WO2010096106A1 - Composition de copolymère bloc cyclique et plaque de guidage à paroi mince constituée de ladite composition - Google Patents
Composition de copolymère bloc cyclique et plaque de guidage à paroi mince constituée de ladite composition Download PDFInfo
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- WO2010096106A1 WO2010096106A1 PCT/US2009/061801 US2009061801W WO2010096106A1 WO 2010096106 A1 WO2010096106 A1 WO 2010096106A1 US 2009061801 W US2009061801 W US 2009061801W WO 2010096106 A1 WO2010096106 A1 WO 2010096106A1
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- block copolymer
- hydrogenation
- cyclic block
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/045—Light guides
-
- 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
Definitions
- this invention relates to certain cyclic block copolymer (CBC) resin compositions and their use in fabricating a thin wall light guide panel (LGP).
- CBC refers to a substantially fully hydrogenated vinyl aromatic-conjugated diene block copolymer.
- Thin and “thin wall” mean a thickness of less than or equal to ( ⁇ ) 0.7 millimeters (mm).
- the thin wall light guide panel may have any diagonal measure, e.g. greater than (>) one inch (2.54 cm).
- the CBC resin compositions are particularly useful in fabricating a thin wall light guide panel with a diagonal measurement of at least (>) 13.3 inches (in.) (33.8 centimeters (cm)).
- a LGP is part of a back light unit (BLU) of a display such as a liquid crystal display (LCD).
- the LGP desirably functions as a means to guide light from a source, e.g. a light emitting diode (LED) to a display device (e.g. a notebook computer or a LCD monitor) and uniformly distribute that light for illumination of the display device.
- a source e.g. a light emitting diode (LED)
- a display device e.g. a notebook computer or a LCD monitor
- Display manufacturers increasingly emphasize a need for thin and light weight LGPs.
- Thin wall LGP fabrication usually occurs via injection molding.
- An alternate technique involves an extrusion process with surface patterning using a patterning roller.
- manufacturers focus their attention on providing a LGP or light guide film (LGF) (a thickness of ⁇ 0.7 mm) with one flat and smooth surface and one featured or patterned surface.
- the featured surface can be designed for either light reflection or light extraction. Irrespective of specific surface design, manufacturers desire as complete a replication of the surface patterns as possible to maximize both homogeneous distribution of light and light output.
- LGF light guide film
- LGP that has all of several characteristics including sufficient toughness and stress crack resistance to avoid breakage, optical clarity with little, preferably no discernible yellowness to minimize and preferably avoid light absorbance with consequent loss of luminance at distal ends of a LGP or LGF or color shift across the LGP or LGF, sufficient surface hardness to minimize, preferably avoid, scratching during LGP handling or assembly, and dimensional stability or lack of warping, especially in humid environments.
- a polymer composition that provides all of these characteristics and has sufficient fluidity to completely fill mold cavities of an injection molding device.
- polymers fail to deliver one or more of the above characteristics or lack sufficient fluidity to completely fill mold cavities used to fabricate LGPs that have a thickness of ⁇ 0.7 mm and a diagonal measurement of > 33.8 cm.
- Polymethylmethacryalte (PMMA) compositions tend to lack sufficient fluidity to completely fill such mold cavities and suffer warping in humid environments.
- Polycarbonate (PC) compositions exhibit high yellowness that leads, in turn, to non-uniform luminance and large color shift (e.g.
- compositions based on a cyclic olefin polymer (COP) or a cyclic olefin copolymer (COC) either lack sufficient fluidity to completely fill such mold cavities or enough toughness and stress crack resistance to avoid breakage when they do fill the mold cavities.
- CBC compositions comprising a CBC with an elongation strain at break of more than (>) 30% and a modulus within a range of from > 150,000 pounds per square inch (psi) (1034 MPa) to less than ( ⁇ ) 270,000 psi (1862 MPa).
- the CBC is preferably results from hydrogenation of a SBSBS-based pentablock copolymer with a pre-hydrogenation styrene content that is > 50 wt% to less than ( ⁇ ) 70 wt%, more preferably from 55 wt% to 65 wt%. each wt% being based upon total pentablock copolymer weight prior to hydrogenation.
- EP 1 189 988 Bl teaches compositions comprising a rigid hydrogenated block copolymer that has at least two distinct blocks of hydrogenated polymerized vinyl aromatic monomer and at least one block of hydrogenated polymerized conjugated diene monomer.
- Donald et al. discusses injection molded articles and lists more than thirty categories or illustrations of such articles, one of which is a light guide. See also counterpart United States Patent (USP) 6,815,475.
- USP 6,633,722 discloses a LGP made of a polymeric resin having an alicyclic structure.
- thermoplastic resin having a melt flow rate (MFR) of at least 50 grams per 10 minutes (g/10 min.) under a load of 2.16 kilogram force (kgf) at a temperature of 28O 0 C.
- MFR melt flow rate
- the thermoplastic resin may be any of a number of resins including polymethyl methacrylates, polymethyl acrylates, and polymers having an alicyclic structure.
- this invention is a CBC composition, the composition comprising a CBC resin that has a shear viscosity at a shear rate of 1000 reciprocal seconds (sec 1 ) and a temperature of 280 degrees centigrade ( 0 C) of less than 50 pascal seconds (Pa- s), and, when formed into a tensile test bar having a thickness of 1/8 in.
- the CBC resin preferably has a pre-hydrogenation polymerized vinyl aromatic monomer content within a range of from 75 percent by weight (wt%) to 90 wt%, based upon total pre-hydrogenation vinyl aromatic-conjugated diene block copolymer weight, and a weight average molecular weight (Mw) within a range of from 30,000 grams per mole (g/M) to 125,000 g/M.
- the CBC compositions can be used to fabricate light guides (LGPs and LGFs) useful for LCD devices or other display devices that require a waveguide.
- the light guide can be fabricated by any known thermoplastic polymer processing technique such as injection molding, extrusion roll molding, extrusion blow molding, blown film, melt casting, and compression molding.
- LGPs and LGFs in particular, at least one side thereof bears a surface pattern for light extraction. This can be achieved either during fabrication or with a subsequent printing (e.g. ultraviolet imprinting) or embossing (e.g. thermal embossing) step.
- the CBC compositions While particularly suited for use in fabricating thin LGPs and thin LGFs, the CBC compositions have utility in fabricating thicker LGPs (e.g. a thickness within a range of from 1 mm to 5 mm) such as those designed for use in large (diagonal measure of 27 inches (68.6 cm) panels for LED television back light units.
- this invention is an article of manufacture fabricated from such a hydrogenated CBC composition, especially a thin LGP, particularly one that has a diagonal measure > 13.3 inches (33.8 cm).
- substantially fully hydrogenated means that > 90 percent (%) of vinyl aromatic (e.g. styrene) double bonds and > 90%, preferably > 95% of conjugated diene (preferably butadiene) double bonds are hydrogenated.
- CBC resins suitable for use in various aspects of this invention preferably have, prior to hydrogenation, a pentablock architecture with alternating styrene (S) blocks and butadiene (B) blocks.
- Representative pre-hydrogenation pentablock copolymers include
- SBSBS pentablock copolymers SBSBS pentablock copolymers.
- S styrene
- B butadiene
- SBSBS-based CBC resins have a pre-hydrogenation styrene content that is preferably from greater than or equal to (>) 75 wt% to less than or equal to ( ⁇ ) 90 wt%, more preferably within a range of from > 80 wt% to ⁇ 90 wt%, each wt% being based upon total pentablock copolymer weight prior to hydrogenation.
- the pentablock copolymers have a pre-hydrogenation Mw that is preferably within a range of from 30,000 g/M to 125,000 g/M, more preferably within a range of from 40,000 g/M to 90,000 g/M, and even more preferably within a range of from 45,000 g/M to 75,000 g/M.
- the hydrogenated, SBSBS-based CBC pentablock copolymers When formed into a tensile test bar having a thickness of 1/8 in (0.3 cm), the hydrogenated, SBSBS-based CBC pentablock copolymers have an unnotched Izod toughness (ASTM test D256) at room temperature that is preferably at least 1.8 ft-lb/in. (315.2 N/m), more preferably > 2 ft-lb/in. (350.2 N/m), and still more preferably > 2.2 ft- lb/in. (385.3 N/m)
- the tensile test bars also have a tensile modulus (ASTM D638) that is preferably > 280,000 psi (1930.5 MPa), more preferably > 300,000 psi (2068.4 MPa).
- the multi-armed and coupled block copolymers contain a residue from a coupling agent.
- Such coupled block copolymers may be represented as, for example, X(BS) n where n is > 2 and X represents a chain coupling agent.
- the coupled block copolymers preferably have the same styrene content and hydrogenation percentage as the sequential SBSBS pentablock copolymers but a broader Mw range that is preferably from 30,000 g/M to 200,000 g/M, more preferably from 40,000 g/M to 150,000 g/M and even more preferably from 45,000 g/M to 125,000 g/M.
- Block copolymers suitable for use in various aspects of this invention have a pre-hydrogenation vinyl aromatic polymerized monomer content that is preferably from 75 wt% to 90 wt%, more preferably from 80 wt% to 90 wt%, and still more preferably from 80 wt% to 87 wt%. Each wt% is passed upon total pre-hydrogenated block copolymer weight.
- CBC compositions suitable for use in various aspects of this invention may include one or more conventional additives including, but not limited to antioxidants, hindered amine light stabilizers (HALS), processing aids or lubricants, and mold release agents.
- HALS hindered amine light stabilizers
- Illustrative antioxidants include hindered phenols (e.g.
- HALS include poly[[6-[(l,l,3,3-tetramethylbutyl)amino]-s-triazine-2,4- diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4- piperidyDimino]] (CHMASSORBTM 944, Ciba Geigy), bis (2,2,6,6,-tetramethyl-4- piperidyl) sebacate (Tinuvin® 770, Ciba Geigy).
- Illustrative mold release agents include glycerol monostearate (e.g., GMS-90, Danisco Inc.), pentaerythritol tetrastearate, amides wax, poly(oxyethylene)nonylphenyl ether, etc.
- Illustrative processing aids include fluorinated polymers (e.g., Kynar Flex® PPA, Arkema), aliphatic amide type of processing aids (e.g., INT-33UDK, Axel Plastics Research Laboratory), etc.
- CBC compositions that include a mold release agent (MRA), a processing aid or both, preferably do so at a loading level for each of the MRA and processing aid of from 200 parts by weight per million parts by weight (ppm) of CBC to 5,000 ppm, more preferably from 300 ppm to 3,000 ppm, and still more preferably from 300 ppm to 2,000 ppm.
- MRA mold release agent
- processing aid preferably do so at a loading level for each of the MRA and processing aid of from 200 parts by weight per million parts by weight (ppm) of CBC to 5,000 ppm, more preferably from 300 ppm to 3,000 ppm, and still more preferably from 300 ppm to 2,000 ppm.
- CBC compositions that include an antioxidant do so at a loading level that is preferably from 300 ppm to 5,000 ppm, more preferably from 500 ppm to 3,000 ppm, and still more preferably from 750 ppm to 2,000 ppm.
- a loading of 1000 ppm produces very satisfactory results.
- CBC compositions suitable for use in some aspects of this invention optionally include one or more of a second CBC resin or a soft polymer such as styrene- ethylene butylene-styrene (SEBS) polymers and styrene-ethylene propylene-styrene (SEPS) polymers.
- SEBS styrene- ethylene butylene-styrene
- SEPS styrene-ethylene propylene-styrene
- an amount of ⁇ one wt% but > 500 ppm improves molding of the compositions.
- the incorporation of soft polymer in such an amount appears to effectively eliminate development of stress whitening spots that might otherwise occur during extended use of molded panels or plates in a humid environment. Addition of a larger amount of soft polymer, e.g. two wt% or more adversely affects optical transparency of articles fabricated from such CBC compositions.
- an article fabricated from a CBC composition may have an abrasion-resistant or hardness coating applied to one or more of the article's external surfaces.
- Suitable coatings may include, for example, ultraviolet (UV) light curable acrylic coating and aliphatic urethane coatings.
- CBC compositions of various aspects of this invention have utility as a LGP.
- the LGP preferably has at least one flat surface with a diagonal measurement of at least
- room temperature and “ambient temperature” are nominally 25 0 C.
- CBC-2, CBC-3, CBC-4, CBC-5 and CBC-6 one triblock (SBS-based) CBC (CBC-7), one cyclic olefin copolymer (COC) (TOPASTM 5013, Ticona Polyplastics), two cyclic olefin polymers (COP-I (ZEONORTM 1060R, Zeon Chemical) and COP-2 (ZEONORTM 1430R,
- Table 1 includes their respective Mw, and wt% styrene (based on total block copolymer weight before hydrogenation). Table 1 also includes physical performance data in terms of shear viscosity at 1000 sec "1 and 28O 0 C, unnotched Izod Impact ((ft- lbs/in.)(/N/m)) (ASTM D256), Tensile Modulus (psi times 1000 or kpsi/MPa) (ASTM
- Ex 1-3 and CEx A-G Prepare a series of LGPs, each of which has a diagonal measure of 13.3 inches (33.8 cm) and a thickness as shown in Table 2 below using a 450 ton (4.082 x IO 5 kilograms (kg)), high speed injection molding machine (Model: SE450HY, Sumitomo Heavy Industries, Ltd.) and processing temperature and mold temperature as shown in Table 2.
- B Brittle - injection molded panels are brittle and easy to crack or crack during de-molding, handling or assembly.
- LGP molding has a diagonal measurement of 13.3 inches (33.8 cm).
- Other CBC compositions, cyclic olefin copolymers (COCs), the PMMA and the COPs do not allow one to make such moldings at all in some instances (e.g. CEx A at 0.4 mm and 0.45 mm) or have them be useful once fabricated as in CEx A.
- the COC, the COPs and the PMMA allow one to make a LGP that receives a subjective "good" rating at a thickness of 0.7 mm, but not at a lower thickness such as 0.6 mm while the CBC compositions of Ex 1-3 achieve the subjective "good" rating at a thickness of 0.6 mm, and Ex 1 does so at a thickness of
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- Physics & Mathematics (AREA)
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Abstract
L'invention concerne une composition de copolymère bloc cyclique, qui comprend une résine de copolymère bloc cyclique dont la teneur en monomère vinylique aromatique polymérisé pré-hydrogéné est comprise dans une plage allant de 75% en poids à 90% en poids, sur la base du poids total du copolymère bloc à diène conjugué-vinyle aromatique pré-hydrogéné, un Mw compris dans une plage allant de 30 000 g/M à 125 000 g/M, une viscosité de cisaillement à une vitesse de cisaillement de 1000 sec-1 et à une température de 280 °C inférieure à 50 pascal secondes (Pa-s), une résistance au choc de type Izod non entaillé (ASTM D256)) à température ambiante ≥ 1,8 pieds-livres par pouce (315,2 newtons par mètre), et un module de traction (ASTM D638) ≥ 280 000 psi (1930,5 MPa). La composition de copolymère bloc cyclique produit une variété d'articles de manufacture, en particulier un panneau de guidage de lumière à paroi mince qui présente une mesure en diagonale ≥ 13,3 pouces (33,8 cm).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US15401709P | 2009-02-20 | 2009-02-20 | |
US61/154,017 | 2009-02-20 |
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WO2010096106A1 true WO2010096106A1 (fr) | 2010-08-26 |
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PCT/US2009/061801 WO2010096106A1 (fr) | 2009-02-20 | 2009-10-23 | Composition de copolymère bloc cyclique et plaque de guidage à paroi mince constituée de ladite composition |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011075229A1 (fr) * | 2009-12-18 | 2011-06-23 | Dow Global Technologies Llc | Fibre optique en matière plastique comprenant un copolymère séquencé cyclique |
WO2018234640A1 (fr) | 2017-06-20 | 2018-12-27 | Aptar France Sas | Dispositif de distribution de produit fluide |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001042355A1 (fr) * | 1999-12-07 | 2001-06-14 | Dow Global Technologies Inc. | Compositions de copolymeres sequences hydrogenes, destinees a des applications de moulage par injection de structures a paroi mince |
JP2003240964A (ja) * | 2002-02-22 | 2003-08-27 | Teijin Ltd | 導光板 |
WO2009085346A1 (fr) * | 2007-12-28 | 2009-07-09 | Dow Global Technologies Inc. | Lentilles thermoplastiques à faible biréfringence et compositions utiles dans la préparation de telles lentilles |
Family Cites Families (1)
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JP3847599B2 (ja) * | 2001-10-22 | 2006-11-22 | ポリプラスチックス株式会社 | 耐衝撃性環状オレフィン系樹脂組成物及び成形品 |
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- 2009-10-23 WO PCT/US2009/061801 patent/WO2010096106A1/fr active Application Filing
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- 2010-02-12 TW TW099104700A patent/TWI461474B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001042355A1 (fr) * | 1999-12-07 | 2001-06-14 | Dow Global Technologies Inc. | Compositions de copolymeres sequences hydrogenes, destinees a des applications de moulage par injection de structures a paroi mince |
JP2003240964A (ja) * | 2002-02-22 | 2003-08-27 | Teijin Ltd | 導光板 |
WO2009085346A1 (fr) * | 2007-12-28 | 2009-07-09 | Dow Global Technologies Inc. | Lentilles thermoplastiques à faible biréfringence et compositions utiles dans la préparation de telles lentilles |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011075229A1 (fr) * | 2009-12-18 | 2011-06-23 | Dow Global Technologies Llc | Fibre optique en matière plastique comprenant un copolymère séquencé cyclique |
US9103966B2 (en) | 2009-12-18 | 2015-08-11 | Dow Global Technologies Llc | Plastic optical fiber comprising cyclic block copolymer |
WO2018234640A1 (fr) | 2017-06-20 | 2018-12-27 | Aptar France Sas | Dispositif de distribution de produit fluide |
US10906728B2 (en) | 2017-06-20 | 2021-02-02 | Aptar France Sas | Device for dispensing a fluid product |
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Publication number | Publication date |
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TW201035216A (en) | 2010-10-01 |
TWI461474B (zh) | 2014-11-21 |
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