# US 2014/0194553 A1 · Epoxidised natural rubber based blend for antistatic footwear application > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0194553 A1 - Document ID: US20140194553A1 - Status: Published application - Kind: A1 - Application number: 14/004,147 - Filed: 2012-03-07 - Published: 2014-07-10 - Earliest claimed: 2011-03-08 - Assignees: Lembaga Getah Malaysia - Inventors: Yong Kok Chong; Ahmad Mohamad Asri - Web page: https://patentgrep.com/patent/US20140194553A1 ## CPC - A43B 1/10: made of rubber - A43B 7/36: with earthing or grounding means - A43B 17/006: {multilayered} - C08J 3/22: using masterbatch techniques - C08J 3/247: {Heating methods} - C08K 3/04: Carbon - C08C 19/06: Epoxidation - C08J 2307/00: Characterised by the use of natural rubber - A43B: CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS ## Abstract Electrically conductive vulcanised epoxidised natural rubber [ENR]-carbon black blends can be produced by using either internal mechanical mixing method or open milling method. These two methods are commercially friendly due to their practicability and high production rate. The addition of vulcanisation system, either sulfur or peroxide type does not affect the electrical properties of the vulcanised blends. All vulcanized blends prepared in this innovation show useful electrical properties with electrical volume resistances as low as the order of 101 ohms. All these vulcanised blends also exhibit good mechanical properties with tensile strengths up to 26.0 MPa and Dunlop rebound resiliencies of 14.0% (i.e. high damping property). The black colour level of all these vulcanised blends is adjustable. As a result of good electrical and mechanical properties (especially high damping property), they have good potential to be used for antistatic footwear manufacturing and application. ## Claims ### Claim 1 An epoxidised natural rubber based blend for antistatic footwear application and manufacturing comprising: epoxidised natural rubber [ENR], carbon blacks, antioxidants, processing oils, processing waxes and vulcanisation agents. ### Claim 2 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the blend composition ranges from: 50.0 to 150.0 part per hundred rubber [p.p.h.r.] of epoxidised natural rubber; 5.0 to 60.0 p.p.h.r. of carbon blacks; 0.1 to 20.0 p.p.h.r. of antioxidants with a purity level of 80.0-100.0 wt %; 1.0 to 60.0 p.p.h.r. of processing oils; 0.05 to 20.0 p.p.h.r. of processing waxes; 0.1 to 10.0 p.p.h.r. of vulcanisation agent with a purity level of 30.0-100.0 wt %. ### Claim 3 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the blend selectively comprises of: 0 to 10.0 p.p.h.r. of vulcanisation accelerators with a purity level of 80.0-100.0 wt %; 0 to 12.5 p.p.h.r. of vulcanisation activators with a purity level of 80.0-100.0 wt %; and 0 to 20.0 p.p.h.r. of vulcanisation coagents. ### Claim 4 (depends on 3) An epoxidised natural rubber based blend according to claim 3, wherein the blend selectively comprises vulcanisation accelerators, vulcanisation activators and vulcanisation coagents in order to accelerate, activate and enhance the epoxidised natural rubber based blends vulcanisation process. ### Claim 5 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the blend further selectively comprises whitening agents in order to adjust its black colour level. ### Claim 6 (depends on 5) An epoxidised natural rubber based blend according to claim 5, wherein the whitening agents selectively range from 0 to 35.0 p.p.h.r. with a purity level of 80.0-100.0 wt %. ### Claim 7 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the vulcanisation agents are selected from either sulfur or peroxide. ### Claim 8 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the epoxidised natural rubber further comprises any solid grades of 10.0 to 60.0 mole % of epoxide contents. ### Claim 9 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the carbon blacks are selected from the list of reinforcing or semi-reinforcing or non-reinforcing or conductive blacks or in any combination thereof. ### Claim 10 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the antioxidants are selected from the list of staining or non-staining or in any combination thereof. ### Claim 11 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the processing oils are selected from the list of natural oil or synthetic oil or in any combination thereof. ### Claim 12 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the processing waxes are selected from the lists of natural wax or synthetic wax or in any combination thereof. ### Claim 13 (depends on 3) An epoxidised natural rubber based blend according to claim 3, wherein the vulcanisation accelerators are selected from the lists of guanidine or sulphenamide or thiazole or thiuram or dithiocarbamate or xanthate or any combination thereof. ### Claim 14 (depends on 3) An epoxidised natural rubber based blend according to claim 3, wherein the vulcanisation activators are selected from the list of either combination of metallic oxide and stearic acid or metallic stearate. ### Claim 15 (depends on 3) An epoxidised natural rubber based blend according to claim 3, wherein the vulcanisation coagents are selected from the list of di-maleimide or trimethecrylate or isocyanate or in any combination thereof. ### Claim 16 (depends on 5) An epoxidised natural rubber based blend according to claim 5, wherein the whitening agents are selected from list of solid or liquid or in any combination thereof. ### Claim 17 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the blend is usable for antistatic footwear application and manufacturing. ### Claim 18 (depends on 1) An epoxidised natural rubber based blend according to claim 1, wherein the blend exhibits electrical volume resistance values equal to the range of 101 to 1010 ohms, tensile strengths equal 16.0 to 26.0 MPa, elongations at break equal 140.0 to 680.0%, tear strengths equal 10.0 to 38.0 N/mm, hardness equals of Shore A 30.0 to 90.0, compression sets equal of 8.0 to 65.0%, Dunlop rebound resiliencies equal 14.0 to 56.0% and Akron abrasions equal 4.0 to 50.0 mm3/500 rev. ### Claim 19 (depends on 1) A method for preparation of epoxidised natural rubber based blend according to claim 1 comprises the steps of: (g) adding epoxidised natural rubber to an internal mechanical mixing device; (h) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, and antioxidants by using an internal mechanical mixing device to produce masterbatch; (i) discharge of the masterbatch from the internal mechanical mixing device; (j) mixing of masterbatch with vulcanisation agents by using an open milling device to produce blend; (k) discharging the blend from the open milling device; and (l) vulcanisation of the blend by heating or microwave. ### Claim 20 (depends on 19) A method according to claim 19, wherein step (b) further comprising the step of adding vulcanisation activators. ### Claim 21 (depends on 19) The method according to claim 19 wherein step (d) further comprises the step of adding either vulcanisation accelerators or vulcanisation coagents or whitening agents or in any combination thereof. ### Claim 22 (depends on 1) A method for preparation of epoxidised natural rubber based blend according to claim 1 comprises the steps of: (f) adding of epoxidised natural rubber to an open milling device; (g) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, antioxidants by using an open milling device to produce masterbatch; (h) mixing of the masterbatch with vulcanisation agents by using an open milling device to produce blend; (i) discharge of the blend from the open milling device; and (j) vulcanisation of the blend by heating or microwave. ### Claim 23 (depends on 22) The method according to claim 22, wherein step (b) further comprising the step of adding vulcanisation activators to the masterbatch. ### Claim 24 (depends on 22) The method according to claim 22, wherein step (c) further comprising the step of adding either vulcanisation accelerators or vulcanisation coagents or whitening agents or in any combination thereof. ### Claim 25 (depends on 19) The method according to claim 19, wherein the vulcanisation process of all ENR based blends are performed at temperature ranges from 100-250° C. by either heating or microwave. ### Claim 26 (depends on 2) An epoxidised natural rubber based blend according to claim 2, wherein the blend selectively comprises of: 0 to 10.0 p.p.h.r. of vulcanisation accelerators with a purity level of 80.0-100.0 wt %; 0 to 12.5 p.p.h.r. of vulcanisation activators with a purity level of 80.0-100.0 wt %; and 0 to 20.0 p.p.h.r. of vulcanisation coagents. ### Claim 27 (depends on 2) An epoxidised natural rubber based blend according to claim 2, wherein the blend further selectively comprises whitening agents in order to adjust its black colour level. ### Claim 28 (depends on 4) An epoxidised natural rubber based blend according to claim 4, wherein the vulcanisation accelerators are selected from the lists of guanidine or sulphenamide or thiazole or thiuram or dithiocarbamate or xanthate or any combination thereof. ### Claim 29 (depends on 4) An epoxidised natural rubber based blend according to claim 4, wherein the vulcanisation activators are selected from the list of either combination of metallic oxide and stearic acid or metallic stearate. ### Claim 30 (depends on 4) An epoxidised natural rubber based blend according to claim 4, wherein the vulcanisation coagents are selected from the list of di-maleimide or trimethecrylate or isocyanate or in any combination thereof. ### Claim 31 (depends on 6) An epoxidised natural rubber based blend according to claim 6, wherein the whitening agents are selected from list of solid or liquid or in any combination thereof. ### Claim 32 (depends on 2) An epoxidised natural rubber based blend according to claim 2, wherein the blend is usable for antistatic footwear application and manufacturing. ### Claim 33 (depends on 2) An epoxidised natural rubber based blend according to claim 2, wherein the blend exhibits electrical volume resistance values equal to the range of 101 to 1010 ohms, tensile strengths equal 16.0 to 26.0 MPa, elongations at break equal 140.0 to 680.0%, tear strengths equal 10.0 to 38.0 N/mm, hardness equals of Shore A 30.0 to 90.0, compression sets equal of 8.0 to 65.0%, Dunlop rebound resiliencies equal 14.0 to 56.0% and Akron abrasions equal 4.0 to 50.0 mm3/500 rev. ### Claim 34 (depends on 3) An epoxidised natural rubber based blend according to claim 3, wherein the blend exhibits electrical volume resistance values equal to the range of 101 to 1010 ohms, tensile strengths equal 16.0 to 26.0 MPa, elongations at break equal 140.0 to 680.0%, tear strengths equal 10.0 to 38.0 N/mm, hardness equals of Shore A 30.0 to 90.0, compression sets equal of 8.0 to 65.0%, Dunlop rebound resiliencies equal 14.0 to 56.0% and Akron abrasions equal 4.0 to 50.0 mm3/500 rev. ### Claim 35 (depends on 4) An epoxidised natural rubber based blend according to claim 4, wherein the blend exhibits electrical volume resistance values equal to the range of 101 to 1010 ohms, tensile strengths equal 16.0 to 26.0 MPa, elongations at break equal 140.0 to 680.0%, tear strengths equal 10.0 to 38.0 N/mm, hardness equals of Shore A 30.0 to 90.0, compression sets equal of 8.0 to 65.0%, Dunlop rebound resiliencies equal 14.0 to 56.0% and Akron abrasions equal 4.0 to 50.0 mm3/500 rev. ### Claim 36 (depends on 5) An epoxidised natural rubber based blend according to claim 5, wherein the blend exhibits electrical volume resistance values equal to the range of 101 to 1010 ohms, tensile strengths equal 16.0 to 26.0 MPa, elongations at break equal 140.0 to 680.0%, tear strengths equal 10.0 to 38.0 N/mm, hardness equals of Shore A 30.0 to 90.0, compression sets equal of 8.0 to 65.0%, Dunlop rebound resiliencies equal 14.0 to 56.0% and Akron abrasions equal 4.0 to 50.0 mm3/500 rev. ### Claim 37 (depends on 6) An epoxidised natural rubber based blend according to claim 6, wherein the blend exhibits electrical volume resistance values equal to the range of 101 to 1010 ohms, tensile strengths equal 16.0 to 26.0 MPa, elongations at break equal 140.0 to 680.0%, tear strengths equal 10.0 to 38.0 N/mm, hardness equals of Shore A 30.0 to 90.0, compression sets equal of 8.0 to 65.0%, Dunlop rebound resiliencies equal 14.0 to 56.0% and Akron abrasions equal 4.0 to 50.0 mm3/500 rev. ### Claim 38 (depends on 2) A method for preparation of epoxidised natural rubber based blend according to claim 2 comprises the steps of: (g) adding epoxidised natural rubber to an internal mechanical mixing device; (h) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, and antioxidants by using an internal mechanical mixing device to produce masterbatch; (i) discharge of the masterbatch from the internal mechanical mixing device; (j) mixing of masterbatch with vulcanisation agents by using an open milling device to produce blend; (k) discharging the blend from the open milling device; and (l) vulcanisation of the blend by heating or microwave. ### Claim 39 (depends on 3) A method for preparation of epoxidised natural rubber based blend according to claim 3 comprises the steps of: (g) adding epoxidised natural rubber to an internal mechanical mixing device; (h) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, and antioxidants by using an internal mechanical mixing device to produce masterbatch; (i) discharge of the masterbatch from the internal mechanical mixing device; (j) mixing of masterbatch with vulcanisation agents by using an open milling device to produce blend; (k) discharging the blend from the open milling device; and (l) vulcanisation of the blend by heating or microwave. ### Claim 40 (depends on 4) A method for preparation of epoxidised natural rubber based blend according to claim 4 comprises the steps of: (g) adding epoxidised natural rubber to an internal mechanical mixing device; (h) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, and antioxidants by using an internal mechanical mixing device to produce masterbatch; (i) discharge of the masterbatch from the internal mechanical mixing device; (j) mixing of masterbatch with vulcanisation agents by using an open milling device to produce blend; (k) discharging the blend from the open milling device; and (l) vulcanisation of the blend by heating or microwave. ### Claim 41 (depends on 5) A method for preparation of epoxidised natural rubber based blend according to claim 5 comprises the steps of: (g) adding epoxidised natural rubber to an internal mechanical mixing device; (h) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, and antioxidants by using an internal mechanical mixing device to produce masterbatch; (i) discharge of the masterbatch from the internal mechanical mixing device; (j) mixing of masterbatch with vulcanisation agents by using an open milling device to produce blend; (k) discharging the blend from the open milling device; and (l) vulcanisation of the blend by heating or microwave. ### Claim 42 (depends on 6) A method for preparation of epoxidised natural rubber based blend according to claim 6 comprises the steps of: (g) adding epoxidised natural rubber to an internal mechanical mixing device; (h) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, and antioxidants by using an internal mechanical mixing device to produce masterbatch; (i) discharge of the masterbatch from the internal mechanical mixing device; (j) mixing of masterbatch with vulcanisation agents by using an open milling device to produce blend; (k) discharging the blend from the open milling device; and (l) vulcanisation of the blend by heating or microwave. ### Claim 43 (depends on 20) The method according to claim 20 wherein step (d) further comprises the step of adding either vulcanisation accelerators or vulcanisation coagents or whitening agents or in any combination thereof. ### Claim 44 (depends on 2) A method for preparation of epoxidised natural rubber based blend according to claim 2 comprises the steps of: (f) adding of epoxidised natural rubber to an open milling device; (g) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, antioxidants by using an open milling device to produce masterbatch; (h) mixing of the masterbatch with vulcanisation agents by using an open milling device to produce blend; (i) discharge of the blend from the open milling device; and (j) vulcanisation of the blend by heating or microwave. ### Claim 45 (depends on 3) A method for preparation of epoxidised natural rubber based blend according to claim 3 comprises the steps of: (f) adding of epoxidised natural rubber to an open milling device; (g) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, antioxidants by using an open milling device to produce masterbatch; (h) mixing of the masterbatch with vulcanisation agents by using an open milling device to produce blend; (i) discharge of the blend from the open milling device; and (j) vulcanisation of the blend by heating or microwave. ### Claim 46 (depends on 4) A method for preparation of epoxidised natural rubber based blend according to claim 4 comprises the steps of: (f) adding of epoxidised natural rubber to an open milling device; (g) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, antioxidants by using an open milling device to produce masterbatch; (h) mixing of the masterbatch with vulcanisation agents by using an open milling device to produce blend; (i) discharge of the blend from the open milling device; and (j) vulcanisation of the blend by heating or microwave. ### Claim 47 (depends on 5) A method for preparation of epoxidised natural rubber based blend according to claim 5 comprises the steps of: (f) adding of epoxidised natural rubber to an open milling device; (g) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, antioxidants by using an open milling device to produce masterbatch; (h) mixing of the masterbatch with vulcanisation agents by using an open milling device to produce blend; (i) discharge of the blend from the open milling device; and (j) vulcanisation of the blend by heating or microwave. ### Claim 48 (depends on 6) A method for preparation of epoxidised natural rubber based blend according to claim 6 comprises the steps of: (f) adding of epoxidised natural rubber to an open milling device; (g) mixing of epoxidised natural rubber with carbon blacks, processing oils, processing waxes, antioxidants by using an open milling device to produce masterbatch; (h) mixing of the masterbatch with vulcanisation agents by using an open milling device to produce blend; (i) discharge of the blend from the open milling device; and (j) vulcanisation of the blend by heating or microwave. ### Claim 49 (depends on 23) The method according to claim 23, wherein step (c) further comprising the step of adding either vulcanisation accelerators or vulcanisation coagents or whitening agents or in any combination thereof. ### Claim 50 (depends on 22) The method according to claim 22, wherein the vulcanisation process of all ENR based blends are performed at temperature ranges from 100-250° C. by either heating or microwave.