CN102134365A - Permanently antistatic thermoplastic elastomer material - Google Patents

Permanently antistatic thermoplastic elastomer material Download PDF

Info

Publication number
CN102134365A
CN102134365A CN 201110112102 CN201110112102A CN102134365A CN 102134365 A CN102134365 A CN 102134365A CN 201110112102 CN201110112102 CN 201110112102 CN 201110112102 A CN201110112102 A CN 201110112102A CN 102134365 A CN102134365 A CN 102134365A
Authority
CN
China
Prior art keywords
elastic material
static
ethylene
characterized
thermoplastic elastic
Prior art date
Application number
CN 201110112102
Other languages
Chinese (zh)
Other versions
CN102134365B (en
Inventor
李明轩
陆云
Original Assignee
南通普力马弹性体技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南通普力马弹性体技术有限公司 filed Critical 南通普力马弹性体技术有限公司
Priority to CN2011101121029A priority Critical patent/CN102134365B/en
Publication of CN102134365A publication Critical patent/CN102134365A/en
Application granted granted Critical
Publication of CN102134365B publication Critical patent/CN102134365B/en

Links

Abstract

The invention discloses a permanently antistatic thermoplastic elastomer material, which consists of styrene elastomer, extending oil, a polyolefine resin, an ionic polymer antistatic agent, a compatilizer, a wearproof additive, an inorganic filler, a lubricating agent and an antioxygen. The material of the invention has permanent antistatic behaviour, water washing resistance, wear resistance and high-temperature resistance and low price and high workability, and the volume resistivity of the material can be reduced to 108 ohm.com.

Description

The thermoplastic elastic material of permanent anti-static

Technical field

The present invention relates to a kind of thermoplastic elastic material.

Background technology

Thermoplastic elastomer (Thermoplastic Elastomer) is to come out in recent years and the fast-developing a kind of novel energy-conserving that gets up, the macromolecular material of environmental protection.It not only has the elasticity, winter hardiness etc. of vulcanized rubber, but also has the workability of plastics, at high temperature can fusion, be suitable for the course of processing and the mould molding of common plastics, and processing is simple, and shaping cycle is short, production efficiency is high.

Have higher insulativity but thermoplastic elastic material and most of rubber, plastics are the same, surface resistivity is generally 10 15More than Ω/sq, in use can produce a large amount of static, static discharge can damage or destroy responsive electronic component, can eliminate or change magnetic medium, also can set off an explosion and fire in inflammable environment.In every year, only estimate just up to 40,000,000,000 yuan on U.S. dollar at the damage of electrostatic discharge of electronic industry.Therefore antistatic material has not replaceable effect in some fields.

What the antistatic material major part that provides was in the market added is the small molecules static inhibitor, this class material is to move to material surface formation hydrophilic layer by small molecules to produce antistatic effect, this material antistatic effect time is short, water-fast washing not, and very big relation is arranged with the humidity of environment for use, when airborne humidity is very low, can have a strong impact on its static resistance.In order to make material have the permanent anti-static effect, the researchist begins to adopt polymer type antistatic agent, because polymericular weight is bigger, can not move, so its static resistance has permanently, and can not change with the variation of ambient moisture.

The research of solid polymer electrolyte (SPEs) starts from the seventies in 20th century, 1973, W right etc. has reported that polyoxyethylene (PEO) and an alkali metal salt are compound and has had an ionic conductivity, Armand in 1979 have confirmed the conclusion of W right, and propose and this system can be used for lithium cell, through the development of decades, the room temperature volume specific resistance of solid polymer electrolyte can be reduced to 10 5About Ω cm, in lithium cell, be widely used.But the solid polymer electrolyte system is less in the application in polymer anti static field, and the present invention is exactly that the good specific conductivity of utilizing the solid polymer electrolyte system to be had prepares the thermoplastic elastic material with permanent anti-static.

Summary of the invention

The object of the present invention is to provide the thermoplastic elastic material of the wash-resistant permanent anti-static of a kind of antistatic property.

Technical solution of the present invention is:

A kind of thermoplastic elastic material of permanent anti-static is characterized in that: said composition is prepared from by the component of following weight part:

Described styrenic elastomerics is styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), one or more mixtures in styrene-ethylene/propylene-styrene segmented copolymer (SEPS), the polystyrene-ethylene-vinyl/propylene-styrene segmented copolymer (SEEPS).

Extending oil is one or more mixtures in naphthenic oil, straight-chain paraffin oil, the fragrant hydrocarbon ils.

The Ionomer static inhibitor is made up of A, B two components; Wherein the A component is the agent of polyethers polymer anti static, as in polyoxyethylene (PEO), PEP-101 (EO-PO), the epoxy ethane-epoxy propane-Racemic glycidol ether copolymer (EO-PO-AGE) one or more.

Polyolefin resin is one or more the mixture in isotatic polypropylene, high density polyethylene(HDPE), linear low density polyethylene, new LDPE (film grade), metallocene PE, metallocene polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, the polystyrene.

Compatilizer is one or more blends in maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride inoculated polypropylene (PP-g-MAH), maleic anhydride graft SEBS (SEBS-g-MAH), maleic anhydride graft polystyrene (PS-g-MAH), ethylene-acrylate-copolymer-maleic anhydride (EMH), the maleic anhydride grafted ethene-propylene copolymer.

Anti-wear additive is silicone master batch, molybdenumdisulphide or ptfe micropowder.

Mineral filler is one or more in lime carbonate, talcum powder, mica, kaolin, the barium sulfate.

The mineral filler particle diameter is 5 μ m~10 μ m.

Lubricant is one or more in amine hydroxybenzene, erucicamide, stearic acid, butyl stearate, ethylene bis stearamide, polyethylene wax, the silicone oil; Oxidation inhibitor is one or more in Hinered phenols, hindered amines, the phosphite ester kind antioxidant.

Material of the present invention has permanent antistatic, water-fastly washes, wear-resisting, high temperature resistant, price is low, processing easily, volume specific resistance can drop to 10 8Ω cm.

The invention will be further described below in conjunction with embodiment.

Embodiment

At first styrenic elastomerics, extending oil are put into high mixer and stir 10min, after treating that elastomerics fully absorbs oil, add polyolefin resin, Ionomer static inhibitor, mineral filler, oxidation inhibitor, lubricant, anti-wear additive, compatilizer, high-speed stirring 5min again, rotating speed 180rad/min.Be at least 48: 1 single screw rod or twin screw extruder extruding pelletization then with length-to-diameter ratio, the processing temperature scope is 200 ℃.

The amounts of components of each embodiment sees Table 1.Performance data sees Table 2.

Embodiment

Material name Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparative Examples SEBS ?100 ?100 ?100 ?100 ?100 ?100 100 Paraffin oil ?100 ?110 ?120 ?130 ?140 ?150 150 Polypropylene ?60 ?70 ?0 ?0 ?30 ?40 40 Polyethylene ?0 ?0 ?60 ?70 ?30 ?40 40 EO-PO ?30 ?50 ?0 ?0 ?20 ?30 0 EO-PO-AGE ?0 ?0 ?30 ?50 ?20 ?30 0 LiClO 4 5 10 0 0 5 0 0 C 4F 9SO 3Li 0 0 5 10 0 10 0 PP-g-MAH 20 30 10 20 0 20 20 SEB?S-g-MAH 0 0 10 10 30 20 20 Lime carbonate 50 55 65 50 55 60 65 Silicone master batch 20 20 20 20 20 20 20 Antioxidant 1010 2 2 2 2 2 2 2 Oxidation inhibitor 168 2 2 2 2 2 2 2 Amine hydroxybenzene 3 3 3 3 3 3 3

Performance data

Surface resistivity and volume specific resistance test voltage are 500V, and the time is 1min, according to the ASTMD257-2007 canonical measure.The washing experimental technique is test materials to be immersed in the water with cotton clean back drying under reduced pressure (130Pa, 70 ℃, 2 hours), is 23 ℃ with sample in temperature again, and humidity is that 50% environment is placed after 24 hours down and measured with megger.

The also available following method preparation of the foregoing description: be divided into for two steps, the first step is used the forcing machine extruding pelletization after earlier styrenic elastomerics, extending oil, polyolefin resin, mineral filler, oxidation inhibitor, anti-wear additive being stirred.Extruding pelletization again after second step mixed with ready-made particle of the first step and Ionomer static inhibitor.The processing temperature scope is 200 ℃~220 ℃.

Each component can adopt:

The styrenic elastomerics is styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), one or more mixtures in styrene-ethylene/propylene-styrene segmented copolymer (SEPS), the polystyrene-ethylene-vinyl/propylene-styrene segmented copolymer (SEEPS).

Extending oil is one or more mixtures in naphthenic oil, straight-chain paraffin oil, the fragrant hydrocarbon ils.

The Ionomer static inhibitor is made up of A, B two components; Wherein the A component is the agent of polyethers polymer anti static, as in polyoxyethylene (PEO), PEP-101 (EO-PO), the epoxy ethane-epoxy propane-Racemic glycidol ether copolymer (EO-PO-AGE) one or more.

Polyolefin resin is one or more the mixture in isotatic polypropylene, high density polyethylene(HDPE), linear low density polyethylene, new LDPE (film grade), metallocene PE, metallocene polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, the polystyrene.

Compatilizer is one or more blends in maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride inoculated polypropylene (PP-g-MAH), maleic anhydride graft SEBS (SEBS-g-MAH), maleic anhydride graft polystyrene (PS-g-MAH), ethylene-acrylate-copolymer-maleic anhydride (EMH), the maleic anhydride grafted ethene-propylene copolymer.

Anti-wear additive is silicone master batch, molybdenumdisulphide or ptfe micropowder.

Mineral filler is one or more in lime carbonate, talcum powder, mica, kaolin, the barium sulfate.

The mineral filler particle diameter is 5 μ m~10 μ m.

Lubricant is one or more in amine hydroxybenzene, erucicamide, stearic acid, butyl stearate, ethylene bis stearamide, polyethylene wax, the silicone oil; Oxidation inhibitor is one or more in Hinered phenols, hindered amines, the phosphite ester kind antioxidant.

Each amounts of components is identical with embodiment 1~6, forms new embodiment.

Claims (10)

1. the thermoplastic elastic material of a permanent anti-static, it is characterized in that: said composition is prepared from by the component of following weight part:
60 ~ 120 parts on styrenic elastomerics
60 ~ 200 parts of extending oils
20 ~ 160 parts of polyolefin resines
10 ~ 80 parts in Ionomer static inhibitor
10 ~ 80 parts of compatilizers
10 ~ 60 parts of anti-wear additives
30 ~ 120 parts of mineral fillers
2 ~ 5 parts of lubricants
2 ~ 5 parts in oxidation inhibitor.
2. the thermoplastic elastic material of permanent anti-static according to claim 1, it is characterized in that: described styrenic elastomerics is styrene-butadiene-styrene block copolymer, styrene-ethylene/butylene-styrene block copolymer, one or more mixtures in styrene-ethylene/propylene-styrene segmented copolymer, the polystyrene-ethylene-vinyl/propylene-styrene segmented copolymer.
3. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2, it is characterized in that: extending oil is one or more mixtures in naphthenic oil, straight-chain paraffin oil, the fragrant hydrocarbon ils.
4. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2, it is characterized in that: the Ionomer static inhibitor is made up of A, B two components; Wherein the A component is one or more the mixture in polyethers polymer anti static agent polyoxyethylene, PEP-101, the epoxy ethane-epoxy propane-Racemic glycidol ether copolymer; The B component is an alkali metal salt LiBF 4, LiClO 4, LiPF 6, NaClO 4, KClO 4, CF 3SO 3Li, LiCl, C 4F 9SO 3Li, (CF 3SO 2) 3CLi, (CF 3CH 2OSO 2) 3Among CLi, the NaPF6 one or more.
5. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2 is characterized in that: polyolefin resin is one or more the mixture in polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, the polystyrene.
6. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2, it is characterized in that: compatilizer is one or more blends in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride graft SEBS, maleic anhydride graft polystyrene, ethylene-acrylate-copolymer-maleic anhydride, the maleic anhydride grafted ethene-propylene copolymer.
7. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2, it is characterized in that: anti-wear additive is silicone master batch, molybdenumdisulphide or ptfe micropowder.
8. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2, it is characterized in that: mineral filler is one or more in lime carbonate, talcum powder, mica, kaolin, the barium sulfate.
9. the thermoplastic elastic material of permanent anti-static according to claim 8, it is characterized in that: the mineral filler particle diameter is 5 μ m ~ 10 μ m.
10. the thermoplastic elastic material of permanent anti-static according to claim 1 and 2, it is characterized in that: lubricant is one or more in amine hydroxybenzene, erucicamide, stearic acid, butyl stearate, ethylene bis stearamide, polyethylene wax, the silicone oil; Oxidation inhibitor is one or more in Hinered phenols, hindered amines, the phosphite ester kind antioxidant.
CN2011101121029A 2011-04-29 2011-04-29 Permanently antistatic thermoplastic elastomer material CN102134365B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011101121029A CN102134365B (en) 2011-04-29 2011-04-29 Permanently antistatic thermoplastic elastomer material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011101121029A CN102134365B (en) 2011-04-29 2011-04-29 Permanently antistatic thermoplastic elastomer material

Publications (2)

Publication Number Publication Date
CN102134365A true CN102134365A (en) 2011-07-27
CN102134365B CN102134365B (en) 2012-11-21

Family

ID=44294305

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011101121029A CN102134365B (en) 2011-04-29 2011-04-29 Permanently antistatic thermoplastic elastomer material

Country Status (1)

Country Link
CN (1) CN102134365B (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090246432A1 (en) * 2005-04-01 2009-10-01 Guanghe Wang Skidproof mat and manufacturing method thereof and skidproof mat assembly
CN102634158A (en) * 2012-04-27 2012-08-15 东莞市信诺橡塑工业有限公司 Permanent antistatic polystyrene composite material and preparation method thereof
CN102634191A (en) * 2012-05-15 2012-08-15 金发科技股份有限公司 Permanent antistatic nylon elastomer material and preparation method thereof
CN103113703A (en) * 2013-01-30 2013-05-22 合肥美的荣事达电冰箱有限公司 Master batch composition, compound board and preparation method of compound board, and refrigeration plant
CN103131118A (en) * 2011-11-28 2013-06-05 上海日之升新技术发展有限公司 Permanent anti-static electricity acrylonitrile butadiene styrene (ABS) composite material and preparation method thereof
CN103524911A (en) * 2013-09-25 2014-01-22 吴江市天源塑胶有限公司 Anti-static wear resisting plastic
CN103724781A (en) * 2013-12-09 2014-04-16 安徽万朗磁塑集团有限公司 TPE door seal granular material for refrigerator door
CN104004261A (en) * 2014-06-05 2014-08-27 东莞市瀛通电线有限公司 Aromatic plastic material for plastic wire and preparation method thereof
CN104140633A (en) * 2014-08-06 2014-11-12 南通普力马弹性体技术有限公司 TPE flame resistant material for coating plastic and preparing method of TPE flame resistant material
CN104788986A (en) * 2015-04-30 2015-07-22 安徽省潜山县创先实业有限公司 Antistatic thermoplastic rubber band and preparation method thereof
CN104987646A (en) * 2015-07-21 2015-10-21 南通普力马弹性体技术有限公司 Thermoplastic styrenic elastomer composition with high elongation and low stretching permanent deformation
CN105733116A (en) * 2016-05-09 2016-07-06 安徽江淮汽车股份有限公司 Wear-resistant high-electroconductivity PE-PS (polyethylene-polystyrene) alloy and preparation method thereof
CN106189280A (en) * 2016-08-03 2016-12-07 南通普力马弹性体技术有限公司 A kind of Antistatic thermoplastic elastomer printed for 3D and preparation method
CN105218970B (en) * 2015-09-30 2017-07-25 东莞市华立实业股份有限公司 A kind of antistatic PVC base wood-plastic composite materials and preparation method thereof
CN107163480A (en) * 2017-07-08 2017-09-15 郭瑞 A kind of plastic formula containing molybdenum disulfide
CN108727767A (en) * 2018-06-26 2018-11-02 南通普力马弹性体技术有限公司 Thermoplastic elastic material and film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1685009A (en) * 2002-10-17 2005-10-19 Ps日本株式会社 Resin composition excellent in antistatic property, surface hardness, and strength
CN101838436A (en) * 2010-06-17 2010-09-22 深圳职业技术学院 SEBS thermoplastic elastomer cable insulation material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1685009A (en) * 2002-10-17 2005-10-19 Ps日本株式会社 Resin composition excellent in antistatic property, surface hardness, and strength
CN101838436A (en) * 2010-06-17 2010-09-22 深圳职业技术学院 SEBS thermoplastic elastomer cable insulation material and preparation method thereof

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8435616B2 (en) * 2005-04-01 2013-05-07 Guanghe Wang Skidproof mat and manufacturing method thereof and skidproof mat assembly
US20090246432A1 (en) * 2005-04-01 2009-10-01 Guanghe Wang Skidproof mat and manufacturing method thereof and skidproof mat assembly
CN103131118A (en) * 2011-11-28 2013-06-05 上海日之升新技术发展有限公司 Permanent anti-static electricity acrylonitrile butadiene styrene (ABS) composite material and preparation method thereof
CN103131118B (en) * 2011-11-28 2015-08-05 上海日之升新技术发展有限公司 A kind of permanent anti-static ABS composite material and preparation method thereof
CN102634158A (en) * 2012-04-27 2012-08-15 东莞市信诺橡塑工业有限公司 Permanent antistatic polystyrene composite material and preparation method thereof
CN102634191A (en) * 2012-05-15 2012-08-15 金发科技股份有限公司 Permanent antistatic nylon elastomer material and preparation method thereof
CN103113703A (en) * 2013-01-30 2013-05-22 合肥美的荣事达电冰箱有限公司 Master batch composition, compound board and preparation method of compound board, and refrigeration plant
CN103524911A (en) * 2013-09-25 2014-01-22 吴江市天源塑胶有限公司 Anti-static wear resisting plastic
CN103524911B (en) * 2013-09-25 2016-04-20 吴江市天源塑胶有限公司 A kind of anti-static and abrasion-resistant plastics
CN103724781A (en) * 2013-12-09 2014-04-16 安徽万朗磁塑集团有限公司 TPE door seal granular material for refrigerator door
CN103724781B (en) * 2013-12-09 2016-01-27 安徽万朗磁塑集团有限公司 A kind of TPE door seal granular material for refrigerator door
CN104004261B (en) * 2014-06-05 2016-04-13 东莞市瀛通电线有限公司 A kind of plastic cement wire rod aromaticity plastic material and preparation method thereof
CN104004261A (en) * 2014-06-05 2014-08-27 东莞市瀛通电线有限公司 Aromatic plastic material for plastic wire and preparation method thereof
CN104140633A (en) * 2014-08-06 2014-11-12 南通普力马弹性体技术有限公司 TPE flame resistant material for coating plastic and preparing method of TPE flame resistant material
CN104788986A (en) * 2015-04-30 2015-07-22 安徽省潜山县创先实业有限公司 Antistatic thermoplastic rubber band and preparation method thereof
CN104987646A (en) * 2015-07-21 2015-10-21 南通普力马弹性体技术有限公司 Thermoplastic styrenic elastomer composition with high elongation and low stretching permanent deformation
CN105218970B (en) * 2015-09-30 2017-07-25 东莞市华立实业股份有限公司 A kind of antistatic PVC base wood-plastic composite materials and preparation method thereof
CN105733116A (en) * 2016-05-09 2016-07-06 安徽江淮汽车股份有限公司 Wear-resistant high-electroconductivity PE-PS (polyethylene-polystyrene) alloy and preparation method thereof
CN105733116B (en) * 2016-05-09 2018-11-16 安徽江淮汽车集团股份有限公司 A kind of PE-PS alloy and preparation method thereof that wear-resistant conductive is high
CN106189280A (en) * 2016-08-03 2016-12-07 南通普力马弹性体技术有限公司 A kind of Antistatic thermoplastic elastomer printed for 3D and preparation method
CN107163480A (en) * 2017-07-08 2017-09-15 郭瑞 A kind of plastic formula containing molybdenum disulfide
CN108727767A (en) * 2018-06-26 2018-11-02 南通普力马弹性体技术有限公司 Thermoplastic elastic material and film

Also Published As

Publication number Publication date
CN102134365B (en) 2012-11-21

Similar Documents

Publication Publication Date Title
CN103890865B (en) The manufacture method of electric wire formed body
Pineri et al. Structure and properties of ionomers
CN101845197B (en) High-performance halogen-free flame retardant ABS modified resin and preparation method thereof
EP0209874B1 (en) Hydrogenated block copolymer compositions
EP1592744B1 (en) Compositions containing polyphenylene ether and/or polystyrene having improved tribological properties and methods for improving tribological properties of polyphenylene ether and/or polystyrene compositions
CN101072832B (en) Conductive poly(arylene ether)-polyamide compositions, and related methods and articles
JP4491337B2 (en) Biodegradable plastic material and molded body
CN102516742B (en) Polyphenylether cable compound for adjusting hardness and preparation method thereof
CN101508835B (en) Halogen-free flame-proof static resistant polycarbonate composition and method for producing the same
TW570948B (en) Thermoplastic resin composition and method for processing thermoplastic resin composition
JP4011972B2 (en) Foamable thermoplastic elastomer composition and method for producing the same
US6841215B2 (en) Heat resistant pipe and method of manufacture thereof
JP4901065B2 (en) Thermoplastic resin composition
CN102234419B (en) Halogen-free flameproof polyphenylene ether resin composition and preparation method thereof
CN101437890B (en) Compatibilized polymer processing additives
CN104592645A (en) Low-density low-shrinkage high-impact polypropylene composite material and preparation method thereof
EP2404965A1 (en) Flame-retardant resin composition
US10273361B2 (en) Conductive polyamide/polyphenylene ether resin composition and automotive molded article manufactured therefrom
Kalkornsurapranee et al. Development and preparation of high‐performance thermoplastic vulcanizates based on blends of natural rubber and thermoplastic polyurethanes
JP4870280B2 (en) Thermoplastic elastomer pellets and moldings
CN102061050A (en) All-weather persistent antistatic master batch capable of being subjected to thermoplastic processing and antistatic composite material
WO1998020503A1 (en) Electrically conductive compositions and methods for producing same
CN105504503B (en) A kind of resistance to scratching, anti-precipitation PP composite material and preparation method thereof
CN103589125B (en) A kind of Polylactic acid/polypropylene blend and preparation method thereof
EP2730613B1 (en) Resin composition and method for producing same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant