂(A)100質量份含有上述受阻胺光穩定劑(B)0.001~1.0質量份。 [2]如[1]中記載之光學用苯乙烯系樹脂組合物,其中上述受阻胺光穩定劑(B)為N-H型受阻胺光穩定劑及/或N-R型受阻胺光穩定劑。 [3]如[2]中記載之光學用苯乙烯系樹脂組合物,其中上述N-H型受阻胺光穩定劑為選自 癸二酸雙(2,2,6,6-四甲基哌啶-4-基)酯、 十六烷酸2,2,6,6-四甲基-4-哌啶酯、十八烷酸2,2,6,6-四甲基-4-哌啶酯、 1,2,3,4-丁烷四羧酸肆(2,2,6,6-四甲基-4-哌啶基)酯、 N,N'-雙(2,2,6,6-四甲基哌啶-4-基)六亞甲基二胺與4-𠰌啉基2,6-二氯-1,3,5-三𠯤之縮聚物、 2,4-二氯-6-(1,1,3,3-四甲基丁基胺基)與1,3,5-三𠯤・N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺之縮聚物、 N,N'-雙(2,2,6,6-四甲基哌啶-4-基)六亞甲基二胺與2,4,6-三氯-1,3,5-三𠯤與N-丁基-1-丁烷胺與N-丁基-2,2,6,6-四甲基-4-哌啶胺之縮聚物、 1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)對稱三𠯤-6-基]胺基十一烷、 1,2,3,4-丁烷四羧酸與2,2,6,6-四甲基-4-哌啶醇與β,β,β',β'-四甲基-2,4,8,10-四氧雜螺[5,5]十一烷-3,9-二乙醇之縮聚物 之至少1種。 [4]如[2]或[3]中記載之光學用苯乙烯系樹脂組合物,其中上述N-R型受阻胺光穩定劑為選自 癸二酸甲酯(1,2,2,6,6-五甲基哌啶-4-基)酯、 癸二酸雙(1,2,2,6,6-五甲基哌啶-4-基)酯、 正丁基3,5-二第三丁基4-羥基苄基丙二酸雙(1,2,2,6,6-五甲基哌啶-4-基)酯、 4-羥基-2,2,6,6-四甲基-1-哌啶乙醇與琥珀酸二甲酯之縮聚物、 1,5,8,12-肆[4,6-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-1,3,5-三𠯤-2-基]-1,5,8,12-四氮雜十二烷、 1,2,3,4-丁烷四羧酸與1,2,2,6,6-五甲基-4-哌啶醇與β,β,β',β'-四甲基-2,4,8,10-四氧雜螺[5,5]十一烷-3,9-二乙醇之縮聚物、 琥珀酸與(4-羥基-2,2,6,6-四甲基哌啶-1-基)乙醇之縮聚物及N,N',N'',N'''-肆-(4,6-雙-(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)胺基)-三𠯤-2-基)-4,7-二氮雜癸烷-1,10-二胺之混合物 之至少1種。 [5]如[1]至[4]中任一項所記載之光學用苯乙烯系樹脂組合物,其相對於上述苯乙烯系樹脂(A)100質量份含有磷系抗氧化劑(C-1)0.001~0.5質量份。 [6]如[5]中記載之光學用苯乙烯系樹脂組合物,其中上述磷系抗氧化劑(C-1)為選自亞磷酸參(2,4-二第三丁基苯基)酯、2,2'-亞甲基雙(4,6-二第三丁基-1-苯氧基)(2-乙基己氧基)磷、雙-(2,4-二第三丁基苯基)季戊四醇二亞磷酸酯、3,9-雙(2,6-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、肆(2,4-二第三丁基苯基)[1,1聯苯]-4,4'-二基雙亞膦酸酯、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)酯乙酯之至少1種。 [7]一種導光板,其係使如[1]至[6]中任一項所記載之光學用苯乙烯系樹脂組合物成形而成。 [8]一種邊緣光型面光源單元,其具有如[7]中記載之導光板、及向該導光板之端面供給LED光之光源。 [9]一種光擴散板,其係使如[1]至[6]中任一項所記載之光學用苯乙烯系樹脂組合物成形而成。 [10]一種直下型面光源單元,其具有如[9]中記載之光擴散板、及向該光擴散板供給LED光之光源。 Various embodiments of the present invention are illustrated below. The embodiments shown below can be combined with each other. [1] An optical styrene-based resin composition containing a styrene-based resin (A) that is a copolymer containing a styrene-based monomer unit and a (meth)acrylate-based monomer unit, and a hindered amine light Stabilizer (B), and the above-mentioned copolymer contains 95 to 20 mass% of the above-mentioned styrene-based monomer units and 5-80 mass% of the above-mentioned (meth)acrylate-based monomer units in 100 mass% of the above-mentioned copolymer, and the above-mentioned The optical styrene-based resin composition contains 0.001 to 1.0 parts by mass of the hindered amine light stabilizer (B) based on 100 parts by mass of the styrene-based resin (A). [2] The optical styrenic resin composition according to [1], wherein the hindered amine light stabilizer (B) is an N-H type hindered amine light stabilizer and/or an N-R type hindered amine light stabilizer. [3] The optical styrenic resin composition according to [2], wherein the N-H type hindered amine light stabilizer is selected from Bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethyl-4-piperidinyl hexadecanoate, 2,2,6,6-tetramethyl-4-piperidinyl octadecanoate, 1,2,3,4-butanetetracarboxylic acid quaternary (2,2,6,6-tetramethyl-4-piperidinyl) ester, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-𠰌linyl 2,6-dichloro-1,3,5- Three condensation polymers, 2,4-Dichloro-6-(1,1,3,3-tetramethylbutylamino) and 1,3,5-trichloro-N,N'-bis(2,2,6,6 -Condensation polymer of tetramethyl-4-piperidinyl)hexamethylenediamine, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 2,4,6-trichloro-1,3,5-trichloro-1,3,5-trimethyldiamine and Condensation polymer of N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, 1,6,11-Shen[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amine) symmetric tris-6-yl ]Amino undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4, Condensation polymer of 8,10-tetraoxasspiro[5,5]undecane-3,9-diethanol At least 1 of them. [4] The optical styrenic resin composition according to [2] or [3], wherein the N-R type hindered amine light stabilizer is selected from Methyl sebacate (1,2,2,6,6-pentamethylpiperidin-4-yl) ester, Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, n-Butyl 3,5-di-tert-butyl 4-hydroxybenzylmalonate bis(1,2,2,6,6-pentamethylpiperidin-4-yl) ester, Condensation polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol and dimethyl succinate, 1,5,8,12-bis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-1, 3,5-Tris-2-yl]-1,5,8,12-tetraazadodecane, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-2, Condensation polymer of 4,8,10-tetraoxasspiro[5,5]undecane-3,9-diethanol, Condensation polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethanol and N,N',N'',N'''-4-(4, 6-Bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-tris-2-yl)-4,7-diazo Mixture of heterodecane-1,10-diamines At least 1 of them. [5] The optical styrene-based resin composition according to any one of [1] to [4], which contains a phosphorus-based antioxidant (C-1) based on 100 parts by mass of the styrene-based resin (A). )0.001~0.5 parts by mass. [6] The optical styrene-based resin composition according to [5], wherein the phosphorus-based antioxidant (C-1) is selected from the group consisting of ginseng (2,4-di-tert-butylphenyl) phosphite , 2,2'-methylenebis(4,6-di-tert-butyl-1-phenoxy)(2-ethylhexyloxy)phosphorus, bis-(2,4-di-tert-butyl) Phenyl) pentaerythritol diphosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9- Diphosphaspiro[5,5]undecane, 4(2,4-di-tert-butylphenyl)[1,1biphenyl]-4,4'-diyl bisphosphonite, phosphorous acid At least one kind of bis(2,4-di-tert-butyl-6-methylphenyl) ethyl ester. [7] A light guide plate formed by molding the optical styrene-based resin composition according to any one of [1] to [6]. [8] An edge light surface light source unit having the light guide plate as described in [7], and a light source that supplies LED light to the end surface of the light guide plate. [9] A light diffusion plate formed by molding the optical styrene-based resin composition according to any one of [1] to [6]. [10] A direct type surface light source unit having the light diffusion plate as described in [9], and a light source that supplies LED light to the light diffusion plate.
以下,對本發明之實施方式進行說明。以下所示之實施方式中所示之各種特徵事項可相互組合。又,各特徵事項獨立地使發明成立。Hereinafter, embodiments of the present invention will be described. Various features shown in the embodiments shown below can be combined with each other. Furthermore, each characteristic matter independently establishes the invention.
1.光學用苯乙烯系樹脂組合物 本發明之一實施方式之光學用苯乙烯系樹脂組合物係含有苯乙烯系樹脂(A)及受阻胺光穩定劑(B)之光學用苯乙烯系樹脂組合物。 1. Styrenic resin composition for optical use An optical styrene resin composition according to one embodiment of the present invention is an optical styrene resin composition containing a styrenic resin (A) and a hindered amine light stabilizer (B).
<苯乙烯系樹脂(A)> 苯乙烯系樹脂(A)係使包含苯乙烯系單體及(甲基)丙烯酸酯系單體之單體共聚而獲得之樹脂。苯乙烯系樹脂(A)係包含苯乙烯系單體單元及(甲基)丙烯酸酯系單體單元之共聚物。共聚物於共聚物100質量%中含有苯乙烯系單體單元95~20質量%及(甲基)丙烯酸酯系單體單元5~80質量%,較佳為含有苯乙烯系單體單元90~25質量%及(甲基)丙烯酸酯系單體單元10~75質量%,更佳為含有苯乙烯系單體單元80~30質量%及(甲基)丙烯酸酯系單體單元20~70質量%,進而較佳為含有苯乙烯系單體單元60~40質量%及(甲基)丙烯酸酯系單體單元40~60質量%。藉由設為此種範圍,能夠同時滿足透明性、色相、尺寸穩定性。藉由將苯乙烯系單體設為90質量%以下,能夠獲得透明性、色相優異之導光板,藉由將苯乙烯單體設為20%以上,能夠獲得尺寸穩定性優異之導光板。苯乙烯系樹脂(A)之(甲基)丙烯酸酯系單體單元之含量具體而言例如為5、6、7、8、9、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80質量%,亦可為此處例示之數值之任意2個之間之範圍內。 <Styrenic resin (A)> The styrene-based resin (A) is a resin obtained by copolymerizing a monomer including a styrene-based monomer and a (meth)acrylate-based monomer. The styrene-based resin (A) is a copolymer containing a styrene-based monomer unit and a (meth)acrylate-based 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, and preferably contains 90 to 80 mass % of styrene monomer units. 25% by mass and 10% to 75% by mass of (meth)acrylate monomer units, more preferably 80% to 30% by mass of styrene monomer units and 20% to 70% by mass of (meth)acrylate monomer units. %, and further preferably contains 60 to 40 mass% of styrene monomer units and 40 to 60 mass% of (meth)acrylate monomer units. By setting it within this range, transparency, hue, and dimensional stability can be satisfied at the same time. By setting the styrene-based monomer content to 90% by mass or less, a light guide plate excellent in transparency and hue can be obtained, and by setting the styrene monomer content to 20% or more, a light guide plate excellent in dimensional stability can be obtained. The content of the (meth)acrylate monomer unit in the styrenic resin (A) is specifically, for example, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45 , 50, 55, 60, 65, 70, 75, 80% by mass, or within the range between any two of the numerical values illustrated here.
苯乙烯系單體例如可例舉:苯乙烯、α-甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、間甲基苯乙烯、乙基苯乙烯、對第三丁基苯乙烯等。該等可單獨使用1種或組合2種以上使用。苯乙烯系單體較佳為苯乙烯。Examples of styrenic monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, and p-tert-butylstyrene. wait. These can be used individually by 1 type or in combination of 2 or more types. The styrenic monomer is preferably styrene.
(甲基)丙烯酸酯系單體例如可例舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯等(甲基)丙烯酸烷基酯;(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸芳基酯;(甲基)丙烯酸環己酯、(甲基)丙烯酸4-第三丁基環己酯、(甲基)丙烯酸2-降𦯉酯、(甲基)丙烯酸異𦯉酯、(甲基)丙烯酸金剛烷-1-基酯、(甲基)丙烯酸2-甲基金剛烷-2-基酯、(甲基)丙烯酸2-乙基-2-金剛烷基酯、(甲基)丙烯酸三環癸酯等(甲基)丙烯酸環烷基酯;(甲基)丙烯酸縮水甘油酯;(甲基)丙烯酸二環戊酯等。該等可單獨使用1種或組合2種以上使用。(甲基)丙烯酸酯系單體較佳為(甲基)丙烯酸烷基酯,更佳為甲基丙烯酸甲酯。Examples of (meth)acrylate monomers include: (meth)acrylate methyl ester, (meth)ethyl acrylate, (meth)acrylate n-propyl ester, (meth)acrylate isopropyl ester, (meth)acrylate n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate )(meth)alkyl acrylates such as lauryl acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; cyclohexyl (meth)acrylate, (meth)acrylate 4-tert-butylcyclohexyl acrylate, 2-norpropyl (meth)acrylate, isopropyl (meth)acrylate, (meth)adamantane-1-yl acrylate, (meth)acrylate (Meth)acrylic acid cycloalkyl esters such as 2-methyladamant-2-yl acrylate, 2-ethyl-2-adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate; Glycidyl (meth)acrylate; dicyclopentyl (meth)acrylate, etc. These can be used individually by 1 type or in combination of 2 or more types. The (meth)acrylate-based monomer is preferably alkyl (meth)acrylate, more preferably methyl methacrylate.
又,苯乙烯系樹脂(A)亦可為使苯乙烯系單體及(甲基)丙烯酸酯系單體與可共聚之單體共聚而獲得之共聚物。作為可共聚之單體,例如可例舉:丙烯酸、甲基丙烯酸等(甲基)丙烯酸;丙烯腈、甲基丙烯腈等丙烯腈;馬來酸酐、富馬酸等α,β-乙烯不飽和羧酸類;苯基馬來醯亞胺、環己基馬來醯亞胺等醯亞胺類。該等可單獨使用1種或組合2種以上使用。Moreover, the styrene-based resin (A) may be a copolymer obtained by copolymerizing a styrene-based monomer and a (meth)acrylate-based monomer with a copolymerizable monomer. Examples of copolymerizable monomers include (meth)acrylic acid such as acrylic acid and methacrylic acid; acrylonitrile such as acrylonitrile and methacrylonitrile; α,β-ethylenically unsaturated such as maleic anhydride and fumaric acid. Carboxylic acids; phenylmaleimide, cyclohexylmaleimide and other imines. These can be used individually by 1 type or in combination of 2 or more types.
苯乙烯系樹脂(A)之重量平均分子量(Mw)較佳為5萬~40萬,更佳為10萬~35萬。又,苯乙烯系樹脂(A)之重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)較佳為1.0~3.5,更佳為1.5~3.0。藉由設為此種範圍,能夠兼顧成形性與導光板之強度。存在若重量平均分子量(Mw)未達5萬則成形品之強度變得不充分,若超過40萬則成形性下降之情形。又,存在若數量平均分子量(Mn)之比(Mw/Mn)未達1.0則成形性下降,若超過3.5則成形品之強度降低之情形。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. Moreover, the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the styrenic resin (A) is preferably 1.0 to 3.5, more preferably 1.5 to 3.0. By setting it in this range, it is possible to achieve both formability 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 may become insufficient, and if it exceeds 400,000, the formability may decrease. In addition, if the number average molecular weight (Mn) ratio (Mw/Mn) is less than 1.0, the formability decreases, and if it exceeds 3.5, the strength of the molded article may decrease.
<受阻胺光穩定劑(B)> 光學用苯乙烯系樹脂組合物相對於苯乙烯系樹脂(A)100質量份含有受阻胺光穩定劑(B)0.001~1.0質量份,較佳為含有0.01~0.3質量份。藉由設為此種範圍,能夠改善透明性、色相、針對LED光源之光穩定性。受阻胺光穩定劑(B)之含量相對於苯乙烯系樹脂(A)具體而言例如為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質量份,亦可為此處例示之數值之任意2個之間之範圍內。又,受阻胺光穩定劑(B)可單獨使用1種或組合2種以上使用。 <Hindered amine light stabilizer (B)> The optical styrene-based resin composition contains 0.001 to 1.0 parts by mass of the hindered amine light stabilizer (B), preferably 0.01 to 0.3 parts by mass, based on 100 parts by mass of the styrene-based resin (A). By setting it within such a range, transparency, hue, and light stability with respect to LED light sources can be improved. The content of the hindered amine light stabilizer (B) relative to the styrenic resin (A) is, for example, 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 parts by mass, or within the range between any two of the numerical values illustrated here. Moreover, the hindered amine light stabilizer (B) can be used individually by 1 type or in combination of 2 or more types.
所謂受阻胺光穩定劑(B)係具有如下通式(1)所表示之結構單元之化合物。The hindered amine light stabilizer (B) is a compound having a structural unit represented by the following general formula (1).
[化1] [Chemical 1]
通式(1)中,X係經由碳原子、氧原子、氮原子而與哌啶基之4-位鍵結之有機基,作為R,可例舉:氫原子、碳數1~10之直鏈狀或支鏈狀烷基、亞甲基、烷氧基。此處,將R為氫原子之情形設為N-H型受阻胺光穩定劑,將R為碳數1~10之直鏈狀或支鏈狀烷基、亞甲基之情形設為N-R型受阻胺光穩定劑,將R為烷氧基之情形設為N-OR受阻胺型光穩定劑。In the general formula (1), Chain or branched alkyl, methylene, alkoxy. Here, when 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 or methylene group having 1 to 10 carbon atoms, it is an N-R type hindered amine. The light stabilizer is an N-OR hindered amine type light stabilizer when R is an alkoxy group.
作為N-H型受阻胺光穩定劑之具體例,可例舉:癸二酸雙(2,2,6,6-四甲基哌啶-4-基)酯(巴斯夫公司製造之TINUVIN770DF)、十六烷酸2,2,6,6-四甲基-4-哌啶酯、十八烷酸2,2,6,6-四甲基-4-哌啶酯(SONGWON公司製造之SABOSTAB UV91)、1,2,3,4-丁烷四羧酸肆(2,2,6,6-四甲基-4-哌啶基)酯(ADEKA公司製造之ADK STAB LA-57)、N,N'-雙(2,2,6,6-四甲基哌啶-4-基)六亞甲基二胺與4-𠰌啉基2,6-二氯-1,3,5-三𠯤之縮聚物(SONGWON公司製造之SABOSTAB UV79)、2,4-二氯-6-(1,1,3,3-四甲基丁基胺基)與1,3,5-三𠯤・N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺之縮聚物(巴斯夫公司製造之Chimassorb944FDL)、N,N'-雙(2,2,6,6-四甲基哌啶-4-基)六亞甲基二胺與2,4,6-三氯-1,3,5-三𠯤與N-丁基-1-丁烷胺與N-丁基-2,2,6,6-四甲基-4-哌啶胺之縮聚物(SONGWON公司製造之SABOSTAB UV40)、1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)對稱三𠯤-6-基]胺基十一烷(巴斯夫公司製造之Chimassorb2020FDL)、1,2,3,4-丁烷四羧酸與2,2,6,6-四甲基-4-哌啶醇與β,β,β',β'-四甲基-2,4,8,10-四氧雜螺[5,5]十一烷-3,9-二乙醇之縮聚物(ADEKA公司製造之ADKSTAB LA-68)、3-(2,2,4,4-四甲基-21-氧代-7-氧雜-3,20-二氮雜二螺(5.1.11.2)二十一烷-20-基)丙酸十二烷基酯、3-(2,2,4,4-四甲基-21-氧代-7-氧雜-3,20-二氮雜二螺(5.1.11.2)二十一烷-20-基)丙酸十四烷基酯(CLARIANT公司製造之HOSTAVIN3030)、2,2,4,4-四甲基-7-氧雜-3,20-二氮雜二螺-(5.1.11.2)二十一烷-21-酮與表氯醇之縮聚物(CLARIANT公司製造之HOSTAVIN N30P)。Specific examples of the N-H type hindered amine light stabilizer include bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN770DF manufactured by BASF), 2,2,6,6-tetramethyl-4-piperidinyl alkanoate, 2,2,6,6-tetramethyl-4-piperidinyl octadecanoate (SABOSTAB UV91 manufactured by SONGWON Corporation), 1,2,3,4-butanetetracarboxylic acid quaternary (2,2,6,6-tetramethyl-4-piperidinyl) ester (ADK STAB LA-57 manufactured by ADEKA), N,N' -Condensation polymerization of bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-𠰌linyl 2,6-dichloro-1,3,5-tri𠯤 (SABOSTAB UV79 manufactured by SONGWON Co., Ltd.), 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino) and 1,3,5-trichloro-N,N' -Condensation polymer of bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine (Chimassorb 944FDL manufactured by BASF), N,N'-bis(2,2,6 ,6-Tetramethylpiperidin-4-yl)hexamethylenediamine and 2,4,6-trichloro-1,3,5-trichloro-1,3,5-trichloro-N-butyl-1-butanamine and N -Condensation polymer of butyl-2,2,6,6-tetramethyl-4-piperidinamine (SABOSTAB UV40 manufactured by SONGWON Co., Ltd.), 1,6,11-bis(N-butyl -N-(2,2,6,6-Tetramethyl-4-piperidinyl)amino)symmetric tris-6-yl]aminoundecane (Chimassorb 2020FDL manufactured by BASF), 1,2 ,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10 -Condensation polymer of tetraoxasspiro[5,5]undecane-3,9-diethanol (ADKSTAB LA-68 manufactured by ADEKA), 3-(2,2,4,4-tetramethyl-21 -Oxo-7-oxa-3,20-diazabispiro(5.1.11.2)ecosan-20-yl)propionic acid dodecyl ester, 3-(2,2,4,4 -Tetramethyl-21-oxo-7-oxa-3,20-diazabispiro(5.1.11.2)necosyl-20-yl)tetradecyl propionate (manufactured by CLARIANT Corporation HOSTAVIN3030), condensation polymer of 2,2,4,4-tetramethyl-7-oxa-3,20-diazabispiro-(5.1.11.2) henosan-21-one and epichlorohydrin (HOSTAVIN N30P manufactured by CLARIANT).
作為N-R型受阻胺光穩定劑之具體例,可例舉:癸二酸甲酯(1,2,2,6,6-五甲基哌啶-4-基)酯、癸二酸雙(1,2,2,6,6-五甲基哌啶-4-基)酯(巴斯夫公司製造之TINUVIN292、TINUVIN765)、正丁基3,5-二第三丁基4-羥基苄基丙二酸雙(1,2,2,6,6-五甲基哌啶-4-基)酯(巴斯夫公司製造之TINUVIN144)、4-羥基-2,2,6,6-四甲基-1-哌啶乙醇與琥珀酸二甲酯之縮聚物(巴斯夫公司製造之TINUVIN622SF)、1,5,8,12-肆[4,6-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-1,3,5-三𠯤-2-基]-1,5,8,12-四氮雜十二烷(巴斯夫公司製造之Chimassоrb119)、1,2,3,4-丁烷四羧酸與1,2,2,6,6-五甲基-4-哌啶醇與β,β,β',β'-四甲基-2,4,8,10-四氧雜螺[5,5]十一烷-3,9-二乙醇之縮聚物(ADEKA公司製造之ADKSTAB LA-63P)、琥珀酸與(4-羥基-2,2,6,6-四甲基哌啶-1-基)乙醇之縮聚物及N,N',N'',N'''-肆-(4,6-雙-(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)胺基)-三𠯤-2-基)-4,7-二氮雜癸烷-1,10-二胺之混合物(巴斯夫公司製造之TINUVIN111FDL)。Specific examples of N-R type hindered amine light stabilizers include: methyl sebacate (1,2,2,6,6-pentamethylpiperidin-4-yl) ester, bis(1) sebacate , 2,2,6,6-pentamethylpiperidin-4-yl) ester (TINUVIN292, TINUVIN765 manufactured by BASF), n-butyl 3,5-di-tert-butyl 4-hydroxybenzylmalonic acid Bis(1,2,2,6,6-pentamethylpiperidin-4-yl) ester (TINUVIN144 manufactured by BASF), 4-hydroxy-2,2,6,6-tetramethyl-1-piperidin The condensation polymer of ethanol and dimethyl succinate (TINUVIN622SF manufactured by BASF), 1,5,8,12-4[4,6-bis(N-butyl-N-(1,2,2,6 ,6-pentamethyl-4-piperidinyl)amino)-1,3,5-tris-2-yl]-1,5,8,12-tetraazadodecane (manufactured by BASF Corporation Chimassоrb119), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl -Condensation polymer of 2,4,8,10-tetraoxasspiro[5,5]undecan-3,9-diethanol (ADKSTAB LA-63P manufactured by ADEKA), succinic acid and (4-hydroxy- Condensation polymer of 2,2,6,6-tetramethylpiperidin-1-yl)ethanol and N,N',N'',N'''-4-(4,6-bis-(butyl- (N-Methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-tris-2-yl)-4,7-diazadecane-1,10- A mixture of diamines (TINUVIN111FDL manufactured by BASF).
作為N-OR型受阻胺光穩定劑之具體例,可例舉:癸二酸雙(1-辛氧基-2,2,6,6-四甲基哌啶基)酯(巴斯夫公司製造之TINUVIN123)、碳酸雙(1-十一烷氧基-2,2,6,6-四甲基哌啶-4-基)酯(ADEKA公司製造之ADKSTAB LA-81)。Specific examples of the N-OR type hindered amine light stabilizer include: bis(1-octyloxy-2,2,6,6-tetramethylpiperidinyl) sebacate (manufactured by BASF Corporation) TINUVIN123), bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (ADKSTAB LA-81 manufactured by ADEKA).
其中,就對光學用苯乙烯系樹脂組合物之透明性、色相之影響較少之方面而言,受阻胺光穩定劑(B)較佳為N-H型受阻胺光穩定劑及/或N-R型受阻胺光穩定劑,更佳為N-R型受阻胺光穩定劑。已知受阻胺光穩定劑(B)一般會被氧、紫外線及過氧化物氧化,產生氮氧自由基。於本實施方式中,雖然尚未解明受阻胺光穩定劑(B)能夠提高針對LED光源之長期使用之光穩定性之機制,但本發明發現了受阻胺光穩定劑(B)之有效性。Among them, the hindered amine light stabilizer (B) is preferably an N-H type hindered amine light stabilizer and/or an N-R type hindered amine light stabilizer in terms of having less influence on the transparency and hue of the optical styrenic resin composition. Amine light stabilizer, preferably N-R type hindered amine light stabilizer. It is known that hindered amine light stabilizer (B) is generally oxidized by oxygen, ultraviolet rays and peroxides to generate nitroxide radicals. In this embodiment, although the mechanism by which the hindered amine light stabilizer (B) can improve the light stability of the LED light source for long-term use has not yet been elucidated, the present invention discovered the effectiveness of the hindered amine light stabilizer (B).
<抗氧化劑(C)> 光學用苯乙烯系樹脂組合物相對於苯乙烯系樹脂(A)100質量份較佳為含有磷系抗氧化劑(C-1)0.001~0.5質量份,進而較佳為0.002~0.4質量份,特佳為0.005~0.3質量份。藉由設為此種範圍,能夠改善透明性、色相。磷系抗氧化劑(C-1)之含量相對於苯乙烯系樹脂(A)100質量份具體而言例如為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質量份,亦可為此處例示之數值之任意2個之間之範圍內。 <Antioxidant (C)> The styrene-based resin composition for optical use preferably contains 0.001 to 0.5 parts by mass of the phosphorus-based antioxidant (C-1), more preferably 0.002 to 0.4 parts by mass, based on 100 parts by mass of the styrene-based resin (A). Preferably, it is 0.005 to 0.3 parts by mass. By setting it to this range, transparency and hue can be improved. Specifically, the content of the phosphorus antioxidant (C-1) is, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, based on 100 parts by mass of the styrenic resin (A). 0.4 and 0.5 parts by mass may also be within the range between any two of the numerical values illustrated here.
所謂磷系抗氧化劑(C-1)係於基本骨架不具有酚性羥基之(亞)磷酸酯類,較佳為作為三價磷化合物之亞磷酸酯類。作為磷系抗氧化劑(C-1)之具體例,可例舉2,2'-亞甲基雙(4,6-二第三丁基-1-苯氧基)(2-乙基己氧基)磷、雙-(2,4-二第三丁基苯基)季戊四醇二亞磷酸酯、亞磷酸參(2,4-二第三丁基苯基)酯、3,9-雙(2,6-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、肆(2,4-二第三丁基苯基)[1,1聯苯]-4,4'-二基雙亞膦酸酯、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)酯乙酯等,該等可單獨使用1種或組合2種以上使用。The phosphorus-based antioxidant (C-1) is a ()phosphite ester having no phenolic hydroxyl group in its basic skeleton, and is preferably a phosphite ester which is a trivalent phosphorus compound. Specific examples of the phosphorus antioxidant (C-1) include 2,2'-methylenebis(4,6-di-tert-butyl-1-phenoxy)(2-ethylhexyloxy) base) phosphorus, bis-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, phosphite (2,4-di-tert-butylphenyl) ester, 3,9-bis(2 ,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 4(2 ,4-di-tert-butylphenyl)[1,1biphenyl]-4,4'-diyl bisphosphonite, bis(2,4-di-tert-butyl-6-methyl phosphite) Phenyl) ester ethyl ester, etc., these can be used individually by 1 type or in combination of 2 or more types.
又,光學用苯乙烯系樹脂組合物相對於苯乙烯系樹脂(A)100質量份亦可含有酚系抗氧化劑(C-2)0~0.5質量份。若酚系抗氧化劑(C-2)之含量超過0.5質量份,則色相會變差,因此不佳。酚系抗氧化劑(C-2)之含量相對於苯乙烯系樹脂(A)100質量份具體而言例如為0、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質量份,亦可為此處例示之數值之任意2個之間之範圍內。Furthermore, the optical styrene-based resin composition may contain 0 to 0.5 parts by mass of the phenolic antioxidant (C-2) based on 100 parts by mass of the styrene-based resin (A). If the content of the phenolic antioxidant (C-2) exceeds 0.5 parts by mass, the hue will deteriorate, which is undesirable. Specifically, the content of the phenolic antioxidant (C-2) is, for example, 0, 0.001, 0.002, 0.003, 0.004, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, based on 100 parts by mass of the styrenic resin (A). 0.3, 0.4, and 0.5 parts by mass may also be within the range between any two of the numerical values illustrated here.
所謂酚系抗氧化劑(C-2)係於基本骨架具有酚性羥基且不為(亞)磷酸酯類之抗氧化劑。作為酚系抗氧化劑(C-2)之具體例,例如可例舉3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯、伸乙基雙(氧伸乙基)雙[3-(5-第三丁基-4-羥基-間甲苯基)丙酸酯]、季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯],該等可單獨使用1種或組合2種以上使用。The so-called phenolic antioxidant (C-2) is an antioxidant that has a phenolic hydroxyl group in the basic skeleton and is not a ()phosphite ester. Specific examples of the phenolic antioxidant (C-2) include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, ethylidene bis( Oxyethylidene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxybenzene base) propionate], these may be used singly or in combination of two or more.
抗氧化劑有如6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚烯般於同一分子內同時具有亞磷酸酯結構及酚結構之磷-酚系化合物。於為此種化合物之情形時,認為光學用苯乙烯系樹脂組合物含有磷系抗氧化劑及酚系抗氧化劑之各者,例如,於相對於苯乙烯系樹脂(A)100質量份含有磷-酚系化合物0.1質量份之情形時,認為含有磷系抗氧化劑0.1質量份、酚系抗氧化劑0.1質量份。Antioxidants such as 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetratert-butyldibenzo[d ,f][1,3,2]dioxaphosphene is a phosphorus-phenol compound that has both a phosphite structure and a phenol structure in the same molecule. In the case of such a compound, it is considered that the optical styrene-based resin composition contains each of a phosphorus-based antioxidant and a phenol-based antioxidant. For example, it contains phosphorus- based on 100 parts by mass of the styrene-based resin (A). In the case of 0.1 parts by mass of the phenolic compound, it is considered that 0.1 parts by mass of the phosphorus-based antioxidant and 0.1 part by mass of the phenolic antioxidant are included.
<其他成分> 光學用苯乙烯系樹脂組合物中之第三丁基兒茶酚(TBC)較佳為10 ppm以下,更佳為5 ppm以下。藉由設為此種範圍,能夠獲得色相及透過率優異之導光板。TBC之含量具體而言例如為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,亦可為此處例示之數值之任意2個之間之範圍內。 <Other ingredients> The tert-butylcatechol (TBC) in the optical styrene-based resin composition is preferably 10 ppm or less, more preferably 5 ppm or less. By setting it within such a range, a light guide plate excellent in hue and transmittance can be obtained. Specifically, 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, or it can be Within the range between any two of the numerical values illustrated here.
光學用苯乙烯系樹脂組合物中之6-第三丁基-2,4-二甲苯酚(TBX)較佳為10 ppm以下,更佳為5 ppm以下。藉由設為此種範圍,能夠獲得色相及透過率優異之導光板。TBX之含量具體而言例如為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,亦可為此處例示之數值之任意2個之間之範圍內。The content of 6-tert-butyl-2,4-xylenol (TBX) in the optical styrene-based resin composition is preferably 10 ppm or less, more preferably 5 ppm or less. By setting it within such a range, a light guide plate excellent in hue and transmittance can be obtained. Specifically, 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, or within the range between any two of the values illustrated here.
於不損害本發明之特性之範圍內,亦可於光學用苯乙烯系樹脂組合物中包含硫系抗氧化劑、內酯系抗氧化劑、紫外線吸收劑、抗靜電劑、親水性添加劑、液態石蠟(礦物油)、聚乙烯蠟、微晶蠟、上藍劑、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸等高級脂肪酸、硬脂醯胺、芥醯胺、伸乙基雙硬脂醯胺等高級脂肪醯胺、單月桂酸甘油酯、單棕櫚酸甘油酯、單硬脂酸甘油酯、單山萮酸甘油酯等高級脂肪酸甘油酯、肉豆蔻醇、鯨蠟醇、硬脂醇等高級醇等離型劑。Within the scope that does not impair the characteristics of the present invention, the optical styrene-based resin composition may also contain sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, antistatic agents, hydrophilic additives, liquid paraffin ( Mineral oil), polyethylene wax, microcrystalline wax, bluing agent, lauric acid, myristic acid, palmitic acid, stearic acid and other higher fatty acids, stearamide, erucamide, ethyl distearamide and other high-grade fatty acid glycerides, high-grade fatty acid glycerides such as glyceryl monolaurate, glyceryl monopalmitate, glyceryl monostearate, and glyceryl monobehenate, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc. Alcohol release agent.
光學用苯乙烯系樹脂組合物於溫度200℃、49 N負載之條件下之熔體質量流率(MFR)較佳為0.5~5.0 g/10分鐘,更佳為1.0~4.0 g/10分鐘。若MFR未達0.5 g/10分鐘,則成形穩定性下降,若MFR超過5.0 g/10分鐘,則強度變得不充分。The melt mass flow rate (MFR) of the optical styrenic resin composition under the conditions of 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 4.0 g/10 minutes. If the MFR is less than 0.5 g/10 minutes, the molding stability decreases, and if the MFR exceeds 5.0 g/10 minutes, the strength becomes insufficient.
光學用苯乙烯系樹脂組合物之維氏軟化溫度較佳為95~104℃,更佳為100~104℃。若維氏軟化溫度未達95℃,則耐熱性不足,根據使用環境,導光板有可能變形。The Vickers softening temperature of the optical styrene-based resin composition is preferably 95 to 104°C, more preferably 100 to 104°C. If the Vickers softening temperature is less than 95°C, the heat resistance is insufficient and the light guide plate may be deformed depending on the usage environment.
<光學用苯乙烯系樹脂組合物之製造方法> 作為苯乙烯系樹脂(A)之聚合方法,可例舉塊狀聚合法、溶液聚合法、懸濁聚合法、乳化聚合法等公知之苯乙烯聚合方法。於品質方面或生產性方面,較佳為塊狀聚合法、溶液聚合法,較佳為連續聚合。作為溶劑,例如可使用苯、甲苯、乙基苯及二甲苯等烷基苯類或丙酮或甲基乙基酮等酮類、己烷或環己烷等脂肪族烴等。 <Production method of styrenic resin composition for optical use> Examples of the polymerization method of the styrenic resin (A) include known styrene polymerization methods such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In terms of quality or productivity, block polymerization and solution polymerization are preferred, and continuous polymerization is preferred. Examples of solvents that can be used include benzene, toluene, alkylbenzenes such as ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane.
於苯乙烯系樹脂(A)之聚合時,視需要可使用聚合起始劑、鏈轉移劑、交聯劑等聚合助劑、其他聚合助劑。作為聚合起始劑,較佳為自由基聚合起始劑,可例舉公知慣用之例如1,1-二(第三丁基過氧基)環己烷、2,2-二(第三丁基過氧基)丁烷、2,2-二(4,4-二第三丁基過氧基環己基)丙烷、1,1-二(第三戊基過氧基)環己烷等過氧縮酮類、氫過氧化異丙苯、第三丁基過氧化氫等過氧化氫類、過氧化異壬酸第三戊酯等過氧化烷基類、第三丁基異丙苯基過氧化物、二第三丁基過氧化物、二異丙苯基過氧化物、二第三己基過氧化物等過氧化二烷基類、過氧化乙酸第三丁酯、過氧化苯甲酸第三丁酯、第三丁基過氧基異丙基單碳酸酯等過氧酯類、第三丁基過氧基異丙基碳酸酯、聚醚四(過氧化碳酸第三丁酯)等過氧化碳酸酯類、N,N'-偶氮雙(環己烷-1-甲腈)、N,N'-偶氮雙(2-甲基丁腈)、N,N'-偶氮雙(2,4-二甲基戊腈)、N,N'-偶氮雙[2-(羥甲基)丙腈]等,可使用該等之1種或組合2種以上使用。作為鏈轉移劑,可例舉:正十二烷基硫醇、第三-十二烷基硫醇等脂肪族硫醇、芳香族硫醇、巰基乙酸、巰基丙酸等硫羧酸類、將乙二醇、四乙二醇、新戊二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇、山梨醇等多元醇羥基藉由巰基乙酸或巰基丙酸進行酯化所得之多官能硫醇、五苯基乙烷、α-甲基苯乙烯二聚物及萜品油烯等。其中,就容易調整分子量之方面而言,較佳為脂肪族硫醇、芳香族硫醇、硫羧酸類、多官能硫醇。When polymerizing the styrenic resin (A), polymerization auxiliaries such as a polymerization initiator, a chain transfer agent, and a cross-linking agent, and other polymerization auxiliaries may be used as necessary. The polymerization initiator is preferably a radical polymerization initiator, and examples of the well-known and commonly used ones include 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)cyclohexane, peroxy)butane, 2,2-di(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-di(tert-pentylperoxy)cyclohexane, etc. Hydroperoxides such as oxyketals, cumene hydroperoxide, tert-butyl hydroperoxide, alkyl peroxides such as tert-amyl peroxyisononanoate, tert-butylcumyl peroxide Oxide, di-tert-butyl peroxide, dicumyl peroxide, di-tert-hexyl peroxide and other dialkyl peroxides, tert-butyl peroxyacetate, tert-butyl peroxybenzoate Peroxy esters such as butyl ester, tert-butyl peroxy isopropyl monocarbonate, tert-butyl peroxy isopropyl carbonate, polyether tetrakis (tert-butyl peroxycarbonate), etc. Carbonates, N,N'-Azobis(cyclohexane-1-carbonitrile), N,N'-Azobis(2-methylbutyronitrile), N,N'-Azobis(2 , 4-dimethylvaleronitrile), N,N'-azobis[2-(hydroxymethyl)propionitrile], etc., one of these can be used or two or more of them can be used in combination. Examples of chain transfer agents include aliphatic mercaptans such as n-dodecyl mercaptan and tertiary dodecyl mercaptan, aromatic mercaptans, sulfur carboxylic acids such as thioglycolic acid and mercaptopropionic acid, and ethanol. Polyfunctional thiols obtained by esterifying the hydroxyl groups of polyols such as glycol, tetraethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid or mercaptopropionic acid. , pentaphenylethane, α-methylstyrene dimer and terpinolene, etc. Among these, aliphatic thiols, aromatic thiols, sulfur carboxylic acids, and polyfunctional thiols are preferable from the viewpoint of easy adjustment of molecular weight.
於連續聚合之情形時,苯乙烯系樹脂(A)可藉由具備聚合步驟、去揮發步驟、造粒步驟之方法進行製造。In the case of continuous polymerization, the styrenic resin (A) can be produced by a method including a polymerization step, a devolatization step, and a granulation step.
首先,於聚合步驟中使用公知之完全混合槽型攪拌槽或塔型反應器等,藉由調整聚合溫度等而控制聚合反應以成為目標之分子量、分子量分佈、反應轉化率。First, in the polymerization step, a well-known complete mixing tank-type stirred tank or tower-type reactor is used, and the polymerization reaction is controlled by adjusting the polymerization temperature and the like to achieve the target molecular weight, molecular weight distribution, and reaction conversion rate.
包含完成了聚合步驟之聚合物之聚合溶液被移送至去揮發步驟,去除未反應之單體及聚合溶劑。去揮發步驟包含附帶加熱器之真空去揮發槽或附帶排氣孔之去揮發擠出機等。完成了去揮發步驟之熔融狀態之聚合物被移送至造粒步驟。於造粒步驟中,將熔融樹脂從多孔模中以線狀擠出,藉由冷切割方式或空中熱切割方式、水中熱切割方式加工為顆粒形狀。The polymerization solution containing the polymer that has completed the polymerization step is transferred to a devolatization step to remove unreacted monomers and polymerization solvent. The devolatilization step includes a vacuum devolatilization tank with a heater or a devolatilization extruder with a vent, etc. The molten polymer that has completed the devolatilization step is transferred to the granulation step. In the granulation step, the molten resin is extruded from the porous mold in a linear shape and processed into a granular shape by cold cutting, aerial thermal cutting, or underwater thermal cutting.
光學用苯乙烯系樹脂組合物可藉由向苯乙烯系樹脂(A)中添加受阻胺光穩定劑(B)、磷系抗氧化劑(C-1)、酚系抗氧化劑(C-2)而製造。受阻胺光穩定劑(B)、磷系抗氧化劑(C-1)、酚系抗氧化劑(C-2)可於苯乙烯系樹脂(A)之聚合前添加至原料溶液中,亦可藉由設置於苯乙烯系樹脂(A)之聚合後、造粒前之擠出機或靜態混合裝置進行混合。又,亦可將苯乙烯系樹脂(A)造粒後之顆粒與受阻胺光穩定劑(B)、磷系抗氧化劑(C-1)、酚系抗氧化劑(C-2)進行乾摻並熔融混練而製造。又,亦可製成將受阻胺光穩定劑(B)、磷系抗氧化劑(C-1)、酚系抗氧化劑(C-2)預先與少量之苯乙烯系樹脂一起進行熔融混練而獲得之顆粒狀母料,將苯乙烯系樹脂(A)與該母料乾摻後,進行熔融混練並製備。The optical styrene-based resin composition can be prepared by adding a hindered amine light stabilizer (B), a phosphorus-based antioxidant (C-1), and a phenol-based antioxidant (C-2) to the styrene-based resin (A). manufacturing. The hindered amine light stabilizer (B), phosphorus antioxidant (C-1), and phenolic antioxidant (C-2) can be added to the raw material solution before the polymerization of the styrene resin (A), or by The extruder or static mixing device installed after the polymerization of the styrenic resin (A) and before the pelletization is used for mixing. Alternatively, the granulated styrenic resin (A) may be dry-blended with the hindered amine light stabilizer (B), phosphorus antioxidant (C-1), and phenolic antioxidant (C-2). Made by melting and kneading. Alternatively, the hindered amine light stabilizer (B), phosphorus antioxidant (C-1), and phenol antioxidant (C-2) may be melt-kneaded together with a small amount of styrene resin in advance. The granular masterbatch is prepared by dry blending the styrenic resin (A) and the masterbatch, and then melting and kneading the masterbatch.
光學用苯乙烯系樹脂組合物中之第三丁基兒茶酚或6-第三丁基-2,4-二甲苯酚之含量可進行苯乙烯系樹脂(A)之聚合開始時之含量之調整及其後之去揮發步驟等中之含量之調整。The content of tert-butylcatechol or 6-tert-butyl-2,4-xylenol in the optical styrene resin composition can be equal to the content at the start of polymerization of the styrene resin (A) Adjustment and adjustment of content in subsequent devolatilization steps, etc.
2.導光板 本發明之一實施方式之導光板係使上述光學用苯乙烯系樹脂組合物成形而成之成形品。導光板係可用於邊緣光型面光源單元之導光板。 2.Light guide plate A light guide plate according to one embodiment of the present invention is a molded product obtained by molding the optical styrene resin composition. The light guide plate is a light guide plate that can be used for edge light surface light source units.
<導光板之形狀> 導光板可於導光板之表面具有凹凸形狀。更詳細而言,可於導光板之表面具有複數個透鏡形狀及/或稜鏡形狀之凸部。凸部較佳為設置於導光板之至少一面,尤其是設置於作為導光板之前表面(發光面)之一面。其他面若有需要亦可設置,但更佳為僅設置於導光板之前表面(發光面)。 <Shape of light guide plate> The light guide plate may have a concave and convex shape on the surface of the light guide plate. More specifically, the surface of the light guide plate may have a plurality of lens-shaped and/or lens-shaped convex portions. The convex portion is preferably provided on at least one surface of the light guide plate, particularly on one surface serving as the front surface (light-emitting surface) of the light guide plate. Other surfaces can also be provided if necessary, but it is better to be provided only on the front surface (light-emitting surface) of the light guide plate.
此處,所謂透鏡形狀之凸部係圓弧狀凸部,剖面之緣形狀為圓弧狀突條體。又,所謂稜鏡形狀係圓弧狀凸部,剖面之緣形狀為三角山形突條體。又,凸部可形成為複數條成為相互平行關係。又,凸部可一體形成於導光板。Here, the so-called lens-shaped convex portion is an arc-shaped convex portion, and the cross-sectional edge shape is an arc-shaped protrusion. Moreover, the shape of the so-called ridge is an arc-shaped convex part, and the edge shape of the cross section is a triangular mountain-shaped protrusion. Moreover, a plurality of convex portions may be formed in a parallel relationship with each other. Moreover, the convex part may be integrally formed with the light guide plate.
導光板之厚度為0.2~3.0 mm,較佳為0.3~2.5 mm,更佳為0.4~2.4 mm。若處於此種範圍內,則於光學用苯乙烯系樹脂組合物之成形中,容易製造優異之擠出穩定性等成形性或強度優異之導光板。The thickness of the light guide plate is 0.2~3.0 mm, preferably 0.3~2.5 mm, more preferably 0.4~2.4 mm. If it is within this range, it is easy to produce a light guide plate with excellent moldability such as excellent extrusion stability and strength during the molding of the optical styrene-based resin composition.
<光學特性> 導光板之光程長度115 mm下之波長380~780 nm之平均透過率較佳為85%以上,更佳為86%以上。 <Optical characteristics> The average transmittance of the light guide plate at a wavelength of 380 to 780 nm under an optical path length of 115 mm is preferably more than 85%, and more preferably more than 86%.
導光板之光程長度115 mm下之YI(Yellowness Index,黃度指數)值較佳為6.0以下,更佳為4.0以下。The YI (Yellowness Index, yellowness index) value of the light guide plate when the optical path length is 115 mm is preferably below 6.0, and more preferably below 4.0.
<導光板之製造方法> 本發明之一實施方式之導光板係使上述光學用苯乙烯系樹脂組合物成形而獲得,作為成形方法,可使用片材擠出成形、或射出成形、壓縮成形等公知之方法,於生產性、容易進行成形品之大型化之方面而言,較佳為具備表面形狀轉印模具之連續片材擠出成形。作為該片材擠出成形之例,可例舉連續片材擠出成形法,其具有:擠出步驟,其將樹脂以加熱熔融狀態供給至進料模組(feed block),從模中連續擠出而製成片材;按壓步驟,其利用壓接輥及冷卻輥將上述樹脂片材夾住;以及搬送步驟,其於按壓步驟後,使樹脂片材邊與冷卻輥密接邊進行搬送;且於冷卻輥之表面具備轉印模具;藉由變更該轉印模具之形狀,能夠將任意之凹凸形狀轉印至片材表面。 <Manufacturing method of light guide plate> The light guide plate according to one embodiment of the present invention is obtained by molding the above-mentioned optical styrene-based resin composition. As a molding method, known methods such as sheet extrusion molding, injection molding, and compression molding can be used. In order to facilitate the enlargement of molded products, continuous sheet extrusion molding with a surface shape transfer mold is preferred. An example of this sheet extrusion molding is a continuous sheet extrusion molding method, which has an extrusion step of supplying resin in a heated and molten state to a feed block (feed block), and continuously extruding it from the die. Extruding to form a sheet; a pressing step, which uses a pressure roller and a cooling roller to clamp the above-mentioned resin sheet; and a conveying step, which after the pressing step, conveys the resin sheet while being in close contact with the cooling roller; Furthermore, a transfer mold is provided on the surface of the cooling roller; by changing the shape of the transfer mold, any uneven shape can be transferred to the surface of the sheet.
又,導光板可於前表面(發光面)具有凹凸形狀,可對背面實施使光漫反射之反射加工。作為反射加工,例如可例舉除了藉由絲網印刷或噴墨印刷以外,藉由雷射照射而賦予點形狀之凹凸之方法,點圖案之印刷可使用具有使光擴散之微粒子之墨水。In addition, the light guide plate may have an uneven shape on the front surface (light-emitting surface), and the back surface may be subjected to reflection processing to diffuse light. Examples of reflective processing include a method of providing dot-shaped irregularities by laser irradiation in addition to screen printing or inkjet printing. Ink containing fine particles that diffuse light can be used for dot pattern printing.
3.邊緣光型面光源單元 本發明之一實施方式之邊緣光型面光源單元係具有上述導光板、及向該導光板之端面供給LED光之光源之邊緣光型面光源單元。邊緣光型面光源單元可良好地用作液晶顯示裝置用面光源裝置。 3. Edge light surface light source unit An edge light surface light source unit according to one embodiment of the present invention is an edge light surface light source unit having the above-mentioned light guide plate and a light source that supplies LED light to an end surface of the light guide plate. The edge light type surface light source unit can be suitably used as a surface light source device for a liquid crystal display device.
4.光擴散板 本發明之一實施方式之光擴散板係使上述光學用苯乙烯系樹脂組合物成形而成之成形品。光擴散板係可用於直下型面光源單元之光擴散板。 4.Light diffusion plate A light diffusion plate according to one embodiment of the present invention is a molded product obtained by molding the optical styrene resin composition. The light diffusion plate is a light diffusion plate that can be used for direct type surface light source units.
<光擴散板之形狀> 本發明之一實施方式之光擴散板之厚度並無限制,例如為1~3 mm。亦可於光擴散板之表面塗佈有抗靜電劑。藉由塗佈有抗靜電劑,從而在將光擴散板安裝於背光源裝置後,能夠抑制靜電所致之灰塵等之附著,因此能夠長時間亮度不下降地使用。又,可對本發明之光擴散板於其兩面或單面形成有壓紋加工等之微小凹凸形狀,亦可於兩面或單面形成有透鏡形狀或稜鏡形狀。 <Shape of light diffusion plate> The thickness of the light diffusion plate according to an embodiment of the present invention is not limited, but is, for example, 1 to 3 mm. An antistatic agent can also be coated on the surface of the light diffusion plate. By coating the antistatic agent, after the light diffusion plate is installed on the backlight device, adhesion of dust and the like caused by static electricity can be suppressed, so that the light diffusion plate can be used without any decrease in brightness for a long time. In addition, the light diffusion plate of the present invention may be formed with minute uneven shapes such as embossing on both sides or one side thereof, or may be formed with a lens shape or a lens shape on both sides or one side.
可於光擴散板中包含相對於光學用苯乙烯系樹脂組合物100重量份為0.1~1.0質量份之光擴散劑。光擴散劑只要為與光學用苯乙烯系樹脂組合物折射率不同之粒子且具有使入射之光擴散之效果者即可使用,例如可使用苯乙烯系聚合物粒子、丙烯酸系聚合物粒子、矽氧烷系聚合物粒子等有機粒子或玻璃珠、二氧化矽粒子、氫氧化鋁粒子、碳酸鈣粒子、硫酸鋇粒子、氧化鈦粒子、滑石等無機粒子。其中,較佳為選自丙烯酸系聚合物粒子、苯乙烯系聚合物粒子、矽氧烷系聚合物粒子之至少1種。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-based resin composition. The light diffusing agent can be used as long as it is particles with a different refractive index from that of the optical styrene-based resin composition and has the effect of diffusing incident light. For example, styrene-based polymer particles, acrylic polymer particles, and silicone can be used. Organic particles such as oxyalkane polymer particles, or inorganic particles such as glass beads, silica particles, aluminum hydroxide particles, calcium carbonate particles, barium sulfate particles, titanium oxide particles, and talc. Among them, at least one type selected from the group consisting of acrylic polymer particles, styrene polymer particles, and siloxane polymer particles is preferred.
<光擴散板之製造方法> 本發明之一實施方式之光擴散板可藉由利用擠出成形、射出成形等各種方法使上述光學苯乙烯系樹脂組合物成形而製造,較佳為藉由擠出成形而製造。作為擠出成形之例,可例舉如下方法,即,使用單軸擠出機或雙軸擠出機對光學苯乙烯系樹脂組合物進行熔融混練,從T模連續擠出後,藉由冷卻輥單元冷卻固化。於在光擴散板之表面形成凹凸形狀之情形時,藉由在冷卻輥之表面具備轉印模具,變更該轉印模具之形狀,能夠形成任意之凹凸形狀。又,在將表面層積層於光擴散板之兩面、單面之情形時,可採用共擠壓法、貼附法、熱接著法、溶劑接著法、流延法、表面塗佈法等方法。 <Manufacturing method of light diffusion plate> The light diffusion plate according to one embodiment of the present invention can be produced by molding the optical styrene-based resin composition using various methods such as extrusion molding and injection molding, and is preferably produced by extrusion molding. As an example of extrusion molding, there is a method in which an optical styrene-based resin composition is melt-kneaded using a single-screw extruder or a twin-screw extruder, and is continuously extruded from a T-die, and then cooled. The roller unit cools and solidifies. When forming an uneven shape on the surface of the light diffusion plate, any uneven shape can be formed by providing a transfer mold on the surface of the cooling roller and changing the shape of the transfer mold. When the surface layer is laminated on both sides or one side of the light diffusion plate, methods such as co-extrusion, adhesion, heat bonding, solvent bonding, casting, and surface coating can be used.
5.直下型面光源單元 本發明之一實施方式之直下型面光源單元係具有上述光擴散板、及向該光擴散板供給LED光之光源之直下型面光源單元。直下型面光源單元可良好地用作液晶顯示裝置用面光源裝置。 [實施例] 5. Direct type surface light source unit A direct type surface light source unit according to one embodiment of the present invention is a direct type surface light source unit including 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 can be suitably used as a surface light source device for a liquid crystal display device. [Example]
以下,舉出實施例,對本發明進一步詳細地進行說明。又,該等均為例示,並不限定本發明之內容。Hereinafter, an Example is given and this invention is demonstrated in further detail. In addition, these are examples and do not limit the content of the present invention.
1.光學用苯乙烯系樹脂組合物之製造 [實施例1] 將作為完全混合型攪拌槽之第1反應器與作為附帶靜態混合器之活塞流型反應器之第2反應器串聯連接而構成聚合步驟,實施苯乙烯系樹脂之製造。各反應器之容量係將第1反應器設為30升,將第2反應器設為12升。相對於苯乙烯(TBC濃度11 μg/g)51質量%、甲基丙烯酸甲酯(TBX濃度7 μg/g)39質量%、乙基苯10質量%之原料組成,於第1反應器之入口,調整為作為聚合起始劑之第三丁基過氧基異丙基單碳酸酯(日油股份有限公司製造:PERBUTYL I)成為150 ppm之添加濃度,作為鏈轉移劑之正十二烷基硫醇(Arkema股份有限公司製造)成為500 ppm之添加濃度(均為相對於單體整體之質量基準之濃度)後,將原料溶液以8.0 kg/h連續供給至設定為128℃之第1反應器。進而,將所獲得之聚合溶液連續供給至第2反應器,使聚合結束。此時之單體之聚合率為70%。再者,於第2反應器中,沿著流動方向設置溫度梯度,調整為中間部分成為130℃,出口部分成為145℃。 繼而,將從第2反應器連續取出之包含聚合物之溶液導入至串聯地由兩段構成之附帶預熱器之真空去揮發槽,以樹脂溫度成為220℃之方式調整預熱器之溫度,於0.8 kPa之壓力下,使未反應苯乙烯及乙基苯分離。將所獲得之熔融聚合物連續供給至擠出機,從添加劑之進料口,添加相對於聚合物100質量份為0.1質量份之受阻胺光穩定劑(770),於設定溫度220℃下混合後,從多孔模中以線狀擠出,藉由冷切割方式,將線料冷卻及切斷,使其顆粒化。所獲得之光學用苯乙烯系樹脂組合物中之TBC濃度為1.5 μg/g,TBX濃度為0.2 μg/g。又,重量平均分子量(Mw)為17萬,重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)為2.0。 1. Production of styrenic resin composition for optical use [Example 1] A first reactor, which is a complete mixing type stirred tank, and a second reactor, which is a plug flow type reactor with a static mixer, are connected in series to form a polymerization step and produce a styrene-based resin. The capacity of each reactor is 30 liters for the 1st reactor, and 12 liters for the 2nd reactor. The raw material composition is 51 mass% styrene (TBC concentration 11 μg/g), 39 mass% methyl methacrylate (TBX concentration 7 μg/g), and 10 mass% ethylbenzene, at the inlet of the first reactor , adjusted so that the addition concentration of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Co., Ltd.: PERBUTYL I) as the polymerization initiator is 150 ppm, and n-dodecyl as the chain transfer agent. After mercaptan (manufactured by Arkema Co., Ltd.) reached an added concentration of 500 ppm (both concentrations are based on the mass of the entire monomer), the raw material solution was continuously supplied to the first reaction set at 128°C at 8.0 kg/h. device. Furthermore, the obtained polymerization solution was continuously supplied to the second reactor to complete the polymerization. At this time, the polymerization rate of the monomer is 70%. Furthermore, in the second reactor, a temperature gradient was set along the flow direction, and the temperature gradient was adjusted so that the middle part became 130°C and the outlet part became 145°C. Then, the solution containing the polymer continuously taken out from the second reactor was introduced into a two-stage vacuum devolatization tank with a preheater in series, and the temperature of the preheater was adjusted so that the resin temperature became 220°C. Under a pressure of 0.8 kPa, separate unreacted styrene and ethylbenzene. The obtained molten polymer was continuously supplied to the extruder, and 0.1 parts by mass of hindered amine light stabilizer (770) was added from the additive inlet relative to 100 parts by mass of the polymer, and mixed at a set temperature of 220°C. Finally, it is extruded from the porous die in a linear shape, and the strand is cooled and cut by cold cutting to pelletize it. The TBC concentration and the TBX concentration in the obtained optical styrene-based resin composition were 1.5 μg/g and 0.2 μg/g, respectively. Moreover, the weight average molecular weight (Mw) was 170,000, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 2.0.
[實施例2~17及比較例1~6] 除了將原料溶液之組成及聚合條件變更為如表1所示,將受阻胺光穩定劑(B)、磷系抗氧化劑(C-1)、酚系抗氧化劑(C-2)、紫外線吸收劑(D)之組成變更為如表2(表2-1及表2-2)~表3般以外,以與實施例1相同之方式製造光學用苯乙烯系樹脂組合物及導光板。將各種測定及評估結果示於表2(表2-1及表2-2)~表3。 [Examples 2 to 17 and Comparative Examples 1 to 6] In addition to changing the composition and polymerization conditions of the raw material solution to those shown in Table 1, the hindered amine light stabilizer (B), phosphorus antioxidant (C-1), phenolic antioxidant (C-2), and ultraviolet absorber An optical styrene-based resin composition and a light guide plate were manufactured in the same manner as in Example 1, except that the composition of (D) was changed to that in Table 2 (Table 2-1 and Table 2-2) to Table 3. Various measurement and evaluation results are shown in Table 2 (Table 2-1 and Table 2-2) to Table 3.
[表1]
[表2-1]
[表2-2]
[表3]
再者,關於表2(表2-1及表2-2)~表3中之受阻胺光穩定劑(B)、磷系抗氧化劑(C-1)、酚系抗氧化劑(C-2)、紫外線吸收劑(D),分別如下所述。Furthermore, regarding the hindered amine light stabilizer (B), phosphorus antioxidant (C-1), and phenolic antioxidant (C-2) in Table 2 (Table 2-1 and Table 2-2) to Table 3 , ultraviolet absorber (D), respectively as follows.
(受阻胺光穩定劑(B)) 770:癸二酸雙(2,2,6,6-四甲基哌啶-4-基)酯(巴斯夫公司製造之TINUVIN770DF) 944:2,4-二氯-6-(1,1,3,3-四甲基丁基胺基)與1,3,5-三𠯤・N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺之縮聚物(巴斯夫公司製造之Chimassоrb944FDL) 292:癸二酸甲酯(1,2,2,6,6-五甲基哌啶-4-基)酯:25%與癸二酸雙(1,2,2,6,6-五甲基哌啶-4-基)酯:75%之混合物(巴斯夫公司製造之TINUVIN292) 123:癸二酸雙(1-辛氧基-2,2,6,6-四甲基哌啶基)酯(巴斯夫公司製造之TINUVIN123) (Hindered Amine Light Stabilizer (B)) 770: Bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN770DF manufactured by BASF) 944: 2,4-Dichloro-6-(1,1,3,3-tetramethylbutylamino) and 1,3,5-tris-N,N'-bis(2,2,6 , 6-tetramethyl-4-piperidinyl) condensation polymer of hexamethylenediamine (Chimassоrb944FDL manufactured by BASF) 292: Methyl sebacate (1,2,2,6,6-pentamethylpiperidin-4-yl) ester: 25% and bis(1,2,2,6,6-pentamethyl sebacate Piperidin-4-yl) ester: 75% mixture (TINUVIN 292 manufactured by BASF) 123: Bis(1-octyloxy-2,2,6,6-tetramethylpiperidinyl) sebacate (TINUVIN 123 manufactured by BASF)
(磷系抗氧化劑(C-1)) 168:亞磷酸參(2,4-二第三丁基苯基)酯(巴斯夫公司製造之Irgafos 168) HP-10:2,2'-亞甲基雙(4,6-二第三丁基-1-苯氧基)(2-乙基己氧基)磷(ADEKA公司製造之ADKSTAB HP-10) 126:雙-(2,4-二第三丁基苯基)季戊四醇二亞磷酸酯(巴斯夫公司製造之Irgafos 126) (Phosphorus antioxidant (C-1)) 168: Irgafos (2,4-di-tert-butylphenyl) phosphite (Irgafos 168 manufactured by BASF) HP-10: 2,2'-methylenebis(4,6-di-tert-butyl-1-phenoxy)(2-ethylhexyloxy)phosphorus (ADKSTAB HP-10 manufactured by ADEKA) 126: Bis-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (Irgafos 126 manufactured by BASF)
(酚系抗氧化劑(C-2)) 1076:3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯(巴斯夫公司製造之Irganox 1076) (Phenolic antioxidant (C-2)) 1076: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecylpropionate (Irganox 1076 manufactured by BASF)
(紫外線吸收劑(D)) P:2-(2-羥基-5-甲基苯基)苯并三唑(巴斯夫公司製造之TINUVIN P) (UV absorber (D)) P: 2-(2-hydroxy-5-methylphenyl)benzotriazole (TINUVIN P manufactured by BASF)
2.評估 表2(表2-1及表2-2)~3中記載之光學用苯乙烯系樹脂組合物之評估係根據下述方法進行。 2.Evaluation The evaluation of the optical styrene-based resin compositions described in Tables 2 (Table 2-1 and Table 2-2) to 3 was performed according to the following method.
<熔體質量流率(MFR)> 熔體質量流率係按照JIS K 7210於溫度200℃、49 N負載之條件下進行測定。 <Melt mass flow rate (MFR)> The melt mass flow rate was measured in accordance with JIS K 7210 at a temperature of 200°C and a load of 49 N.
<維氏軟化溫度> 維氏軟化溫度係按照JIS K 7206於升溫速度50℃/hr、試驗負載50 N下進行測定。 <Vickers Softening Temperature> The Vickers softening temperature is measured in accordance with JIS K 7206 at a heating rate of 50°C/hr and a test load of 50 N.
<光學用苯乙烯系樹脂組合物中TBC及TBX之含量> 於將光學用苯乙烯系樹脂組合物0.2 g溶解於少量之THF後,添加BSTFA(M,O-雙(三甲基矽烷基)三氟乙醯胺)200 μL,實施三甲基矽烷基衍生物化處理,利用THF(tetrahydrofuran,四氫呋喃)定容10 mL後,針對藉由離心分離而分離之上清液,藉由氣相層析質量分析(GC/MS)於以下之條件下進行測定。再者,濃度之確定係使用預先製成之校準曲線。 GC裝置:Agilent公司製造之7890A 管柱:Agilent公司製造之DB-5ms(0.25 mm i.d.×30 m)液相膜厚0.25 μm 管柱溫度:50℃(1 min)→(20℃/min升溫)→320℃(6.5 min)合計20 min 注入口:300℃,1.5 mL/min,(分流比1:5) 注入量:1 μL MS裝置:Agilent公司製造之5975C 介面溫度:320℃ MS檢測條件:SIM測定 TBC(定量用m/z 295,確認用m/z 310) <Content of TBC and TBX in styrenic resin composition for optical use> After dissolving 0.2 g of the optical styrene-based resin composition in a small amount of THF, 200 μL of BSTFA (M,O-bis(trimethylsilyl)trifluoroacetamide) was added to perform trimethylsilyl derivatization. After physical and chemical treatment, the volume was adjusted to 10 mL with THF (tetrahydrofuran), and the supernatant liquid was separated by centrifugation and measured by gas chromatography mass analysis (GC/MS) under the following conditions. Furthermore, the concentration is determined using a pre-made calibration curve. GC device: 7890A manufactured by Agilent Column: DB-5ms (0.25 mm i.d.×30 m) manufactured by Agilent Company, liquid phase film thickness 0.25 μm Column temperature: 50℃(1 min)→(20℃/min temperature rise)→320℃(6.5 min) for a total of 20 minutes Injection port: 300℃, 1.5 mL/min, (split ratio 1:5) Injection volume: 1 μL MS device: 5975C manufactured by Agilent Interface temperature: 320℃ MS detection conditions: SIM determination of TBC (m/z 295 for quantification, m/z 310 for confirmation)
<光學用苯乙烯系樹脂組合物中受阻胺光穩定劑(B)、磷系抗氧化劑(B-1)、酚系抗氧化劑(B-2)之含量> 於將光學用苯乙烯系樹脂組合物1.0 g完全溶解於20 mL之THF中之後,滴加甲醇5 mL,攪拌20分鐘。以4000 rpm進行10分鐘離心分離,針對分離之上清液,藉由氣相層析法(GC)於以下之條件下進行測定。再者,濃度之確定係使用預先製成之校準曲線。 GC裝置:島津製作所公司製造之GC2010 Plus 管柱:DB-1(30 m×0.25 mm i.d.,df=0.10 μm) 管柱溫度:240℃(1 min)→(10℃/min升溫)→320℃(15 min) 注入口:320℃,1.02 mL/min(分流比1:5) 注入量:1 μL <Contents of hindered amine light stabilizer (B), phosphorus antioxidant (B-1), and phenolic antioxidant (B-2) in the optical styrene resin composition> After completely dissolving 1.0 g of the optical styrene-based resin composition in 20 mL of THF, 5 mL of methanol was added dropwise and stirred for 20 minutes. Centrifuge at 4000 rpm for 10 minutes, and the separated supernatant is measured by gas chromatography (GC) under the following conditions. Furthermore, the concentration is determined using a pre-made calibration curve. GC device: GC2010 Plus manufactured by Shimadzu Corporation Column: DB-1 (30 m×0.25 mm i.d., df=0.10 μm) Column temperature: 240℃(1 min)→(10℃/min temperature rise)→320℃(15 min) Injection port: 320℃, 1.02 mL/min (split ratio 1:5) Injection volume: 1 μL
<重量平均分子量(Mw)> 重量平均分子量(Mw)及Z平均分子量(Mz)、數量平均分子量(Mn)係使用凝膠滲透層析法(GPC)於如下條件下進行測定。 GPC機種:昭和電工股份有限公司製造之Shodex GPC-101 管柱:Polymer Laboratories公司製造之PLgel 10 μm MIXED-B 流動相:四氫呋喃 試樣濃度:0.2質量% 溫度:烘箱40℃,注入口35℃,檢測器35℃ 檢測器:示差折射計 分子量係根據單分散聚苯乙烯之溶出曲線計算出各溶出時間中之分子量,以聚苯乙烯換算之分子量之形式算出者。 <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. GPC model: Shodex GPC-101 manufactured by Showa Denko Co., Ltd. Column: PLgel 10 μm MIXED-B manufactured by Polymer Laboratories Mobile phase: tetrahydrofuran Sample concentration: 0.2 mass% Temperature: oven 40℃, injection port 35℃, detector 35℃ Detector: Differential Refractometer The molecular weight is calculated by calculating the molecular weight at each dissolution time based on the dissolution curve of monodisperse polystyrene, and calculating it in the form of polystyrene-converted molecular weight.
3.導光板之製造及評估 <導光板之製造> 將上述光學用苯乙烯系樹脂組合物供給至螺桿直徑90 mm、L/D=32之單軸附帶排氣孔之擠出機,於200~235℃下熔融混練後,利用模唇寬度1000 mm、模唇開度3.0 mm之T模,於T模溫度245~250℃下流出,利用縱型三輥冷卻輥進行冷卻固化後,修整端面,獲得寬度800 mm、厚度2.0 mm之導光板。 3. Manufacturing and evaluation of light guide plates <Manufacturing of light guide plate> The above optical styrene-based resin composition is supplied to a single-axis vented extruder with a screw diameter of 90 mm and L/D=32, and after melting and kneading at 200 to 235°C, a die lip width of 1000 mm is used. . A T-mold with a die lip opening of 3.0 mm is flowed out at a T-mold temperature of 245 to 250°C. After cooling and solidification using a vertical three-roller cooling roller, the end face is trimmed to obtain a light guide plate with a width of 800 mm and a thickness of 2.0 mm.
<導光板之評估> 對表2~表3中之導光板之平均透過率、YI值、尺寸穩定性(吸濕變形)、LED耐久性如下所述地進行評估。 <Evaluation of light guide plate> The average transmittance, YI value, dimensional stability (hygroscopic deformation), and LED durability of the light guide plates in Tables 2 and 3 were evaluated as follows.
<導光板之平均透過率及YI值> 平均透過率及YI值係藉由如下步序進行測定。 從上述所獲得之導光板切下115 mm×85 mm之試驗片,藉由拋光研磨對端面進行研磨,製成於端面具有鏡面之板狀成形品。針對研磨後之板狀成形品,使用日本分光股份有限公司製造之紫外線可見分光光度計V-670,測定於大小20×1.6 mm、擴散角度0°之入射光下,光程長度115 mm下之波長350 nm~800 nm之分光透過率,依據JIS K7105計算出C光源中之視野2°下之YI值。平均透過率(全光線透過率)係以波長380~780 nm下之分光透過率之平均之形式算出。 <Average transmittance and YI value of light guide plate> The average transmittance and YI value are measured by the following steps. A test piece of 115 mm × 85 mm was cut from the light guide plate obtained above, and the end surface was ground by polishing to produce a plate-shaped molded product with a mirror surface on the end surface. For the plate-shaped molded product after grinding, the ultraviolet-visible spectrophotometer V-670 manufactured by Nippon ASCO Co., Ltd. was used to measure the incident light with a size of 20×1.6 mm, a diffusion angle of 0°, and an optical path length of 115 mm. The spectral transmittance of wavelengths 350 nm to 800 nm is calculated according to JIS K7105 and the YI value under the visual field of 2° in C light source. The average transmittance (total light transmittance) is calculated as the average of the spectral transmittance at a wavelength of 380 to 780 nm.
<尺寸穩定性(吸濕變形)> 從上述所獲得之導光板切下200 mm×300 mm之試驗片,將試驗片於溫度60℃、相對濕度90%之條件下保管500小時,測定保管前後之長邊之尺寸變化,根據以下之式計算變形率。 變形率=((保管後之長邊長度)-(保管前之長邊長度))÷(保管前之長邊之長度)×100(%) 將變化率未達0.10%者記為〇,將0.10~0.15%者記為△,將超過0.15%者記為×,評估導光板之尺寸穩定性(吸濕變化)。 <Dimensional stability (hygroscopic deformation)> Cut a 200 mm × 300 mm test piece from the light guide plate obtained above, store the test piece for 500 hours at a temperature of 60°C and a relative humidity of 90%, and measure the dimensional change of the long side before and after storage. According to the following Calculate the deformation rate with the formula. Deformation rate = ((length of the long side after storage) - (length of the long side before storage)) ÷ (length of the long side before storage) × 100 (%) The change rate of less than 0.10% was marked as 0, the change rate of 0.10 to 0.15% was marked as △, and the change rate of more than 0.15% was marked as ×. The dimensional stability (hygroscopic change) of the light guide plate was evaluated.
<LED耐久性> 從上述所獲得之導光板切下115 mm×85 mm之試驗片,使用端面研磨機(美佳羅科技股份有限公司製造之GCPB-500),利用以8000 rpm之速度旋轉之鑽石刀以2.0 m/min之進給速度對端面進行0.2 mm研磨,製成於端面具有鏡面之板狀成形品。針對研磨後之板狀成形品,於距端面0.5 mm之位置配置TV(television,電視)用平板型藍色LED光源(峰波長445 nm),在80℃之環境下、0.05 W/mm 2之輸入電流下,照射500 h之LED光。針對試驗後之板狀成形品,使用日本分光股份有限公司製造之紫外線可見分光光度計V-670,測定於大小20×1.6 mm、擴散角度0°之入射光下,光程長度115 mm下之波長350 nm~800 nm之分光透過率,依據JIS K7105計算出C光源中之視野2°下之YI值。將試驗後之YI值減去試驗前之YI值所得之值設為ΔYI。又,藉由目視確認試驗後之板狀成形品之LED入光部,將無變化者記為〇,將發生碳化者記為×,評估LED耐久性。 <LED durability> A test piece of 115 mm x 85 mm was cut out from the light guide plate obtained above, and an end grinder (GCPB-500 manufactured by Megaro Technology Co., Ltd.) was used, using a diamond rotating at a speed of 8000 rpm. The end surface of the knife is ground to 0.2 mm at a feed speed of 2.0 m/min to produce a plate-shaped molded product with a mirror surface on the end surface. For the plate-shaped molded product after grinding, a flat-panel blue LED light source (peak wavelength 445 nm) for TV (television) is placed 0.5 mm away from the end surface, and the temperature is 0.05 W/mm 2 in an environment of 80°C. Under the input current, the LED light is irradiated for 500 hours. For the plate-shaped molded product after the test, the ultraviolet-visible spectrophotometer V-670 manufactured by Japan ASCO Co., Ltd. was used to measure the incident light with a size of 20×1.6 mm, a diffusion angle of 0°, and an optical path length of 115 mm. The spectral transmittance of wavelengths 350 nm to 800 nm is calculated according to JIS K7105, and the YI value under the visual field of 2° in C light source is calculated. The value obtained by subtracting the YI value before the test from the YI value after the test is set as ΔYI. In addition, the LED light-incident part of the plate-shaped molded product after the test was visually confirmed, and those with no change were marked as 0, and those with carbonization were marked as ×, and the LED durability was evaluated.
於實施例1~17中,透明性、色相、尺寸穩定性良好,LED暴露後不發生碳化,且色相穩定性優異。In Examples 1 to 17, the transparency, hue, and dimensional stability are good, no carbonization occurs after the LED is exposed, and the hue stability is excellent.
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