CN107698736A - Adhesive for shoes preparation method - Google Patents

Adhesive for shoes preparation method Download PDF

Info

Publication number
CN107698736A
CN107698736A CN201711061390.3A CN201711061390A CN107698736A CN 107698736 A CN107698736 A CN 107698736A CN 201711061390 A CN201711061390 A CN 201711061390A CN 107698736 A CN107698736 A CN 107698736A
Authority
CN
China
Prior art keywords
parts
acetone
adhesive
minutes
reaction
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.)
Withdrawn
Application number
CN201711061390.3A
Other languages
Chinese (zh)
Inventor
应建忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yongjia Xincheng Technology Service Co Ltd
Original Assignee
Yongjia Xincheng Technology Service Co Ltd
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 Yongjia Xincheng Technology Service Co Ltd filed Critical Yongjia Xincheng Technology Service Co Ltd
Priority to CN201711061390.3A priority Critical patent/CN107698736A/en
Publication of CN107698736A publication Critical patent/CN107698736A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives

Abstract

The present invention relates to a kind of adhesive for shoes preparation method, mainly using the PEPA of macromolecule as main material, and combine toluene di-isocyanate(TDI) and hexamethylene diisocyanate progress prepolymerization, after reaction is accomplished to predetermined extent, directly cooling and diamino sulfonic acid reactant salt, and before frozen water emulsification, first and ethylenediamine fast reaction chain extension, then frozen water emulsification is added, by adjusting the amount of ethylenediamine, remaining isocyano in monoethanolamine at normal temperatures maturing process by carrying out terminating reaction；Used using sulfamate as emulsifying agent, using the combination of toluene di-isocyanate(TDI) and hexamethylene diisocyanate；Have the advantages that cost is low, production efficiency is high, production technology controllability is good, production yield rate is high.

Description

Adhesive for shoes preparation method
Technical field
The invention belongs to polymeric material field, especially with respect to a kind of water-based polyurethane adhesive and preparation method.This hair It is bright to be applied to adhesive for shoes.
Background technology
China is global maximum footwear producing country, country of consumption and exported country, footwear annual production tens pairs, accounts for global footwear More than the 50% of class production.The provinces such as Zhejiang, Fujian, Guangdong, Shandong, Sichuan and Chengdu turn into shoemaking industry intensively, 20,000 many enterprises are concentrated, producing footwear 80% needs to use adhesive, and the dosage of shoes-used glue is more than more than 20 ten thousand tons.Shoes-used glue glues Agent since the chloroprene rubber adhesive agent of the first generation, the Forecast of Grafted Adhesive of the second generation, the third generation solvent borne polyurethane adhesive, now Develop towards forth generation water-based polyurethane adhesive.Well-known shoes manufacturing enterprise has begun to use and promotes aqueous polyurethane shoes-used glue The use of stick, the product of US and European is especially exported to, very high is required to product environmental protection index, promotes aqueous polyurethane The fast development of adhesive for shoes.Since German Schlack is once in the presence of emulsifying agent, since preparing polyaminoester emulsion, The Beyer Co., Ltd of Germany is on the forefront in terms of polyurethane aqueousization always.The United States Patent (USP) of Beyer Co., Ltd, US PATENT In 5334690, using polyadipate BDO esterdiol, the polyalcohol that molecular weight is 2000 is raw material, with hexa-methylene Diisocyanate and IPDI press 66：34 ratio is reacted；Reaction to after predetermined extent using Isosorbide-5-Nitrae- Butanediol carries out chain extension；Hereafter 60 are cooled to0C or so and 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium, 45% is containing remaining admittedly Water, reacted, while chain extending reaction occurs；Then emulsified, and chain extension after being carried out with ethylenediamine, aqueous polyurethane is made Adhesive for shoes emulsion.Its product is market-oriented, and wherein Dispercoll U-53, U-54 have excellent footwear adhesive Performance.Water-based polyurethane adhesive currently on the market uses this technical scheme to be prepared substantially.Such as China Patent No. Preparation method described in CN201410713165.3 and some other report, such as South China Science ＆ Engineering University's chemistry and Cao of chemical engineering institute A kind of adhesive for shoes preparation method that Gao Hua et al. is reported on the Journal of Chemical Industry and Engineering in April, 2014, it is essentially all Bayer public affairs Take charge of the deriving technology of this United States Patent (USP).Its major defect is：2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium with through Isosorbide-5-Nitrae-fourth two Viscosity build is exceedingly fast during molecule chain reaction after alcohol chain extension, need to add substantial amounts of acetone and be diluted, and emulsification otherwise will be caused to lose Lose, its added acetone about accounts for 1.5-1.8 times of polymer, this result in acetone recovery and feed intake cost the problem of；Moreover, Per batch, production is only capable of producing the product of inventory half or so, and remaining is butanone, acetone for vacuumizing removing and coming out etc. Solvent, this brings very big trouble, and the principal element of low production efficiency to the manufacturing；Chain extending reaction pair at high viscosities It is high in the operation technological requirement of commercial process, if without controlling well, it is easy to cause emulsification failure or The problems such as adhesive tack weakens or failed, causes yield rate low.
The content of the invention
The shortcomings that present invention exists for prior art, there is provided a kind of cost is low, production efficiency is high, production technology controllability Adhesive for shoes preparation method good, production yield rate is high.
The preparation method of adhesive for shoes of the present invention：
1）30 parts of 1560 parts of the polyadipate that feeds intake BDO esterdiol and polyethylene glycol adipate glycol enter 6000L reactions Kettle, it is warming up to 1150C, dehydration 0.5 hour is vacuumized, open reflux condensation mode valve, be passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 200 parts of butanone that feed intake in order, 2 parts of antioxidants, 34.8 parts of aromatic series two are different Cyanate enters above reactor, reacts 1.0 hours；
3）Feed intake 67.2 parts of hexamethylene diisocyanates, 0.6 part of catalyst enters above reactor, and 800It is small that C continues reaction 1.0 When；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；Under high speed shear（Scattered plate edge Linear velocity is more than 12m/s）, rapidly join 2- [(2- aminoethyls) amino] 50.8 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao Speed stirring 30 minutes；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine class chain extender-ethylenediamines and acetone in advance, input is anti-under high velocity agitation Kettle is answered, and is reacted 5 minutes；
6）Rapidly join 1660 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 4.9 parts of monoethanolamine and the mixture of 44.1 parts of deionized water in advance, once put into above reactor, cut at a high speed Cut 5 minutes；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to requiring Value；
10）Using deionized water adjust solid content, and with 10-15 parts thickener adjustment viscosity, add a small amount of substrate wetting agents or Levelling agent 0.2-0.5 parts, after qualified after testing, packed by packaging instruction with 80 mesh filter screen filtrations.
Compared with the prior art, the invention has the advantages that：
1st, using the PEPA of macromolecule as main material, and toluene di-isocyanate(TDI) and the isocyanide of hexa-methylene two are combined Acid esters carries out prepolymerization, after reaction is accomplished to predetermined extent, directly cooling and diamino sulfonic acid reactant salt, and emulsified in frozen water Before, first with ethylenediamine fast reaction chain extension, frozen water emulsification is then added, by adjusting the amount of ethylenediamine, remaining isocyano leads to Cross monoethanolamine and carry out terminating reaction in maturing process at normal temperatures, preventing the isocyano of residual influences the first viscous of adhesive Property；
2nd, used using sulfamate as emulsifying agent, prepared emulsion 50% it is solid containing when have very low viscosity, eliminate The chain extension step of BDO, and the macromolecule PEPA of Isosorbide-5-Nitrae-fourth dimerization is employed, reactions steps are simplified, In sulfamate chain extension, required solvent greatly reduces, and reduces about 40%, and the cost that integrally feeds intake reduces 15%-20%, The effective debris deposit in emulsion is improved, production efficiency greatly improves；And a small amount of polyethylene glycol adipate glycol is used, can To be distributed among macromolecule PEPA, while strand crystallization, extend the open hour, reduce activation temperature and Performed polymer viscosity, reduce the usage amount of solvent；
3rd, using the combination of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, the activation temperature of adhesive is effectively reduced, Initial adhesive strength, crystal property, heat resistance are improved, reduces cost；
4th, using chain extension and monoethanolamine terminating reaction before being emulsified before ethylenediamine, tack can be effectively ensured, and avoid storing When adhesive aging the problem of, ensure the stability of product quality.
Embodiment
The adhesive for shoes preparation method of the present invention is as follows：
1）It is anti-that 30 parts of 1560 parts of the polyadipate that feeds intake BDO esterdiol and polyethylene glycol adipate glycol enter 6000L Kettle is answered, is warming up to 1150C, dehydration 0.5 hour is vacuumized, open reflux condensation mode valve, be passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 200 parts of butanone that feed intake in order, 2 parts of antioxidants, 34.8 parts of aromatic series two are different Cyanate enters above reactor, reacts 1.0 hours；Antioxidant uses four【β-（3,5- di-tert-butyl-hydroxy phenyls）Third Acid】Pentaerythritol ester；
3）Feed intake 67.2 parts of hexamethylene diisocyanates, 0.6 part of catalyst enters above reactor, and 800It is small that C continues reaction 1.0 When；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；Under high speed shear（Scattered plate edge Linear velocity is more than 12m/s）, rapidly join 2- [(2- aminoethyls) amino] 50.8 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao Speed stirring 30 minutes；Continued that 400 parts of acetone are at the uniform velocity added dropwise in 30 minutes, to keep viscosity when reacting；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine class chain extender-ethylenediamines and acetone in advance, input is anti-under high velocity agitation Kettle is answered, and is reacted 5 minutes；
6）Rapidly join 1660 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 4.9 parts of monoethanolamine and the mixture of 44.1 parts of deionized water in advance, once put into above reactor, cut at a high speed Cut 5 minutes；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to requiring Value；
10）Using deionized water adjust solid content, and with 10-15 parts thickener adjustment viscosity, add a small amount of substrate wetting agents or Levelling agent 0.2-0.5 parts, after qualified after testing, packed by packaging instruction with 80 mesh filter screen filtrations.
The injected volume " part " of each material is a mass unit in method made above, typically uses 1Kg as a quality Unit, the injected volume of each material can increase and decrease in proportion according to reactor capacity or batch size, the amount of each material in the present embodiment Than being relative preferred values with the reaction time.

Claims (1)

  1. A kind of 1. preparation method of adhesive for shoes, it is characterized in that using following processing step：
    1）30 parts of 1560 parts of the polyadipate that feeds intake BDO esterdiol and polyethylene glycol adipate glycol enter 6000L reactions Kettle, it is warming up to 1150C, dehydration 0.5 hour is vacuumized, open reflux condensation mode valve, be passed through nitrogen protection；
    2）It is cooled to 800C, under moderate-speed mixer, the 200 parts of butanone that feed intake in order, 2 parts of antioxidants, 34.8 parts of isocyanides of aromatic series two Acid esters enters above reactor, reacts 1.0 hours；
    3）Feed intake 67.2 parts of hexamethylene diisocyanates, 0.6 part of catalyst enters above reactor, and 800It is small that C continues reaction 1.0 When；
    4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；Under high speed shear, 2- is rapidly joined [(2- aminoethyls) amino] 50.8 parts of ethyl sulfonic acid sodium hydrophilic chain extender, then high-speed stirred 30 minutes；
    5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine class chain extender-ethylenediamines and acetone in advance, input is anti-under high velocity agitation Kettle is answered, and is reacted 5 minutes；
    6）Rapidly join 1660 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
    7）Prepare 4.9 parts of monoethanolamine and the mixture of 44.1 parts of deionized water in advance, once put into above reactor, cut at a high speed Cut 5 minutes；
    8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
    9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to required value；
    10）Using deionized water adjust solid content, and with 10-15 parts thickener adjustment viscosity, add a small amount of substrate wetting agents or Levelling agent 0.2-0.5 parts, after qualified after testing, packed by packaging instruction with 80 mesh filter screen filtrations.
CN201711061390.3A 2017-11-02 2017-11-02 Adhesive for shoes preparation method Withdrawn CN107698736A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711061390.3A CN107698736A (en) 2017-11-02 2017-11-02 Adhesive for shoes preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711061390.3A CN107698736A (en) 2017-11-02 2017-11-02 Adhesive for shoes preparation method

Publications (1)

Publication Number Publication Date
CN107698736A true CN107698736A (en) 2018-02-16

Family

ID=61176663

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711061390.3A Withdrawn CN107698736A (en) 2017-11-02 2017-11-02 Adhesive for shoes preparation method

Country Status (1)

Country Link
CN (1) CN107698736A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109288193A (en) * 2018-09-28 2019-02-01 瑞安市军中鞋业有限公司 A kind of high-risk chemical industry place safety shoe corrosion-resistant high-temperature boots and preparation method thereof
CN109880041A (en) * 2019-01-22 2019-06-14 合肥科天水性科技有限责任公司 A kind of high-molecular aqueous polyurethane resin and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109288193A (en) * 2018-09-28 2019-02-01 瑞安市军中鞋业有限公司 A kind of high-risk chemical industry place safety shoe corrosion-resistant high-temperature boots and preparation method thereof
CN109880041A (en) * 2019-01-22 2019-06-14 合肥科天水性科技有限责任公司 A kind of high-molecular aqueous polyurethane resin and preparation method thereof

Similar Documents

Publication Publication Date Title
CN107760247A (en) Waterborne polyurethane shoe adhesive and preparation method thereof
CN101921381B (en) Preparation method of aqueous polyurethane latex as vacuum plastic-absorption adhesive
CN101173031B (en) Polyurethane prepolymer, aquosity polyurethane binder and uses thereof
CN101824299B (en) Method for preparing single-component high-solid content water-based polyurethane adhesive
CN1639220A (en) Polyurethane
CN109536112B (en) Hot-melt polyurethane adhesive for attaching waterproof fabric and preparation method thereof
CN107189746B (en) Reactive polyurethane medical adhesive and preparation method thereof
CN103254867A (en) Preparation method of sulfonic acid type waterborne polyurethane adhesive
CN102618202A (en) Water-based polyurethane composite adhesive for tanning and preparation method and application of composite adhesive
TWI773891B (en) Method for preparing waterborne polyurethane dispersion
CN1786055A (en) Bicompenent high solid content aqueous polyurethane, its preparation method and application
CN107698736A (en) Adhesive for shoes preparation method
CN104017532A (en) High-strength solvent-free polyurethane adhesive and preparation method thereof
CN106520052A (en) High solid content low-viscosity aqueous polyurethane adhesive and preparing method thereof
CN107459960A (en) A kind of environment-friendly type bi-component polyurethane adhesive and its preparation and application
CN109609074A (en) A kind of preparation method of wet-solidifying single-component polyurethane hot melt adhesive
CN108456504A (en) Monocomponent polyurethane powder adhesive of one-step synthesis method and preparation method thereof
JP2003501529A (en) High raw strength reactive hot melt by pre-polymerization in main reactor
CN109468112B (en) Low-residue high-temperature-resistant high-strength polyether polyurethane adhesive for high-speed compounding and preparation method thereof
CN102391821B (en) Aqueous polyurethane adhesive for bead planting and preparation method thereof
CN105017503A (en) Synthetic method of reaction type PU (polyurethane) hot melt adhesive prepolymer
US20060283548A1 (en) Lignocellulosic composites having improved resistance to heat, adhesive systems, and process
CN110330935A (en) A kind of water-based polyurethane adhesive and preparation method thereof
CN116178671A (en) Solvent-free polyurethane resin for yellowing-resistant synthetic leather, and preparation method and application thereof
CN110016117B (en) Self-crosslinking polyurethane dispersion and preparation method and application thereof

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
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20180216