CN103436208A - Moisture-proof urea-formaldehyde resin adhesive and production method thereof - Google Patents
Moisture-proof urea-formaldehyde resin adhesive and production method thereof Download PDFInfo
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- CN103436208A CN103436208A CN2013103796761A CN201310379676A CN103436208A CN 103436208 A CN103436208 A CN 103436208A CN 2013103796761 A CN2013103796761 A CN 2013103796761A CN 201310379676 A CN201310379676 A CN 201310379676A CN 103436208 A CN103436208 A CN 103436208A
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- Prior art keywords
- urea
- formaldehyde
- formaldehyde resin
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- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 55
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 title claims abstract description 44
- 239000000853 adhesive Substances 0.000 title claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 17
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000008098 formaldehyde solution Substances 0.000 claims description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000004816 latex Substances 0.000 claims description 7
- 229920000126 latex Polymers 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- GMIMEXBGMYDQTO-UHFFFAOYSA-N C=O.C=O.NC(N)=O Chemical compound C=O.C=O.NC(N)=O GMIMEXBGMYDQTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 14
- 239000000839 emulsion Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 3
- 238000012856 packing Methods 0.000 abstract 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000004513 sizing Methods 0.000 description 15
- 239000002023 wood Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MSAVICZWFPQFPO-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.C=C.CC(O)=O MSAVICZWFPQFPO-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a moisture-proof urea-formaldehyde resin adhesive. The moisture-proof urea-formaldehyde resin adhesive comprises the following raw materials in parts by weight: 40 to 60 parts of urea resin, 5 to 10 parts of ylate emulsion, 0.5 to 1 part of polydimethylsiloxane, 20 to 30 parts of packing, and 2 to 5 parts of EVA (Ethylene Vinyl Acetate) emulsion. The preparation method comprises the following steps that urea resin is prepared firstly, wherein formaldehyde is blanked at one time, and urea is blanked at three times; the urea resin is produced in three stages, namely, prepolymerization, polymerization and later polymerization; ylate emulsion, polydimethylsiloxane and EVA emulsion are added after the later polymerization is done; and the packing is added after the stirring and reaction are completely performed. By adopting the process, the gel phenomenon is avoided; the obtained urea resin is narrow in molecular weight distribution and low in residual formaldehyde and can be used for producing an artificial board, in particular a ceiling decorative board; and the moisture-proof urea-formaldehyde adhesive is low in formaldehyde emission and is applied to occasions with high humidity in the South.
Description
Technical field
The present invention relates to a kind of urea-formaldehyde resin adhesive, particularly a kind of waterproof, humidity resistance are good, the urea-formaldehyde resin adhesive that residual formaldehyde is low, and relate to its production method.
Background technology
The incomplete statistics of Forest Industry in China association, approximately 3.77 hundred million square metres of China's floor production and marketing in 2012, produce these floors and expended a large amount of timber, is unfavorable for conserving forests.In order to save timber; conserve forests; country encourages to produce sawdust, wood shavings, bark, sanding powder, brush wood in the surplus thing of three in production of forestry, wood working, bamboo processing and Wood-based Panel Production, and the receive all kinds of stalks, nutshell etc. of rear generation of farm crop are the raw material production wood-based plate.Wood-based plate with these woodss, agricultural and sideline product production is called shaving board, density board.The production process of shaving board and density board needs a large amount of sizing agent, particularly 1 cubic metre of density board of every production, needs to use the sizing agent of 100～400kg.The most frequently used sizing agent is urea-formaldehyde resin or modified urea-formaldehyde resin.One of raw materials for production of urea-formaldehyde resin or modified urea-formaldehyde resin are formaldehyde, and therefore, shaving board, density board be inevitable release formaldehyde all.Formaldehyde is healthy stealthy killer, and indoor concentration of formaldehyde is greater than 10mg/m3, and the people stays 5 hours at such environment, will feel dizzy, be in for a long time concentration of formaldehyde and be greater than 10mg/m3, will be carcinogenic, so burst size of methanal is an important factor of restriction shaving board, density board development.Wood-based plate poor water resistance because the raw materials such as all kinds of stalks, nutshell are made, make the bow warping distortion because producing bulging force difference after moisture absorption.Therefore how to improve water tolerance, the reduction residual formaldehyde of urea-formaldehyde resin, become the primary problem solved of shaving board and density board industry development.
Summary of the invention
The purpose of this invention is to provide a kind ofly have excellent water-resistance, humidity resistance is good, the urea-formaldehyde resin adhesive that residual formaldehyde is low; Another object of the present invention is the production method that discloses this sizing agent.
Technological method of the present invention is:
Moistureproof urea-formaldehyde resin adhesive, its raw material and parts by weight comprise:
40～60 parts of urea-formaldehyde resins;
5～10 parts of polyacrylate dispersions;
0.5～1 part of polydimethylsiloxane;
20～30 parts of fillers;
2～5 parts of EVA latexes.
The production method of this protection against the tide urea-formaldehyde resin adhesive is at first to prepare urea-formaldehyde resin, and formaldehyde is disposable feeding intake, and urea divides and feeds intake for three times; The production of urea-formaldehyde resin is divided into prepolymerization, polymerization and later stage polymerization three phases, the later stage polymerization adds polyacrylate dispersion, polydimethylsiloxane and EVA latex later, add filler after being uniformly mixed, with the three-roller type shredder, grind 30min, obtain moistureproof urea-formaldehyde resin adhesive.
Described prepolymerisation stage: the disposable formaldehyde solution that adds in polymerization reaction kettle is 2～2.5 with the first acid for adjusting pH value, adds the urea of formaldehyde solution weight 15%, is warming up to 46 ℃, insulation reaction 60min.
Described polymerization stage: prepolymerisation stage finishes, and the pH value that adds alkali conditioned reaction liquid is 8～8.5, adds the urea of formaldehyde solution weight 30%, adds temperature reaction liquid to 88～92 ℃ then, insulation reaction 90min in 40～60min.
Described polymerization later stage: polymerization stage finishes, and adds the urea of formaldehyde solution weight 30～40%, in 40～60min, adds, and then reduces temperature of reaction to 70～85 ℃, reacts 60～90min, is cooled to room temperature, obtains urea-formaldehyde resin.
Polymerization later stage or employing are filtered, remove not tolerant, after obtaining low residual formaldehyde urea-formaldehyde resin, add polyacrylate dispersion, polydimethylsiloxane and EVA latex, add filler after being uniformly mixed, grind 30min with the three-roller type shredder, obtain moistureproof urea-formaldehyde resin adhesive.
Described polyacrylate dispersion is that very to contain chemical industry company limited model be the general pure-acrylic emulsion of M-862 in Guangzhou, it all adopts acrylate is raw material, through letex polymerization, form, there is good water resistance and weathering resistance, together with urea-formaldehyde resin as the raw material of sizing agent, can improve the water tolerance of urea-formaldehyde resin, improve the humidity resistance of sizing agent.
Described polydimethylsiloxane is that Dow Corning Corporation produces, and model is XIAMETER
?the silicone oil of PMX-200, have high surfactant, in sizing agent, as defoamer and flow agent, improves the wettability of sizing agent to base material, strengthens bonding strength.And, because the polydimethylsiloxane height is hydrophobic, can improve waterproof, the humidity resistance of sizing agent.
The composition that described filler is any or they in the above calcium carbonate of 200 orders, kaolin, titanium dioxide.Filler can dilute the component of sizing agent main component, reduces production costs, and because the urea-formaldehyde resin component is diluted, the urea-formaldehyde resin that the wood-based plate of unit volume contains reduces, and can reduce burst size of methanal.And filler can increase substantially polymer materials mechanical strength, dimensional stability and heat-drawn wire, the bonding strength that improves sizing agent and base material is played a key effect.
Described EVA latex is ethene-acetic acid ethylene copolymer emulsion, comes from Celanese Corp. and produces the EVA latex that the trade mark is Ateva.With polyethylene, compare, EVA is owing to having introduced Vinyl Acetate Monomer in molecular chain, thereby reduced high-crystallinity, snappiness, shock resistance, filler intermiscibility and heat seal performance have been improved, the stopping property of wood-based plate be can improve in the hot pressing production process of wood-based plate, waterproof, humidity resistance improved.
The positively effect that the present invention produces is:
1. the production of urea-formaldehyde resin of the present invention adopts and once adds formaldehyde, add the technique of urea three times, it is steady that polymerization rate remains, avoided the generation of polyreaction gel effect, formaldehyde monomers almost or complete reaction, gained urea-formaldehyde resin residual formaldehyde is low, thereby the sizing agent burst size of methanal of making is few.
2. moistureproof urea-formaldehyde resin adhesive of the present invention adds polyacrylate dispersion, polydimethylsiloxane and EVA latex on urea-formaldehyde resin, improved the water tolerance of urea-formaldehyde resin, sizing agent waterproof, the humidity resistance made are good, can improve the sealing property of wood-based plate, make moisture, moisture be difficult to infiltrate wood-based plate inside, improve the water tolerance of wood-based plate.
Embodiment
Embodiment 1
The production of urea-formaldehyde resin, comprise the steps:
Prepolymerisation stage: the disposable formaldehyde solution that adds in polymerization reaction kettle is 2～2.5 with the first acid for adjusting pH value, adds the urea of formaldehyde solution weight 15%, is warming up to 46 ℃, insulation reaction 60min.
Polymerization stage: prepolymerisation stage finishes, and the pH value that adds alkali conditioned reaction liquid is 8～8.5, adds the urea of formaldehyde solution weight 30%, adds temperature reaction liquid to 88～92 ℃ then, insulation reaction 90min in 40～60min.
The polymerization later stage: polymerization stage finishes, and adds the urea of formaldehyde solution weight 30～40%, in 40～60min, adds, and then reduces temperature of reaction to 70～85 ℃, reacts 60～90min, is cooled to room temperature, obtains urea-formaldehyde resin.
Embodiment 2
40 parts of the urea-formaldehyde resins that embodiment 1 obtains, add 8 parts of polyacrylate dispersions under stirring, 2 parts of 0.5 part of polydimethylsiloxane and EVA latexes, after being uniformly mixed, add 20 parts of calcium carbonate (300 order), with the three-roller type shredder, grind 30min, obtain moistureproof urea-formaldehyde resin adhesive.
Embodiment 3
50 parts of the urea-formaldehyde resins that embodiment 1 obtains, add 5 parts of polyacrylate dispersions under stirring, 3 parts of 0.7 part of polydimethylsiloxane and EVA latexes, after being uniformly mixed, add 25 parts of titanium dioxides (400 order), with the three-roller type shredder, grind 30min, obtain moistureproof urea-formaldehyde resin adhesive.
Embodiment 4
60 parts of the urea-formaldehyde resins that embodiment 1 obtains, add 10 parts of polyacrylate dispersions under stirring, 4 parts of 1 part of polydimethylsiloxane and EVA latexes, after being uniformly mixed, add 27 parts of calcium carbonate (200 order), with the three-roller type shredder, grind 30min, obtain moistureproof urea-formaldehyde resin adhesive.
Embodiment 5
46 parts of the urea-formaldehyde resins that embodiment 1 obtains, add 7 parts of polyacrylate dispersions under stirring, 5 parts of 0.6 part of polydimethylsiloxane and EVA latexes, after being uniformly mixed, add 30 parts of kaolin (300 order), with the three-roller type shredder, grind 30min, obtain moistureproof urea-formaldehyde resin adhesive.
In sizing agent, the mensuration of the residual quantity of formaldehyde adopts the methyl ethyl diketone spectrophotometry, residual formaldehyde %=measured value/example weight * %, make shaving board (thickness is 20～25mm) with sizing agent, detect shaving board 24h thickness swelling rate according to GB/T4897.7-2003, result is as shown in the table:
| Project | Residual formaldehyde/% | Expansion rate of water absorption/% |
| Embodiment 1 | 0.06 | 12 |
| Embodiment 2 | 0.028 | 0.44 |
| Embodiment 3 | 0.03 | 0.58 |
| Embodiment 4 | 0.029 | 0.65 |
| Embodiment 5 | 0.026 | 0.35 |
From the table data find out, moistureproof urea-formaldehyde resin adhesive residual formaldehyde of the present invention is low, shaving board waterproof, the humidity resistance made are good, are particularly suitable for producing the top ceiling finishing material.
Claims (3)
1. a moistureproof urea-formaldehyde resin adhesive, it is characterized in that: its raw material and parts by weight comprise:
40～60 parts of urea-formaldehyde resins;
5～10 parts of polyacrylate dispersions;
0.5～1 part of polydimethylsiloxane;
20～30 parts of fillers;
2～5 parts of EVA latexes.
2. moistureproof urea-formaldehyde resin adhesive according to claim 1, it is characterized in that: the production method of this protection against the tide urea-formaldehyde resin adhesive is at first to prepare urea-formaldehyde resin, and formaldehyde is disposable feeding intake, urea divides and feeds intake for three times; The production of urea-formaldehyde resin is divided into prepolymerization, polymerization and later stage polymerization three phases, the later stage polymerization adds polyacrylate dispersion, polydimethylsiloxane and EVA latex later, add filler after being uniformly mixed, with the three-roller type shredder, grind 30min, obtain moistureproof urea-formaldehyde resin adhesive;
The composition that described filler is any or they in the above calcium carbonate of 200 orders, kaolin, titanium dioxide;
Described prepolymerisation stage: the disposable formaldehyde solution that adds in polymerization reaction kettle is 2～2.5 with the first acid for adjusting pH value, adds the urea of formaldehyde solution weight 15%, is warming up to 46 ℃, insulation reaction 60min;
Described polymerization stage: prepolymerisation stage finishes, and the pH value that adds alkali conditioned reaction liquid is 8～8.5, adds the urea of formaldehyde solution weight 30%, adds temperature reaction liquid to 88～92 ℃ then, insulation reaction 90min in 40～60min;
Described polymerization later stage: polymerization stage finishes, and adds the urea of formaldehyde solution weight 30～40%, in 40～60min, adds, and then reduces temperature of reaction to 70～85 ℃, reacts 60～90min, is cooled to room temperature, obtains urea-formaldehyde resin.
3. moistureproof urea-formaldehyde resin adhesive according to claim 2, it is characterized in that: polymerization later stage or employing are filtered, remove not tolerant, after obtaining low residual formaldehyde urea-formaldehyde resin, add polyacrylate dispersion, polydimethylsiloxane and EVA latex, stirring reaction adds filler to obtain moistureproof urea-formaldehyde resin adhesive fully later.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310379676.1A CN103436208B (en) | 2013-08-28 | 2013-08-28 | Moisture-proof urea-formaldehyde resin adhesive and production method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310379676.1A CN103436208B (en) | 2013-08-28 | 2013-08-28 | Moisture-proof urea-formaldehyde resin adhesive and production method thereof |
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| CN103436208A true CN103436208A (en) | 2013-12-11 |
| CN103436208B CN103436208B (en) | 2015-04-15 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772794A (en) * | 2015-03-30 | 2015-07-15 | 广西宾阳县荣良新材料科技有限公司 | Production process of low-formaldehyde laminboard |
| CN105419704A (en) * | 2015-11-23 | 2016-03-23 | 苏州盖德精细材料有限公司 | Urea-formaldehyde resin adhesive and preparation method thereof |
| CN106189885A (en) * | 2016-07-21 | 2016-12-07 | 柳州市五源科技有限公司 | Paste fluid sealant |
| CN106675472A (en) * | 2016-12-17 | 2017-05-17 | 浦北县建业胶合板有限责任公司 | Urea-formaldehyde resin adhesive and preparation method thereof |
| CN108659758A (en) * | 2018-05-24 | 2018-10-16 | 广东东美实业有限公司 | A kind of composite plate formaldehyde-free rubber water formula |
| CN117621200A (en) * | 2023-12-25 | 2024-03-01 | 云南新泽兴人造板有限公司 | An E0-level environmentally friendly particleboard production method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772794A (en) * | 2015-03-30 | 2015-07-15 | 广西宾阳县荣良新材料科技有限公司 | Production process of low-formaldehyde laminboard |
| CN104772794B (en) * | 2015-03-30 | 2017-05-03 | 广西宾阳县荣良新材料科技有限公司 | Production process of low-formaldehyde laminboard |
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| CN105419704B (en) * | 2015-11-23 | 2018-07-31 | 苏州盖德精细材料有限公司 | A kind of urea-formaldehyde resin adhesive and preparation method thereof |
| CN106189885A (en) * | 2016-07-21 | 2016-12-07 | 柳州市五源科技有限公司 | Paste fluid sealant |
| CN106675472A (en) * | 2016-12-17 | 2017-05-17 | 浦北县建业胶合板有限责任公司 | Urea-formaldehyde resin adhesive and preparation method thereof |
| CN108659758A (en) * | 2018-05-24 | 2018-10-16 | 广东东美实业有限公司 | A kind of composite plate formaldehyde-free rubber water formula |
| CN117621200A (en) * | 2023-12-25 | 2024-03-01 | 云南新泽兴人造板有限公司 | An E0-level environmentally friendly particleboard production method |
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|---|---|
| CN103436208B (en) | 2015-04-15 |
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Inventor after: Gong Longbing Inventor after: Xiang Jinsong Inventor after: Shen Huihua Inventor after: Wu Haiping Inventor before: Lu Meiling Inventor before: Ma Zhaoxing Inventor before: Ma Yun Inventor before: Lai Guangye Inventor before: Ma Zhaojian Inventor before: Mo Mingxin |
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Effective date of registration: 20161207 Address after: 201514 Shanghai city Jinshan District Zhangyan town Qin village seven groups Patentee after: SHANGHAI HANSI INDUSTRIAL CO., LTD. Address before: Binyang Lixin road Nanning City, No. 306 the Guangxi Zhuang Autonomous Region 530417 Patentee before: Lu Meiling |