(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Bureau
`
`1 July 2010 (01.07.2010) (10) International Publication Number
`
`(43) International Publication Date
`
`WO 2010/074789 Al
`
`
`(51)
`
`International Patent Classification:
`C08L 51/00 (2006.0 1)
`C08F 8/04 (2006.0 1)
`C08L 53/00 (2006.0 1)
`8328 7/02 (2006.0 1)
`C08L 53/02 (2006.01)
`B32B 25/16 (2006.01)
`
`(74)
`
`(81)
`
`(21)
`
`International Application Number:
`
`PCT/US2009/0595 37
`
`(22)
`
`International Filing Date:
`
`5 October 2009 (05.10.2009)
`
`Filing Language:
`
`Publication Language:
`
`English
`
`English
`
`Priority Data:
`61/122,931
`
`16 December 2008 (16.12.2008)
`
`US
`
`(84)
`
`(for all designated States except US): DOW
`Applicant
`GLOBAL TECHNOLOGIES INC.
`[US/US];
`2040
`Dow Center, Midland, MI 48674 (US).
`
`(25)
`
`(26)
`
`(30)
`
`(71)
`
`(72)
`(75)
`
`Agent: HOWARD, Dan; PO. Box
`Michigan 48641-1967 (US).
`
`1967, Midland,
`
`Designated States (unless otherwise indicated, for every
`kind if national protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ,
`CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO,
`DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
`HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP,
`KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD,
`ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI,
`NO, NZ, OM, PE, PG, PH, PL, PT, R0, RS, RU, SC, SD,
`SE, SG, SK, SL, SM, ST, SV, SY, TJ, TM, TN, TR, TT,
`TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`Designated States (unless otherwise indicated, for every
`kind if regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ,
`TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE,
`ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
`MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM,
`TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
`NIL, MR, NE, SN, TD, TG).
`
`Inventors; and
`(for US only): ZHOU, Weijun
`Inventors/Applicants
`[CN/US];
`108 River Oaks Drive, Lake Jackson, TX
`77566 (US). HAHN, Stephen [US/US]; 4013 Sudbury
`Court, Midland, MI 48642 (US). ISANHART, Bowdie
`[US/US]; 2361 North Alamando Road, Coleman, MI Published:
`4861 8 (US).
`with international search report (Art, 21(3))
`
`
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`W02010/074789A1|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
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`(54) Title: CYCLIC BLOCK COlVIPOLYlVIER COlVIPOSITIONS AND ARTICLES OF MANUFACTURE FABRICATED
`THEREFROM
`
`(57) Abstract: Convert cyclic block copolymer compositions into mono-layer sheets or multi-layer sheets that have at least one
`cyclic block copolymer composition layer and transform the sheets into articles of manufacture such as orthodontic appliances.
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`PCT/USZOO9/059537
`
`CYCLIC BLOCK COMPOLYMER COMPOSITIONS AND ARTICLES OF
`
`MANUFACTURE FABRICATED THEREFROM
`
`This application is a non-provisional application claiming priority from the US.
`
`Provisional Patent Application No. 61/122,931, filed on December 16, 2008, entitled
`
`5
`
`"CYCLIC BLOCK COPOLYMER COMPOSITIONS AND ARTICLES OF
`
`MANUFACTURE FABRICATED THEREFROM," the teachings of which are
`
`incorporated by reference herein, as if reproduced in full hereinbelow.
`
`This invention relates to cyclic block copolymer (CBC) compositions, mono-layer
`
`sheets fabricated from such compositions, multi-layer sheets having at
`
`least one layer
`
`10
`
`fabricated from such compositions,
`
`and articles of manufacture (eg. an orthodontic
`
`appliance) fabricated, at least in part, from a mono-layer sheet, a multi-layer sheet or both a
`
`mono-layer sheet and a multi-layer sheet.
`
`A growing trend exists that focuses on use of clear, transparent plastic orthodontic
`
`devices to align human teeth. Growth stems, at least in part, from ease of use and relative
`
`15
`
`aesthetic beauty relative to conventional orthodontic braces or devices based upon metal.
`
`Manufacturers of plastic orthodontic devices desire a plastic material that allows for
`
`or promotes movement of human teeth in a controlled, uniform and safe manner for as large
`
`a portion of the human population as possible.
`
`In attempts to satisfy this desire,
`
`manufacturers currently use transparent,
`
`thermoplastic resins or materials such as rigid,
`
`20
`
`thermoplastic polyurethane (TPU), polycarbonate (PC) or saturated polyester. Devices
`
`fabricated from PC resins tend to undergo environmental stress cracking when exposed to
`
`human saliva. Devices fabricated from rigid TPU or polyester resins often show undesirable
`
`levels of creep when exposed to human saliva, possibly due in part to a tendency of such
`
`resins toward plasticization when immersed in water.
`
`25
`
`United States Patent
`
`(US) 6,964,564 (Phan et al.) discloses improved devices,
`
`systems and methods for repositioning teeth from an initial tooth arrangement to a final
`
`tooth arrangement. The system comprises a series of polymeric shell appliances configured
`
`to receive teeth and incrementally reposition individual teeth in a series of incremental steps.
`
`See also related USP 6,454,565 (Phan et a1.) and USP 6, 424,101 (Phan et a1).
`
`30
`
`United States Patent Application Publication (U SPAP) 2006/0078841 (DeSimone et
`
`a1.)
`
`teaches forming a polymeric shell of a removable dental positioning appliance from
`
`transparent polymeric materials having a tensile strength at yield of greater than 6,000
`
`-1-
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`

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`WO 2010/074789
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`pounds per square inch (psi), an elongation at yield of greater than 4%, an elongation at
`
`break of greater than 80%, a tensile modulus greater than 200,000 psi, a flexural modulus
`
`greater than 200,000 psi,
`
`stress relaxation over time of not more than 50%, and a
`
`transmissivity of light between 400 nm and 800 nm greater than 75%.
`
`5
`
`In some aspects, this invention is a CBC composition, the composition comprising a
`
`CBC that
`
`is a substantially fully hydrogenated vinyl aromatic-conjugated diene block
`
`copolymer, said substantially fully hydrogenated block copolymer having an elongation
`
`strain at break of more than 30% and a modulus that is within a range of from greater than
`
`or equal to 150,000 pounds per square inch (psi) (1034 megapascals (MPa) to less than
`
`10
`
`270,000 psi (1862 MPa). Determine both elongation strain at break and modulus in accord
`
`with American Society for Testing and Materials (ASTM) Test D638-02a.
`
`In some aspects,
`
`the CBC is a functionalized CBC. Examples include but not
`
`restricted to, silane-grafted CBCs, maleic anhydride grafted CBCs, acrylate-grafted CBCs,
`
`methacrylate-grafted CBCs and siloxanes-grafted CBCs.
`
`Silane-grafted CBCs employ a
`
`15
`
`grafting moiety such as vinyl trimethoxy silane (VTMS) or vinyl triethoxy silane (VTES)
`
`which crosslinks upon hydrolysis. Siloxane grafted CBCs employ a grafting moiety such as
`
`a vinyl
`
`terminated polydimethyl
`
`siloxane that does not undergo crosslinking upon
`
`hydrolysis.
`
`In some aspects, the aforementioned CBC composition further comprises an amount
`
`20
`
`of at least one other polymer or copolymer selected from a group consisting of a non-
`
`hydrogenated vinyl aromatic-conjugated diene block copolymer or random copolymer, a
`
`hydrogenated vinyl aromatic homopolymer, a cyclic olefin polymer, or a cyclic olefin
`
`copolymer.
`
`The CBC compositions disclosed above have utility in that they may readily be
`
`25
`
`formed (e.g. extruded, or injection molded) into a sheet, either mono-layer or multi-layer.
`
`The sheet, in turn, has utility in that it can be thermoformed into a shaped article such as an
`
`orthodontic appliance.
`
`In view of these utilities, additional aspects follow in succeeding
`
`paragraphs.
`
`In some aspects, this invention is a multi-layer, thermoformable, polymeric sheet, the
`
`30
`
`sheet comprising at least one hard layer and at least one soft layer, the hard layer comprising
`
`the CBC composition described in the immediately preceding two paragraphs and the soft
`
`layer comprising an elastomeric, substantially fully hydrogenated CBC composition,
`
`the
`
`-2-
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`

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`WO 2010/074789
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`PCT/U82009/059537
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`elastomeric CBC composition comprising a substantially fully hydrogenated vinyl aromatic-
`
`conjugated diene block copolymer composition, said composition having aprehydrogenated
`
`vinyl aromatic content of less than 50 percent by weight (wt%), based upon total vinyl
`
`aromatic-conjugated diene block copolymer weight prior to hydrogenation, and a number
`
`5
`
`average molecular weight (Mn) within a range of from 30,000 grams per mole (g/M) to
`
`250,000 g/M.
`
`In some aspects,
`
`this invention is a multi-layer,
`
`thermoformable, polymeric sheet
`
`having a hard layer as described above, but with a soft layer that comprises a polymer
`
`composition other than the elastomeric CBC composition, such other polymer composition
`
`10
`
`comprising at least one of a cyclic vinyl aromatic-conjugated diene block copolymer in
`
`which only the diene block is substantially fully hydrogenated and the vinyl aromatic block
`
`is substantially free of hydrogenation (e.g. styrene-ethylene-propylene-styrene
`
`(SEPS) or
`
`styrene-ethylene-butylene-styrene
`
`(SEBS)),
`
`an olefin elastomer
`
`and a thermoplastic
`
`polyurethane (TPU).
`
`15
`
`In some aspects, this invention is a mono-layer sheet, preferably an extruded mono—
`
`layer sheet or an injection molded sheet comprising the CBC composition described
`
`hereinabove. A "mono-layer sheet" has a thickness of at least 20 mils (0.51 millimeters
`
`(mm)). The thickness preferably lies within a range of from 20 mils (0.5 mm) to 60 mils
`
`(1.5 mm) and more preferably within a range of from 25 mils (0.6 mm) to 40 mils (1 mm).
`
`20
`
`In some aspects, this invention is a process for preparing a thermoformed sheet, the
`
`process comprising subjecting a sheet selected from the multi-layer sheet and the mono-
`
`layer sheet, each of which is described hereinabove,
`
`to thermoforming conditions,
`
`the
`
`thermoforming conditions including use of a thermoforming device, and a thermoforming
`
`temperature within a range of from the cyclic block copolymer composition's
`
`glass
`
`25
`
`transition temperature (Tg) to a temperature 100 degrees centigrade (0C) in excess of the Tg,
`
`preferably within a range of from Tg + 5 0C to Tg + 50 0C. The thermoforming conditions
`
`preferably include a pressure sufficient to effect,
`
`in conjunction with the thermoforming
`
`device and the thermoforming temperature, a change in shape from sheet form to a desired
`
`shape, e.g. that of an orthodontic appliance when the thermoforming device includes a die
`
`30
`
`that facilitates forming the desired shape.
`
`

`

`WO 2010/074789
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`
`PCT/U82009/059537
`
`When ranges are stated herein, as in a range of from 2 to 10, both end points of the
`
`range (e. g. 2 and 10) and each numerical value, whether such value is a rational number or
`
`an irrational number, are included within the range unless otherwise specifically excluded.
`
`Expressions of temperature may be in terms either of degrees Fahrenheit
`
`(0F)
`
`5
`
`together with its equivalent in 0C or, more typically, simply in 0C.
`
`Unless stated to the contrary, implicit from the context, or customary in the art, all
`
`parts and percents are based on weight.
`
`A thermoformed sheet
`
`in a form such as an orthodontic appliance has certain
`
`property advantages relative to a thermoformed sheet fabricated solely from rigid TPU. The
`
`10
`
`advantages include an improved creep resistance and a slightly lower modulus, both relative
`
`to rigid TPU.
`
`The CBC compositions of various aspects of this invention have certain processing
`
`advantages over rigid TPU compositions, especially when such compositions are destined
`
`for use in an orthodontic appliance. One may, for example, feed CBC composition pellets
`
`15
`
`to an extruder as is when forming a sheet without resort to a drying step commonly required
`
`for rigid TPU pellets. A CBC sheet similarly need not be dried before thermoforming into a
`
`device such as an orthodontic appliance. A rigid TPU sheet typically requires a drying step
`
`at an elevated temperature (e.g., 80°C) for at least 12 hrs. Elimination of drying steps
`
`translates to energy savings and reduction in manufacturing costs.
`
`20
`
`The CBC is a substantially fully hydrogenated vinyl aromatic-conjugated diene
`
`block copolymer with an elongation strain at break, determined in accordance with
`
`American Society for Testing and Materials (ASTM) D638 that is preferably at least (>)
`
`30%, more preferably 2 50%, and even more preferably at least 100%. The cyclic block
`
`copolymer also preferably has a modulus, determined in accord with ASTM D638, that is 3
`
`25
`
`150,000 psi (1034 MPa) but less than (<) 270,000 psi (1862 MPa).
`
`"Substantially fully hydrogenated" means that at
`
`least 90 percent
`
`(%) of vinyl
`
`aromatic double bonds and at least 95% of conjugated diene double bonds are hydrogenated.
`
`The
`
`substantially fully hydrogenated vinyl
`
`aromatic-conjugated diene block
`
`copolymers preferably have, prior
`
`to hydrogenation,
`
`a pentablock architecture with
`
`30
`
`alternating styrene (S) blocks and either butadiene (B) blocks or isoprene (1) blocks.
`
`Representative prehydrogenation pentablock copolymers
`
`include
`
`SB SBS pentablock
`
`copolymers and 81818 pentablock copolymers. The styrene (S) blocks may, but need not be
`
`-4-
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`PCT/U82009/059537
`
`of equal length. Similarly, the butadiene (B) blocks and isoprene (1) blocks may, but need
`
`not be of equal length.
`
`The SBSBS-based and SISIS-based CBC pentablock copolymers have a pre-
`
`hydrogenation styrene content that is preferably greater than 50 percent by weight (wt%) to
`
`5
`
`less than 70 wt%, more preferably within a range of from 55 wt% to 65 wt%, each wt%
`
`being based upon total pentablock copolymer weight prior
`
`to hydrogenation.
`
`The
`
`pentablock copolymers have a pre-hydrogenation Mn that is preferably within a range of
`
`from 40,000 g/M to 150,000 g/M, more preferably within a range of from 50,000 g/M to
`
`120,000 g/M, and even more preferably within a range of from 60,000 g/M to 90,000 g/M.
`
`10
`
`Following hydrogenation,
`
`at
`
`least 90 percent
`
`(%) of vinyl aromatic
`
`(e.g.
`
`styrene)
`
`unsaturation (double bonds) present prior to hydrogenation and at least 90 % of conjugated
`
`diene
`
`(e.g.
`
`butadiene
`
`or
`
`isoprene) unsaturation
`
`(double bonds) present prior
`
`to
`
`hydrogenation are hydrogenated or converted to saturated bonds. The percentage more
`
`preferably equals or exceeds 95 %.
`
`15
`
`While
`
`sequentially
`
`polymerized pentablock
`
`copolymers may be preferred,
`
`satisfactory results
`
`also occur with use of triblock, multi-armed or coupled block
`
`copolymers. 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 1 and X represents a chain coupling agent. The coupled block
`
`20
`
`copolymers preferably have the same styrene content and hydrogenation percentage as the
`
`sequential SBSBS and 81818 pentablock copolymers but a broader Mn range that
`
`is
`
`preferably from 40,000 g/M to 250,000 g/M, more preferably from 50,000 g/M to 200,000
`
`g/M and even more preferably from 60,000 g/M to 160,000 g/M.
`
`The CBC compositions of at least some aspects of this invention may be modified
`
`25
`
`by one or more procedures, one of which is silane-grafting. USP 5,266,627 and USPAP
`
`20060 199914Al teach suitable procedures for silane grafting using a silane compound such
`
`as vinyltrimethoxysilane and a catalyst such as 2,5-di-tert-butylperoxy-2,5-dimethylhexane.
`
`See Patrice Lucas and Jean-Jacques Robin, "Silicone-Based Polymer Blends: An
`
`Overview of the Materials and Processes", Advanced Polymer Science (2007), volume 209,
`
`30
`
`pages 111-147, for a discussion of siloxane and silane technology in general and blending
`
`and grafting in particular.
`
`See Kuk Young Cho et al, "Grafting of Glycidyl Methacrylate onto High-Density
`
`-5-
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`

`

`WO 2010/074789
`67646-WO-PCT
`
`PCT/U82009/059537
`
`Polyethylene with Reaction Time in the Batch Mixer", Journal of Applied Polymer Science,
`
`Volume
`
`108, pages 1093-1099 (2008),
`
`for general
`
`teachings relative to methacrylate
`
`grafting.
`
`See also Shenglong Ding et al, "The Study of Melt Grafting Mechanism of
`
`Acrylic Acid and Butyl Acrylate onto Low Density Polyethylene and Its Application as
`
`Internal Plasticizer", Journal of Applied Polymer Science, Volume 108, pages 423-430
`
`5
`
`(2008) for general teachings relative to acrylate grafting.
`
`In addition, see K. E. Russell,
`
`"Free radical graft polymerization and copolymerization at higher temperatures", Progress
`
`in Polymer Science, Volume 27 (2002), pages 1007-1038, for teachings relative to graft
`
`addition of vinyl monomers to poly olef1ns.
`
`10
`
`The CBC compositions of at least some aspects of this invention yield optically
`
`transparent, thermoformable sheets or films. Optical transparency makes such sheets and the
`
`compositions
`
`that form the sheets very desirable from an aesthetic point of view in
`
`orthodontic appliances, especially those used for tooth alignment
`
`(otherwise known as
`
`"braces").
`
`15
`
`While orthodontic appliances represent a preferred end use application for CBC
`
`compositions of some aspects of this invention and thermoformable sheets of other aspects
`
`of this invention,
`
`the compositions and sheets have utility in other end use applications.
`
`Such other end use applications include, but are not limited to, display films, signage sheets,
`
`and medical/pharmaceutical vials and bottles.
`
`20
`
`The CBC compositions of at least some aspects of this invention further comprise
`
`any one or more members of three groups of polymers. The groups are: a) hydrogenated
`
`vinyl aromatic-conjugated diene
`
`block copolymers; b) hydrogenated random vinyl
`
`aromatic-conjugated diene copolymers; c) hydrogenated vinyl aromatic homopolymers, d)
`
`cyclic olefin polymers;
`
`e) and cyclic olefin copolymers.,
`
`f) non-hydrogenated vinyl
`
`25
`
`aromatic-conjugated diene block copolymers; and g) non-hydrogenated random vinyl
`
`aromatic-conjugated diene copolymers.
`
`Conversion of CBC compositions of
`
`some
`
`aspects of this
`
`invention into
`
`thermoformable sheets of other aspects of this invention employs conventional processes.
`
`Such conventional processes
`
`include
`
`extrusion,
`
`injection molding and compression
`
`30
`
`molding. Any of these processes readily forms a plaque suitable for thermoforming into an
`
`article of manufacture, such as an orthodontic appliance of some aspects of this invention.
`
`Compositions of some aspects of this invention have utility as a layer of a multi-
`
`-6-
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`

`

`WO 2010/074789
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`
`layer structure, especially as a hard outer
`
`layer of a multi-layer
`
`structure such as a
`
`coextruded multi-layer structure. The hard outer layer provides creep resistance. A softer,
`
`relative to the hard outer layer,
`
`inner layer provides a degree of wearer comfort
`
`in an
`
`orthodontic appliance wherein the inner layer is in contact with the wearer's teeth and the
`
`5
`
`hard outer layer is spaced apart from the wearer's teeth by the inner layer. Materials suitable
`
`for use in fabricating the inner or soft layer include, but are not limited to, styrene-ethylene-
`
`butylene-styrene
`
`copolymers,
`
`styrene-ethylene-propylene-styrene
`
`copolymers,
`
`olefin
`
`elastomers, and thermoplastic polyurethanes.
`
`Extruded sheets, either mono-layer or multi-layer, of some aspects of this invention
`
`10
`
`lend themselves to thermoforming into various structures, one of which is an orthodontic
`
`appliance.
`
`Suitable
`
`thermoforming
`
`temperatures
`
`satisfy
`
`a
`
`relationship wherein
`
`thermoforming temperature (T) lies within a range that has a lower limit established by glass
`
`transition temperature (Tg) of CBCs of some aspects of this invention and an upper limit of
`
`100° C greater than the Tg. The range is preferably from Tg + 5°C to Tg + 500C.
`
`15
`
`Compositions of some aspects of this invention may include one or more
`
`conventional additives.
`
`Illustrative additives include antioxidants, mold release agents,
`
`ultraviolet light stabilizers, processing aids, lubricants, anti-static agents, antimicrobial
`
`agents (eg. ALPHASANTM RC2000 or MICROBANTM), colorants, coloring agents, and
`
`dyes.
`
`20
`
`Examples
`
`The following examples illustrate, but do not limit, the present invention. All parts
`
`and percentages are based upon weight, unless otherwise stated. All temperatures are in 0C.
`
`Examples (Ex) of the present invention are designated by Arabic numerals and Comparative
`
`Examples (Comp Ex or CEx) are designated by capital alphabetic letters. Unless otherwise
`
`25
`
`stated herein, "room temperature" and "ambient temperature" are nominally 250C.
`
`Table lbelow lists three pentablock (SBSBS-based) CBCs (CBC-I, CBC-2 and
`
`CBC-3), and one TPU (ISOPLASTTM 2530, commercially available from The Dow
`
`Chemical Company). For the CBCs, Table lincludes their respective Mn, wt% styrene
`
`(based on total CBC weight before hydrogenation) and wt% 1,2-vinyl (based on total
`
`30
`
`butadiene (B) content before hydrogenation) content . Table lalso includes physical
`
`performance data in terms of strain at break and modulus (thousand psi or kpsi and MPa),
`
`both determined in accord with ASTM D638.
`
`-7-
`
`

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`WO 2010/074789
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`

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`WO 2010/074789
`67646-WO-PCT
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`PCT/US2009/059537
`
`Table 1
`
`
`Material
`
`Mn (g/M)
`
`Styrene
`
`1,2-vinyl
`
`content
`
`content
`
`Strain@break Modulus
`
`(%)
`
`(kpsi/MPa)
`
`(wt%)
`(wt%)
`
`
`
`
`
`
`
`
`CBC—1
`72,800
`60
`8
`240
`220/1517
`
`
`CBC-2
`69,000
`55
`8
`300
`155/1069
`
`
`CBC-3
`70,500
`70
`11
`20
`244/1682
`
`
`TPU
`
`N/A
`
`N/A
`
`N/A
`
`160
`
`270/1862
`
`
`
`Determine Tg of hydrogenated vinyl aromatic block copolymers by dynamic
`
`mechanical analysis using a rheometer
`
`(e.g., ARES rheometer manufactured by TA
`
`Instruments). Defme Tg by its tan 8 peak measured from a solid state temperature ramp of
`
`linear Viscoelastic spectrum data (storage modulus G',
`
`loss modulus G" and tan8 = G'VG')
`
`between room temperature and 160°C at a temperature ramp rate of 3°C/min and an
`
`oscillatory frequency of 1 radian per second (rad/s). Use a solid rectangular shaped
`
`specimen of approximate 45 millimeter (mm) length, 12.5 mm width and 3.2 mm thickness
`
`for testing. Compression mold test specimens at a temperature of 2500C and a pressure of
`
`approximately 500 pounds per square inch (psi) (3447 kilopascals (KPa) using a standard
`
`compression molder
`
`(e.g., TetrahedronTM 1401 from Tetrahedron Associates
`
`Inc, San
`
`Diego, CA).
`
`Conduct molecular weight analysis of a hydrogenated vinyl aromatic-conjugated
`
`diene block copolymer by subjecting the block copolymer, prior to its hydrogenation, to gel
`
`permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent for the block
`
`copolymer. Calibrate GPC columns using narrow molecular weight polystyrene standards
`
`from Polymer Labs, Inc. The Mn of the standards ranges from 580 g/M to 3,900,000 g/M.
`
`Prepare six standard cocktails that have three or four standards per cocktail, each standard in
`
`the cocktail differing in molecular weight from others in the cocktail by a factor of
`
`approximately ten. Determine peak elution volume of each standard and generate a column
`
`calibration of molecular weight versus elution volume by fitting the narrow standard data
`
`with a 5th order polynomial
`
`fit. Report Mn of pre-hydrogenated block copolymers as
`
`polystyrene-equivalent values.
`
`10
`
`15
`
`20
`
`-9-
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`Test Methods
`
`PCT/U82009/059537
`
`A. Determination of Resistance to Stress Cracking
`
`Use ASTM D638 Type IV (dog bone type) microtensile test specimens and a clamp
`
`equipped with a strain jig that applies a five percent
`
`(5%) strain deformation to each
`
`5
`
`specimen for stress crack testing. Place a clamped specimen into a container that holds a
`
`volume of water sufficient to allow complete sample immersion and fully immerse the
`
`clamped specimen in the water for one week at a set point temperature of 37°C.
`
`Following the one week immersion, remove each clamped specimen from the water
`
`and then remove each specimen from the strain jig, then pat the sample specimen dry using
`
`10
`
`paper towels before subjecting it to tensile testing.
`
`Prescreen specimens for tensile testing by inspecting each dried specimen for visual
`
`defects such as craze lines, stress marks and breakage. Set aside any test specimens that
`
`contain a visual defect. Mount each specimen that lacks visual defects in an Instron machine
`
`and subject
`
`it to ASTM D638 tensile testing. Record strain at break for each tested
`
`15
`
`specimen and compare it to an untreated sample (no strain or immersion in water).
`
`A reduction in elongation strain at break, relative to the untreated sample, of less
`
`than 25% merits a pass rating, with values that approach a reduction of 0% being very
`
`desirable.
`
`B. Determination of Creep Resistance
`
`20
`
`Using test specimens measuring 4 inches (in) (10.2 centimeter (cm)) x 0.5 in (1.3
`
`cm) x 0.030 in (0.08 cm), conduct a three point bending test to characterize a material's
`
`resistance to creep. Die cut the test specimens from compression molded plaques that
`
`measure five (5) inches (in.) (12.7 centimeters (cm)) x 5 in. (12.7 cm) x 0.030 in. (0.08 cm).
`
`Before loading a test specimen onto the testing fixture of an Instron machine, soak the
`
`25
`
`specimen in the water for 30 minutes and then pat the specimen dry using paper towels.
`
`Place each dried test specimen on the Instron machine's two lower loading noses
`
`with a support span of 16 millimeters (mm). Quickly (no more than six (6) seconds between
`
`zero strain and 5% strain deformation) apply a 5% strain deformation to the test specimen,
`
`then allow it to relax over time and record stress relaxation over time. As between two
`
`30
`
`materials, one with a faster stress decay also has a poorer creep resistance. A slower
`
`decaying rate of stress relaxation is desirable for the application.
`
`-10-
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`PCT/U82009/059537
`
`Analyze the stress relaxation data to obtain both initial stress decay rate (171) and long
`
`term stress decay rate (12). As a first step, normalize stress versus time data based upon
`
`measured maximum stress value applied to a test specimen. The stress value typically
`
`reaches a maximum some three to six seconds after starting the stress relaxation test. Fit the
`
`normalized stress (6) versus time (t) (in seconds) data in a second order exponential decay
`
`function:
`
`f
`
`f
`
`6 :A0 +A1exp(-—1)+ A2exp(-—1)
`1
`2
`
`Where, 6 is the normalized stress value from 0 to 1, A0, Ai, A2,Ti and T2 are data fitting
`
`parameters,
`
`10
`
`15
`
`T
`r1--—L,60
`
`T
`2
`3600
`
`13 =
`'
`
`Increasing values for 171 and ”C2 indicate slowing rates of applied stress decay.
`Exl
`
`Compression mold CBC-I at a temperature of 250°C into plaques measuring 5 in
`
`(12.7 cm) x 5 in (12.7 cm) and having a thickness of 0.030 in 0.08 cm). Die cut test
`
`specimens from the plaques. Measure tensile properties of this material with and without
`
`the water immersion described above for determining resistance to stress cracking. Measure
`
`elongation strain at break and stress relaxation in accord with procedures detailed above and
`
`summarize measurements in Table 2 below.
`Ex2
`
`20
`
`Replicate Ex lbut use CBC-2 rather than CBC-I.
`
`Summarize measurements in
`
`Table 2 below
`CEx A
`
`Replicate Ex 1 but use TPU rather than CBC-I. Summarize measurements in Table
`
`25
`
`2 below
`CEx B
`
`Replicate Ex lbut use CBC-3 rather than CBC-I.
`
`Summarize measurements in
`
`Table 2 below
`
`-11-
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`PCT/U82009/059537
`
`Table 2
`
`Ex/CEx
`
`Strain at Break (no
`
`Strain at Break (with
`
`Initial
`
`Long term
`
`immersion/treatment)
`
`immersion/treatment) Stress
`
`Stress
`
`
`
`
`
`
`
`
`(0/0)
`
`240
`
`300
`
`160
`
`20
`
`1
`
`2
`
`A
`
`B
`
`(%)
`
`213
`
`300
`
`187
`
`10
`
`Decay rate Decay
`
`(minutes)
`
`Rate
`
`6.7
`
`nm
`
`4.2
`
`1.7
`
`(hours)
`
`2.2
`
`nm
`
`1.5
`
`1.5
`
`"nm" means not measured
`
`The results in Table 2 show that both initial and long term stress decay rates are
`
`more than 50% slower for CBC-I than for CEx A (TPU). The results also show that not all
`
`CBCs perform equally well in that CEx B (CBC-3, 70 wt% styrene content) with a much
`
`lower elongation strain at break than either CBC-I
`
`(Ex 1) or CBC-2 (Ex 2) at 20% versus,
`
`respectively, 240% and 300%, has a very low strain at break (10%) relative to Ex 1 (240 %)
`
`and a much more rapid initial stress decay rate at 1.7 minutes than either TPU (4.2 minuets)
`
`or CBC-I
`
`(6.7 minutes). The long term stress decay rate of CBC-3 is also more rapid than
`
`CBC-I at 1.5 hours versus 2.2 hours. CBC-I shows an improvement over TPU in terms of
`
`strain at break (before and after immersion) and both initial and long term stress decay rates
`
`while CBC-3 performs worse than TPU in the same properties. On that basis, CBC-I
`
`represents a viable candidate for use in orthodontic applications, but CBC-3 does not. CBC-
`
`2 should also be a viable candidate based on its higher, relative to CBC-I, strain at break.
`
`Based on information and belief, human saliva exposure, especially over extended
`
`periods of time, increases magnitude of performance differences between TPU and CBC.
`
`Ex 3. Silane modified CBC material
`
`In a container, mix three (3) parts by weight (pbw) of liquid vinyltrimethoxysilane
`
`(VTMS) (Dow Corning Z-3600, CAS number 2768-02-7) and 0.08 pbw of liquid 2,5-Di-
`
`tert-butylperoxy-2,5-dimethylhexane (LUPEROXTM 101, Aldrich, CAS number 78-63-7) to
`
`100 pbw CBC-2 resin. Allow the liquids to diffuse and imbibe into the CBC-2 resin at
`
`room temperature (nominally 25 degrees centigrade (0C) overnight (at least 12 hours).
`
`10
`
`15
`
`20
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`PCT/U82009/059537
`
`Feed the container contents into an 18 millimeter (mm) Leistritz ZSE- 18 twin screw
`
`extruder (Leistritz Corporation, Somerville, NJ) equipped with a pelletizer to effect reactive
`
`extrusion compounding of the container contents. The extruder operates at a set point
`
`temperature of 220°C with an extruder output of 5 pounds per hour (lbs/hr) (11 kilograms
`
`5
`
`per hour (kg/hr)).
`
`Place the pellets in a vacuum oven operating at a set point temperature of 90°C
`
`overnight (at least 12 hours) to remove ungrafted silane (VTMS).
`
`Compression mold the compounded, pelletized container contents (also known as
`
`"silane-grafted CBC material" into plaques as in EX 1, but use amold temperature of 220°C
`
`10
`
`rather than 25 00C.
`
`Prepare the plaques for physical property testing by immersing them in an aqueous
`
`dodecylbenzenesulfonic acid solution (10 wt% dodecylbenzenesulfonic acid, based on total
`
`solution weight) heated to a set point temperature of 800C for 72 hours in an effort to
`
`promote siloxanes crosslinking.
`
`15
`
`'The plaques have atensfle n10dulus of 168,000 pounds per squareinch (psD (1158
`
`kilopascals (kPa)) and an average elongation strain at break (with immersion) of 92%. The
`
`plaques have an initial stress decay rate (also known as "short term decay rate") of 6.5
`
`minutes and a long term stress decay rate of 2.1 hours.
`
`EX 3 demonstrates that functionalized CBC polymers are also suitable for the use in
`
`20
`
`orthodontic applications.
`
`-13-
`
`

`

`WO 2010/074789
`67646-WO-PCT
`
`WHAT IS CLAIMED IS:
`
`PCT/U82009/059537
`
`1.
`
`A cyclic block copolymer composition, the composition comprising a
`
`cyclic block copolymer that is a substantially fully hydrogenated Vinyl aromatic-conjugated
`
`diene block copolymer, said substantially fully hydrogenated block copolymer having an
`
`5
`
`elongation strain at break of more than 30% and a modulus that is within a range of from
`
`greater than or equal to 150,000 psi (1034 MPa ) to less than 270,000 psi (1862 MPa), both
`
`elongation strain at break and modulus being determined in accord with American Society
`
`for Testing and Materials (ASTM) Test D638-02a.
`
`2.
`
`The cyclic block copolymer composition of Claim 1, wherein the
`
`10
`
`elongation strain at break is at least 50%.
`
`3.
`
`The cyclic block copolymer composition of Claim 1 or Claim 2,
`
`wherein the block copolymer
`
`is selected from a group consisting of a sequentially-
`
`polymerized pentablock copolymer, a sequentially-polymerized triblock copolymer, a multi-
`
`armed block copolymer, or a coupled block copolymer.
`
`15
`
`4.
`
`The cyclic block copolymer composition of any of Claims 1 through
`
`3, wherein the composition further comprises an amount of at least one other polymer or
`
`copolymer selected from a group consisting of a) hydrogenated Vinyl aromatic-conjugated
`
`diene
`
`block copolymers, b) hydrogenated random Vinyl aromatic-conjugated diene
`
`copolymers, c) hydrogenated Vinyl aromatic homopolymers; d) cyclic olefin polymers, e)
`
`20
`
`and cyclic olefin copolymers., f) non-hydrogenated Vinyl aromatic-conjugated diene block
`
`copolymers, and g) non-hydrogenated random Vinyl aromatic-conjugated diene copolymers.
`
`5.
`
`The cyclic block copolymer composition of any of Claims 1 throu