CN102181038B - Preparation method of polyurethane stock solution for automobile steering wheel - Google Patents
Preparation method of polyurethane stock solution for automobile steering wheel Download PDFInfo
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- CN102181038B CN102181038B CN 201110086028 CN201110086028A CN102181038B CN 102181038 B CN102181038 B CN 102181038B CN 201110086028 CN201110086028 CN 201110086028 CN 201110086028 A CN201110086028 A CN 201110086028A CN 102181038 B CN102181038 B CN 102181038B
- Authority
- CN
- China
- Prior art keywords
- stock solution
- preparation
- steering wheel
- automobile steering
- polyester polyol
- 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.)
- Expired - Fee Related
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 23
- 239000004814 polyurethane Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011550 stock solution Substances 0.000 title claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- -1 Polymethylene Polymers 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 229920002545 silicone oil Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 230000001012 protector Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种汽车方向盘用聚氨酯原液的制备方法，其技术方案包括（1）硅油改性的聚酯多元醇制备：（2）汽车方向盘用聚氨酯原液的制备。本发明提供的羟基硅油改性的聚酯多元醇，是一种通过化学反应方法将硅氧键加到聚酯多元醇的分子中，使聚酯多元醇具有一定疏水性。当使用该聚酯多元醇制备成聚氨酯慢回弹软泡塑料时，聚氨酯软泡的极性较小，不沾手，手感滑爽。The invention discloses a method for preparing a polyurethane stock solution for automobile steering wheels. The technical proposal comprises (1) preparation of silicone oil-modified polyester polyol; (2) preparation of polyurethane stock solution for automobile steering wheels. The polyester polyol modified by hydroxyl silicone oil provided by the present invention is a kind of chemical reaction method in which silicon-oxygen bonds are added to the molecules of the polyester polyol, so that the polyester polyol has a certain degree of hydrophobicity. When the polyester polyol is used to prepare polyurethane slow-rebound flexible foam plastics, the polarity of the polyurethane flexible foam is small, non-sticky, and smooth to the touch.
Description
Technical field
The present invention relates to the synthetic field of chemical industry, be specifically related to polyurethane stock solution, refer to especially new polyurethane material of a kind of polyurethane stock solution for automobile steering wheel and preparation method thereof.
Background technology
Along with the development of automobile industry, automobile has entered the ordinary people family.The city resident can drive to go to work, travel or finish some public affair at present.The officer who drives holds bearing circle, can be to the place that you think.According to incompletely statistics, have the driver of car to drive at least two hours average every day, hand will contact bearing circle two hours.Driving if hold a strong bearing circle of comfortableness, is a kind of enjoyment.The comfortableness of bearing circle thoughts also is a standard of automobile class simultaneously.Comfortableness when bearing circle is held in raising so people also try every possible means, thus various types of vehicle steering comes out with sheath.Fabric protecting casing of steering wheel, leather sheath, synthetic leather sheath that various materials are arranged in the market.The sheath higher gears of leather wherein.The sheath of synthetic leather is owing to airtight, so that the comfortableness of sheath is relatively poor.So the steering wheel protector for car of the synthetic leather that the exploitation comfortableness is strong becomes the very interested problem of urethane resin production.
In fact since the sixties in last century, the flexible PU foam sheath has been housed all on nearly all vehicle steering.But this sheath is general flexible PU foam, and is airtight and have a high resilience, namely constantly gives pressure of hand, so hand is felt very ill.Occur a kind of slow rebound polyurethane stoste on the markets in 2008, be applied on the steering wheel protector for car, the quality of steering wheel protector for car is obviously improved.But we find that this sheath has the surface of polarity, very easily adsorb dust and be difficult to clean.When every day hand all contact sheath, have sweat stain on the sheath, more breed bacteria.Have automatic cleaning action the slow rebound polyurethane stoste that can be used for steering wheel protector for car have no report.
Summary of the invention
The objective of the invention is the shortcoming and defect that exists in order to overcome prior art, and provide have germicidal action, the preparation method of a kind of polyurethane stock solution for automobile steering wheel of the self-cleaning function such as decomposing protein.
For achieving the above object, technical scheme of the present invention is to comprise following operation:
(1) silicon oil modified polyester polyol preparation:
Butyleneglycol 100 parts, hydroxy silicon oil is added in the reactor, behind the 75-85 ℃ of vacuum hydro-extraction 2-2.5h, the adipic acid that adds 50 parts, be warming up to 150-180 ℃, temperature remains unchanged, water constantly is excluded from reactive system, until after not having water to get rid of from system, the temperature of reactive system continues to raise, temperature rises to 230-250 ℃, insulation 1-2h, whole operating under the protective atmosphere carried out, and carries out vacuum pumping, keeps vacuumizing state and getting its sample and analyze, determine hydroxyl value and acid number, if the acid number of sample does not reach 0.3-0.5mgKOH/g, hydroxyl value does not reach 60-70 mgKOH/g, continues to vacuumize, until hydroxyl value and acid number reach above-mentioned requirements, temperature in the kettle remains on 220～230 ℃ during vacuumizing;
(2) preparation of polyurethane stock solution for automobile steering wheel:
Put A material and B material by following set of dispense, the acquisition polyurethane stock solution for automobile steering wheel, in mass fraction:
The A material:
Silicon oil modified polyester polyol 30-60
Slow resilience polyethers 20-30
Suds-stabilizing agent 0.4-1.5
Amino catalyzer 2.0-4.5
Tin-based catalyst 0.5-1.2
Nano TiO 2 4-8
Water 0.5-2.5
The B material:
Liquefied mdi 70-80
PAPI 30-40。
Further arrange is that the control condition that described step (1) vacuumizes is carried out vacuum pumping for opening vacuum pump with the condition of 0.02MPa 1h, 0.04MPa 1.5h, 0.06MPa 1.5h, 0.08 MPa 1.5h, 0.099 Mpa 4h successively.
Further arranging is that described protective atmosphere is nitrogen atmosphere.
Advantage of the present invention is
(a
)The present invention improves a kind of hydroxyl silicon oil modified polyester polyol
Hydroxyl silicon oil modified polyester polyol provided by the invention is a kind ofly by chemical reaction method siloxane bond to be added in the molecule of polyester polyol, makes polyester polyol have certain hydrophobicity.When using this polyester polyol to be prepared into the soft bubble plastics of polyurethane slow rebound, the polarity of flexible PU foam is less, does not touch with one's hand, and feel is smooth.
(b) the present invention is by chemical additive process, with nano-TiO
2Add in the flexible PU foam.
Nano-TiO
2Be a kind of inorganic oxide, can strengthen the mechanical property of polyurethane material, simultaneously nano-TiO
2Has germicidal action.The what is more important nano-TiO
2A kind of optical catalysts, under the irradiation of UV-light, can decomposing protein etc. biomass, so can automatically remove microorganism on the polyurethane foam.
(c) the invention provides the preparation method that a kind of preparation steering wheel protector for car is used polyurethane stock solution.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
At 0.5m
3Reactor in add the butyleneglycol of 50kg, 10kg hydroxy silicon oil, sealed reactor.Add thermal material to 80 ℃, begin to vacuumize to system, vacuum tightness 0.01MPa stops behind the 2h vacuumizing.Open reactor, add the 300kg adipic acid.Pass into nitrogen protection to reactor, and heat up, temperature rises to 110 ℃ has the water of a little to get rid of reactor, and temperature continues to rise, until 150 ℃, temperature remains unchanged, until the water of reactive system is got rid of fully.Temperature continues to heat up, and keeps temperature of reaction under 220 ℃, and 4h is carried out in reaction, and the acid number of assaying reaction sample is when acid number reaches 20 mgKOH/g.Beginning progressively vacuumizes, 0.02MPa 1h, 0.04MPa 1.5h, 0.06MPa 1.5h, 0.08 MPa 1.5h, then begin pumping high vacuum (0.099 Mpa, 4h), get its sample and analyze, determine hydroxyl value and acid number, if the hydroxyl value of sample and acid number do not reach requirement, continue to vacuumize, until hydroxyl value and acid number reach requirement (acid number 0.3-0.5mgKOH/g, hydroxyl value reaches 60-70 mgKOH/g).Temperature in the kettle remains on 230 ℃ during this period.Can not stop vacuum pump during sampling analysis during noting vacuumizing, change to prevent product quality.Reach the hydroxyl value and acid number of needs until sample after, discharging namely obtains silicon oil modified polyester polyol.
Get the silicon oil modified polyester polyol 30kg of above-mentioned preparation, slow resilience polyethers 20kg, suds-stabilizing agent 0.4 kg, amino catalyzer 2.0 kg, tin-based catalyst 0.5 kg, nano-TiO
24 kg, water 0.5 kg form the A material; Liquefied mdi 70kg, PAPI 30kg form the B material.
MDI of the present invention is diphenylmethanediisocyanate, and PAPI is polymethylene multi-phenenyl isocyanate, by those skilled in the art are known.
Embodiment 2
At 0.5m
3Reactor in add the butyleneglycol of 50kg, 10kg hydroxy silicon oil, sealed reactor.Add thermal material to 100 ℃, begin to vacuumize to system, vacuum tightness 0.01MPa stops behind the 2h vacuumizing.Open reactor, add the 300kg adipic acid.Pass into nitrogen protection to reactor, and heat up, temperature rises to 110 ℃ has the water of a little to get rid of reactor, and temperature continues to rise, until 160 ℃, temperature remains unchanged, until the water of reactive system is got rid of fully.Temperature continues to heat up, and keeps temperature of reaction under 230 ℃, and 4h is carried out in reaction, and the acid number of assaying reaction sample is when acid number reaches 30 mgKOH/g.Beginning progressively vacuumizes, 0.02MPa 1h, 0.04MPa 1.5h, 0.06MPa 1.5h, 0.08 MPa 1.5h, then begin pumping high vacuum (0.099 Mpa, 4h), get its sample and analyze, determine hydroxyl value and acid number, if the hydroxyl value of sample and acid number do not reach requirement, continue to vacuumize, until hydroxyl value and acid number reach requirement (acid number 0.3-0.5mgKOH/g, hydroxyl value reaches 60-70 mgKOH/g).Temperature in the kettle remains on 220～230 ℃ during this period.Can not stop vacuum pump during sampling analysis during noting vacuumizing, change to prevent product quality.Reach the hydroxyl value and acid number of needs until sample after, discharging namely obtains silicon oil modified polyester polyol.
Embodiment 3
At 0.5m
3Reactor in add the butyleneglycol of 50kg, 10kg hydroxy silicon oil, sealed reactor.Add thermal material to 90 ℃, begin to vacuumize to system, vacuum tightness 0.01MPa stops behind the 2h vacuumizing.Open reactor, add the 300kg adipic acid.Pass into nitrogen protection to reactor, and heat up, temperature rises to 110 ℃ has the water of a little to get rid of reactor, and temperature continues to rise, until 155 ℃, temperature remains unchanged, until the water of reactive system is got rid of fully.Temperature continues to heat up, and keeps temperature of reaction under 225 ℃, and 4h is carried out in reaction, and the acid number of assaying reaction sample is when acid number reaches 25 mgKOH/g.Beginning progressively vacuumizes, 0.02MPa 1h, 0.04MPa 1.5h, 0.06MPa 1.5h, 0.08 MPa 1.5h, then begin pumping high vacuum (0.099 Mpa, 4h), get its sample and analyze, determine hydroxyl value and acid number, if the hydroxyl value of sample and acid number do not reach requirement, continue to vacuumize, until hydroxyl value and acid number reach requirement (acid number 0.3-0.5mgKOH/g, hydroxyl value reaches 60-70 mgKOH/g).Temperature in the kettle remains on 230 ℃ during this period.Can not stop vacuum pump during sampling analysis during noting vacuumizing, change to prevent product quality.Reach the hydroxyl value and acid number of needs until sample after, discharging namely obtains silicon oil modified polyester polyol.
With polyurethane stock solution for automobile steering wheel of the present invention for the manufacture of automobile steering wheel cover, first the component weighing in each component in the A material and the B material is dropped into batch mixing reactor separately, start stirring, after two batching kettles stir 0.5h respectively, A material and B material are heated to respectively 45 ℃, A is expected, the B material is poured into rapidly in the mould that has been heated to required temperature, build and cover tightly mould lid, cross 10～15min, open mould lid, take out sample, put into temperature and be 65 ℃ baking oven, go out about 5 minutes, cooling off its density of mensuration of carrying out density in about 5 minutes is 35kg/m
3
Claims (3)
1. the preparation method of a polyurethane stock solution for automobile steering wheel is characterized in that comprising following operation:
(1) silicon oil modified polyester polyol preparation:
Butyleneglycol 100 parts, hydroxy silicon oil is added in the reactor, behind the 70-90 ℃ of vacuum hydro-extraction 2-2.5h, the adipic acid that adds 50 parts, be warming up to 150-160 ℃, temperature remains unchanged, water constantly is excluded from reactive system, until after not having water to get rid of from system, the temperature of reactive system continues to raise, temperature rises to 230-240 ℃, insulation 1-2h, whole operating under the protective atmosphere carried out, and carries out vacuum pumping, keeps vacuumizing state and getting its sample and analyze, determine hydroxyl value and acid number, if the acid number of sample does not reach 0.3-0.5mgKOH/g, hydroxyl value does not reach 60-70 mgKOH/g, continues to vacuumize, until hydroxyl value and acid number reach above-mentioned requirements, temperature in the kettle remains on 220～230 ℃ during vacuumizing;
(2) preparation of polyurethane stock solution for automobile steering wheel:
Put A material and B material by following set of dispense, the acquisition polyurethane stock solution for automobile steering wheel, in mass fraction:
The A material:
Silicon oil modified polyester polyol 30-60
Slow resilience polyethers 20-30
Suds-stabilizing agent 0.4-1.5
Amino catalyzer 2.0-4.5
Tin-based catalyst 0.5-1.2
Nano TiO 2 4-8
Water 0.5-2.5
The B material:
The diphenylmethanediisocyanate 60-80 of liquefaction
Polymethylene multi-phenenyl isocyanate 25-35.
2. the preparation method of a kind of polyurethane stock solution for automobile steering wheel according to claim 1 is characterized in that: the control condition that described step (1) vacuumizes is carried out vacuum pumping for opening vacuum pump with the condition of 0.02MPa 1h, 0.04MPa 1.5h, 0.06MPa 1.5h, 0.08 MPa 1.5h, 0.099 Mpa 4h successively.
3. the preparation method of a kind of polyurethane stock solution for automobile steering wheel according to claim 1, it is characterized in that: described protective atmosphere is nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110086028 CN102181038B (en) | 2011-04-07 | 2011-04-07 | Preparation method of polyurethane stock solution for automobile steering wheel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110086028 CN102181038B (en) | 2011-04-07 | 2011-04-07 | Preparation method of polyurethane stock solution for automobile steering wheel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102181038A CN102181038A (en) | 2011-09-14 |
| CN102181038B true CN102181038B (en) | 2013-02-20 |
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|---|---|---|---|
| CN 201110086028 Expired - Fee Related CN102181038B (en) | 2011-04-07 | 2011-04-07 | Preparation method of polyurethane stock solution for automobile steering wheel |
Country Status (1)
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| CN (1) | CN102181038B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374111B (en) * | 2012-04-27 | 2015-02-11 | 温州市登达化工有限公司 | Preparation method of slow-resilience polyurethane flexible foam stock solution for automotive steering wheel |
| CN105131242A (en) * | 2015-08-21 | 2015-12-09 | 安徽天堂唯高塑业科技有限公司 | Non-sweat-absorbing sheath material of protective layer of steering wheel and preparation method for sheath material |
| CN109553741A (en) * | 2018-12-06 | 2019-04-02 | 上海应用技术大学 | A kind of preparation method of low-cost polyurethane steering wheel |
| CN109575231A (en) * | 2018-12-06 | 2019-04-05 | 上海应用技术大学 | A kind of preparation method of low VOC polyurethane automobile steering wheel |
| CN109553751A (en) * | 2018-12-06 | 2019-04-02 | 上海应用技术大学 | A kind of preparation method of polyurethane steering wheel |
| CN110358065B (en) * | 2019-08-05 | 2022-02-25 | 美瑞新材料股份有限公司 | Polysiloxane-ester polyol, and preparation method and application thereof |
| CN115260439B (en) * | 2022-08-11 | 2023-09-22 | 山东一诺威新材料有限公司 | Super-hydrophobic polyurethane material for automobile paint protective film and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223323A (en) * | 1990-01-30 | 1991-10-02 | Sanyo Chem Ind Ltd | Polyurethane resin composition and its production |
| JPH0525239A (en) * | 1991-07-23 | 1993-02-02 | Toagosei Chem Ind Co Ltd | Polyurethane emulsion |
| JP4149882B2 (en) * | 2003-09-02 | 2008-09-17 | 大日精化工業株式会社 | Synthetic artificial leather and method for producing the same |
| DE102004010456A1 (en) * | 2004-03-01 | 2005-09-22 | Carl Freudenberg Kg | Process for the preparation of a lightfast synthetic leather and products made therefrom |
| KR100883514B1 (en) * | 2007-07-02 | 2009-02-11 | 주식회사 엘지화학 | Integral Skin Polyurethane Foam Composition, Integral Skin Polyurethane Foam Prepared Using Them, and Integral Skin Polyurethane Foam Characterization Method |
| CN101328247B (en) * | 2008-07-29 | 2010-12-22 | 中国科学技术大学 | Preparation of siloxane modified polyurethane-acrylic ester composite emulsion |
| CN101348554B (en) * | 2008-08-08 | 2011-05-04 | 山东东大一诺威聚氨酯有限公司 | Organosilicon modified aqueous polyurethane resin and preparation thereof |
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2011
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Effective date of registration: 20240204 Address after: No. 99 Shangqin Road, Lucheng District, Wenzhou City, Zhejiang Province, 325000 Patentee after: Wenzhou Dongye Electronic Technology Co.,Ltd. Country or region after: China Address before: 325000 China Shoes Capital Phase III, Lucheng District, Wenzhou City, Zhejiang Province Patentee before: WENZHOU DENGDA CHEMICAL Co.,Ltd. Country or region before: China |
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