(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property
`Organization
`International Bureau
`
`1111111111111111 IIIIII IIIII 1111111111111111111111111111111111111111 lllll 11111111111111111111111
`
`( 43) International Publication Date
`14 October 2004 (14.10.2004)
`
`PCT
`
`(10) International Publication Number
`WO 2004/087804 Al
`
`(51) International Patent Classification 7:
`23/14, 23/04, C08K 3/00, 5/14, H0lB 7/00
`
`COSL 23/02,
`
`(21) International Application Number:
`PCT /US2004/009501
`
`(22) International Filing Date: 26 March 2004 (26.03.2004)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`English
`
`English
`
`(30) Priority Data:
`60/458,517
`
`28 March 2003 (28.03.2003) US
`
`(71) Applicant (for all designated States except US): DOW
`GLOBAL TECHNOLOGIES INC. [US/US]; Washing(cid:173)
`ton Street, 1790 Building, Midland, Ml 48674 (US).
`
`(72) Inventors; and
`(75) Inventors/Applicants (for US only): WALTHER, Brian,
`W. [US/US]; 630 Highway 332, Lake Jackson, TX 77566
`(US). BAKER, Carl, F. [US/US]; 217 Dewbeny Drive,
`Lake Jackson, TX 77566 (US). BAKER, Sharon, L.
`[US/US]; 217 Dewbeny, Lake Jackson, TX 77566 (US).
`CASSIDAY, Michael, D. [US/US]; 133 Papaya Drive,
`Lake Jackson, TX 77566 (US). DIEHL, Charles, F.
`[US/US]; 119 Dewberry Drive, Lake Jackson, TX 77566
`(US). LIANG, Wenbin [US/US]; 6319 Aspen Cove
`Court, Sugar Land, TX 77479 (US). WRIGHT, David, P.
`[US/US]; 46 Whitby Circle, Somerset, NJ 08873 (US).
`
`(74) Agent: HOPPE, James, T.; The Dow Chemical Company,
`Intellectual Property Section, P.O. Box 1967, Midland, Ml
`48674-1967 (US).
`
`(81) Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,
`CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, Fl,
`GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE,
`KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD,
`MG, MK, MN, MW, MX, MZ, NA, NI, NO, NZ, OM, PG,
`PH, PL, PT, RO, RU, SC, SD, SE, SG, SK, SL, SY, TJ, TM,
`TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, YU, ZA, ZM,
`zw.
`
`(84) Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW),
`Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), Euro(cid:173)
`pean (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, Fl, FR,
`GB, GR, HU, IE, IT, LU, MC, NL, PL, PT, RO, SE, SI, SK,
`TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
`ML, MR, NE, SN, TD, TG).
`
`Published:
`with international search report
`before the expiration of the time limit for amending the
`claims and to be republished in the event of receipt of
`amendments
`
`For two-letter codes and other abbreviations, refer to the "Guid(cid:173)
`ance Notes on Codes and Abbreviations" appearing at the begin(cid:173)
`ning of each regular issue of the PCT Gazette.
`
`---iiiiiiiiiiii
`iiiiiiiiiiii -
`
`Q0
`t--(cid:173)
`QO
`
`--
`--iiiiiiiiiiii
`iiiiiiiiiiii ----
`,....i <
`"" Q
`Q --(cid:173)"" Q
`
`(54) Title: LOW GLOSS THERMOFORMABLE FLOORING STRUCTURE
`
`Schematic of Thermoform Embossability Index (EI) Measurement.
`
`Thermo form
`sheet
`
`0
`(57) Abstract: A novel flooring composition was developed based on a blend comprising: a) an elastomer; b) a random propylene/al(cid:173)
`M pha-olefin copolymer; c) a cross linking agent; and optionally d) a melt strength enhancing polymer. This composition achieves a
`0 unique balance of properties, exhibiting often-conflicting performance requirements. These include low gloss and excellent pattern
`
`: , duplication in embossing, low modulus, minimal odor, excellent grain acceptance and abrasion resistance, while remaining thermo(cid:173)
`;;, formable and maintaining minimal shift in viscosity during recycle.
`
`EX1067
`Yita v. MacNeil
`IPR2020-01139
`
`

`

`WO 2004/087804
`
`PCT/0S2004/009501
`
`LOW GLOSS THERMOFORMABLE FLOORING STRUCTURE
`
`Many polymer-processing methods involve the application of temperature and pressure to a
`
`resin formulation to fabricate a specific part. Examples of such processes include
`
`thermoforming, blow molding, injection molding and overmolding, calendaring, fiber
`
`forming, wire and cable, and extrusion coating. The parts resulting from these processes are
`
`often required to exhibit a variety of often-conflicting properties and thus industry is always
`
`looking for new fonnulations able to exhibit a desired combination of properties for a given
`
`processing method.
`
`A variety of blend compositions have been formulated in an attempt to meet the
`
`requirements of the various molding processes. For instance, US Patent No. 5,639,818
`
`describes a peroxide modified propylene homopolymer/polyethylene blend that exhibit
`
`superior extrusion coating properties, especially increased melt strength and reduced draw
`
`resonance behavior rendering them suitable for a wide variety of applications including
`
`thermoforming, blow molding as well as extrusion coating.
`
`US Patent No. 6,433,062 Bl describes a process for the preparation of a thermoplastic
`
`elastomeric composition by melt kneading an organic peroxide with a mixture of a block
`
`copolymer ( or hydrogenated block copolymer), a non-aromatic softening agent for rubber,
`
`an ethylene homopolymer or copolymer, and a propylene homopolymer or copolymer. The
`
`resulting composition exhibits improved heat deformation resistance, mechanical strength,
`
`moldability and processability.
`
`US Patent No. 6,407,172 Bl describes a composition suitable for thermoforming, which
`
`demonstrates good grain retention and low cost. The composition comprises a mixture of a
`
`propylene homopolymer or copolymer, an ethylene-containing ionomer, a copolymer of
`
`ethylene
`
`and
`
`a glycidyl acrylate, polyethylene, optionally
`
`an uncrosslinked
`
`ethylene/propylene copolymer rubber, and optionally an ethylene alpha-olefin copolymer
`
`elastomer.
`
`US Patent Application Publication No. 2001/0016620 Al describes a crosslinked olefin
`
`thermoplastic composition comprising a crystalline polyolefin, an olefin-based copolymer
`
`rubber, and a paraffinic mineral oil softening agent which after molding results in articles
`
`with improved antifogging properties and high gloss.
`
`-1-
`
`

`

`WO 2004/087804
`
`PCT/0S2004/009501
`
`US Patent No. 6,407,172 B 1 describes thermoplastic polymer alloy composition comprising
`
`a blend of polypropylene, uncrosslinked ethylene copolymer, an ionomeric copolymer of
`
`ethylene and an a,~-unsaturated carboxylic acid, a crosslinking agent and a silicone
`
`elastomer. The compositions are said to be useful for forming interior skin sheets for
`
`applications where low gloss and high scuff resistance are desired.
`
`US Patent No. 6,451,894 Bl describes molded articles made from thermoplastic blends of a
`
`crystalline or semi crystalline polyolefin and a multimodal elastomer of sequentially
`
`polymerized ethylene/alpha olefin monomers. Molded articles made from such blends
`
`exhibit increased paint adherence and improved resistance to fluid as well as higher weld
`
`line strength and low temperature ductility.
`
`US Patent No. 6,506,842 B 1 describes a rheology-modified thermoplastic elastomer
`
`composition. The composition is prepared by peroxide-modification of a melt blend of an
`
`ethylene/alpha-olefin copolymer or a diene-modified ethylene/alpha-olefin copolymer and a
`
`high melting point polymer such as a polypropylene or a propylene/alpha olefin. The
`
`composition is peroxide modified sufficient to result in an increase in solidification
`
`temperature (that is, the temperature of the highest temperature peak endotherm measured
`
`during cooling by differential scanning calorimeter (DSC)) that is at least 10°C greater than
`
`that of the unmodified composition. These compositions have improved heat resistance and
`
`thus must be processed at higher temperatures.
`
`Finally, US Patent Application Publication No. 2002/0115796 Al describes thermoplastic
`
`elastomer compositions comprising a melt blend of an ethylene/alpha-olefin copolymer and
`
`a high melting point polymer such as a polypropylene or a propylene/alpha which is
`
`rheology modified using a combination of a peroxide and free radical coagents. The use of
`
`the coagent is said to increase the melt toughness and high temperature tensile properties as
`
`compared to the same compositions, which are rheology modified by peroxides alone.
`
`Thermoforming is another of the family of processes that deal with the pressing or
`
`squeezing of pliable plastic into a final shape, and is the general term used for the process of
`
`making plastic parts from a flat sheet of plastic, through the application of pressure and
`
`temperature. However, thennoforming is differentiated from extrusion or blow molding, as
`
`in the former, the initial resin state is fluid rather than solid, whereas thermoforming always
`
`begins with a contiguous sheet of rubbery plastic. This sheet has been processed from resin
`
`-2-
`
`

`

`WO 2004/087804
`
`PCT/0S2004/009501
`
`pellets or powder by casting, calendaring, rolling, extruding, compression molding or other
`
`techniques. The thermoforming process is a result of four subsequent steps, namely; 1)
`
`heating the sheet, 2) stretching it; 3) cooling it on the mold surface; and 4) trimming the
`
`resulting part from its surroundings
`
`These deformation processes must occur while the polymer is in a rubbery solid state that is,
`
`above its glass transition temperature (Tg) but below its crystalline melting temperature
`
`(Tm) allowing easy uptake of the mold configuration. Thus the glass transition temperature,
`
`Tg, is the absolute lowest temperature at which the polymer can be formed. As processing
`
`temperatures increase above· Tg, amorphous polymers become increasingly easier to
`
`process, but in crystalline polymers, the crystallite order restricts amorphous phase chain
`
`morphology, until the melting point is reached. Thus the normal thermoforming or
`
`"forming" temperature for an amorphous polymer is closely related to Tg, but for crystalline
`
`polymers the forming temperature is more dependent on the Tm. Typically, for single
`
`component amorphous materials, the lower forming temperature is about 20-30°C above Tg,
`
`and the normal forming temperature is 70-100°C above Tg.
`
`In contrast, the forming
`
`temperature range for crystalline polymers is quite narrow and the recommended forming
`
`temperature is often within a few degrees of the polymer Tm.
`
`Once the plastic sheet is at the proper thermoforming temperature it can be stretched. The
`
`various thermoplastic sheet-forming techniques include, vacuum forming, pressure forming,
`
`matched mold forming, all of which require clan1ping, heating and shaping the sheet into or
`
`over a mold. Before forming, the heated sheet is virtually stress free. When properly
`
`formed, the sheet is almost completely stretched at the fom1ing temperature before it is
`
`cooled against the mold. This results in a minimum of internal stress in the finished part.
`
`In order to be readily formable, the heated sheet, when at forn1ing temperature, must have
`
`certain physical properties including high melt strength, over a broad temperature range.
`
`The physical properties and melt strength of some thermoplastic polymers can be improved
`
`by the use of crosslinking agents, including peroxide and irradiation. A small amount of
`
`crosslinking serves to partially immobilize the polymer while above its traditional melting
`
`point by the introduction of a small amount of ultra high molecular weight material within
`
`the bulk polymer matrix resulting in an increase in the low shear viscosity and storage
`
`modulus. Thus, instead of becoming fluids above their melting points, lightly crosslinked
`
`thermoplastics remain soft thermoformable solids extending the range of the thermoforming
`
`-3-
`
`

`

`WO 2004/087804
`
`PCT/US2004/009501
`
`temperature for such materials. However, too high a degree of crosslinking restricts the type
`
`of gross deformation required for successful thermoforming.
`
`In addition to having the necessary strength requirements for molding the heated sheet,
`
`many applications require the resulting article to be embossed and also exhibit a specific
`
`gloss level. The degree of gloss can be regulated to some degree by the processing
`
`conditions such as extrudate or sheet temperature. Low gloss usually results from low
`
`extrudate or sheet temperature. In addition, while remaining relatively constant up to a
`
`certain thermoforming temperature, above this temperature, gloss begins to increase
`
`exponentially with further temperature increase. However, embossability increases much
`
`more linearly across the same temperature range.
`
`The introduction of crosslinking in a polymer causes a decrease in the level of gloss of a
`
`finished part as a small amount of ultra high molecular weight material within the bulk
`
`polymer matrix causes distortions in the surface on cooling which in turn leads to a lower
`
`s'urface gloss. These distortions are due to the increased relaxation time of the ultra high
`
`molecular weight fraction relative to the bulk polymer matrix.
`
`Flooring applications such as automotive flooring mats and liners have historically required
`
`the use of polymer compositions that exhibit both good thermoformability and excellent
`
`embossing pattern retention. Furthermore, such applications also generally require low
`
`surface gloss of the flooring for aesthetics and non-marking performance attributes.
`
`Recently, industry has developed the additional needs that such compositions also exhibit
`
`improved softer hand feel.
`
`To date, typical polymer formulations used for such applications are made primarily of
`
`thermoplastic polyolefin (TPO) with polypropylene as the major component of the
`
`polymeric blend. Polypropylene is used as it has good abrasion resistance and thermal
`
`dimensional stability (that is, very important in automotive applications, which often require
`
`a high temperature dimensional stability and abrasion resistance). Flooring that is
`
`thermoformed from such compositions typically exhibit good thermoformability with
`
`excellent embossability. However, the flooring has relatively high stiffness.
`
`Therefore it would be highly advantageous if new polymer compositions could be
`
`discovered which typically exhibit good thermoformability and excellent embossability and
`
`also exhibit low surface gloss for aesthetics and non-marking performance attributes.
`
`-4-
`
`

`

`WO 2004/087804
`
`PCT/US2004/009501
`
`The present invention relates to thermoplastic polymer compositions, articles made from
`
`such compositions, which exhibit the often-conflicting performance requirements of low
`
`gloss and excellent pattern duplication in embossing, while also exhibiting low modulus,
`
`minimal odor issues, excellent grain acceptance and abrasion resistance and maintained
`
`minimal shift in viscosity during recycle. While applicable to all molding and other
`
`processes requiring low gloss, the compositions of the present invention are especially
`
`suitable for thermoforming due to the range of processing temperatures used relative to the
`
`onset of high gloss. In addition, the ability to control gloss and embossability is especially
`
`important for thermoforming, which has no opportunity for additional process steps to
`
`reduce gloss other than polymer composition or temperature variation within the
`
`thermoforming window.
`
`Novel :flooring compositions have been developed based on a blend comprising; A) an
`
`elastomer; B) a random propylene/alpha-olefin copolymer; C) a cross linking agent; and
`
`optionally D) a melt strength enhancing polymer. This composition achieves a unique
`
`balance of properties. The final blend composition surprisingly exhibits the often-conflicting
`
`performance requirements of low gloss and excellent pattern duplication in embossing,
`
`while also exhibiting low modulus, minimal odor issues, excellent grain acceptance and
`
`abrasion resistance and maintained minimal shift in viscosity during recycle remaining
`
`thermoformable.
`
`The cross linking agent generates a small amount of ultra high molecular weight material
`
`which increases its storage modulus and its low shear viscosity allowing the polymer to
`
`remain rubbery, at a given forming temperature. In addition the ultra high molecular weight
`
`material's increased relaxation time (relative to the bulk matrix) caused distortions in the
`
`polymer surface on cooling also leading to lower gloss.
`
`Thus the incorporation lower melting point random propylene/alpha olefin copolymer in the
`
`blend compositions of the present invention lowers the overall melting point, which in turn
`
`allows the use of lower thermoforming temperatures, (that is, lower than that temperature at
`
`which the gloss begins to increase exponentially). This along with the incorporation of
`
`peroxide into these compositions, which also reduces gloss, allows the preparation of
`
`embossed parts, which exhibit low gloss and excellent embossability, as well as excellent
`
`physical properties, including good abrasion and heat resistance.
`
`-5-
`
`

`

`WO 2004/087804
`
`PCT/US2004/009501
`
`DESCRIPTION OF THE DRAWINGS
`
`Figure 1 shows position of a thermoform template, with regular raised cross sections of 0.87
`
`mm height throughout the template, in the bottom of the flat female mold. The screen did
`
`not cover the entire area of the thermoformed part.
`
`Figure 2 shows how embossability can be expressed by thermoforming a sheet sample over
`
`an edge with 90° angle. The measurement of embossability uses the ratio of the height of
`
`the sheet at the mid point of the raised emboss pattern divided by the distance from this
`
`point to the location at which the sheet returns to the base.
`
`Definitions
`
`Any numerical values recited herein include all values from the lower value to the upper
`
`value in increments of one unit provided that there is a separation of at least 2 units between
`
`any lower value and any higher value. As an example, if it is stated that the amount of a
`
`component or a value of a process variable such as, for example, temperature, pressure, time
`
`is from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that
`
`values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this
`
`specification. For values which are less than one, one unit is considered to be 0.0001,
`
`0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended
`
`and all possible combinations of numerical values between the lowest value and the highest
`
`value enumerated are to be considered to be expressly stated in this application in a similar
`
`manner.
`
`The tem1 "polymer" as used herein refers to a polymeric compound prepared by
`
`polymerizing monomers whether of the same or a different type. The generic term polymer
`
`thus embraces the term homopolymer, usually employed to refer to polymers prepared from
`
`only one type of monomer, and the term interpolymer as defined hereinafter.
`
`The term "interpolymer" as used herein refers to polymers prepared by the polymerization
`
`of at least two different types of monomers. The generic term interpolymer thus includes
`
`copolymers, usually employed to refer to polymers prepared from two different monomers,
`
`and polymers prepared from more than two different types of monomers.
`
`Statements herein that a polymer or interpolymer comprises or contains certain monomers,
`
`mean that such polymer or interpolymer comprises or contains polymerized therein units
`
`-6-
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`

`

`WO 2004/087804
`
`PCT/0S2004/009501
`
`derived from such a monomer. For example, if a polymer is said to contain ethylene
`
`monomer, the polymer will have incorporated in it an ethylene derivative, that is, -CH2-
`
`The term "monomer residue" or "polymer units derived from such monomer" means that
`
`portion of the polymerizable monomer molecule, which resides in the polymer chain as a
`
`result of being polymerized with another polymerizable molecule to make the polymer
`
`chain.
`
`Component A - Elastomer
`
`The elastomers, which can be employed as Component A include, but are not, limited to
`
`homogeneously- or heterogeneously-branched ethylene/alpha olefin elastomers and
`
`plastomers.
`
`The terms "heterogeneous" and "heterogeneously branched" are used in the conventional
`
`sense, and refer to a linear ethylene interpolymer where (1) the a-olefin comonomer is not
`
`randomly distributed within a given polymer molecule, (2) substantially all of the polymer
`
`molecules do not have the same ethylene-to-comonomer ratio, and (3) the interpolymer
`
`typically exhibits a measurable high density (crystalline) polymer fraction as measured by
`
`known fractionation techniques such as, for example, a method that involves polymer
`
`fractional elution as a function of temperature. Commercial examples of heterogeneously
`
`
`
`branched linear interpolymers include ATTANE'1' ULDPE polymers (a product and
`
`trademark of The Dow Chemical Company) and FLEXOMER™ VLDPE polymers (a
`
`product and trademark of Union Carbide Corporation, a Subsidiary of The Dow Chemical
`
`Company).
`
`The terms "homogeneous" and "homogeneously-branched" means that in an ethylene/a.(cid:173)
`
`olefin interpolymer (1) the a-olefin comonomer is randomly distributed within a given
`
`polymer molecule, (2) substantially all of the polymer molecules have the same ethylene-to(cid:173)
`
`comonomer ratio, and (3) the interpolymer essentially lacks a measurable high density
`
`(crystalline) polymer fraction as measured by known fractionation techniques such as, for
`
`example, a method that involves polymer fractional elution as a function of temperature.
`
`-7-
`
`

`

`WO 2004/087804
`
`PCT/0S2004/009501
`
`The homogeneously branched ethylene interpolymers that can be used in the practice of this
`
`invention
`
`include
`
`linear ethylene
`
`interpolymers, and substantially
`
`linear ethylene
`
`interpolymers.
`
`Included amongst the homogeneously branched linear ethylene interpolymers useful as
`
`elastomers in the compositions of the present invention are ethylene polymers which do not
`
`have long chain branching, but do have short chain branches derived from the comonomer
`
`polymerized into the interpolymer which are homogeneously distributed both within the
`
`same polymer chain and between different polymer chains. That is, homogeneously
`
`branched linear ethylene interpolymers have an absence of long chain branching just as is
`
`the case for the linear low density polyethylene polymers or linear high density polyethylene
`
`polymers made using uniform branching distribution polymerization processes as described,
`
`for example, by Elston in USP No. 3,645,992. Commercial examples of homogeneously
`
`branched linear ethylene/a-olefin interpolymers include TAFMER ™ polymers supplied by
`
`the Mitsui Chemical Company and EXACT™ polymers supplied by Exxon Chemical
`
`Company.
`
`The substantially linear ethylene interpolymers used in the present invention are described in
`
`US Patent Nos. 5,272,236 and 5,278,272, 6,054,544 and 6,335,410 Bl, the entire contents
`
`of all of which are herein incorporated by reference. The substantially linear ethylene
`
`interpolymers useful as elastomers in the compositions of the present invention are those in
`
`which the comonomer is randomly distributed within a given interpolymer molecule and in
`
`which substantially all of the interpolymer molecules have the same ethylene/comonomer
`
`ratio within
`
`that
`
`interpolymer.
`
`Substantially
`
`linear ethylene
`
`interpolymers are
`
`homogeneously branched ethylene polymers having long chain branching. The long chain
`
`branches have the same comonomer distribution as the polymer backbone and can have
`
`about the same length as the length of the polymer backbone. "Substantially linear" means
`
`that the bulk polymer is substituted, on average, with 0.01 long chain branches/1000 total
`
`carbons (including both backbone and branch carbons) to 3 long chain branches/1000 total
`
`carbons. Preferred polymers are substituted with 0.01 long chain branches/1000 total
`
`carbons to I long chain branch/1000 total carbons, more preferably from 0.05 long chain
`
`branches/I 000 total carbons to I long chain branch/I 000 total carbons, and especially from
`
`0.3 long chain branches/1000 total carbons to I long chain branch/1000 total carbons.
`
`Commercial examples of substantially linear polymers include the ENGAGE™ polymers
`
`-8-
`
`

`

`WO 2004/087804
`
`PCT/0S2004/009501
`
`(available from DuPont Dow Elastomers L.L.C.), and AFFINITY™ polymers (available
`
`from The Dow Chemical Company).
`
`Suitable unsaturated comonomers useful for polymerizing with ethylene to prepare suitable
`
`heterogeneously- or homogeneously-branched linear ethylene interpolymers include, for
`
`example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes,
`
`polyenes, etc. Examples of such comonomers include the C3-C20 a-olefins such as
`propylene, isobutylene, I-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-
`
`nonene, 1-decene, and the like. Preferred comonomers include propylene, 1-butene, 1-
`
`hexene, 4-methyl-1-pentene and 1-octene, with octene-1 being especially preferred. Other
`
`suitable monomers include styrene, halo-or-alkyl-substituted styrenes, tetrafluoroethylenes,
`
`vinylbenzocyclobutanes, butadienes, isoprenes, pentadienes, hexadienes, octadienes and
`
`cycloalkenes, for example, cyclopentene, cyclohexene and cyclooctene. Typically and
`
`preferably, the heterogeneously- or homogeneously-branched linear ethylene interpolymer is
`
`a copolymer in which ethylene is copolymerized with one C3-C20 a-olefin. Most preferably,
`
`the heterogeneously- or homogeneously-branched linear ethylene interpolymer is a
`
`copolymer of ethylene and 1-octene or a copolymer of ethylene and I-butene.
`
`Also included as elastomer component of the compositions of the present invention are the
`
`substantially random interpolymers comprising polymer units derived from one or more a(cid:173)
`
`olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or a hindered
`
`aliphatic or cycloaliphatic vinyl or vinylidene monomers). The substantially random
`
`interpolymers include the pseudo-random interpolymers as described in EP-A-0,416,815 and
`
`EP-A-0,765,888 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J.
`
`Timmers. The substantially random interpolymers also include the substantially random
`
`terpolymers as described in US Patent No. 5,872,201. Also suitable are the substantially
`
`random interpolymers, which comprise at least one a-olefin/vinyl aromatic/vinyl aromatic/a.(cid:173)
`
`olefin tetrad disclosed in US Patent No. 6,191,245 Bl.
`
`The substantially random interpolymers can be prepared by polymerizing a mixture of
`
`polymerizable monomers in the presence of one or more metallocene or constrained geometry
`
`catalysts in combination with various cocatalysts. Preferred operating conditions for the
`
`polymerization reactions are pressures from atmospheric up to 3000 atmospheres and
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`-9-
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`temperatures from-30°C'to 200°C. Examples of processes used to prepare the substantially
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`random interpolymers are described in US Patent Nos. 6,048,909 and 6,231,795 B 1.
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`Exampies of suitable catalysts and methods for preparing the substantially random
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`interpolymers are disclosed in EP-A-0,416,815; EP-A-514,828 (US Patent No.6,118,013);EP(cid:173)
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`A-520,732 (US Patent No. 5,721,185); as well as U.S. Patents: 5,055,438; 5,057,475;
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`5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696; and
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`5,399,635; 5,470,993; 5866,704; 5,959,047; 6150,297; and 6,015,868.
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`Also included as the elastomer component of the compositions of the present invention are
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`ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), and ethylene/acrylic acid
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`(EAA) copolymers, rubbers such as polyisoprene, ethylene/octene, polybutadiene, natural
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`rubbers, ethylene/propylene and propylene/ethylene rubbers, ethylene/prowlene diene
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`(EPDM) rubbers, silicone rubbers, styrene/butadiene rubbers and thermoplastic
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`polyurethanes. The elastomer can also be a styrenic block copolymer such SBS, SIS, SEBS,
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`CPE, buna rubber, and nitriles.
`
`More preferred elastomers as Component A of the present invention are the ethylene/alpha
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`olefin and ethylene/vinyl aromatic monomer interpolymers, with the ethylene/butene, and
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`ethylene/octene heterogeneously- or homogeneously-branched linear ethylene interpolymers
`
`and ethylene/styrene substantially random interpolymers being the most preferred.
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`Component B - Random Propylene/alpha-Olefin Copolymer
`
`Component B is a random propylene/alpha-olefin copolymer. Preferred are propylene/C2-
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`C20 alpha olefin copolymers, Examples of such C2-C20 a-olefins ( excluding propylene)
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`include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene,
`
`and the like. Preferred comonomers include ethylene, I-butene, 1-hexene, 4-methyl-1-
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`pentene and 1-octene, with random propylene/ethylene, propylene/butene, propylene/hexene
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`and propylene/octene copolymers being more preferred and random propylene/ethylene
`
`copolymers being most preferred. The random propylene/alpha olefin copolymer may also
`
`be used as a blend with homopolymer polypropylene in the formulations of the present
`
`invention. If used as a blend with propylene homopolymer the random propylene/alpha
`
`olefin copolymer component must be present in said blend in an amount greater than 50,
`
`preferably greater than 60, more preferably greater than 70 weight percent, (based on the
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`combined weight of propylene homopolymer and copolymer).
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`Component C - Crosslin.king Agent
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`Suitable crosslinking agents include peroxides, phenols, azides, aldehyde-amine reaction
`
`products, substituted ureas, substituted guanidines; substituted xanthates; substituted
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`dithiocarbamates;
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`sulfur-containing
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`compounds,
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`such
`
`as
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`thiazoles,
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`imidazoles,
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`sulfonamides, thiuramidisulfides, paraquinonedioxime, dibenzoparaquinonedioxime, sulfur;
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`silanes, ebeam radiation, and combinations thereof. See Encyclopedia of Chemical
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`Technology, Vol. 17, 2nd edition, Interscience Publishers, 1968; also Organic Peroxides,
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`Daniel Seem, Vol. 1, Wiley-Interscience, 1970).
`
`Suitable peroxides include aromatic diacyl peroxides; aliphatic diacyl peroxides; dibasic
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`acid peroxides; ketone peroxides; alkyl peroxyesters; alkyl hydroperoxides (for example,
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`diacetylperoxide; dibenzoylperoxide; bis-2,4-dichlorobenzoyl peroxide; di-tert-butyl
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`peroxide; dicumylperoxide; tert-butylperbenzoate; tert-butylcumylperoxide; 2,5-bis (t(cid:173)
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`butylperoxy)-2,5-dimethylhexane; 2,5-bis (t-butylperoxy)-2,5-dimethylhexyne-3; 4,4,4' ,4'(cid:173)
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`tetra-(t-butylperoxy)-2,2-dicyclohexylpropane;
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`1,4-bis-(t-butylperoxyisopropyl)-benzene;
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`1, 1-bis-( t-buty lperoxy )-3 ,3 ,5-trimethy lcyclohexane;
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`lauroy 1 peroxide;
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`succinic
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`acid
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`peroxide; cyclohexanone peroxide; t-butyl peracetate; butyl hydroperoxide; etc. It is also
`
`known to those skilled in the art that the choice of peroxide will also seek to minimize any
`
`odor in the resulting final part.
`
`Suitable phenols are disclosed in USP 4,311,628. One example of a phenolic crosslinking
`
`agent is the condensation product of a halogen substituted phenol or a C1-C10 alkyl
`
`substituted phenol with an aldehyde in an alkaline medium, or by condensation of
`
`bifunctional phenoldialcohols. One such class of phenolic crosslinking agents is dimethylol
`
`phenols substituted in the para position with C5-C10 alkyl group(s). Also suitable are
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`halogenated alkyl substituted phenol crosslinking agents, and crosslinking systems
`
`comprising methylol phenolic resin, a halogen donor, and a metal compound.
`
`Suitable azides include azidoformates, such as tetramethylenebis(azidoformate) (see, also,
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`USP 3,284,421, Breslow, Nov. 8, 1966); aromatic polyazides, such as 4,4'-diphenylmethane
`
`diazide (see, also, USP 3,297,674, Breslow et al., Jan. 10, 1967); and poly(sulfonyl azides)
`
`which are any compound having at least two sulfonyl azide groups (-SO2N3) reactive with
`
`the polymer or polymer blend. Preferably the poly(sulfonyl azide)s have a structure X-R-X
`
`wherein each X is SO2N3 and R represents an unsubstituted or inertly substituted
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`hydrocarbyl, hydrocarbyl ether or silicon-containing group, preferably having sufficient
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`carbon, oxygen or silicon, preferably carbon, atoms to sep