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    • 专利摘要:
    oil-diluted block olefinic copolymer composition and molded oil-diluted block olefinic copolymer composition, oil-diluted block olefinic copolymer compositions with low or no tackiness are disclosed. the unique comonomer content in the soft segment of the obs together with the presence of a polyolefin provides the present obc composition diluted in oil, with softness, low (or no) tackiness, and low (or no) oil drainage.
    公开号:BR112012031996B1
    申请号:R112012031996-5
    申请日:2011-06-14
    公开日:2021-04-06
    发明作者:Ashish Batra；Dana Breed；Pradeep Jain；José Rego；Robert Johnston；Alec Wang；Jeffrey C. Munro
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    [0001] [0001] Olefinic block copolymers (OBCs) are useful for producing soft compounds such as soft touch articles. OBCs find application in soft compounds such as overmolded cables because the OBC block architecture results in good tensile strength, compression deformation and temperature resistance. To prepare soft compositions (that is, compositions with a low durometer value and / or a low Shore A hardness value), OBCs are mixed with an oil. However, when exposed to high temperatures, these oil-diluted compositions can exhibit stickiness. Stickiness is problematic because it produces undesirable touch sensitivity (adhesion) and / or undesirable surface appearance in articles made with these compounds.
    [0002] [0002] There is a need for OBC compositions diluted in oil with low or no tackiness. There is still a need for an OBC composition diluted in oil with low or no tackiness when exposed to high temperatures for an extended period of time. Summary of the invention
    [0003] [0003] The present invention relates to OBC compositions diluted in oil with low or no tackiness. The unique comonomer content in the soft segment of OBS together with the presence of a polyolefin and a filler provides the present OBC compositions diluted in oil, with little or no tackiness.
    [0004] [0004] In an embodiment, an olefinic block copolymer composition diluted in oil is provided which includes an olefinic block copolymer. The block olefinic copolymer contains hard segments and soft segments. The soft segments include comonomer content of about 9 mol% to less than 15 mol%. The composition also includes an oil, one or more polyolefins, and a filler. The composition has, after exposure to 70 ° C for one week, the following properties: (I) a tackiness force of less than 0.1 N, and (II) a Shore A hardness of about 40 to about 90.
    [0005] [0005] The present disclosure provides another composition. In one embodiment, an oil-diluted block olefinic copolymer composition is provided that includes an block olefinic copolymer. The block olefinic copolymer contains hard segments and soft segments. The soft segments include comonomer content of about 9 mol% to less than 15 mol%. The composition also includes an oil, one or more polyolefins, and a filler.
    [0006] [0006] The composition has, after exposure to 70 ° C for one week, the following properties: (I) a standard oil drainage index of less than 50, and (II) a Shore A hardness of about 40 to about 90.
    [0007] [0007] The present disclosure provides another composition. In one embodiment, an oil-diluted block olefinic copolymer composition is provided that includes an block olefinic copolymer. The block olefinic copolymer contains hard segments and soft segments. The soft segments include comonomer content of about 9 mol% to less than 15 mol%. The composition also includes an oil, one or more polyolefins, and a filler. The composition has, after exposure to 70 ° C for one week, the following properties: (I) a tackiness force of less than 0.013 N, and (II) a Shore A hardness of about 40 to about 90.
    [0008] [0008] The present disclosure provides another composition. In one embodiment, an oil-diluted block olefinic copolymer composition is provided that includes an block olefinic copolymer. The block olefinic copolymer contains hard segments and soft segments. The soft segments include comonomer content of about 9 mol% to less than 15 mol%. The composition also includes an oil, a polyethylene, an ethylene / propylene rubber / diene monomer (EPDM) and a filler. The composition has, after exposure to 70 ° C for one week, the following properties: (I) a tackiness force of less than 0.1 N, and (II) a Shore A hardness of about 40 to about 90.
    [0009] [0009] An advantage of the present disclosure is the provision of an OBC composition diluted in oil with low or no tackiness.
    [0010] [0010] An advantage of the present disclosure is the provision of an OBC composition diluted in oil with little or no oil drainage.
    [0011] [0011] An advantage of the present disclosure is the provision of an OBC composition diluted in oil with softness and / or low (or no) tackiness and / or low (or no) oil drainage.
    [0012] [0012] An advantage of the present disclosure is the provision of an OBC composition diluted in oil that is halogen free. Brief description of the drawings
    [0013] [0013] Figure 1 shows examples of various gray scales used for the normalized oil drainage index (NOBI);
    [0014] [0014] Figure 2 is a graph showing the stickiness strength and Shore A hardness values for various comparative and inventive oil-diluted compositions;
    [0015] [0015] Figure 3 is a graph showing the NOBI and Shore A hardness values for various comparative and inventive oil-diluted compositions;
    [0016] [0016] Figure 4 is a graph showing NOBI and Shore A hardness values for various comparative and inventive oil-diluted compositions;
    [0017] [0017] Figure 5 is a graph showing the compression strain and Shore A hardness values for various comparative and inventive oil-diluted compositions;
    [0018] [0018] Figure 6 shows stickiness strength data for Examples 4-11 and Comparative Examples A-E;
    [0019] [0019] Figure 7 shows the rheology ratio (viscosity ratio determined by DMS at 190 ° C in 100 s-1 to that in 0.1 s-1;
    [0020] [0020] Figure 8 shows the final tensile strength for Examples 4-11 and Comparative Examples A-E;
    [0021] [0021] Figure 9 shows the compression strain at 70 ° C for Examples 4-11 and Comparative Examples AE;
    [0022] [0022] Figure 10 shows stickiness strength data for Examples 12-15 and Comparative Examples F-K;
    [0023] [0023] Figure 11 shows the compression strain at 70 ° C for Examples 12-15 and for Comparative Examples F-K; and
    [0024] [0024] Figure 12 shows the final tensile strength for Examples 12-15 and Comparative Examples F-K. Detailed Description
    [0025] [0025] The present disclosure provides an olefinic block copolymer (OBC) composition diluted in oil. When used herein, the term "OBC composition diluted in oil" means an OBC composition that contains (I) an OBC and (II) at least 20% by weight of oil, based on the total weight of the composition. In one embodiment, an oil-diluted block olefinic copolymer composition is provided that includes a block olefinic copolymer, an oil, one or more polyolefins, and a filler. 1. Block olefinic copolymer
    [0026] [0026] The term "block olefinic copolymer" or "OBC" is a copolymer in ethylene / α-olefin multiblocks and includes one or more copolymerizable α-olefinic comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. The terms "interpolymer" and "copolymer" are used here to allow for exchange and / or replacement. In some incorporations, the multi-block copolymer can be represented by the following formula: (AB) n where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or greater, "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably A and B bond in a substantially linear manner, as opposed to the substantially branched or substantially star-shaped manner. In other incorporations, blocks A and blocks B are randomly distributed along the polymeric chain. In other words, block copolymers do not usually have a structure as follows. AAA-AA-BBB-BB
    [0027] [0027] In other embodiments, block copolymers do not usually have a third block comprising different comonomers. In other embodiments, each block A and each block B have monomers or comonomers distributed substantially randomly within the block. In other words, neither block A nor block B comprises two or more segments (or sub-blocks) of different composition, such as an end segment, which has a substantially different composition from the rest of the block.
    [0028] [0028] Ethylene m and multiblock interpolymers typically comprise various amounts of "hard" and "soft" segments. "Hard" segments are blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, or less than about 2 weight percent based on the total weight of the polymer. In some incorporations, the hard segments include all or substantially all ethylene-derived units. "Soft" segments are blocks of polymerized units in which the content of comonomers (content of monomers other than ethylene) is greater than about 5 percent by weight, or greater than about 8 percent by weight, greater than about 10 weight percent, or greater than 15 weight percent based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments may be greater than about 20 percent by weight, greater than about 25 percent by weight, greater than about 30 percent by weight, greater than about 35 percent in weight, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 percent.
    [0029] [0029] The soft segments can be present in an OBC of about 1 weight percent to about 99 weight percent of the total weight of the OBC, or from about 5 weight percent to about 95 weight percent , from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 percent weight weight, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 percent by weight, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the CBO. On the other hand, the hard segments can be present in similar bands. You can calculate the percentage by weight of soft segments and the percentage by weight of hard segments based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in US patent No. 7,608,668, entitled “Ethylene / α-Olefin Block Interpolymers”, filed on March 15, 2006, in the name of Colin LP Shan, Lonnie Hazlitt, et al. , and assigned to Dow Global Technologies Inc., the disclosure of which is hereby incorporated by reference in its entirety. In particular the weight percentages of hard and soft segments and comonomer content can be determined as described in column 57 to column 63 of US 7,608,668.
    [0030] [0030] If used, the term "crystalline" refers to a polymer that has a crystalline melting point or first order transition (Tm) determined by differential scanning calorimetry (DSC) or equivalent technique. The term can be used interchangeably with the term "semi-crystalline". The term "amorphous" refers to a polymer without a crystalline melting point determined by differential scanning calorimetry (DSC) or equivalent technique.
    [0031] [0031] The term "multi-block copolymer" or "segmented copolymer" is a polymer comprising two or more chemically distinct segments or regions (also referred to as "blocks") which, preferably, come together in a linear manner, i.e. a polymer comprising chemically differentiated units that join end-to-end with respect to polymerized ethylene functionality, rather than in pendant or grafted mode. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated in them, density, amount of crystallinity, size of crystallite attributable to a polymer of such composition, type and degree of tacticity (isotactic or syndiotactic), regio-regularity or regioirregularity, amount of branching, including long-chain or hyper-branching branching, homogeneity, or for any other chemical or physical property. Compared to block interpolymers of the prior art, including interpolymers produced by sequential monomer addition techniques, fluxionary catalysts, or anionic polymerization, the OBC present is characterized by unique polydispersity index distributions (PDI or Mw / Mn), length distribution block, and / or distribution of block numbers due, in an incorporation, to the effect of chain exchange agents in combination with multiple catalysts used in their preparation.
    [0032] [0032] In an incorporation, the OBC is produced in a continuous process and has a polydispersity index, PDI, from 1.7 to 3.5, or from about 1.8 to about 3, or from about 1.8 to 2.5, or about 1.8 to about 2.2. When produced in a batch or semi-batch process, OBC has PDI of about 1.0 to about 3.5, or about 1.3 to 3, or from about 1.4 to about 2.5 , or from about 1.4 to about 2.
    [0033] [0033] In addition, the block olefinic copolymer has a PDI adapting to a Schultz-Flory distribution instead of a Poisson distribution. The OBC present has both a polydispersed block distribution as well as a polydispersed distribution of block sizes. This results in the formation of polymeric products having distinguishable and improved physical properties. The theoretical benefits of a polydispersed block distribution were previously modeled and discussed in Potemkin, Physical Review E (1998) 57 (6), pages 6902-6912, and in Dobrynin, J. Chem. Phys. (1997) 107 (21), pages 9234-9238.
    [0034] [0034] In an embodiment, the block olefinic copolymer present has a very likely distribution of block lengths. In an embodiment, the block olefinic copolymer is defined as having: (A) Mw / Mn of about 1.7 to about 3.5, at least one melting point, Tm, in ° C, and density, d, in g / cm3, where the numerical values of Tm and d correspond the relationship: Tm 200 -2002.9 + 4538.5 (d) - 2422.2 (d) ²; and / or (B) Mw / Mn from about 1.7 to about 3.5, and is distinguished by a heat of fusion, ∆H, in J / g, and a delta quantity, ∆T, in ° C, defined as the temperature difference between the maximum DSC peak and the maximum CRYSTAF peak, with the numerical values of ∆T and ∆H having the following relationships: ∆T ˃ -0.1299 (∆H) + 62.81 for ∆H greater than zero and up to 130 J / g; ∆T ≥ 48 ° C for ∆H greater than 130 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C; and / or (C) Percentage elastic recovery, Re, in deformation of 300 percent, and 1 cycle, measured with a film molded by compression of the ethylene / α-olefin interpolymer, and has a density, d, in grams per cubic centimeter, being that the numerical values of Re ed satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of a cross-linked phase: Re ˃ 1481 - 1629 (d); and / or (D) A molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by having a comonomer molar content of at least 5 percent, greater than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, the said comparable random ethylene interpolymer having the same comonomers and having a melting index, density, and molar comonomer content (based on the entire polymer) within the 10 percent range of that of the ethylene interpolymer / α-olefin; and / or (E) A storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), the ratio G '(25 ° C) being G '(100 ° C) is in the range of about 1: 1 to about 9: 1.
    [0035] [0035] The ethylene / α-olefin interpolymer may also have: (F) A molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by the fact that the fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution, Mw / Mn, greater than about 1.3; and / or (G) Average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw / Mn, greater than about 1.3. It is understood that the olefinic block copolymer may have one, some, all, or any combination of properties (A) - (G).
    [0036] [0036] Suitable monomers for use in the preparation of the present OBC include ethylene and one or more monomers polymerizable by addition other than ethylene. Examples of suitable comonomers include 3 to 30 standard or branched α-olefins, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene , 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cycloolefins from 3 to 30, preferably from 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl- 1,4,5,8- dimethane-1,2,3,4,4a, 5,8,8a-octahydro naphthalene; diolefins and polyolefins such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, norbornene ethylidene, norbornene vinyl, di-cyclopentadiene, 7-methyl1,6-octadiene, 4-ethylidene -8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decathriene; and 3-phenyl propene, 4-phenyl propene, 1,2-difluoro-ethylene, tetrafluoro-ethylene, and 3,3,3-trifluoro-1-propene.
    [0037] [0037] In an embodiment, the OBC has a density of about 0.85 g / cm3 to about 0.89 g / cm3, or about 0.86 g / cm3 to about 0.88 g / cm3, or from about 0.870 g / cm3 to about 0.879 g / cm3.
    [0038] [0038] In an embodiment, the OBC has a melt index (MI) of about 0.1 g / 10 min to about 30 g / 10 min, or about 0.1 g / 10 min to about 10 g / 10 min, or from about 0.1 g / 10 min to about 1.0 g / 10 min, or from about 0.5 g / 10 min to about 0.5 g / 10 min or about 0.3 g / 10 min to about 0.6 g / 10 min, measured by ASTM D 1238 (190 ° C / 2.16 kg).
    [0039] [0039] The OBC has an elasticity modulus of 2% greater than zero and less than about 150, or less than about 140, or less than about 120, or less than about 100000 kPa (100 MPa) measured by ASTM D 882-02 procedure.
    [0040] [0040] The present CBO has a melting point less than about 125 ° C. The melting point is measured by the differential scanning calorimetry (DSC) method described in WO 2005/090427 (US2006 / 0199930), the entire content of which is incorporated by reference.
    [0041] [0041] In an embodiment, the CBO contains from about 5% by weight to about 30% by weight, or from about 10% by weight to about 25% by weight, or from about 11% by weight to about 20% by weight of a hard segment. The hard segment contains from about 0.0 mol% to less than 0.9 mol% of comonomer derived units. OBC also contains from about 70% by weight to about 95% by weight, or from about 75% by weight to about 90% by weight, or from about 80% by weight to about 89% by weight of a soft segment. The soft segment contains less than 15 mol%, or from about 9 mol% to about 14.9 mol% of comonomer derived units. In an embodiment, the comonomer is butene or octene.
    [0042] [0042] Surprisingly, applicants have found that the provision of a soft segment comonomer content in the range of less than 15 mol%, or from about 9 mol% to about 14.9 mol%, unexpectedly produces a polymeric composition with no, or substantially none, stickiness or adhesion. For example, it was found that OBC with a comonomer content greater than or equal to 18 mol% in the soft segment develops stickiness after aging at a temperature greater than or equal to 50 ° C. Surprisingly, applicants have found that decreasing the soft segment comonomer content to less than 15 mol%, or from about 9 mol% to about 14.9 mol%, increases the soft segment crystallinity and unexpectedly reduces the adherence or stickiness of manufactured articles.
    [0043] [0043] In an embodiment, the OBC composition diluted in oil includes from about 20% by weight to about 40% by weight, or from about 25% by weight to about 30% by weight of OBC based on weight total composition diluted in oil. In an additional embodiment, OBC is a copolymer in ethylene / octene multiblocks with from about 5% by weight to about 30% by weight of hard segment and from about 95% by weight to about 70% by weight of segment based on the total weight of the copolymer. The soft segment contains about 9 mol% to 14.9 mol% of units derived from octene. OBC has an overall octene content of 6.0 mol% to 14.2 mol%.
    [0044] [0044] In some embodiments, OBC is present in an amount of 10 phr to 90 phr (2% by weight to about 36% by weight based on the total weight of the composition diluted in oil), or in an amount of 30 phr at 70 phr (6% by weight to about 28% by weight based on the total weight of the composition diluted in oil) or in an amount of 40 phr to 60 phr (8% by weight to about 24% by weight based on weight total composition diluted in oil), based on the total elastomer being 100 phr (20% by weight to about 40% by weight based on the total weight of the composition diluted in oil). 2. Oil
    [0045] [0045] The OBC composition diluted in oil includes an oil. The oil can be an aromatic oil, a mineral oil, a naphthenic oil, a paraffinic oil, a vegetable oil based on triglyceride such as castor oil, a synthetic hydrocarbon oil such as polypropylene oil, a silicone oil, or any combination of them. A non-limiting example of an appropriate oil is a white mineral oil sold under the trade name HYDROBRITE® 550.
    [0046] [0046] In an embodiment, the OBC composition diluted in oil contains from about 20% by weight to about 60% by weight of oil, or from about 30% by weight to about 50% by weight of oil. The weight percentage is based on the total weight of the OBC composition diluted in oil. 3. Polyolefin
    [0047] [0047] The OBC composition diluted in oil includes one or more polyolefins. The polyolefin can be a different OBC, a polyethylene (or ethylene-based polymer), a polypropylene (or propylene-based polymer), an EPDM and any combination thereof.
    [0048] [0048] In an embodiment, the polyolefin is a polyethylene. Polyethylene is selected from ultra low density polyethylene (ULDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high density polyethylene high melt strength (HMS-HDPE), ultra high density polyethylene (UHDPE), and combinations thereof. In an additional embodiment, the polyethylene has a density greater than 0.950 g / cm3 (i.e., an HDPE).
    [0049] [0049] In an embodiment, the polyolefin is a polypropylene. Polypropylene is selected from random copolymer polypropylene (rcPP), impact copolymer polypropylene (hPP + at least one elastomeric impact modifier) (ICPP) or high impact polypropylene (HIPP), high melt strength polypropylene (HMS- PP), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), and combinations thereof.
    [0050] [0050] In an embodiment, the polyolefin is an ethylene / propylene rubber / diene monomer (EPDM). EPDM materials are linear interpolymers of ethylene, propylene, and an unconjugated diene such as 1,4-hexadiene, di-cyclopentadiene, or noridene ethylidene. A preferred class of interpolymers having the properties disclosed herein is obtained from the polymerization of ethylene, propylene and an unconjugated diene to prepare an EPDM elastomer. Suitable unconjugated diene monomers can be a branched or cyclic hydrocarbon diene having 6 to 15 carbon atoms. Examples of suitable unconjugated dienes include, but are not limited to, standard chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, acyclic dienes of branched chain, such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and isomeric mixtures of dihydromyricene and dihydrocinene, alicyclic dienes of a single ring, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene, and di-ring bridged or alicyclic fused, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta-2,5-diene, alkenyl norbornenes, alkylidene, cycloalkenyl and cycloalkylidene, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2 - norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentyl) - 2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinylnorbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, particularly preferred dienes are: 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2 -norbornene (MNB), and di-cyclopentadiene (DCPD). Especially preferred dienes are: 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
    [0051] [0051] In some embodiments, EPDM polymers have an ethylene content of about 50% to about 70% by weight, a propylene content of about 20% to about 49% by weight, and a content of unconjugated diene of about 1 to about 10% by weight, all percentages by weight based on the total weight of the polymer. Examples of representative EPDM polymers for use include NORDEL IP 4770R, NORDEL 3722 IP obtainable from The Dow Chemical Company, Midland, MI, VISTALON 3666 obtainable from ExxonMobil, Baton Rouge, LA, and KELTAN 5636A obtainable from DSM Elastomers Americas, Addis, LA .
    [0052] [0052] EPDM polymers, also known as elastomeric copolymers of ethylene, a higher alpha-olefin and a polyene, have molecular weights of about 20,000 to about 2,000,000 daltons or more. Its physical form ranges from waxy materials to rubbers to polymers such as hard plastics. They have viscosities in diluted solution (DSV) of about 0.5 to about 10 dL / g, measured at 30 ° C in a solution of 0.1 gram of polymer in 100 cm 3 of toluene. EPDM polymers also have a Mooney viscosity greater than 50 ML (1 + 4) at 125 ° C, and a density of 0.870 g / cm3 to 0.885 g / cm3 or 0.875 g / cm3 to 0.885 g / cm3.
    [0053] [0053] In some embodiments, EPDM is present in an amount of 10 phr to 90 phr (2% by weight to about 36% by weight based on the total weight of the composition diluted in oil), or in an amount of 30 phr at 70 phr (6% by weight to about 28% by weight based on the total weight of the composition diluted in oil) or in an amount of 40 phr to 60 phr (8% by weight to about 24% by weight based on weight total composition diluted in oil), based on the total elastomer being 100 phr (20% by weight to about 40% by weight based on the total weight of the composition diluted in oil).
    [0054] [0054] In an embodiment, the OBC composition diluted in oil includes from about 5% by weight to about 25% by weight of polyolefin, or from about 5% by weight to about 15% by weight of polyolefin. In an additional embodiment, the polyolefin is HDPE.
    [0055] [0055] In another embodiment, the OBC composition diluted in oil includes an OBC, a polyethylene and EPDM. 4. Load
    [0056] [0056] The composition of OBC diluted in oil includes a charge. Non-limiting examples of appropriate fillers include talc, calcium carbonate, chalk, calcium sulphate, clay, kaolin, silica, glass, fumed colloidal silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as trihydrated alumina, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, sawdust, glass fibers, carbon fibers, carbon black, marble powder, cement powder, magnesium oxide , magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide and titanates.
    [0057] [0057] In an embodiment the OBC composition diluted in oil contains from about 10% by weight to about 50% by weight of charge, or about 20% by weight to about 30% by weight of charge. In an additional incorporation, the filler is calcium carbonate.
    [0058] [0058] OBC, oil, polyolefin, and filler are combined to form the OBC composition diluted in oil such as by means of melt mixing and / or extrusion mixing, for example. The composition can then be molded into desired structures such as plates, films, and / or pellets.
    [0059] [0059] In an embodiment, the OBC composition diluted in oil is halogen free.
    [0060] [0060] In an embodiment, the OBC composition diluted in oil is phthalate free.
    [0061] [0061] Surprisingly, applicants have found that the provision of (I) an OBC with a soft segment comonomer content in the range of less than 15 mol%, or from about 9 mol% to about 14.9 mol%, and (II) a polyolefin in the present composition diluted in oil and (III) a charge unexpectedly produces an OBC composition diluted in oil with no, or substantially none, stickiness or adhesion. When used here, the term “stickiness” is the ability of a material to adhere to another material. Stickiness is quantified in terms of stickiness strength. The “stickiness force” is a measure of the force (in Newton) required to separate two materials in contact with each other. The measurement of the stickiness strength is described in detail in the following section “test methods”. When used herein, the term "tack free" is a polymeric composition with a tack strength less than 0.013 N after exposure to 70 ° C for one week.
    [0062] [0062] After exposure to 70 ° C for one week, the present OBC composition diluted in oil has a tackiness strength of 0.0 N to less than 0.1 N, or about 0.00 or greater N less than about 0.05 N, or about greater than or equal to 0.00 N less than about 0.03 N, or about greater than or equal to 0.00 N less than about 0.02 N, or about greater than or equal to 0.00 N less than about 0.013 N.
    [0063] [0063] Surprisingly, applicants found that a composition diluted in oil with (I) 2% -60% by weight of OBC, OBC having a soft segment comonomer content of about 9 mol% to less than 15 mol% mixed with (II) a polyolefin unexpectedly reduces oil drainage while maintaining softness in OBC compositions diluted in oil. The term "oil bleed" or "oil drain" is a phenomenon whereby oil migrates from the interior of a polymeric component to the surface of the polymeric component. Oil drainage makes the surface sticky and / or slippery. Typically, oil drainage results in adverse "touch" (haptics) and / or "optics" (visual appearance). The term "oozing oil" is the process of moving oil from an interior location to a surface of a polymeric component. The oozing of oil produces oil drainage. In other words, oil drainage is the end result of oozing oil. Oil drainage is accelerated by high temperatures.
    [0064] [0064] Oil drainage is assessed by means of a standardized oil drainage (bleed) index (NOBI). The normalized oil bleed index (NOBI) is an optical measure of the amount of oil absorbed in cigarette paper from a polymeric composition containing oil. NOBI is calculated according to the following equation: Normalized oil drainage index = 100 • (% of gray scale sample -% of gray scale control) (100 -% of gray scale control)
    [0065] [0065] The term “% of gray scale sample” is the percentage of gray scale measured in the aged sample and “% of gray scale control” is a measure on an untreated and un aged sheet of cigarette paper. NOBI has a range of 0 to 100. When NOBI = 100, the paper is saturated and the test does not register any bleeding of oil beyond that level.
    [0066] [0066] In an embodiment, the OBC composition diluted in oil has a normalized oil drainage (bleed) index of less than 20, or less than 10, or 0 to less than 20, or 0 to less than 10, or from 0 to less than 5, after 1 week at 23 ° C.
    [0067] [0067] In an embodiment, the OBC composition diluted in oil has a NOBI less than 20, or about 5 to less than 20, after 3 weeks at 23 ° C.
    [0068] [0068] In an embodiment, the OBC composition diluted in oil has a NOBI less than 50, or from 0 to less than 50, or from 0 to less than 10 after 3 weeks at 70 ° C.
    [0069] [0069] In an embodiment, the present OBC composition diluted in oil has Shore A hardness of about 40 to about 90, or about 50 to about 90.
    [0070] [0070] Disclosure provides another composition. In one embodiment, an oil-diluted block olefinic copolymer composition is provided that includes an OBC, an oil, a polyolefin, and a filler. OBC is a copolymer in ethylene / α-olefin multiblocks with hard and soft segments. The soft segments contain from about 9 mol% to less than 15 mol% of comonomer content. The Composition has a NOBI value of less than 50, or 10 to less than 50, after exposure to 70 ° C for one week, and / or exposure to 70 ° C for three weeks. The composition also has a Shore A hardness of about 50 to about 90.
    [0071] [0071] In an embodiment, the composition when exposed to 70 ° C for a week exhibits a tackiness force of less than 0.1 N, or of about a value greater than or equal to 0.0 N less than about 0, 05 N, or about a value greater than or equal to 0.0 N less than about 0.04 N, or about a value greater than or equal to 0.0 N less than about 0.03 N , or about a value greater than or equal to 0.0 N less than about 0.02 N, or about a value greater than or equal to 0.0 N less than about 0.013 N.
    [0072] [0072] In an embodiment, the polyolefin is a polyethylene with a density greater than 0.950 g / cm3 (a high density polyethylene).
    [0073] [0073] In an embodiment, the composition includes from about 20% by weight to about 30% by weight of OBC, from about 30% by weight to about 40% by weight of oil, from about 5% by weight to about 15% by weight of polyethylene, and from about 25% by weight to about 30% by weight of cargo. In an additional embodiment, OBC is a copolymer in ethylene / octene multiblocks.
    [0074] [0074] Disclosure provides another composition. In one embodiment, an oil-diluted block olefinic copolymer composition is provided that includes an OBC, a polyethylene, and a filler. OBC is a copolymer in ethylene / α-olefin multiblocks with hard segments and soft segments, the soft segments containing from about 9 mol% to less than 15 mol% of comonomer content. The composition has the following properties after exposure to 70 ° C for one week: (I) a tackiness force less than 0.013 N, or 0.0 N less than 0.013 N; and (II) a Shore A hardness of about 40 to about 90, or about 50 to about 70.
    [0075] [0075] In an embodiment, the composition has a NOBI less than 50, or 0 to less than 50, after 1 week at 70 ° C. In a further embodiment, the composition has a NOBI of less than 50, or 0 to less than 50, or 0 to less than 10 after 3 weeks at 70 ° C.
    [0076] [0076] In an embodiment, polyethylene has a density greater than 0.95 g / cm3.
    [0077] [0077] In an embodiment, the composition has a compression strain value of about 40% to about 70%, or from about 45% to about 65%, or from about 50% to about 60%. Compression strain is measured according to ASTM D 395.
    [0078] [0078] Any of the olefinic block copolymer compositions diluted in oil may comprise two or more embodiments disclosed herein.
    [0079] [0079] The OBC can be modified by processes such as treatment with peroxide or electron beam in order to change the rheology of the polymer. Electron beam and peroxide are provided as examples only and are non-limiting. These treatments result in both chain splitting and crosslinking events. When these events are properly balanced, for example, by controlling the electron beam dose, the OBC rheology ratio can be increased without a significant decrease in the molecular weight of the polymer.
    [0080] [0080] Any of the previous olefinic block copolymer compositions diluted in oil can be transformed into an article or a component of an article. Non-limiting examples of suitable articles include durable articles for automotive, construction, medical, food and beverage, electrical, furniture, commercial, and consumer applications. In some embodiments, compositions are used to manufacture flexible durable articles or parts selected from toys, suitcases, door handles and soft touch handles, bumper wear bands, floors, car floor mats, wheels, casters, furniture feet and appliances, labels, hydraulic seals, gaskets such as static and dynamic gaskets, automotive doors, bumper strips, grille components, oscillator panels, hoses, linings, office supplies, coatings, diaphragms, tubes, caps, caps , injection pistons, distribution systems, kitchen utensils, footwear, shoe buffers and shoe soles.
    [0081] [0081] In some incorporations, compositions are used to manufacture durable articles or parts that require high tensile strength and low compression deformation. In additional incorporations, compositions are used to manufacture durable articles or parts that require a high service temperature and a low modulus. Definitions
    [0082] [0082] All references to the Periodic Table of Elements here will refer to the Periodic Table of Elements published and registered by CRC Press, Inc., 2003. Likewise, any references to a Group or Groups will be to a Group or Groups shown in this Table Periodic Table of Elements using the IUPAC system to number groups. Unless stated to the contrary, implicit in context, or customary in the technique, all parts and percentages are based on weight and all testing methods are current as of the filing date of this disclosure. For United States patent practice purposes, the contents of any patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is also incorporated by reference) especially with respect to the dissemination of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge of the technique.
    [0083] [0083] Any numerical range mentioned here, includes all values from the lower value to the upper value, in increments of one unit, as long as there is a separation of at least two units between any lower value and any higher value. As an example, if it is stated that the quantity of a component, or a value of a composition or physical property, such as, for example, quantity of a mixing component, softening temperature, melting index, etc., is between 1 and 100, it is intended that all individual values, such as, 1, 2, 3, etc., and sub-ranges, such as, 1 to 20, 55 to 70, 97 to 100, etc., are expressly listed in this report. For ranges containing values that are less than one, or containing fractional numbers greater than one (for example, 1.1, 1.5, etc.) a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, when appropriate. For ranges containing single digit numbers less than ten (for example, 1 to 5), a unit is typically considered to be 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical values between the minimum and maximum values listed will be considered to be expressly established in this patent application. Numeric ranges have been mentioned, discussed here, with reference to melt index, melt flow rate, and other properties.
    [0084] [0084] When used herein, the terms "mixture" or "polymeric mixture", mean a mixture of two or more polymers. Such a mixture may or may not be miscible (not separated into phases at the molecular level). Such a mixture may or may not be separated into phases. Such a mixture may or may not contain one or more domain configurations, determined by electronic transmission spectroscopy, light scattering, X-ray scattering, and other methods known in the art.
    [0085] [0085] When used here, the term "composition" includes a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
    [0086] [0086] The term "comprising" and its derivatives is not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. In order to avoid any doubt, all compositions claimed herein using the term "comprising" may include any additive, adjuvant, or compound, polymeric or not, additional, unless otherwise stated. In contrast, the term, “consisting essentially of” excludes any other component, step or procedure from the scope of any subsequent mention, except those that are not essential to operability. The term "consisting of" excludes any component, step or procedure not specifically described or listed. Unless otherwise stated, the term "or" refers to members listed individually as well as in any combination.
    [0087] [0087] The normalized oil bleed index (NOBI) is an optical measure of the amount of oil absorbed in cigarette paper from a polymeric composition containing oil.
    [0088] [0088] When used here, the term "polymer" refers to a macromolecular compound prepared by polymerizing monomers, whether of the same or different types. The term "polymer" includes homopolymers, copolymers, terpolymers, interpolymers, etc. The term "interpolymer" means a polymer prepared by the polymerization of at least two different types of monomers or comonomers. It includes, but is not limited to, copolymers (usually used to refer to polymers prepared from two different types of monomers or comonomers), terpolymers (usually used to refer to polymers prepared from three different types of monomers or comonomers), tetrapolymers (usually used to refer to polymers prepared from four different types of monomers or comonomers) and the like. Testing methods
    [0089] [0089] Compression strain is measured according to ASTM D-395. The sample is prepared by stacking round disks with a diameter of 25.4 mm, 3.2 mm, 2.0 mm, and 0.25 mm in thickness until a total thickness of 12.7 mm is reached. The discs are cut from injection molded plates that are 101.6 x 152.4 x 3.2 mm (4 ”by 6” by 0.125 ”). Compression strain is measured after 24 hours at 25% strain at 70 ° C or 23 ° C.
    [0090] [0090] Density is measured according to ASTM D 792.
    [0091] [0091] Differential scanning calorimetry is performed on compression molded specimens using DS Instruments q100 or Q1000 from TA Instruments and a fold-sealed Perkin Elmer pan. The samples are equilibrated at –90 ° C for 5 min, then heated at 10 ° C / min to 180 ° C (capturing the “1st heating DSC curve”), maintained for 5 min, then cooled to 10 ° C / min to -90 ° C (capturing the “crystallization curve”), maintained for 5 min, then heated at 10 ° C / min to 180 ° C (capturing the “2nd heating DSC curve”). The data is analyzed using universal TA analysis software after completing the operation.
    [0092] [0092] The melt index is measured according to ASTM D 1238, condition 190 ° C / 2.16 kg.
    [0093] [0093] The normalized oil drainage (bleed index) (NOBI) is an optical measure for comparing oil bleed characteristics. Molded plates are aged for 24 hours, 1 week, and 3 weeks (at 23 ° C and 70 ° C) while resting on sheets of ZigZag ™ cigarette paper obtainable from ZigZag Corp.). After aging, the cigarette paper is removed and scanned optically against a black background to measure the extent of oil drainage.
    [0094] [0094] Scanning is performed using the Xerox WorkCentre ™ M118i copier / fax / scanner (scanner). The image is scanned in “text” mode at 200 dpi, and saved as a TIFF file. The TIFF file is opened in MS Paintbrush, harvested on both sides, then saved. The image is then opened in Photoshop CS2 (v.9) and cropped on the other two sides. The “text mode” image is a bitonal image. The percentage of black pixels in the image is the desired result. The text mode image is obtained in this software by first converting it to an 8-bit gray scale image in order to create a gray scale histogram, with exactly 2 levels of gray scale, 0 (black) to 255 (white). The percentile of the gray scale level 0 in the histogram is the same as the percentage of black pixels. (This value is called “% of gray scale, but it can be more accurately described as“% of black pixels ”in the bitonal image.
    [0095] [0095] The normalized oil bleeding index (NOBI) is calculated according to the following equation: Normalized oil drainage index (NOBI) = 100 • (% of gray scale sample -% of gray scale control) (100 -% of gray scale control).
    [0096] [0096] The term “% of gray scale sample” is the percentage of gray scale measured in the aged sample and “% of gray scale control” is a measure on an untreated and un aged sheet of cigarette paper. NOBI has a range of 0 to 100. When NOBI = 100, the paper is saturated and the test does not register oil drainage beyond that level. Figure 1 shows four examples of gray scale: gray scale of 20.1%, 34.6%, 51.6%, and 100%.
    [0097] [0097] Shore A hardness is measured on plates molded according to ASTM D 2240. This test method allows hardness measurements based on the initial notch or notch after a specified period of time, or both. In this case, a specified time of 10 seconds is used.
    [0098] [0098] Small angle X-ray scattering (SAXS) data is collected using a Rigaku Microsupply X-ray generator with Cu radiation and a 2D area detector. The samples are positioned in the beam using a precision PC-controlled step motor using Labview software. The data is analyzed using SCATTER and is corrected for air level.
    [0099] [0099] The stickiness force is measured as follows. The samples are compression molded or injection molded into 3.2 mm (0.125 inch) thick plates. The samples are cut into strips of 25.4 x 152.4 mm (1 ”x 6”) and marked at intervals of 25.4 mm (1 ”). If justified, the samples are aged at an elevated temperature. MYLAR® sheets are cut into strips of 25.4 x 152.4 mm (1 ”x 6”), formed into handles with dimensions of 25.4 x 127.0 mm (1 ”x 5”). After aging, the samples are cooled to room temperature. Double-sided tape is used to secure the sample to the platform to prevent it from leaving the surface. The handle is placed on the pneumatic clips of INSTRON ™ 5564 and aligned parallel to the plate. The handle is lowered at a rate of 300% / minute covering the surface of 25.4 x 25.4 mm (1 ”x 1”) of the plate. A new loop is used with each measurement performed. The average stickiness strength (in N) and the standard deviation are reported after five readings per specimen. One measurement is taken for each 25.4 x 25.4 mm (1 ”x 1”) portion of a sample. Surface roughness
    [0100] [0100] Surface roughness is created in a mold by sanding a finished mirror plate. The surface roughness of the mold is measured using a profilometer (Dektak 150 stylus profilometer) using the following parameters. Surface roughness is measured both in a parallel and in a direction perpendicular to the sanding direction. The reported values for surface roughness are Ra, medium roughness, for the perpendicular direction. Ra (mean roughness), formerly known as arithmetic mean (AA) and mean centerline (CL) is the mean arithmetic deviation from the midline within the evaluation length.
    [0101] [0101] Ten line scans per sample
    [0102] [0102] Standard scan type scan
    [0103] [0103] Stylus radius: 2.5 µm
    [0104] [0104] Scan length: 15000.0 µm
    [0105] [0105] Duration: 90 seconds
    [0106] [0106] Resolution: 0.556 µm / sample
    [0107] [0107] Strength: 1.00 mg
    [0108] [0108] Measuring range: 524 µm
    [0109] [0109] Profile: Hills & Valleys
    [0110] [0110] Display range: Automatic
    [0111] [0111] Short pass filter cut: 100.0 µm
    [0112] [0112] Long pass filter cut: 1500.0 µm
    [0113] [0113] Cursor pos. R .: 100.0 µm Width: 40.0 µm
    [0114] [0114] Pos. Cursor M .: 14750.0 µm Width: 40.0 µm
    [0115] [0115] Examples of the present disclosure are now provided. These examples illustrate without limiting the present disclosure. EXAMPLES 1. Materials A. Block olefinic copolymer
    [0116] (I) INFUSE™ 9007 – copolímero olefínico em bloco (OBC) de MI 0,5 g/10 min e densidade 0,866 g/cm3, com divisão em peso de segmento duro/mole de 11/89 e 18% molar de octeno no segmento mole, e 15,6% molar de octeno total. (II) INFUSE™ 9000 – OBC de MI 0,5 g/10 min e densidade 0,877 g/cm3, com divisão em peso de segmento duro/mole de 25/75 e 18% molar de octeno no segmento mole, e 12,7% molar de octeno total. (III) OBC 3 - OBC de MI 0,5 g/10 min e densidade 0,877 g/cm3, 130 ppm de Zn, com divisão em peso de segmento duro/mole de 11/89 e 13% molar de octeno no segmento mole, e 11,2% molar de octeno total. A Tabela 1 abaixo mostra as propriedades dos três OBCs.
    [0117] [0117] HYDROBRITE 550 (Sonneborn) - mineral oil with nominal content of 70% paraffinic and 30% naphthenic, and average MW of 541. C. Polyolefin
    [0118] [0118] DMDA-8920 NT 7 Dow (HDPE Dow 8920) is a high density polyethylene obtainable from The Dow Chemical Company. HDPE Dow 8920 has a density of 0.954 g / cm3, MI of 20 g / 10 min, and a melting point of 130 ° C.
    [0119] [0119] hPP Dow 700-12 is a polypropylene obtainable from The Dow Chemical Company. The Dow 700-12 hPP has a density of 0.900 g / cm3 (ASTM D792), and a melt flow rate of 12 (230 ° C / 2.16 kg, ASTM D 1238).
    [0120] [0120] NORDEL IP 4770 is an ethylene / propylene / diene monomer (EPDM) rubber obtainable from The Dow Chemical Company (Midland, MI) and has the following properties: density of 0.872 g / cm3, Mooney viscosity (ML 1+ 4.257 ° F) of 70, ethylene content of 70% by weight and ENB content of 5% by weight.
    [0121] [0121] VISTALON 3666 is an EPDM obtainable from ExxonMobil Chemical Company (Houston, TX) and has the following properties: Mooney viscosity of 52, ethylene content of 64% by weight and ENB content of 4.5% by weight. D. Cargo
    [0122] [0122] Calcium carbonate - ATOMITE (obtainable from IMERYS Performance Minerals). 2. Preparation
    [0123] [0123] Table 2 below provides the compositions of samples A ', B', 1, 2 and 3. Samples A and B are comparative. Quantities are given in weight percent based on the total weight of the composition.
    [0124] [0124] Samples 1-3 in Table 2 are combined using a two-screw extruder ZSK-30 from Werner & Pleiderer, and a Zenith pump powered by a Dayton DC motor. Samples 1-3 are pelletized with an LPU Gala underwater laboratory pelletizing system. Tables 3-4 below show the processing conditions.
    [0125] [0125] Samples 1-3 are provided on polished mirror plates of 101.6 x 152.4 x 3.2 mm (4 "by 6" by 0.125 ") under the following conditions shown in Table 4 below.
    [0126] [0127] Figure 2 shows the values of stickiness strength and Shore A hardness for samples 1-3 after exposure to 70 ° C for 1 week. Figure 2 also shows a stickiness-free zone indicated by the upper horizontal line of the box which indicates a stickiness force of 0.013 N. The samples below this line are stickiness-free.
    [0127] [0128] Figure 3 shows the NOBI and Shore A hardness values for samples 1-3 after exposure to 23 ° C for 3 weeks.
    [0128] [0129] Figure 4 shows the NOBI and Shore A hardness values for samples 1-3 after exposure to 70 ° C for 3 weeks.
    [0129] [0130] Figure 5 shows the values of compression strain (%) and Shore A hardness for samples 1-3 after exposure to 70 ° C for 24 hours.
    [0130] [0131] The data in Figures 2-5 show samples 1-3 with low tackiness (or free from tackiness), with low oil drainage (NOBI less than 50), and smoothness (Shore A 50-90).
    [0131] [0132] Table 5 shows the properties of samples A, B and 1-3.
    [0132] [0133] The following set of examples is prepared in a similar manner to that of Examples 1-3. Tables 6 and 7 show formulations and properties of samples with 160 phr of oil and 190 phr of oil respectively.
    [0133] [0134] Figures 6 and 9 showed that inventive examples 4-11 of Table 5 with 160 phr of oil have low tackiness and low compression deformation. The inventive examples combine the advantage of formulations prepared with NORDEL 4770 (EPDM), that is, low tackiness and high ratio of rheology, with the advantage of formulations prepared with OBC, that is, low compression strain in the low Shore A range. In general, formulations prepared with OBC or OBC + EPDM have the lowest values of compression deformation in materials prepared in the Shore A range. In the meantime, low stickiness performance is achieved for EPDM formulations and for formulations of OBC / EPDM to below about Shore A of 50. Table 6 shows Examples 12-15 with 190 phr of oil. Again, a combination of low tackiness and low compression deformation is achieved with the inventive examples formulated with OBC / EPDM mixtures. The tackiness and compression strain data for the examples in Table 6 are shown in Figures 10 and 11.
    [0134] [0135] This inventive combination of low tackiness and low compression deformation is especially unexpected when considering other properties. For a property such as final tensile strength, property values are obtained that are close to the average values between the two single component elastomer cases (see Figure 8), instead of values that are close to those of an elastomer case one component or the other. Examples of surface texture effect
    [0135] [0136] Examples of the effect of surface texture on tackiness for two different compounds are shown in Table 8 below. As shown, when using textured molds, the stickiness strength is significantly less. The level of surface roughness required to achieve low tackiness varies with the formulation, but as illustrated, a mold with a roughness of 0.41 µm results in low tackiness for both formulations. The molding conditions used for these examples are included below. Note that these molding conditions differ from those used in the other examples.
    [0136] [0137] Specifically, it is intended that the present disclosure is not limited to the embodiments and illustrations contained herein, but that it includes modified forms of those incorporations including portions of the incorporations and combinations of elements of different incorporations as being within the limits of the scope of the following claims .
    权利要求:
    Claims (10)
    [0001]
    Composition of olefinic block copolymer diluted in oil, characterized by the fact that it comprises: - an olefinic block copolymer comprising hard segments and soft segments, the soft segments comprising comonomer content of 9 mol% to less than 15 mol%; - an oil; - one or more polyolefins; - a load; and the composition having the following properties after exposure to 70 ° C for one week: - a tackiness force of less than 0.1 N or a standard oil drainage index of less than 50; and - a Shore A hardness of 40 to 90.
    [0002]
    Composition according to claim 1, characterized in that the olefinic block copolymer comprises a copolymer in ethylene / octene multiblocks comprising from 5% by weight to 30% by weight of hard segments and from 95% by weight to 70% by weight of soft segments, and having after exposure to 70 ° C for one week, a stickiness force of less than 0.1 N.
    [0003]
    Composition according to either of Claims 1 and 2, characterized in that it comprises from 2% by weight to 40% by weight of olefinic block copolymer, from 20% by weight to 50% by weight of oil, 5% by weight at 50% by weight of polyolefin, and from 20% by weight to 40% by weight of load, and having a sticky force of less than 0.1 N. after exposure to 70 ° C for one week.
    [0004]
    Composition according to any one of claims 1 to 3, characterized by the fact that after exposure to 70 ° C for a week, a tackiness force of less than 0.1 N; and the polyolefin being selected from the group consisting of a polyethylene, a polypropylene, an ethylene / propylene rubber / diene monomer and combinations thereof.
    [0005]
    Composition of olefinic block copolymer diluted in oil, according to claim 1, characterized by the fact that it has a Shore A hardness of 50 to 90.
    [0006]
    Composition according to claim 5, characterized in that it comprises from 2% by weight to 30% by weight of olefinic block copolymer, from 30% by weight to 40% by weight of oil, from 5% by weight to 25 % by weight of polyethylene, and from 25% by weight to 30% by weight of cargo, and having after exposure to 70 ° C for one week, a standardized oil drainage index of less than 50.
    [0007]
    Composition of olefinic block copolymer diluted in oil, according to claim 1, characterized by the fact that it comprises: - one or more polyolefins; - a polyethylene; and the composition having the following properties after exposure to 70 ° C for one week: - a tackiness force of less than 0.020 N.
    [0008]
    Composition according to claim 7, characterized by the fact that it also comprises an ethylene / propylene / diene monomer rubber.
    [0009]
    Composition of olefinic block copolymer diluted in molded oil, characterized by the fact that it comprises: - an olefinic block copolymer comprising hard segments and soft segments, the soft segments comprising comonomer content of 9 mol% to less than 15 mol%; - an oil; - one or more polyolefins; - a load; and the composition having the following properties after exposure to 70 ° C for one week: - a tackiness force of less than 0.1 N; and - Shore A hardness of 50 to 90. the molded composition being prepared using a 0.41 µm surface roughness mold.
    [0010]
    Composition diluted in molded oil, according to claim 9, characterized by the fact that it also comprises an ethylene / propylene rubber / diene monomer.
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    同族专利:
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    ES2538976T3|2015-06-25|
    JP2013532214A|2013-08-15|
    CN103068912A|2013-04-24|
    WO2011159649A1|2011-12-22|
    US20150259524A1|2015-09-17|
    US20110306715A1|2011-12-15|
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    法律状态:
    2020-09-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-10-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US35430910P| true| 2010-06-14|2010-06-14|
    US61/354,309|2010-06-14|
    PCT/US2011/040266|WO2011159649A1|2010-06-14|2011-06-14|Olefin block copolymer composition with low tack|
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