WO2009064299A1

WO2009064299A1 - Slip-coat compositions and polymeric laminates

Info

Publication number: WO2009064299A1
Application number: PCT/US2007/084835
Authority: WO
Inventors: Eric P. Jourdain; Sunny Jacob
Original assignee: Advanced Elastomer Systems, L.P.
Priority date: 2007-11-15
Filing date: 2007-11-15
Publication date: 2009-05-22

Abstract

Laminates of the present invention include a substrate layer and at least one slip-coat layer. The slip-coat layer has a relatively low coefficient of friction. In one embodiment, the laminate forms at least a portion of a weather seal with the slip-coat making contact with, for example, a movable window of an automobile. In one aspect, the slip-coat includes (i) a high density polyethylene mixture including (a) a first high density polyethylene having a relatively low I2 and (b) a second high density polyethylene having a relatively high I2 (ii) a plastomer; (iii) a styrenic block copolymer; and (iv) a thermoplastic vulcanizate, and optionally (v) a low density polyethylene graft copolymer. In a particular embodiment, fatty acid amide slip agents are absent from the slip-coat composition.

Description

SLIP-COAT COMPOSITIONS AND POLYMERIC LAMINATES

FIELD OF THE INVENTION

[0001] This invention relates to slip-coat compositions and polymeric laminates and weather seals that include these compositions.

BACKGROUND OF THE INVENTION

[0002] Window channels are commonly employed to mate glass to a window frame. These window channels are typically soft, resilient materials that provide structural integrity and often advantageously provide an environmental or acoustical seal. As a result, many window channels are referred to as weather seals. The terms "window channel", "glass-run channel" and "weather seal" are used interchangeably.

[0003] In certain uses, such as in automobiles and the like, the weather seal also provides a surface against which a retractable window can slide and seal. In addition to providing an adequate seal, it is desirable that the weather seal is abrasion resistant and demonstrates a low coefficient friction.

[0004] In one instance, window channels are enhanced with a slip-coat that can include a polymeric film or layer that is applied over a substrate layer, which is typically a rubbery material. For example, US 5,447,671 discloses a weather seal that includes a contacting layer applied to a substrate. The substrate comprises a resilient and flexible synthetic resin or synthetic rubber, and the contacting layer can include a blend of high molecular weight polyethylene (300,000 g/mol) and ultra-high molecular weight polyethylene (1,300,000 g/mol). This patent suggests that the distinct high density polyethylenes result in a rough contacting surface, which ostensibly is believed to reduce friction.

[0005] In order to overcome disadvantages that can be associated with the use of ultra-high molecular weight resins, such as ultra-high molecular weight polyethylenes, US 6,146,739 discloses a glass-run channel that includes a contact part that includes a substrate layer and a slide -resin layer. The substrate layer includes a thermoplastic elastomer (e.g., a blend of a rubber and thermoplastic resin), and the slide-resin layer includes an ultra-high molecular weight polyolefm having an intrinsic viscosity of 7 to 40 dl/g as measured in a solvent at 135°C decalin (which is assumed to include polymers having a weight average molecular weight in excess of 400,000 g/mol, where the equivalency is based upon an empirical assessment of a range of polymers), a polyolefm having an intrinsic viscosity of 0.1 to 5 dl/g as measured in a solvent at 135°C decalin, and a thermoplastic elastomer that includes a rubber and a thermoplastic resin. [0006] Other disclosures of slip-coat-type of compositions include EP 0 095 098 Bl, WO

2002/28965A1, WO 2005/118652, JP 02053849, US H2096 Hl, US 4,894,408, US 4,978,717,

US 5,110,685, US 5,183,613, US 5,159,016, US 5,301,463, US 6,051,655, US 6,541,568, US

6,660,360, US 6,803,398, US 6,989,189, US 7,193,018, US Publication No. 2006/0030667 and

US Publication No. 2005/0261434 Al.

[0007] Despite advancements that have been made thus far in the art, there remains a need to improve weather seals and particularly the slip-coatings of the weather seals. There remains a need to improve the elasticity of these slip-coatings and thus decreasing the problem of cracking of the slip-coats that will allow water leakage and air noise. Further, there remains a need to decrease the amount of slip agents needed in the slip-coatings, which can gradually leach out and cause a breakdown in the weather seal's performance.

SUMMARY

[0008] One aspect of the invention is directed to a laminate comprising (A) a substrate; and

(B) a slip-coat covering at least a portion of the substrate, where the slip-coat comprises: (i) a high density polyethylene mixture comprising (a) a first high density polyethylene having an melt index (I₂, ASTM D-1238, 23O⁰C @ 2.16 kg) of from 0.01 to less than 2.0 dg/min and density greater than 0.940 g/cm³; and (b) a second high density polyethylene having an I₂ of from 2 to 16 dg/min and density greater than 0.940 g/cm³; (ii) a plastomer; (iii) a styrenic block copolymer; and (iv) a thermoplastic vulcanizate.

[0009] Another aspect of the invention is directed to a laminate comprising (A) a substrate; and (B) a slip-coat covering at least a portion of the substrate, where the slip-coat comprises: (i) a high density polyethylene mixture comprising (a) a first high density polyethylene having an I₂ of from 0.01 to less than 2.0 dg/min and density greater than 0.940 g/cm³; and (b) a second high density polyethylene having an I₂ of from 2 to 16 dg/min and density greater than 0.940 g/cm³;

(ii) a plastomer; (iii) a low density polyethylene graft copolymer; (iv) a styrenic block copolymer; and (v) a thermoplastic vulcanizate.

[0010] Insofar as certain ranges of the features of the slip-coat and laminates are described, it is understood that any desirable upper limit of that range can be combined with any desirable lower limit of that range, as disclosed herein, to achieve a preferred range.

DETAILED DESCRIPTION

[0011] Laminates of the present invention include a substrate layer (or "substrate") and a slip-coat layer. The slip-coat layer (or "slip-coat") has a relatively low coefficient of friction. In one embodiment, the laminate forms at least a portion of a weather seal with the slip-coat making contact with, for example, a movable window of an automobile. [0012] In one embodiment, the slip-coat comprises (consists essentially of in one embodiment) (i) a high density polyethylene mixture comprising (consisting essentially of in one embodiment) (a) a "first" high density polyethylene and (b) a "second" high density polyethylene (ii) a plastomer; (iii) a styrenic block copolymer; (iv) a thermoplastic vulcanizate, and optionally (v) a low density polyethylene graft copolymer. In a particular embodiment, fatty acid amides are not present in the slip-coat. In yet another embodiment, ultrahigh molecular weight polyolefms are not present in the slip-coat; ultrahigh molecular weight polyolefms being those possessing an intrinsic viscosity in excess of 6 dl/g and more preferably in excess of 7 dl/g; and/or ultrahigh molecular weight polyolefms possessing a number average molecular weight in excess of 500,000 g/mole and more preferably in excess of 600,000 g/mole. The combination of these components can be referred to as the slip-coat composition or simply the slip-coat. [0013] Thermoplastic vulcanizates — blends of a thermoplastic and an at least partially cured rubber — are well known in the art. The rubber employed to form the thermoplastic vulcanizate is not limited to any one particular rubber. As used herein, "rubber" refers to elastomeric polymers or those polymers that exhibit a glass transition temperature (T₂) of less than 0⁰C, preferably less than -20⁰C, and even more preferably less than -65°C that are able to undergo dynamic vulcanization. The slip-coat compositions described herein include one or more thermoplastic vulcanizates.

[0014] As used herein, "thermoplastic vulcanizate" ("TPV") refers generally to a blend of at least one thermoplastic and at least one rubber that is at least partially cured; a dynamically- vulcanized alloy ("DVA") is one type of TPV. As used herein, the term "dynamic vulcanization" means vulcanization or curing of a curable rubber blended with a thermoplastic resin under conditions of shear at temperatures sufficient to plasticize the mixture and form a thermoplastic vulcanizate, or more specifically, a dynamically-vulcanized alloy. A "fully vulcanized" (or fully cured or fully crosslinked) rubber in which a given percentage range of the crosslinkable rubber is extractable in boiling xylene or cyclohexane, e.g., 5 wt% or less, or 4 wt% or less, or 3 wt% or less, or 2 wt% or less, or 1 wt% or less. The percentage of extractable rubber can be determined by the technique set forth in US 4,311 ,628.

[0015] Useful rubbery polymers preferably contain some degree of unsaturation. Examples of rubbery polymers include olefϊnic elastomeric copolymers, butyl rubber, natural rubber, styrene -butadiene copolymer rubber, butadiene rubber, acrylonitrile rubber, halogenated rubber such as brominated and chlorinated isobutylene-isoprene copolymer rubber, butadiene-styrene- vinyl pyridine rubber, urethane rubber, polyisoprene rubber, epichlolorohydrin terpolymer rubber, and polychloroprene. [0016] The phrase "olefϊnic elastomeric copolymer" refers to rubbery copolymers polymerized from ethylene, at least one α-olefm monomer, and optionally at least one diene monomer. The α-olefms can include, but are not limited to, propylene, 1-butene, 1-hexene, A- methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. The preferred α -olefins are propylene, 1-hexene, 1-octene or combinations thereof. The diene monomers can include, but are not limited to, 5-ethylidene-2-norbornene; 1,4-hexadiene; 5-methylene-2-norbornene; 1,6- octadiene; 5 -methyl- 1,4-hexadiene; 5-vinyl-2-norbornene; 3,7-dimethyl-l,6-octadiene; 1,3- cyclopentadiene; 1 ,4-cyclohexadiene; dicyclopentadiene; or a combination thereof. In the event that the copolymer is prepared from ethylene, α -olefin, and diene monomers, the copolymer can be referred to as a terpolymer or even a tetrapolymer in the event that multiple α-olefϊns or dienes are used.

[0017] The preferred olefϊnic elastomeric copolymers include from 45 to 85 wt%, more preferably from 55 to 75 wt%, still more preferably from 60 to 70 wt%, and even more preferably from 61 to 66 wt% ethylene-derived units based on the weight of the copolymer; and from 0 to 15 wt%, more preferably from 0.5 to 12 wt%, still more preferably from 1 to 10 wt%, and even more preferably from 2 to 8 wt% diene units deriving from diene monomer by weight of the olefϊnic elastomeric copolymers, with the balance including α-olefm units (preferably propylene) deriving from α-olefm monomer. Expressed in mole percent, the preferred terpolymer preferably includes from 0.1 to 5 mole percent, more preferably from 0.5 to 4 mole percent, and even more preferably from 1 to 2.5 mole percent diene units deriving from diene monomer.

[0018] The preferred olefϊnic elastomeric copolymers have a weight average molecular weight (M_w) that is preferably greater than 50,000 g/mole, more preferably greater than 100,000 g/mole, even more preferably greater than 200,000 g/mole, and still more preferably greater than 300,000 g/mole; and the weight average molecular weight of the preferred olefϊnic elastomeric copolymers is preferably less than 1,200,000 g/mole, more preferably less than 1,000,000 g/mole, still more preferably less than 900,000 g/mole, and even more preferably less than 800,000 g/mole. The preferred olefϊnic elastomeric copolymers have a number average molecular weight (M_n) that is preferably greater than 20,000 g/mole, more preferably greater than 60,000 g/mole, even more preferably greater than 100,000, and still more preferably greater than 150,000 g/mole; and the number average molecular weight of the preferred olefϊnic elastomeric copolymers is preferably less than 500,000 g/mole, more preferably less than 400,000 g/mole, still more preferably less than 300,000 g/mole, and even more preferably less than 250,000 g/mole.

[0019] The preferred olefmic elastomeric copolymers can also be characterized by having a pre-vulcanized Mooney viscosity (MI^₁₊₄₎ at 125°C), per ASTM D 1646, of from 50 to 500, and more preferably from 75 to 450. Where higher molecular weight olefmic elastomeric copolymers are employed within the thermoplastic vulcanizates of this invention, these high molecular weight polymers can be obtained in an oil-extended form. These oil-extended copolymers typically include from 15 to 100 phr (per 100 parts rubber) of a paraffinic oil. The Mooney viscosity of these oil-extended copolymers is from 45 to 80, and more preferably from 50 to 70.

[0020] Olefmic elastomeric copolymers, especially so called ethylene-propylene rubbers and ethylene-propylene-diene rubbers ("EPDM") are commercially available under the tradenames Vistalon™ (ExxonMobil Chemical Co., Houston, Texas), Keltan™ (DSM Geleen The Netherlands), Nordel™ IP (Dow Chemical), Nordel MG™ (Dow Chemical), and Buna™ (Lanxess GmbH, Germany).

[0021] The rubber is cured by employing a dynamic vulcanization technique in one embodiment. In such a case, the rubber is vulcanized under conditions of shear and extension at a temperature at or above the melting point of the thermoplastic resin. The rubber is preferably simultaneously crosslinked and dispersed (preferably as fine particles) within the thermoplastic resin matrix, although other morphologies, such as co-continuous morphologies, can exist depending on the degree of cure, the rubber to plastic viscosity ratio, the intensity of mixing, the residence time, and the temperature.

[0022] After dynamic vulcanization, the rubber is in the form of finely-divided and well- dispersed particles of vulcanized or cured rubber within a continuous thermoplastic phase or matrix, although a co-continuous morphology is also possible. In those embodiments where the cured rubber is in the form of finely-divided and well-dispersed particles within the thermoplastic medium, the rubber particles typically have an average diameter that is less than 50 μm, preferably less than 30 μm, even more preferably less than 10 μm, still more preferably less than 5 μm and even more preferably less than 1 μm. In preferred embodiments, at least 50%, more preferably at least 60%, and even more preferably at least 75% of the particles have an average diameter of less than 5 μm, more preferably less than 2 μm, and even more preferably less than 1 μm.

[0023] The rubber within the thermoplastic vulcanizate of the slip-coat is preferably at least partially cured. In one embodiment, the rubber is advantageously completely or fully cured. The degree of cure can be measured by determining the amount of rubber that is extractable from the thermoplastic vulcanizate by using cyclohexane or boiling xylene as an extractant. Preferably, the rubber has a degree of cure where not more than 15 wt%, preferably not more than 10 wt%, more preferably not more than 5 wt%, and still more preferably not more than 3 wt% is extractable by cyclohexane at 23°C as described in US 4,311,628, US 5,100,947 and US 5,157,081. Alternatively, the rubber has a degree of cure such that the crosslink density is preferably at least 4 x 10^'5, more preferably at least 7 x 10^'5, and still more preferably at least 10 x 10'⁵ moles per milliliter of rubber. See Crosslink Densities and Phase Morphologies in Dynamically Vulcanized TPEs, by Ellul et al, 68 RUBBER CHEMISTRY AND TECHNOLOGY, 573- 584 (1995).

[0024] Any curative that is capable of curing or crosslinking the rubber can be used in the dynamic vulcanization. For example, silicon-containing curatives can be employed as disclosed in US 5,936,028. Also, phenolic resins can be employed as disclosed in US 2,972,600, US 3,287,440, US 5,952,452, and US 6,437,030. Peroxide curatives can also be employed as disclosed in US 5,656,693. Where the rubber is a butyl rubber, useful cure systems are described in US 5,013,793, US 5,100,947, US 5,021,500, US 5,100,947, US 4,978,714, and US 4,810,752. [0025] The thermoplastic portion of the thermoplastic vulcanizate can be any thermoplastic known in the art such as propylene-based polymers (60 to 100 wt% propylene derived units), ethylene -based polymers (60 to 100 wt% ethylene derived units), and polyamides. In a preferred embodiment, propylene polymers form the thermoplastic portion of the thermoplastic vulcanizate. The propylene polymers and copolymers include polypropylene homopolymers and copolymers that are formed by polymerizing propylene with one or more of ethylene, 1-butene, 1-hexene, 1-octene, 2-methyl-l-propene, 3-methyl-l-pentene, 4-methyl-l-pentene, 5-methyl-l- hexene, and mixtures thereof. Specifically included are the reactor, impact, and random copolymers of propylene with ethylene or the higher α-olefms, described above, or with C₁₀-C₂₀ diolefms. Comonomer contents for these propylene copolymers will typically be from 1 to 30 wt% of the polymer. Blends or mixtures of two or more polyolefm thermoplastics such as described herein, or with other polymeric modifiers, are also suitable in accordance with this invention. The thermoplastic is preferably a propylene homopolymer or copolymer comprising from 0.1 to 15 wt% ethylene-derived units, most preferably a homopolymer copolymer comprising from 0.5 to 10 wt% ethylene-derived units.

[0026] The preferred propylene polymers and copolymers have a glass transition temperature (Tg) of from -135 to 110⁰C, preferably from -100 to 50⁰C, and even more preferably from -20 to 20⁰C. They can also be characterized by a melt temperature that is from 50⁰C to 180⁰C, preferably from 80 to 180⁰C, and even more preferably from 120 to 180⁰C. These resins can also be characterized by having a melt flow rate (ASTM D-1238, 23O⁰C @ 2.16 kg) that is from 0.005 to 750 dg/min, preferably from 0.01 to 100 dg/min, and even more preferably from 0.10 to 18 dg/min.

[0027] Useful propylene polymers and copolymers can also be characterized as semi- crystalline, crystalline, or crystallizable resins. In one embodiment, they have a crystallinity, as measured by differential scanning calorimetry, of from 10 to 80%, preferably from 20 to 70%, and even more preferably from 30 to 65%.

[0028] In one embodiment, the propylene polymers and copolymers preferably have a weight average molecular weight (M_w) from 200,000 to 700,000 g/mole, and a number average molecular weight (M_n) from 80,000 to 200,000 g/mole. More preferably, these resins have a M_w from 300,000 to 600,000 g/mole and a Mn from 90,000 to 150,000 g/mole. An especially preferred propylene polymer or copolymer includes high-crystallinity isotactic or syndiotactic polypropylene.

[0029] The thermoplastic vulcanizate comprises from 5 to 40 wt% thermoplastic in one embodiment, and from 10 to 30 wt% of the thermoplastic in another embodiment. As is known in the art, the thermoplastic vulcanizate may also include processing oils and other minor components.

[0030] A preferred TPV has a Shore A hardness (ASTM D2240) of from 30 to 120, in one embodiment, and from 35 to 100 in another embodiment, and from 40 to 80 in yet another embodiment; and has an Elongation at Break of from greater than 200 in one embodiment, and greater than 300 in another embodiment, and greater than 400 in yet another embodiment (ASTM D 412). An example of a useful commercial TPV is Santoprene™ 8201-60. [0031] The slip-coat compositions described herein include one or more poly ethylenes described as the "first" high density polyethylene, and one or more polyethylenes described as the "second" high density polyethylene. The "first" high density polyethylene includes polymers having substantially all polymeric units deriving from ethylene. Preferably, at least 90%, more preferably at least 95%, and even more preferably at least 99% of the polymeric units derive from ethylene. In one embodiment, the first high density polyethylene is a polyethylene homopolymer.

[0032] The first high density polyethylene can be characterized by having a weight average molecular weight of from 110,000 to 140,000 g/mole, optionally from 115,000 to 135,000 g/mole, and optionally from 120,000 to 130,000 g/mole, as determined by Gel Permeation Chromatography using polystyrene standards. This first high density polyethylene is also preferably characterized by having a MWD that is less than 12 in one embodiment, and less than

11 in another embodiment, and less than 10 in yet another embodiment, and less than 9 in yet another embodiment, and a MWD of greater than 2.5 in yet another embodiment, and greater than 3.5 in yet another embodiment.

[0033] In one embodiment, the first high density polyethylene possesses a high load melt index (I₂₁, ASTM D-1238 at 190⁰C @ 21.6 kg load) from 5.0 to 20 dg/min, and from 5.0 to 16 dg/min in another embodiment, and from 6.0 to 14.0 dg/min in yet another embodiment.

[0034] In one embodiment, the first high density polyethylene possesses an I₂ that is from

0.01 up to 2.00 dl/g, and from 0.05 to 1.8 dl/g in another embodiment, and from 0.1 to 1.4 dl/g in yet another embodiment.

[0035] The first high density polyethylene is characterized in one embodiment as having a density, as measured per ASTM D4883, of greater than 0.940 g/cm³, and greater than 0.945 g/cm³ in another embodiment; and a density ranging from 0.945 to 0.965 g/cm³ in yet another embodiment, and ranging from 0.948 to 0.958 g/cm³ in yet another embodiment.

[0036] Polymers useful as the first high density polyethylene are commercially available under the tradename HD7960.13 (ExxonMobil Chemical, Houston, TX).

[0037] The "second" high density polyethylene includes polymers having substantially all polymeric units deriving from ethylene. Preferably, at least 90%, more preferably at least 95%, and even more preferably at least 99% of the polymeric units derive from ethylene. In one embodiment, the second high density polyethylene is a polyethylene homopolymer.

[0038] The second high density polyethylene can be characterized by having a weight average molecular weight of from 50,000 to 109,999 g/mole in one embodiment, and from

54,000 to 90,000 g/mole in another embodiment, and from 58,000 to 70,000 g/mole in yet another embodiment. This second high density polyethylene can also be characterized by having a MWD that is less than 12 in one embodiment, and less than 11 in another embodiment, and less than 10 in yet another embodiment, and less than 9 in yet another embodiment, and a MWD of greater than 2.5 in yet another embodiment, and greater than 3.5 in yet another embodiment.

[0039] In one embodiment, the second high density polyethylene possesses an I₂ that is from

2.0 to 16 dg/min, and from 3.0 to 14 dg/min in another embodiment, and from 4.0 to 12 dg/min in yet another embodiment.

[0040] The first high density polyethylene is characterized in one embodiment as having a density, as measured per ASTM D4883, of greater than 0.940 g/cm³, and greater than 0.945 g/cm in another embodiment; and a density ranging from 0.945 to 0.965 g/cm in yet another embodiment, and ranging from 0.948 to 0.958 g/cm in yet another embodiment.

[0041] Polymers useful as the second high density polyethylene are commercially available under the tradename HD6706 (ExxonMobil).

[0042] The compositions of the present invention include one or more plastomers. A plastomer comprises ethylene-derived units and at least one of C3 to Cs α-olefm derived units from 1 wt% to 40 wt% of the plastomer in one embodiment, and from 5 to 35 wt% of the plastomer in another embodiment, and from 5 to 30 wt% of the plastomer in yet another embodiment. More particularly, a plastomer is a copolymer of ethylene-derived units and at least one of non-cyclic mono-olefms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and

4-methyl-l-pentene. However, cyclic mono-olefms and both linear and cyclic dienes can also be used in copolymerization with ethylene to form the plastomer. It is desirable in some applications to use ethylene-α-olefm-diene terpolymers. This is advantageous in that it provides the plastomer with residual unsaturation to allow a functionalization reaction or cross-linking in the rubber phase of the finished product.

[0043] In a preferred embodiment, the plastomer is a copolymer of ethylene derived units and

1-hexene or 1-octene derived units, wherein the 1-hexene or 1-octene derived units are present from 5 to 35 wt% of the plastomer in one embodiment, from 5 to 30 wt% of the plastomer in another embodiment, and from 10 to 28 wt% in another embodiment, and from 15 to 27 wt% in yet another embodiment.

[0044] In one embodiment of the invention, the plastomer has a density in the range of 0.860 to 0.915 g/cm , and a density of from 0.880 to 0.915 g/cm³ in another embodiment, and from 0.865 to 0.915 g/cm in one embodiment, and in the range of from 0.870 to 0.910 g/cm in another embodiment, and in the range of 0.880 to 0.908 g/cm in yet another embodiment, and in the range of 0.880 to 0.906 g/cm in yet another embodiment.

[0045] The I₂ of the plastomer is in the range of from 0.10 to 40 dg/min in one embodiment, and from 0.5 to 10 dg/min in another embodiment, and from 1.0 to 6.0 dg/min in another embodiment, and from 1.5 to 5.0 dg/min in yet another embodiment.

[0046] Desirable plastomers are sold, for example, under the trademark Exact™ (ExxonMobil Chemical Company, Houston, Texas), such as Exact 0203. The invention can also be practiced using Engage™ polymers (also Affinity™ and Versify™; Dow Chemical Company, Midland, Michigan) and Tafmer™ (Mitsui Petrochemical Co.). The propylene-based polymer Vistamaxx™ (ExxonMobil Chemical Co.) may also be used as the one or more plastomers. [0047] In one embodiment, a low density polyethylene graft copolymer ("LDPE graft copolymer") is present in the slip-coat composition. The one or more LDPE graft copolymers contemplated as part of the slip-coat comprises low density polyethylene bound to a functional group either as a side chain or as part of the polyethylene backbone. The functional group can comprise hydroxyls, hydrocarbyls, halogens, ethers, esters, silanes, sulfates, sulfites, phosphates, phosphates, or combination thereof, these groups being bound alone to the LDPE backbone or as part of an alkyl radical. A preferred LDPE graft copolymer is one comprising silane groups. [0048] The slip-coat compositions and laminates described herein are not limited to the method of making the LDPE graft copolymer. The LDPE graft copolymer can be produced by any means known in the art. Examples of such disclosures as US 4,707,517 and GB 1 415 194 teach methods of making such graft copolymers. In a particular embodiment, the LDPE graft copolymer is a copolymer of ethylene-derived units, silane-containing units, and optionally another α-olefm. In another embodiment, the LDPE graft copolymers comprise from 50 to 99 wt% ethylene-derived units based on the weight of the entire low density polyethylene graft copolymers, and from 60 to 90 wt% ethylene-derived units in another embodiment, the remainder being silane-containing units.

[0049] In one embodiment, the LDPE graft copolymer is formed by copolymerizing a silane and at least ethylene. The silane that is used to form the graft copolymer in one embodiment is selected from structures represented by the general formula RR'_nSi(R")₃__n,wherein R is a monovalent organic radical having from 2 to 10 carbon atoms and containing terminal ethylenic unsaturation, said radical being bound to the silicon atom; R' is a monovalent hydrocarbon radical free of unsaturation, and each R" is an alkoxy radical having less than 6 carbon atoms, and n is 0 or 1. In one method of making the LDPE graft copolymer, the silane and ethylene, and optionally another olefin, are copolymerized in the presence of a catalyst to form the graft copolymer containing from 0 to 20 wt% olefm-derived units, and from 1 to 50 wt% silane derived units.

[0050] In another embodiment, the LDPE graft copolymer is made by compounding a low density polyethylene containing functional comonomer units with a silicon oil containing functional end groups, resulting in a low density polyethylene having silicon side chains. [0051] The density of the LDPE graft copolymers ranges from 0.890 to 0.935 g/cm³ in one embodiment, and from 0.910 to 0.930 g/cm³ in another embodiment.

[0052] The melt index (I₂) of the LDPE graft copolymers ranges from 1 to 10 dg/min in one embodiment, and from 1.5 to 9 dg/min in another embodiment, and from 2 to 8 dg/min in yet another embodiment. [0053] Suitable LDPE graft copolymers include Lubotene™ 4003, 4006 and 4009 release and low friction graft polyethylenes (Opatech Corporation).

[0054] The slip-coat composition also includes one or more styrenic block copolymers. The styrenic block copolymers contemplated for use herein are materials having blocks of monoalkenyl arene polymer and blocks of conjugated diene polymer. The polymer blocks have the general configuration:

A-B-A and are arranged such that there are at least two monoalkenyl arene polymer end blocks A and at a least one elastomeric conjugated diene mid block B. These polymer blocks can optionally be hydrogenated to eliminate the unsaturation in the mid block B. The monoalkenyl arene copolymer blocks comprise from 8 to 55 wt% of the block copolymer in one embodiment. [0055] The term "monoalkenyl arene" includes those particular compounds of the benzene series such as styrene and its analogues and homologues including o-methyl styrene and p- methyl styrene, p-tert-butyl styrene, 1,3-dimethyl styrene, p-methyl styrene and other ring alkylated styrenes, particularly ring methylated styrenes, and other monoalkenyl polycyclic aromatic compounds such as vinyl naphthalene, vinyl anthrycene and the like. For the present invention, the preferred monoalkenyl arenes are monovinyl, monocyclic arenes such as styrene and p-methyl styrene, styrene being particularly preferred.

[0056] In certain embodiments the amount of monoalkenyl arene does not exceed 50 wt% of the weight of the copolymer, nor comprise an amount less than 8 wt% of the copolymer. Preferred amounts of monoalkenyl arene in the block copolymer are from 20 to 40 wt%, and more preferably from 25 to 35 wt%. The elastomeric block copolymers are optionally "oil extended" by the addition of a hydrocarbon oil and allows for improved processability. The oils are optionally added to the commercial elastomeric copolymers in amounts of between 10 to 40 wt% by weight of the styrenic block copolymer.

[0057] The block B comprises homopolymers of conjugated diene monomers, copolymers of two or more conjugated dienes, and copolymers of one or more of the dienes with a monoalkenyl arene as long as the blocks B are predominantly conjugated diene units. The conjugated dienes preferably used herein contain from 4 to 8 carbon atoms. Examples of such suitably conjugated diene monomers include: 1,3-butadiene (butadiene); 2-methyl-l,3-butadiene; isoprene; 2,3- dimethyl-l,3-butadiene; 1,3-pentadiene (piperylene); 1,3-hexadiene; combinations thereof, and the like. Hydrogenation of the unsaturated elastomer (Block B) results in a saturated tri-block copolymer (A-B-A). [0058] For the instant laminates, the preferred monoalkenyl arene polymer is polystyrene; and the preferred conjugated diene polymers are polybutadiene and polyisoprene, especially preferred being polybutadiene. Even more preferable are hydrogenated versions of such styrenic block copolymers. Thus, in one embodiment, the styrenic block copolymer is selected from the group consisting of styrene-ethylene-ethylene-propylene-styrene block copolymers and styrene- ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene copolymer and mixtures thereof.

[0059] The styrenic block copolymers useful in the present invention have a Shore A hardness (ASTM D2244) ranging from 20 to 120 in one embodiment, and from 30 to 80 in another embodiment. The molecular weight of the block copolymer is such that its melt index is less than 100 dg/min (ASTM D 1238, 200⁰C @ 5 kg) in one embodiment, and from 1 to 30 dg/min in another embodiment. The preferred elastomeric block copolymers are commercially available as linear tri-block copolymers (A-B-A) from the Kuraray America, Inc., Houston, Tex., under the trade name Septon™ 4044, Septon 4077, Septon 4055; and Kraton™ G-1651H from Kraton Polymers LLC (Houston, TX) and Kraton G2832.

[0060] Fillers that can optionally be included in the slip-coat composition include those reinforcing and non-reinforcing fillers or extenders that are conventionally employed in the compounding of polymeric materials. Useful fillers include carbon black, calcium carbonate, clays, silica, talc, and titanium dioxide.

[0061] Plasticizers, extender oils, synthetic processing oils, or a combination thereof can also be optionally added to the blend. The extender oils can include, but are not limited to, aromatic, naphthenic, and paraffmic extender oils. Exemplary synthetic processing oils are polylinear α- olefins, polybranched α-olefms, and hydrogenated polyalphaolefms. The compositions of this invention can include organic esters, alkyl ethers, or combinations thereof. Polymeric aliphatic esters and aromatic esters were found to be significantly less effective, and phosphate esters were for the most part ineffective. Synthetic polyalphaolefins are also useful in lowering the glass transition temperature (T_g). Commercially available poly-α-olefms that can be useful include Elevast™ A30, and Elevast L30 (ExxonMobil Chemical, Houston). Oligomeric (e.g., Indopol™, BP, Great Britain) and polymeric processing additives can also be used.

[0062] Fatty acid amide slip aids are absent from the slip-coat in one embodiment, meaning that they are not added to the slip-coat compositions of the invention. Exemplary fatty acid amides include lauramide, palmitamide, stearamide and behenamide; unsaturated fatty acid amides such as erucamide, oleamide, brassidamide and elaidamide; and bis-fatty acid amides such as methylene-bis-stearamide, methylene-bis-oleamide, ethylene-bis-stearamide and ethylene-bis-oleamide.

[0063] Other slip aids that can be present in the slip-coat include siloxane polymers, non- amide containing fatty acids, fatty acid triglycerides, esters, fluoropolymers, graphite, molybdenum, silica, boron nitride, silicon carbide, and mixtures thereof.

[0064] Useful siloxane polymers include dialkyl polysiloxanes and silicone oils. Useful dialkyl polysiloxanes include dimethyl polysiloxane, phenylmethyl polysiloxane, fluorinated polysiloxanes, tetramethyltetraphenyltrisiloxane and the hydroxy-functionalized polysiloxanes thereof. Preferred siloxane polymers include those having a weight average molecular weight of from 200 to 500,000 g/mole, preferably from 10,000 to 400,000 g/mole, and more preferably from 100,000 to 380,000 g/mole.

[0065] Useful fatty acids include those obtained from both animal and plant sources, and include both saturated and unsaturated acids. Exemplary saturated fatty acids include butyric acid, lauric acid, palmitic acid, and stearic acid. Exemplary unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, and palymitoleic acid. Triglycerides of these fatty acids can also be employed. In one embodiment, this type of fatty acid is also absent in the slip-coat, meaning that no fatty acids are added or present in the slip-coat.

[0066] Stability-enhancing agents can optionally be included in the slip-coat. These agents include those commonly employed in the art such as antioxidants, UV stabilizers, antiozonants, and biostats.

[0067] The slip-coat includes from 5 to 35 wt% of the first high density polyethylene (based on the weight of the slip-coat composition) in one embodiment, and from 8 to 30 wt% in another embodiment, and from 10 to 26 wt% in yet another embodiment.

[0068] The slip-coat includes from 4 to 30 wt% of the second high density polyethylene (based on the weight of the slip-coat composition) in one embodiment, and from 5 to 25 wt% in another embodiment, and from 6 to 20 wt% in yet another embodiment.

[0069] The slip-coat includes from 10 to 50 wt% of the thermoplastic vulcanizate (based on the weight of the slip-coat composition) in one embodiment, and from 15 to 40 wt% in another embodiment, and from 20 to 35 wt% in yet another embodiment.

[0070] When present, the slip-coat includes from 0.5 to 20 wt% of low density polyethylene graft copolymer (based on the weight of the slip-coat composition) in one embodiment, and from 1 to 18 wt% in yet another embodiment, and from 1.5 to 16 wt% in yet another embodiment, and from 1.5 to 10 wt% in yet another embodiment. [0071] The slip-coat includes from 2 to 20 wt% of styrenic block copolymer (based on the weight of the slip-coat composition) in one embodiment, and from 3 to 18 wt% in another embodiment, and from 4 to 16 wt% in yet another embodiment.

[0072] The slip-coat includes from 10 to 50 wt% of plastomer (based on the weight of the slip-coat composition) in one embodiment, and from 15 to 40 wt% in another embodiment, and from 16 to 35 wt% in yet another embodiment.

[0073] The slip-coat includes from 0 to 16 wt% of carbon black (based on the weight of the slip-coat composition) in one embodiment, and from 1 to 14 wt% in yet another embodiment, and from 2 to 12 wt% in yet another embodiment.

[0074] The slip-coat includes from 0 to 6 wt% of a siloxane (based on the weight of the slip- coat composition) in one embodiment, and from 0.1 to 4 wt% siloxane in another embodiment, and from 0.5 to 3 wt% in yet another embodiment.

[0075] When present, the slip-coat includes from 0.10 to 5 wt% of fatty acid amine (based on the weight of the slip-coat composition) in one embodiment, and from 0.1 to 3 wt% in another embodiment, and from 1 to 2 wt% in yet another embodiment.

[0076] In one embodiment, a composition for forming the slip-coat is prepared by first forming a thermoplastic vulcanizate feed stock that includes the rubber, which is at least partially cured, and the propylene polymer or copolymer resin. The first and second high density polyethylenes, the low density polyethylene graft copolymer, plastomer and the styrenic block copolymer are subsequently added to the thermoplastic vulcanizate to form the slip-coat composition. In one embodiment, the slip-coat can be prepared by extruding the slip-coat composition, preferably in conjunction with the base layer, by using coextrusion techniques. [0077] The high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer are preferably added to the thermoplastic vulcanizate feed stock after the rubber has been sufficiently cured to achieve phase inversion. As those skilled in the art appreciate, dynamic vulcanization can begin by including a greater volume fraction of rubber than thermoplastic resin. As such, the thermoplastic resin is present as the discontinuous phase. As dynamic vulcanization proceeds, the viscosity of the rubber increases and phase inversion occurs. In other words, the thermoplastic resin phase becomes continuous. In one embodiment, the rubber becomes a discontinuous phase. In another embodiment, a co-continuous morphology or pseudo co-continuous morphology can be achieved where both the rubber and the thermoplastic resin are continuous phases. In one embodiment, the high density polyethylenes are added after 50%, preferably 75%, and more preferably 90% of the curative is consumed. In preferred embodiments, the high density polyethylenes and low density polyethylene graft copolymer are added after the curative is completely consumed or full cure has been achieved. [0078] In yet another embodiment, the pre-prepared thermoplastic vulcanizate is simply combined simultaneously or nearly so with the other ingredients. All of the slip-coat ingredients are then melt-blended at from 180 to 220 ⁰C, more preferably from 190 to 210 ⁰C. [0079] In one embodiment, the high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer are added while the thermoplastic vulcanizate is in its molten state; that is, the thermoplastic vulcanizate is at a temperature sufficient to achieve flow of the thermoplastic resin phase. Preferably, the thermoplastic vulcanizate is maintained in its molten state from the time of dynamic vulcanization until the high density polyethylenes are added.

[0080] The addition of the high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer can occur by using a variety of techniques. In one embodiment, each high density polyethylene is sequentially added to the thermoplastic vulcanizate. In other words, the first high density polyethylene can be added, followed by the second high density polyethylene, and ultimately followed by the third high density polyethylene. The order of addition can vary.

[0081] Alternatively, the high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer can be preblended prior to combining them with the already-formed thermoplastic vulcanizate. In one embodiment, the first, second, and third high density polyethylenes can be melt blended and subsequently added to the thermoplastic vulcanizate. This subsequent addition after melt blending can occur in the liquid (molten) or solid state. Alternatively, solid forms (e.g., pellets) of the first and second high density polyethylenes can be preblended or mixed. The subsequent addition of these premixed pellets or powders can occur in the solid or molten state.

[0082] Where the high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer is added to the thermoplastic vulcanizate in the liquid or molten state, the temperature at which the resins are added is in excess of 150⁰C, preferably from 160⁰C to 200⁰C, and even more preferably from 170⁰C to 190⁰C. The liquid or molten addition of the high density polyethylenes can occur by employing a variety of techniques. For example, a single or twin-screw extruder can be used to add the high density polyethylenes (either individually or as a blend) while in the molten state. In one embodiment, where the thermoplastic vulcanizate is prepared in a continuous extruder process, a side extruder downstream of the vulcanization zone can be used to add molten high density polyethylene. [0083] In those embodiments where the high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer (either individually or as a blend) is added in the solid state, various techniques can be employed to add the solid high density polyethylene to the thermoplastic vulcanizate. For example, crammer feeders or pellet feeders can be employed.

[0084] In another embodiment, the high density polyethylenes, LDPE graft copolymer (when present), plastomer and styrenic block copolymer (either individually or as a blend) can be added to or combined with the ingredients used to prepare the thermoplastic vulcanizates prior to dynamic vulcanization of the rubber. In other words, dynamic vulcanization takes place in the presence of not only the propylene polymer or copolymer but also the high density polyethylene blend. In those embodiments where the high density polyethylene blend is present during dynamic vulcanization, the rubber preferably includes an ethylene-propylene-5-vinyl-2- norbornene and the curative is preferably a silicon-containing curative.

[0085] In one embodiment, the slip-coat has a kinetic coefficient of friction, per ASTM D 1894-99 on glass at room temperature, of from less than 1.0 in one embodiment, and from less than 0.90 in another embodiment, and from less than 0.80 in yet another embodiment, and from less than 0.74 in another embodiment, and from less than 0.65 in yet another embodiment, and from less than 0.50 in yet another embodiment, and from less than 0.35 in yet another embodiment, and from less than 0.33 in another embodiment; and from 0.20 to 0.80 in yet another embodiment, and from 0.20 to 0.34 in yet another embodiment, and from 0.22 to 0.30 in yet another embodiment.

[0086] In another embodiment, the slip-coat has a static coefficient of friction per ASTM D 1894-99 on glass at room temperature, of from less than 1.0 in one embodiment, and from less than 0.90 in another embodiment, and from less than 0.80 in yet another embodiment, and from less than 0.74 in another embodiment, and from less than 0.65 in yet another embodiment, and from less than 0.50 in yet another embodiment, and from less than 0.35 in yet another embodiment, and from less than 0.33 in another embodiment; and from 0.20 to 0.80 in yet another embodiment, and from 0.20 to 0.34 in yet another embodiment, and from 0.22 to 0.30 in yet another embodiment.

[0087] In yet another embodiment, the slip-coat has a Shore D hardness of from less than 46, and from less than 43 in another embodiment, and from 10 to 45 in yet another embodiment, and from 10 to 40 in yet another embodiment.

[0088] In yet another embodiment, the slip-coat has a 50% Modulus of less than 13 MPa, and less than 11 MPa in another embodiment, and from 2 to 12 MPa in yet another embodiment, and from 4 to 10 MPa in yet another embodiment; and less than 12 MPa, and less than 10 MPa in another embodiment, and from 2 to 12 MPa in yet another embodiment, and from 4 to 10 MPa in yet another embodiment.

[0089] In yet another embodiment, the slip-coat possesses a Compression Set after 24 hours at 70⁰C under 25% deflection of from 40 to 70%, and from 42 to 65% in another embodiment, and from 45 to 64% in yet another embodiment.

[0090] In yet another embodiment, the slip-coat has an Elongation at Break (or Ultimate

Elongation) that is greater than 200 %, and greater than 250 % in another embodiment, and greater than 300 % in yet another embodiment, and greater than 400 % in yet another embodiment, and from 200 to 900% in yet another embodiment, and from 400 to 850% in yet another embodiment.

[0091] The second layer, which can also be referred to as the substrate or base layer, is preferably prepared from compositions that include at least one polymer characterized by having a glass transition temperature (Tg) that is lower than ambient temperature, preferably less than

0⁰C, more preferably less than -20⁰C, and even more preferably less than -65°C. In preferred embodiments, these compositions include at least one rubbery polymer. In one embodiment, these compositions can include one or more rubbery polymers. In other embodiments, these compositions can include one or more block copolymers that include a soft or rubbery segment (i.e., a segment having a glass transition temperature that is less than 0⁰C). In other embodiments, these compositions can include blends of rubbery polymers together with thermoplastic polymers.

[0092] Useful rubbery polymers include natural or synthetic rubbery polymers. Synthetic rubbery polymers include homopolymers of one or more conjugated dienes and copolymers of conjugated dienes and vinyl aromatics such as styrene. Other useful rubbery copolymers include copolymers of ethylene, propylene, and diene monomers. Examples of such rubbers include EPDM and EPR rubbers. The copolymers include both random copolymers (e.g. styrene- butadiene rubber) as well as block copolymer (e.g. styrene-butadiene-styrene block copolymers (S-B-S) and the hydrogenated derivatives thereof (S-E/B-S)). Useful polymeric blends include thermoplastic vulcanizates, which are blends of cured (either fully or partially) rubber and thermoplastic resins. In one embodiment, the thermoplastic vulcanizate includes cured copolymers of ethylene, propylene, and diene monomers dispersed within a continuous poly α- olefϊn (e.g. polypropylene) phase. In another embodiment, the blends include a poly α-olefϊn (e.g. polypropylene) and a block copolymer (e.g. S-B-S or S-E/B-S). These can include blends of polyolefin with crosslinkable/crosslinked styrenic block copolymers. [0093] Laminates of this invention can be prepared by employing a variety of techniques. In one embodiment, the slip-coat and the substrate are co-extruded to form an integral laminate. In other embodiments, the substrate layer is first prepared by using a variety of techniques including molding or extruding, and then the slip-coat is subsequently extruded onto the substrate. [0094] Although the invention is not particularly limited to any particular thicknesses of the slip-coat upon (or adhered to) the substrate, the thickness of the slip-coat in one embodiment is from 50 μm to 500 μm, more from 60 μm to 300 μm in another embodiment, and from 75 μm to 100 μm in yet another embodiment. The thickness of the substrate layer can vary greatly depending on the construction of the laminate or the glass run channel.

[0095] The substrate being at least partially coated with the slip-coat, preferably through co- extrusion molding, thus forms the laminate. The laminates can be made having any number of profiles such as, for example, a profile that includes a channel for mating an automobile window within the door to keep water and noise out of the interior of the automobile: window channels or weather seals. In a desirable embodiment, only that portion of the substrate (e.g., weather seal substrate) that is contacting the glass window is slip-coated.

[0096] In order to demonstrate the practice of the present invention, the following examples have been prepared and tested. The examples should not, however, be viewed as limiting the scope of the invention. EXAMPLES

[0097] Slip-coat composition with LDPE graft copolymer. The data in Table 1 shows the formulations of inventive compositions 1-9 and one comparative composition ("Comp"). The TPV was Santoprene™ 8201-60 (ExxonMobil Chemical Co.) having a Shore A hardness of 60 and a compression set (ASTM D 412) of 19%; the first HDPE was HD 7960.13 (ExxonMobil Chemical Co.), having an I₂ value of 0.060 dg/min, and I₂₁ of 10.0 dg/min, and density of 0.952 g/cm³; the second HDPE was HD6706.17 (ExxonMobil Chemical Co.) having an I₂ of 6.7 and a density of 0.952 g/cm³; the "high I₂" HDPE was HD6733.17 (ExxonMobil Chemical Co.) having an I₂ of 33 dg/min and a density of 0.950 g/cm³; the styrenic block copolymer ("SBC") was Septon™ 4055 (styrene-ethylene-ethylene-propylene-styrene) having a styrene content of 30 wt%; the plastomer was Exact™ 0203 (ethylene-octene copolymer) with a density of 0.902 g/cm and an I₂ of 3.0; the carbon black is Ampacet™ 19470 carbon black masterbatch, 40 wt% carbon black in 60 wt% LLDPE, I₂ of 20 dg/min and density of 0.92 g/cm³; the siloxane was SiMB 50-314 as a 50 % masterbatch of high molecular weight siloxane having a weight average molecular weight of about 360,000 g/mole, and 50 % HDPE, I₂ of about 60 dg/min; the low density polyethylene graft copolymer is Lubotene™ silane grafted LDPE, having a I₂ of 4 dg/min and density of 0.923 g/cm³, Lubotene 4003 having a dynamic COF of 0.25 (LDPE-graft copolymer A), Lubotene 4006 having a dynamic COF of 0.20 (LDPE-graft copolymer B), Lubotene 4006 having a dynamic COF of 0.15 (LDPE-graft copolymer C), and the fatty acid amide was Kemamide™ E, an erucamide (Crompton).

[0098] The Kemamide is added to the composition to improve (lower) the coefficient of friction (COF). The fatty acid amide typically forms a film on the surface of the extrudate as it is not compatible with the polyolefm/rubber matrix, thus lowering the coefficient of friction of the slip-coat composition. Similarly, the siloxane is added to reduce the COF of the slip-coat. [0099] The components above were melt blended together on a 43 mm twin screw extruder, at temperature of about 180-210⁰C. Pellets were made of this extruded product. Molded plaques were made of this slip-coat composition and its properties measured.

K)

O

[00100] The measured physical properties of inventive compositions 1-9 and the comparative example ("Comp") slip-coat composition with LDPE graft copolymer are in Table 2. Shore D hardness was determined according to ISO 868, which is similar to ASTM D-2240. Ultimate tensile strength, Elongation at break, and 50% modulus were determined according to ISO 527, which is similar to ASTM D-412 at 23⁰C by using an Instron testing machine. Static and kinetic Coefficient of Friction (COF) was determined substantially in accordance with ASTM D 1894-99 by using a Thwing- Albert Friction/Peel Tester Model 225.1. In particular, in the measurement of COF, a 200 g sledge of slip-coat material was placed across window glass at 150 mm/min for 150 mm length; COF is calculated by the machine, based on the resistant force against the movement.

[00101] Compression Set was measured by making a plaque of the slip-coat composition, cutting those into small disk(s), and plying them according ASTM 395B for testing. The test is done in a compression molding jig, the disk(s) compressed to a certain deflection (25%), then released after 24 hours (7O⁰C), then allowed to relax for 30 min at about 21⁰C, and then measuring residual dimension compared to the original. The "molded" Compression Set data refers to the instance when a single button of about Vi inch thickness is tested; whereas "plied" refers to thinner slices of the slip-coat material being stacked to Vi inch thickness. The Compression Set is an indication of elastic recovery, a value between 0 and 100%. Ideally, the lower the Compression Set the better.

K) K)

[00102] Slip-coat composition without LDPE graft copolymer. The data in Table 3 shows the formulations of inventive compositions 10-18 and one comparative composition ("Comp"). The TPV was Santoprene™ 8201-60 (ExxonMobil Chemical Co.) having a Shore A hardness of 60 and a compression set (ASTM D 412) of 19%; the first HDPE was HD 7960.13 (ExxonMobil Chemical Co.), having an I₂ value of 0.060 dg/min, and I₂₁ of 10.0 dg/min, and density of 0.952 g/cm ; the second HDPE was HD6706.17 (ExxonMobil Chemical Co.) having an I₂ of 6.7 and a density of 0.952 g/cm³; the "high I₂" HDPE was HD6733.17 (ExxonMobil Chemical Co.) having an I₂ of 33 dg/min and a density of 0.950 g/cm³; the styrenic block copolymer ("SBC") was Septon™ 4055 (styrene-ethylene-ethylene-propylene-styrene) having a styrene content of 30 wt%; the plastomer was Exact™ 0203 (ethylene-octene copolymer) with a density of 0.902 g/cm³ and an I₂ of 3.0; the carbon black is Ampacet™ 19470 carbon black masterbatch, 40 wt% carbon black in 60 wt% LLDPE, I₂ of 20 dg/min and density of 0.92 g/cm³; the siloxane was SiMB 50-314 as a 50 % masterbatch of high molecular weight siloxane having a weight average molecular weight of about 360,000 g/mole, and 50 % HDPE, I₂ of about 60 dg/min; and the fatty acid amide was Kemamide™ E, an erucamide (Crompton).

[00103] The Kemamide is added to the composition to improve (lower) the coefficient of friction (COF). The fatty acid amide typically forms a film on the surface of the extrudate as it is not compatible with the polyolefm/rubber matrix, thus lowering the coefficient of friction of the slip-coat composition. Similarly, the siloxane is added to reduce the COF of the slip-coat. [00104] The components above were melt blended together on a 43 mm twin screw extruder, at temperature of about 180-210⁰C. Pellets were made of this extruded product. Molded plaques were made of this slip-coat composition and its properties measured.

[00105] The measured physical properties of inventive compositions 10-18 and the comparative example are in Table 4. The test methods are the same as above.

K)

K) Oi

Having been demonstrated as advantageous, aspects of the present invention can be described by the numbered embodiments below:

1. A laminate comprising:

(A) a substrate; and

(B) a slip-coat covering at least a portion of the substrate, where the slip-coat comprises: (i) a high density polyethylene mixture comprising:

(a) a first high density polyethylene having an I₂ of from 0.01 to less than 2.0 dg/min and density greater than 0.940 g/cm³; and

(b) a second high density polyethylene having an I₂ of from 2 to 16 dg/min and density greater than 0.940 g/cm³;

(ii) a plastomer;

(iii) a styrenic block copolymer; and

(iv) a thermoplastic vulcanizate.

2. The laminate of numbered embodiment 1, wherein the slip-coat further comprises a low density polyethylene graft copolymer.

3. The laminate of numbered embodiment 1 and 2, wherein the plastomer has a density of from 0.860 to 0.915 g/cm³.

4. The laminate of any one of the preceding numbered embodiments, wherein the plastomer has a density of from 0.910 to 0.880 g/cm³.

5. The laminate of any one of the preceding numbered embodiments, wherein the plastomer is a copolymer of ethylene and from 1 to 40 wt% of α-olefm wt% of the plastomer, wherein the α-olefm is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1- heptene, 1-octene and combinations thereof.

6. The laminate of any one of the preceding numbered embodiments, wherein the plastomer has an I₂ of from 0.5 to 10 dg/min.

7. The laminate of any one of the preceding numbered embodiments, wherein the styrenic block copolymer is selected from the group consisting of styrene-ethylene-ethylene- propylene-styrene block copolymers and styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene copolymer and mixtures thereof.

8. The laminate of any one of the preceding numbered embodiments, wherein the thermoplastic vulcanizate comprises an at least partially cured rubber selected from the group consisting of olefinic elastomeric copolymers, butyl rubber, natural rubber, styrene- butadiene copolymer rubber, butadiene rubber, acrylonitrile rubber, halogenated rubber such as brominated and chlorinated isobutylene-isoprene copolymer rubber, butadiene - styrene-vinyl pyridine rubber, urethane rubber, polyisoprene rubber, epichlolorohydrin terpolymer rubber, polychloroprene, and mixtures thereof.

9. The laminate of any one of the preceding numbered embodiments, wherein the thermoplastic vulcanizate comprises an at least partially cured olefmic elastomeric copolymers of ethylene, at least one α-olefm monomer, and optionally at least one diene monomer; wherein the α -olefins are selected from the group consisting of propylene, 1- butene, 1-hexene, 4-methyl-l-pentene, 1-octene, 1-decene and combinations; and, if present, the diene monomers are selected from the group consisting of 5-ethylidene-2- norbornene; 1,4-hexadiene; 5-methylene-2-norbornene; 1,6-octadiene; 5-methyl-l,4- hexadiene; 5-vinyl-2-norbornene; 3, 7-dimethyl- 1,6-octadiene; 1,3-cyclopentadiene; 1,4- cyclohexadiene; dicyclopentadiene and combinations thereof.

10. The laminate of any one of the preceding numbered embodiments, wherein the slip-coat has a Shore D hardness of from less than 46 (ASTM 2240).

11. The laminate of any one of the preceding numbered embodiments, wherein the slip-coat has an Elongation at break of from greater than 200% (ASTM D 412).

12. The laminate of any one of the preceding numbered embodiments, wherein the slip-coat further comprises from 1 to 20 wt% of carbon black wt% of the slip-coat.

13. The laminate of any one of the preceding numbered embodiments, wherein the slip-coat possesses a static coefficient of friction (ASTM D 1894-99 on glass at room temperature) of from less than 0.90.

14. The laminate of any one of the preceding numbered embodiments, low density polyethylene graft copolymer is a copolymer of ethylene-derived units, silane-containing units, and optionally another α-olefm.

15. The laminate of any one of the preceding numbered embodiments, wherein fatty acid amide slip agents are absent from the slip-coat.

16. An automobile weather seal formed from the laminate of any one of the preceding numbered embodiments.

17. The laminate of any one of the preceding numbered embodiments, wherein ultrahigh molecular weight polyolefms are absent from the slip-coat.

18. The process of any one of the preceding numbered embodiments, wherein the thermoplastic vulcanizate has a Shore A hardness (ASTM D2240) of from 30 to 120.

19. A process for manufacturing a laminate of any one of the preceding numbered embodiments, the process comprising:

(A) providing the thermoprocessable composition for forming a substrate; (B) preparing a thermoprocessable composition for forming a slip-coat by melt- blending the slip-coat components (i) through (iv);

(C) coextruding the composition for forming the substrate and the composition for forming the slip-coat, thereby forming a laminate including a substrate and a slip- coat covering at least a portion of the substrate.

Another aspect of the invention is directed to the use of a slip-coat composition as a slip- coat layer on a weather seal substrate, the slip-coat comprising: (i) a high density polyethylene mixture comprising:

(b) a second high density polyethylene having an I₂ of from 2 to 16 dg/min and density greater than 0.940 g/cm ;

(ii) a plastomer;

(iii) a styrenic block copolymer; and

(iv) a thermoplastic vulcanizate;

(v) optionally, a low density polyethylene graft copolymer.

Claims

CLAIMSWhat is claimed is:

1. A laminate comprising:

(A) a substrate; and

(ii) a plastomer;

(iii) a styrenic block copolymer; and

(iv) a thermoplastic vulcanizate.

2. The laminate of claim 1, wherein the slip-coat further comprises a low density polyethylene graft copolymer.

3. The laminate of claim 1, wherein the plastomer has a density of from 0.860 to 0.915 g/cm³.

4. The laminate of claim 1, wherein the plastomer has a density of from 0.910 to 0.880 g/cm .

5. The laminate of claim 1, wherein the plastomer is a copolymer of ethylene and from 1 to 40 wt% of α -olefin wt% of the plastomer, wherein the α-olefm is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and combinations thereof.

6. The laminate of claim 1, wherein the plastomer has an I₂ of from 0.5 to 10 dg/min.

7. The laminate of claim 1, wherein the styrenic block copolymer is selected from the group consisting of styrene-ethylene-ethylene-propylene-styrene block copolymers and styrene- ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene copolymer and mixtures thereof.

8. The laminate of claim 1, wherein the thermoplastic vulcanizate comprises an at least partially cured rubber selected from the group consisting of olefinic elastomeric copolymers, butyl rubber, natural rubber, styrene-butadiene copolymer rubber, butadiene rubber, acrylonitrile rubber, halogenated rubber such as brominated and chlorinated isobutylene-isoprene copolymer rubber, butadiene-styrene-vinyl pyridine rubber, urethane rubber, polyisoprene rubber, epichlolorohydrin terpolymer rubber, polychloroprene, and mixtures thereof.

9. The laminate of claim 1, wherein the thermoplastic vulcanizate comprises an at least partially cured olefinic elastomeric copolymers of ethylene, at least one α-olefm monomer, and optionally at least one diene monomer; wherein the α-olefms are selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, 1-octene, 1-decene and combinations; and, if present, the diene monomers are selected from the group consisting of 5-ethylidene-2-norbornene; 1 ,4-hexadiene; 5-methylene-2-norbornene; 1,6- octadiene; 5 -methyl- 1 ,4-hexadiene; 5-vinyl-2-norbornene; 3,7-dimethyl-l,6-octadiene; 1,3- cyclopentadiene; 1 ,4-cyclohexadiene; dicyclopentadiene and combinations thereof.

10. The laminate of claim 1, wherein the slip-coat has a Shore D hardness of from less than 46 (ASTM 2240).

11. The laminate of claim 1 , wherein the slip-coat has an Elongation at break of from greater than 200% (ASTM D 412).

12. The laminate of claim 1, wherein the slip-coat further comprises from 1 to 20 wt% of carbon black wt% of the slip-coat.

13. The laminate of claim 1, wherein the slip-coat possesses a static coefficient of friction (ASTM D 1894-99 on glass at room temperature) of from less than 0.90.

14. The laminate of claim 1, wherein the slip-coat possesses a kinetic coefficient of friction (ASTM D 1894-99 on glass at room temperature) of from less than 0.90.

15. The laminate of claim 1, low density polyethylene graft copolymer is a copolymer of ethylene-derived units, silane-containing units, and optionally another α-olefm.

16. The laminate of claim 1, wherein fatty acid amide slip agents are absent from the laminate.

17. An automobile weather seal formed from the laminate of claim 1.

18. A process for manufacturing a laminate, the process comprising:

(A) providing a thermoprocessable composition for forming a substrate;

(B) preparing a thermoprocessable composition for forming a slip-coat by melt- blending the following components together:

(i) a high density polyethylene mixture comprising:

(a) a first high density polyethylene having an I₂ of from 0.01 to less than 2.0 dg/min and density greater than 0.940 g/cm ; and

(ii) a plastomer;

(iii) a styrenic block copolymer; and

(iv) a thermoplastic vulcanizate.

(C) coextruding the composition for forming the substrate and the composition for forming the slip-coat, thereby forming a laminate including a substrate and a slip-coat covering at least a portion of the substrate.

19. The process of claim 18, wherein a low density polyethylene graft copolymer is also blended with the components (i) - (iv).

20. The process of claim 18, wherein the plastomer has a density of from 0.860 to 0.915 g/cm³.

21. The process of claim 18, wherein the plastomer has a density of from 0.0.910 to 0.880 g/cm³.

22. The process of claim 18, wherein the plastomer has an I₂ of from 0.5 to 10 dg/min.

23. The process of claim 18, wherein the slip-coat has a Shore D hardness of from less than 46 (ASTM 2240).

24. The process of claim 18, wherein the slip-coat has an Elongation at break of from greater than 200% (ASTM D 412).

25. The process of claim 18, wherein the slip-coat further comprises from 1 to 20 wt% of carbon black wt% of the slip-coat.

26. The process of claim 18, wherein the slip-coat possesses a static coefficient of friction (ASTM D 1894-99 on glass at room temperature) of from less than 0.90.

27. The process of claim 18, wherein the slip-coat possesses a kinetic coefficient of friction (ASTM D 1894-99 on glass at room temperature) of from less than 0.90.

28. The process of claim 18, low density polyethylene graft copolymer is a copolymer of ethylene-derived units, silane-containing units, and optionally another α-olefm.

29. The process of claim 18, wherein fatty acid amide slip agents are absent from the slip-coat.

30. The process of claim 18, wherein the thermoplastic vulcanizate has a Shore A hardness (ASTM D2240) of from 30 to 120.