CN110628135A - Ultrahigh-fluidity TPV material - Google Patents
Ultrahigh-fluidity TPV material Download PDFInfo
- Publication number
- CN110628135A CN110628135A CN201810658843.9A CN201810658843A CN110628135A CN 110628135 A CN110628135 A CN 110628135A CN 201810658843 A CN201810658843 A CN 201810658843A CN 110628135 A CN110628135 A CN 110628135A
- Authority
- CN
- China
- Prior art keywords
- parts
- flow
- ultrahigh
- ultra
- tpv material
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a TPV material with ultrahigh fluidity, which is characterized by comprising the following raw materials in parts by weight: 5-50 parts of ethylene propylene diene monomer; 1-40 parts of high-flow polypropylene or polyolefin; 1-40 parts of ultrahigh-flow hydrogenated styrene butadiene block copolymer; 0-50 parts of white oil; 0-40 parts of a filler; 0-5 parts of a lubricating additive; 0-1 part of a crosslinking assistant; the ultra-high fluidity TPV material has ultra-high fluidity which can be far more than 20g/10min (@190 ℃/2.16kgf), thereby overcoming the defects of the two materials and meeting the special requirements of certain applications on the ultra-high fluidity.
Description
Technical Field
The invention relates to the technical field of TPV materials, in particular to a TPV material with ultrahigh fluidity.
Background
TPV is a Thermoplastic Vulcanization elastomer or Thermoplastic dynamic vulcanizate, for short, and is an elastomeric material composed of highly vulcanized rubber particles dispersed in a continuous plastic phase. TPV has physical and functional characteristics similar to those of thermosetting rubber at normal temperature, has the characteristics of melt flow and repeated processing of thermoplastic plastics at high temperature, and has the advantages of convenient molding and processing, recyclable materials, excellent comprehensive performance and the like.
TPV materials are low in cost, excellent in mechanical property, high in impact strength, oil resistance, aging resistance and weather resistance, gradually replace non-recyclable thermosetting materials, have excellent physical and mechanical properties of elastomers, can be recycled, save resources, are clean and environment-friendly, and improve the yield of products. Due to excellent product performance and convenient processing technology, more and more TPV materials are applied to industries of automobiles, household electrical appliances and the like. In the automobile industry, a plurality of large parts are changed into the prior engineering plastic parts from the prior metal parts, and some soft rubber parts are also changed into elastomer materials from the prior rubber parts. Meanwhile, due to the convenient processing mode, the advantages of the injection molded elastomer soft rubber part in modern production and application are more and more obvious. The traditional TPV material has high crosslinking degree, poor material flowability and low MI value due to a special complete dynamic vulcanization system, and cannot obtain a good product when large-scale thin-wall parts are subjected to injection molding.
For example, the formulation system of the patent application No. 200810032799.7 uses hydrogenated styrene to prepare a new high strength, high clarity thermoplastic elastomer without any plasticizer and without any processing oil.
The formula of a high-fluidity TPV material with the application number of 201510752955 needs to be matched with a three-time twin-screw extrusion process, the fluidity of the prepared TPV is very low, the melt index is usually less than 20g/10min (@190 ℃/2.16kgf), the highest value in the TPV is 57g/10min, no pressure is noted, and therefore, the TPV cannot be used for injection molding on slightly larger thin-wall parts, and if TPE materials are adopted, the TPV cannot meet the requirements on the application of automotive interior parts due to the fact that the TPV has the performances of matte, solvent resistance and the like.
Disclosure of Invention
The invention aims to provide an ultra-high fluidity TPV material, which has ultra-high fluidity which can be far more than 20g/10min (@190 ℃/2.16kgf), thereby overcoming the defects of the two materials and meeting the special requirements of certain applications on high fluidity.
The invention adopts the following technical scheme: the TPV material with ultrahigh fluidity comprises the following raw materials in parts by weight:
5-50 parts of ethylene propylene diene monomer or other rubber;
1-40 parts of high-flow polypropylene or high-flow polyolefin;
1-40 parts of ultrahigh-flow hydrogenated styrene butadiene block copolymer;
0-50 parts of white oil;
0-40 parts of a filler;
0-5 parts of a lubricating additive;
0-1 part of crosslinking assistant.
In a preferable scheme, the ethylene propylene diene monomer is a terpolymer obtained by polymerizing ethylene, propylene and non-conjugated diene; the non-conjugated diene is ethylidene norbornene or dicyclopentadiene; the mol ratio of the ethylene to the propylene to the non-conjugated diene is 30-50: 35-55: 5-16.
Preferably, the polyolefin is selected from ultrahigh-flow homo-or co-polypropylene, or high-flow other polyolefin, or a mixture of multiple polyolefins.
Preferably, the ultrahigh-flow hydrogenated styrene butadiene block copolymer can be replaced by an ultrahigh-flow hydrogenated styrene isoprene block copolymer or a mixture of the two, wherein the styrene content is from 10% to 50%, and the butadiene content is from 50% to 90%.
Preferably, the white oil is mineral base oil consisting of straight-chain alkane and cycloalkane or synthetic base oil resynthesized by natural gas cracking.
Preferably, the white oil is a mixture of mineral base oil consisting of straight-chain paraffin and cycloparaffin and synthetic base oil resynthesized by natural gas cracking.
Preferably, the filler is selected from one or a mixture of more of calcium carbonate, talcum powder, barium sulfate, hydrotalcite powder, mica powder, wollastonite and glass fiber.
Compared with the prior art, the invention has the advantages that:
(1) the fluidity is very high and is far greater than 20g/10min (@ 190)oC/2.16kgf) and thus can overcome the drawbacks of the two materials mentioned above, meeting the special requirements for high flow for certain applications;
(2) the addition of white oil can be used for improving fluidity and increasing softness;
(3) the addition of the filler can be used for reducing the shrinkage rate, shortening the molding period, reducing the cost, reducing the transparency of the material and increasing the rigidity.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described; obviously; the described embodiments are only some of the embodiments of the invention; but not all embodiments, are based on the embodiments of the invention; all other embodiments obtained by a person skilled in the art without making any inventive step; all fall within the scope of protection of the present invention.
The invention relates to a TPV material with ultrahigh fluidity, which comprises the following raw materials in parts by weight:
5-50 parts of ethylene propylene diene monomer;
1-40 parts of high-flow polypropylene or high-flow polyolefin;
hydrogenating 1-40 parts of an ultrahigh-flow styrene-butadiene block copolymer;
0-50 parts of white oil;
0-40 parts of a filler;
0-5 parts of a lubricating additive;
0-1 part of crosslinking assistant.
The ethylene propylene diene monomer is a terpolymer obtained by polymerizing ethylene, propylene and non-conjugated diene; the non-conjugated diene is ethylidene norbornene or dicyclopentadiene; the mol ratio of the ethylene to the propylene to the non-conjugated diene is 30-50: 35-55: 5-16.
The polyolefin is selected from ultrahigh-flow homo-or co-polypropylene, such as MF650Y MFI from Basell: 1800g/10min, @230 ℃/2.16kg, or an ultra high flow TPO multiolefin copolymer, such as Vistamaxx2330, MFI 300 g/10min, @230 ℃/2.16 kg; for example, the MF650Y MFI from Basell: 1800g/10min @230 ℃/2.16 kg.
The ultrahigh-flow hydrogenated styrene isoprene block copolymer is used for replacing the ultrahigh-flow hydrogenated styrene butadiene block copolymer, or the mixture of the ultrahigh-flow hydrogenated styrene isoprene block copolymer and the ultrahigh-flow hydrogenated styrene butadiene block copolymer, wherein the styrene content is 10-50%, the butadiene content is 50-90%, and the copolymer can also be SEPS or SIS, SBS and the like; for example Kraton MD1648, MFI 220g/10min, @230 ℃/2.16 kg.
The white oil is mineral base oil mixed with straight-chain alkane and cyclane or synthetic base oil synthesized by natural gas cracking, is used for increasing fluidity and softness, and is KN4010 produced by petroleum in the embodiment.
The white oil may also be a mixture of a mineral base oil consisting of straight-chain paraffins and naphthenes and a synthetic base oil resynthesized from natural gas cracking.
The filler is one or a combination of more of calcium carbonate, talcum powder, barium sulfate, hydrotalcite powder, mica powder, wollastonite and glass fiber, and is used for reducing shrinkage, shortening molding cycle, reducing cost, reducing transparency of materials, increasing rigidity and the like.
The above; but are merely preferred embodiments of the invention; the scope of the invention is not limited thereto; any person skilled in the art is within the technical scope of the present disclosure; the technical scheme and the improved concept of the invention are equally replaced or changed; are intended to be covered by the scope of the present invention.
Claims (7)
1. The TPV material with ultrahigh fluidity is characterized by comprising the following raw materials in parts by weight:
5-50 parts of ethylene propylene diene monomer or other rubber;
1-40 parts of high-flow polypropylene or high-flow polyolefin;
1-40 parts of ultrahigh-flow hydrogenated styrene butadiene block copolymer;
0-50 parts of white oil;
0-40 parts of a filler;
0-5 parts of a lubricating additive;
0-1 part of crosslinking assistant.
2. The ultra-high flow TPV material of claim 1, wherein: the ethylene propylene diene monomer is a terpolymer obtained by polymerizing ethylene, propylene and non-conjugated diene; the non-conjugated diene is ethylidene norbornene or dicyclopentadiene; the mol ratio of the ethylene to the propylene to the non-conjugated diene is 30-50: 35-55: 5-16.
3. The ultra-high flow TPV material of claim 1, wherein: the polyolefin is selected from ultrahigh-flow homopolymerized or copolymerized polypropylene, or high-flow other polyolefin, or a mixture of multiple polyolefins.
4. The ultra-high flow TPV material of claim 1, wherein: the ultrahigh flow hydrogenated styrene butadiene block copolymer can be replaced by an ultrahigh flow hydrogenated styrene isoprene block copolymer or a mixture of the two, wherein the styrene content is 10-50%, and the butadiene content is 50-90%.
5. The ultra-high flow TPV material of claim 1, wherein: the white oil mainly comprises mineral base oil consisting of straight-chain alkane and cycloalkane or synthetic base oil synthesized by natural gas cracking.
6. The ultra-high flow TPV material of claim 1, wherein: the white oil is a mixture of mineral base oil consisting of straight-chain alkane and cycloalkane and synthetic base oil resynthesized by natural gas cracking.
7. The ultra-high flow TPV material of claim 1, wherein: the filler is selected from one or a mixture of more of calcium carbonate, talcum powder, barium sulfate, hydrotalcite powder, mica powder, wollastonite and glass fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810658843.9A CN110628135A (en) | 2018-06-25 | 2018-06-25 | Ultrahigh-fluidity TPV material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810658843.9A CN110628135A (en) | 2018-06-25 | 2018-06-25 | Ultrahigh-fluidity TPV material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110628135A true CN110628135A (en) | 2019-12-31 |
Family
ID=68966717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810658843.9A Pending CN110628135A (en) | 2018-06-25 | 2018-06-25 | Ultrahigh-fluidity TPV material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110628135A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048083A1 (en) * | 1999-12-27 | 2001-07-05 | Japan Polychem Corporation | Polypropylene resin composition excellent in moldability and physical properties |
| CN101148528A (en) * | 2007-11-02 | 2008-03-26 | 上海金发科技发展有限公司 | Method for preparing low-contraction high-fluidity high-toughness polypropylene |
| KR20080093788A (en) * | 2007-04-18 | 2008-10-22 | 현대모비스 주식회사 | Thermoplastic elastomer resin with high flow property |
| CN101838423A (en) * | 2010-06-10 | 2010-09-22 | 南京聚隆科技股份有限公司 | Modified polypropylene material for thin-wall bumper and preparation method thereof |
| CN101885878A (en) * | 2010-08-12 | 2010-11-17 | 株洲时代工程塑料制品有限责任公司 | Polypropylene resin composite |
| CN103819817A (en) * | 2014-03-11 | 2014-05-28 | 株洲时代新材料科技股份有限公司 | Polypropylene composition with high fluidity and high dimensional stability and preparation method thereof |
| CN104744825A (en) * | 2013-12-31 | 2015-07-01 | 中纺投资发展股份有限公司 | Thermoplastic vulcanizate elastomer composition and preparation method thereof |
| CN105295196A (en) * | 2015-11-09 | 2016-02-03 | 安徽韧达高分子材料有限公司 | High-fluidity TPV material and preparing method thereof |
| CN105385041A (en) * | 2014-09-04 | 2016-03-09 | 丹阳市国美汽配有限公司 | Thin-walled bumper modified polypropylene material and preparation process thereof |
-
2018
- 2018-06-25 CN CN201810658843.9A patent/CN110628135A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001048083A1 (en) * | 1999-12-27 | 2001-07-05 | Japan Polychem Corporation | Polypropylene resin composition excellent in moldability and physical properties |
| KR20080093788A (en) * | 2007-04-18 | 2008-10-22 | 현대모비스 주식회사 | Thermoplastic elastomer resin with high flow property |
| CN101148528A (en) * | 2007-11-02 | 2008-03-26 | 上海金发科技发展有限公司 | Method for preparing low-contraction high-fluidity high-toughness polypropylene |
| CN101838423A (en) * | 2010-06-10 | 2010-09-22 | 南京聚隆科技股份有限公司 | Modified polypropylene material for thin-wall bumper and preparation method thereof |
| CN101885878A (en) * | 2010-08-12 | 2010-11-17 | 株洲时代工程塑料制品有限责任公司 | Polypropylene resin composite |
| CN104744825A (en) * | 2013-12-31 | 2015-07-01 | 中纺投资发展股份有限公司 | Thermoplastic vulcanizate elastomer composition and preparation method thereof |
| CN103819817A (en) * | 2014-03-11 | 2014-05-28 | 株洲时代新材料科技股份有限公司 | Polypropylene composition with high fluidity and high dimensional stability and preparation method thereof |
| CN105385041A (en) * | 2014-09-04 | 2016-03-09 | 丹阳市国美汽配有限公司 | Thin-walled bumper modified polypropylene material and preparation process thereof |
| CN105295196A (en) * | 2015-11-09 | 2016-02-03 | 安徽韧达高分子材料有限公司 | High-fluidity TPV material and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 克拉曼: "《润滑剂及其有关产品》", 31 July 1990, 烃加工出版社 * |
| 卢英才 等: "《新编润滑油脂实用手册》", 30 April 1989, 辽宁科学技术出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101100593B (en) | Environmental protection type SEBS thermoplastic elastic body sealing strip material and preparation method thereof | |
| CN102372893B (en) | Styrenic thermoplastic elastomer composition and preparation method thereof | |
| US4031169A (en) | Thermoplastic elastomeric polymer blend | |
| CN103980621A (en) | High-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof | |
| CN103113680A (en) | Low-gloss polyolefin elastomer composite material and preparation method thereof | |
| CN101845193A (en) | Dynamically vulcanized styrene thermoplastic elastomer and preparation method thereof | |
| KR20050020003A (en) | Thermoplastic elastomer composition and Method for preparing the same | |
| CN105295196A (en) | High-fluidity TPV material and preparing method thereof | |
| CN104672626A (en) | High-elasticity thermoplastic elastomer material and preparation method thereof | |
| CN111057306B (en) | TPV composition and preparation method thereof | |
| CN111303536A (en) | Low-shrinkage polypropylene material and preparation method thereof | |
| CN104817804A (en) | TPE (Thermoplastic Elastomer) material for medical supplies | |
| CN102875948A (en) | Matte thermoplastic elastomer composition and preparation method thereof | |
| CN112574579A (en) | Scratch-resistant thermoplastic elastomer and preparation method thereof | |
| CN111053945B (en) | Environment-friendly high-strength high-resilience TPE (thermoplastic elastomer) tourniquet material and preparation method thereof | |
| CN112662075A (en) | Polypropylene composite material capable of eliminating appearance defects of ghost and tiger skin | |
| CN111718587A (en) | Low-compression permanent deformation thermoplastic elastomer material and preparation method thereof | |
| CN103102578A (en) | Low temperature-resistant thermoplastic elastomer and preparation method thereof | |
| CN109971109A (en) | A kind of high sound-absorbing damping thermoplastic elastomer blend | |
| CN109233095A (en) | Modified polypropylene material for refrigerator ice milk layer drawer | |
| CN106750987A (en) | A kind of modified poly propylene composition | |
| KR101350890B1 (en) | Optimal foam process of thermo plastic elastomer using improved melt strength thermoplastic resin | |
| CN102731910B (en) | Non-elastomer/polypropylene blended composite material | |
| CN110628135A (en) | Ultrahigh-fluidity TPV material | |
| CN105295566A (en) | Coating material dedicated to thermoplastic elastomer and preparation method of coating material. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191231 |
|
| RJ01 | Rejection of invention patent application after publication |