CN101497749A - Surface modified nano silicon dioxide and acrylic resin coating containing the same - Google Patents
Surface modified nano silicon dioxide and acrylic resin coating containing the same Download PDFInfo
- Publication number
- CN101497749A CN101497749A CNA2009100965348A CN200910096534A CN101497749A CN 101497749 A CN101497749 A CN 101497749A CN A2009100965348 A CNA2009100965348 A CN A2009100965348A CN 200910096534 A CN200910096534 A CN 200910096534A CN 101497749 A CN101497749 A CN 101497749A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- compound
- silicon dioxide
- acrylic resin
- resin coating
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011248 coating agent Substances 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 38
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 34
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 32
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 229940126062 Compound A Drugs 0.000 claims description 13
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 5
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 238000007306 functionalization reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006011 modification reaction Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims 2
- 229920002635 polyurethane Polymers 0.000 claims 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 5
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a nano-silicon dioxide which is functionalized by acrylic ester and modified on surface by perfluoro alkoxy, a method for preparing the nano-silicon dioxide, and an acrylic resin coating containing the nano-silicon dioxide. The acrylic resin coating containing the nano-silicon dioxide also contains single-functional acrylic ester, acrylic ester containing at least two acrylic ester groups, alcoholic solvent and evocating agent. The acrylic resin coating containing fluorine and silicon can be quickly solidified, and the coating film hereby formed has excellent oil resistance, water resistance, weather resistance, pollution resistance, surface hardness and surface gloss.
Description
Technical Field
The invention relates to surface modified nano silicon dioxide and fluorine-containing acrylic resin coating containing the nano silicon dioxide.
Background
The acrylate resin/nano-silica composite is an important component of high-performance coating, and a coating film formed by the acrylate resin/nano-silica composite has excellent hardness and scratch resistance. In order to achieve good compatibility between the nanosilica and organic components such as acrylate resin in the coating, the nanosilica is usually subjected to surface chemical modification, such as acrylate functionalization. The surface chemical modification of nanosilica is usually carried out by esterification or condensation reactions of hydroxyl functional groups on the surface. For example, CN1978553 discloses a nano silica with organic functional molecules grafted on the surface and a preparation method thereof. On the other hand, fluorine-containing resins or materials modified with fluorine-containing compounds generally have low surface energy, high thermal stability and chemical stability. However, since direct blending of the fluorine-containing resin or fluorine-containing compound with the acrylic resin and nano-silica is difficult to be effectively achieved, the characteristics of the fluorine-containing compound and the characteristics of the nano-silica in the prior art cannot produce a synergistic effect in the acrylic resin-based coating.
Disclosure of Invention
The invention provides novel surface modified nano silicon dioxide by anchoring a perfluoroalkoxy group to the surface of nano silicon dioxide by a chemical method and simultaneously carrying out acrylic ester functionalization on silanol hydroxyl on the surface of the nano silicon dioxide.
The invention also provides a preparation method of the surface modified nano silicon dioxide.
The invention also provides a silicon-containing fluorine-containing acrylic resin coating, namely, the surface modified nano silicon dioxide is added into the acrylic resin coating, so that the coating has the effects of nano silicon dioxide and fluorine-containing organic groups, and the coating is endowed with excellent hardness, oil resistance, water resistance and stain resistance. Furthermore, the compatibility of the coating can be adjusted according to actual needs.
A surface modified nano silicon dioxide is prepared by carrying out acrylate functionalization and perfluoroalkoxy modification reaction on surface silanol hydroxyl of the nano silicon dioxide by a compound A and a compound B;
wherein,
the structural general formula of the compound A is as follows:
in the formula: r1Is H or CH3；
The structural general formula of the compound B is as follows:
in the formula: x is S or NH
RfThe general structural formula is as follows:
in the formula: n is 1, 2 or 3
After the modification reaction, through covalently bonding to the surface modified nano-silica RfThe molar ratio of the groups to the acrylate groups is 1:1 to 1: 20. The molar ratio can be adjusted appropriately depending on the compatibility of the coating components and the different requirements for oil and water resistance and surface hardness of the coating film. If the coating film is required to have high water and oil resistance and surface hardness, the feed ratio of the compound B can be properly increased in the preparation process, so that the R covalently bonded to the surface modified nano-silicafThe relative amount of groups is somewhat higher; but if R isfToo high a relative amount of groups may result in too poor compatibility of the surface-modified nanosilica with the acrylate resin coating.
The reaction scheme for preparing the nano-silica with the acrylate functionalization and the perfluoroalkoxy group surface modification is shown in the attached figure 1, and the specific preparation process is as follows: sequentially placing nano silicon dioxide, an organic solvent, water, a compound A and a compound B into a container to be mixed, wherein the weight ratio of the nano silicon dioxide to the compound A to the compound B is (20-30) to (5-15) to (2-10); and then adding a hydrochloric acid solution to adjust the pH value to 4-5, heating to 70-80 ℃, stirring, reacting for 3-4 hours, and cooling to obtain a milky jelly product.
Wherein,
the commercially available nano-silica is selected, and the nano-silica with the particle size of 5-25 nm is preferably adopted, because the over-large particles of the nano-silica can cause uneven mixing and over-small surface area.
The organic solvent is at least one of isopropanol, ethylene glycol, glycerol and ethylene glycol monomethyl ether.
The structural general formula of the compound A is as follows:
in the formula: r1Is H or CH3；
The compound A can be directly prepared from commercial products or synthesized by conventional chemical methods, and one of the specific preparation schemes is as follows: the allyl (meth) acrylate is subjected to addition reaction with alkoxy hydrosilane to obtain H2PtCl6The reaction is carried out at 50-60 ℃ by taking the/i-PrOH as a catalyst and 2, 5-di-tert-butylhydroquinone as a polymerization inhibitor.
The structural general formula of the compound B is as follows:
in the formula: x is S or NH
RfThe general structural formula is as follows:
in the formula: n is 1, 2 or 3;
compound B can be prepared from compound C and compound D according to the following reaction scheme:
r in Compound CfWith R in the compound BfThe same definition is applied. X in compound D is as defined for X in compound B.
In the present invention, compound C is available from Kjeldahl group, Zhejiang.
The compound D is 3-mercaptopropyltrimethoxysilane or 3-aminopropyltrimethoxysilane. Compound D can also be replaced by other alkoxysilane analogues, such as: 3-mercaptopropyltriethoxysilane or 3-aminopropyltriethoxysilane, etc.
The specific procedure for preparing compound B is as follows:
mixing equimolar compound C and compound D, diluting with a small amount of solvent (such as anhydrous ether), reacting for 2-3 hours under slow reflux condition, and evaporating to remove the solvent to obtain compound B, wherein the product is colorless transparent liquid.
A silicon-containing fluorine-containing acrylic resin coating comprises the following components: the surface modified nano-silica of the invention, the monofunctional (meth) acrylate, the acrylate containing at least 2 acrylate groups, the alcohol solvent and the initiator are described above.
The silicon-containing fluorine-containing acrylic resin coating comprises the following components in parts by weight:
2-20 parts of surface modified nano silicon dioxide
20-80 parts of monofunctional (methyl) acrylate
5-20 parts of acrylate containing at least 2 acrylate groups
2-20 parts of alcohol solvent
2-10 parts of an initiator;
preferably, the composition of the silicon-containing fluorine-containing acrylic resin coating is as follows: (in parts by weight)
5-15 parts of surface modified nano silicon dioxide
40-80 parts of monofunctional (methyl) acrylate
5-15 parts of acrylate containing at least 2 acrylate groups
5-10 parts of alcohol solvent
2-5 parts of an initiator.
In the present invention, the monofunctional (meth) acrylate plays a main role in dilution in the system, and it also plays a dominant role in dissolution of the photoinitiator and flexibility of the cured film, and is preferably at least one of methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and monofunctional aliphatic urethane acrylate (e.g., Gencure PUA550/565/569/5126/5127/5129 may be used), and is more preferably at least one of isodecyl acrylate, and monofunctional aliphatic urethane acrylate (e.g., Gencure PUA569 may be used).
In the present invention, the acrylate containing at least 2 acrylate groups is preferably an acrylate containing 2 or 3 acrylate groups, such as: tripropylene glycol diacrylate, trimethylolpropane triacrylate, bisphenol A epoxy diacrylate (e.g., EBECRYL 600, EBECRYL 605 available from UCB, Belgium), aromatic urethane diacrylate (e.g., EBECRYL 210 available from UCB, Belgium), aliphatic urethane diacrylate (e.g., EBECRYL 270 available from UCB, Belgium), and trimethylolpropane triacrylate; more preferably at least one of tripropylene glycol diacrylate and trimethylolpropane triacrylate.
In the invention, the alcohol solvent is at least one of isopropanol, glycol, glycerol and ethylene glycol monomethyl ether, and the content of the alcohol solvent is determined according to the compatibility of each component of the coating and the coating construction requirement.
In the present invention, the initiator is a variety of commercially available initiators, preferably a commercially available radical photoinitiator, such as: 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone (Irgacure 369), 1-hydroxycyclohexyl phenyl methanone (Irgacure 184) or 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur 1173), preferably Irgacure 184. The initiators are all produced by Ciba.
The fluorine-containing and silicon-containing acrylic resin coating can be obtained by using a conventional method after uniformly mixing the surface-modified nano-silica, the monofunctional acrylate monomer, the acrylate containing at least 2 acrylate groups, the alcohol solvent and the initiator in proportion.
The fluorine-containing and silicon-containing acrylic resin coating can form a coating film with excellent oil resistance, water resistance, stain resistance, surface hardness and good surface glossiness after being rapidly cured by heating, ultraviolet irradiation or electron beam irradiation.
Drawings
FIG. 1 is a reaction scheme for preparing surface-modified nano-silica. Wherein R is1Is H or CH3(ii) a X is S or NH; rfThe general structural formula is as follows:
in the formula: n is 1, 2 or 3.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1:
0.5 mol of the molecular formula:
the compound C (manufacturer: Zhejiang university group Co.) and 0.5 mol of 3-mercaptopropyltrimethoxysilane (compound D) were mixed in a round-bottomed flask, diluted with a small amount of anhydrous ether, reacted for 2 hours under slow reflux conditions, and the solvent was distilled off to obtain a compound having the formula:
the product of Compound B of (1) is a colorless transparent liquid.
According to the weight parts, 23 parts of silicon dioxide (manufacturer: Zhejiang Wanjing materials Co., Ltd.) with the particle size of 5-25 nm, 21 parts of isopropanol, 9 parts of water, 10 parts of 3- (methacryloyloxy) propyl trimethoxy silane (compound A) and 4 parts of the compound B obtained in the above step are put into a three-mouth bottle, then diluted hydrochloric acid solution is added to adjust the pH value to 4-5, stirring is carried out at 75 ℃, and after reaction for 3 hours, cooling is carried out to obtain the acrylate functionalized and perfluoroalkoxy surface modified nano silicon dioxide, wherein the product is a milky white colloid.
The surface-modified nano-silica is prepared from 5 parts by weight of the surface-modified nano-silica, 40 parts by weight of isodecyl acrylate, 30 parts by weight of monofunctional aliphatic urethane acrylate (PUA569), 15 parts by weight of trimethylolpropane triacrylate, 5 parts by weight of isopropanol and 5 parts by weight of Irgacure 184. The components are uniformly mixed to obtain the silicon-containing fluorine-containing acrylic resin coating.
The coating is coated on a flat glass slide, the coating thickness is 130-150 mu m, and the coating is irradiated by ultraviolet rays (the wavelength is 254nm, the power is 240 mW/cm)2) And irradiating for 20s to form the silicon-containing fluorine-containing acrylic resin coating film.
Example 2:
3-mercaptopropyltrimethoxysilane (compound D) in example 1 was replaced with 3-aminopropyltriethoxysilane (compound D) under the same conditions as in example 1 to give a compound of the formula:
the compound B and corresponding acrylic ester functionalized and perfluoroalkoxy surface modified nano silicon dioxide.
A silicon-containing fluorine-containing acrylic resin coating was prepared in the same manner as in example 1 and cured by irradiation with light to form a silicon-containing fluorine-containing acrylic resin coating film.
Example 3:
3-aminopropyltrimethoxysilane (Compound D) was used in place of 3-mercaptopropyltrimethoxysilane (Compound D) in example 1, and the other conditions were the same as in example 1, to prepare a compound having the formula:
the compound B and corresponding acrylic ester functionalized and perfluoroalkoxy surface modified nano silicon dioxide.
A silicon-containing fluorine-containing acrylic resin coating was prepared in the same manner as in example 1 and cured by irradiation with light to form a silicon-containing fluorine-containing acrylic resin coating film.
Example 4:
0.5 mol of a compound of the formula
The compound C (manufacturer: Zhejiang university group Co.) and 0.5 mol of 3-mercaptopropyltrimethoxysilane (compound D) were mixed in a round-bottomed flask, diluted with a small amount of anhydrous ether, reacted for 2 hours under slow reflux conditions, and the solvent was distilled off to obtain a compound having the formula:
the product of Compound B of (1) is a colorless transparent liquid.
According to parts by weight, 20 parts of silicon dioxide (manufacturer: Zhejiang Wanjing materials Co., Ltd.) with the particle size of 5-25 nm, 21 parts of isopropanol, 9 parts of water, 12 parts of 3- (methacryloyloxy) propyl trimethoxy silane (compound A) and 5 parts of the compound B obtained in the previous step are placed into a three-mouth bottle, then diluted hydrochloric acid solution is added to adjust the pH value to 4-5, stirring is carried out at 75 ℃, and after reaction for 3 hours, cooling is carried out to obtain the acrylate functionalized and perfluoroalkoxy surface modified nano silicon dioxide, wherein the product is a milky white colloid.
A silicon-containing fluorine-containing acrylic resin coating was prepared in the same manner as in example 1 and cured by irradiation with light to form a silicon-containing fluorine-containing acrylic resin coating film.
Example 5:
acrylate functionalized and perfluoroalkoxy surface modified nanosilica were prepared in the same manner as in example 4.
The surface-modified nano silica is prepared from 10 parts by weight of the obtained surface-modified nano silica, 40 parts by weight of isodecyl acrylate, 30 parts by weight of monofunctional aliphatic urethane acrylate (PUA569), 10 parts by weight of aliphatic urethane diacrylate (EBECRYL 270), 5 parts by weight of trimethylolpropane triacrylate, 5 parts by weight of isopropanol and 5 parts by weight of Irgacure 184. The components are uniformly mixed to obtain the silicon-containing fluorine-containing acrylic resin coating.
The coating is coated on flat glass, the thickness of the coating is 130-150 mu m, and the coating is irradiated by ultraviolet rays (the wavelength is 254nm, and the power is 240 mW/cm)2) And irradiating for 20s to form the silicon-containing fluorine-containing acrylic resin coating film.
Example 6:
acrylate functionalized and perfluoroalkoxy surface modified nanosilica were prepared in the same manner as in example 4.
The surface-modified nano silica was prepared by taking 5 parts by weight of the obtained surface-modified nano silica, 40 parts by weight of isodecyl acrylate, 35 parts by weight of monofunctional aliphatic urethane acrylate (PUA569), 10 parts by weight of aliphatic urethane diacrylate (EBECRYL 270), 5 parts by weight of tripropylene glycol diacrylate, 5 parts by weight of isopropyl alcohol, and 5 parts by weight of Irgacure 184. The components are uniformly mixed to obtain the silicon-containing fluorine-containing acrylic resin coating.
Applying the coating to a flat panelCoating on glass, the thickness of the coating is 130-150 mu m, and ultraviolet radiation (wavelength 254nm, power 240 mW/cm)2) And irradiating for 20s to form the silicon-containing fluorine-containing acrylic resin coating film.
The properties of the coating film formed from the coating material of the present invention were tested in the following manner.
Water resistance: the contact angle of the coating film surface with water is characterized, and the contact angle measurement is carried out on a CTS-200 contact angle measuring instrument.
Solvent resistance: after a 10X 2.5cm glass slide having a coating film on one surface thereof was immersed in N, N-Dimethylformamide (DMF) solvent at room temperature for 1 hour, changes in the coating film such as breakage and surface gloss were observed. The evaluation was based on the following criteria: A) no abnormality; B) the surface gloss is reduced; C) the coating swells.
Hardness: characterized by pencil hardness based on GB/T6739-1996
The following table 1 shows the results of the performance tests performed on the examples 1 to 6 according to the above method, and the results show that: the coating film has excellent oil and water resistance and surface hardness.
TABLE 1
| Hardness of pencil | Water contact Angle (°) | Solvent resistance (DMF) | |
| Example 1 | 4H | 102 | A |
| Example 2 | 4H | 100 | B |
| Example 3 | 4H | 98 | B |
| Example 4 | 4H | 90 | B |
| Example 5 | 4H | 115 | A |
| Example 6 | 3H | 90 | B |
Claims (10)
1. A surface-modified nano-silica is characterized in that: the surface silanol hydroxyl of the nano silicon dioxide is subjected to acrylate functionalization and perfluoroalkoxy modification reaction through a compound A and a compound B to obtain the nano silicon dioxide; wherein,
the structural general formula of the compound A is as follows:
in the formula: r1Is H or CH3；
The structural general formula of the compound B is as follows:
in the formula: x is S or NH
RfThe general structural formula is as follows:
in the formula: n is 1, 2 or 3
R on the surface modified nano silicon dioxidefThe molar ratio of the groups to the acrylate groups is 1:1 to 1: 20.
2. The method of preparing the surface-modified nano-silica of claim 1, comprising:
sequentially placing nano silicon dioxide, an organic solvent, water, a compound A and a compound B in a container for mixing, adding a hydrochloric acid solution to adjust the pH value to 4-5, heating to 70-80 ℃, stirring, reacting for 3-4 hours, and cooling to obtain the nano silicon dioxide-organic solvent-water emulsion; wherein,
the structural general formula of the compound A is as follows:
in the formula: r1Is H or CH3；
The structural general formula of the compound B is as follows:
in the formula: x is S or NH
RfThe general structural formula is as follows:
in the formula: n is 1, 2 or 3
The weight ratio of the nano silicon dioxide to the compound A to the compound B is (20-30): (5-15): (2-10);
the organic solvent is at least one of isopropanol, ethylene glycol, glycerol and ethylene glycol monomethyl ether.
3. The method of claim 2, wherein: the particle size of the nano silicon dioxide is 5-25 nm.
4. The silicon-containing fluorine-containing acrylic resin coating is characterized in that: comprises the following components in parts by weight,
2-20 parts of surface modified nano silicon dioxide
20-80 parts of monofunctional (methyl) acrylate
5-20 parts of acrylate containing at least 2 acrylate groups
2-20 parts of alcohol solvent
2-10 parts of an initiator.
5. The silicon-containing fluorine-containing acrylic resin coating according to claim 4, wherein: the monofunctional (methyl) acrylate is at least one of methyl (methyl) acrylate, n-butyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, isodecyl (methyl) acrylate and monofunctional aliphatic urethane acrylate.
6. The silicon-containing fluorine-containing acrylic resin coating according to claim 5, wherein: the monofunctional (methyl) acrylate is at least one of isodecyl acrylate and monofunctional aliphatic urethane acrylate.
7. The silicon-containing fluorine-containing acrylic resin coating according to claim 4, wherein: the acrylate containing at least 2 acrylate groups is an acrylate containing 2 or 3 acrylate groups.
8. The silicon-containing fluorine-containing acrylic resin coating according to claim 7, wherein: the acrylate containing at least 2 acrylate groups is at least one of tripropylene glycol diacrylate, bisphenol A epoxy resin diacrylate, aromatic polyurethane diacrylate, aliphatic polyurethane diacrylate and trimethylolpropane triacrylate.
9. The silicon-containing fluorine-containing acrylic resin coating according to claim 8, wherein: the acrylate containing at least 2 acrylate groups is at least one of tripropylene glycol diacrylate and trimethylolpropane triacrylate.
10. The silicon-containing fluorine-containing acrylic resin coating according to claim 4, wherein: the alcohol solvent is at least one of isopropanol, ethylene glycol, glycerol and ethylene glycol monomethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100965348A CN101497749B (en) | 2009-03-06 | 2009-03-06 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100965348A CN101497749B (en) | 2009-03-06 | 2009-03-06 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497749A true CN101497749A (en) | 2009-08-05 |
| CN101497749B CN101497749B (en) | 2012-02-15 |
Family
ID=40945025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100965348A Expired - Fee Related CN101497749B (en) | 2009-03-06 | 2009-03-06 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497749B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875710A (en) * | 2010-06-30 | 2010-11-03 | 长兴化学材料(珠海)有限公司 | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof |
| CN102086333A (en) * | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
| CN102408757A (en) * | 2011-09-15 | 2012-04-11 | 中国科学院金属研究所 | A kind of solvent-type nano silicon dioxide concentrated slurry and preparation method thereof |
| CN103395790A (en) * | 2013-08-01 | 2013-11-20 | 广州大学 | Preparation method of esterified nano-SiO2 hydroxyl acrylate organic dispersion |
| CN103709800A (en) * | 2013-11-19 | 2014-04-09 | 北京化工大学常州先进材料研究院 | High glass adhesion UV (ultraviolet) resin |
| CN104312285A (en) * | 2014-09-26 | 2015-01-28 | 力嘉包装(深圳)有限公司 | Water-based ink and preparation method thereof |
| CN104341799A (en) * | 2014-09-23 | 2015-02-11 | 中国石油大学(华东) | Fluorine-containing acrylic ester polymer-modified nano silicon dioxide scrubbing oil system, and preparation method and application thereof |
| CN104761939A (en) * | 2015-04-28 | 2015-07-08 | 重庆卡勒斯通科技有限公司 | Stone surface protection nano coating and preparing process thereof |
| WO2018047686A1 (en) * | 2016-09-08 | 2018-03-15 | ダイキン工業株式会社 | Composition containing perfluoro(poly)ether-modified amide silane compound |
| CN109233423A (en) * | 2018-09-26 | 2019-01-18 | 广州市嵩达新材料科技有限公司 | A kind of modified Nano particle and preparation method thereof and super-hydrophobic selfreparing photocureable coating prepared therefrom |
| CN109890920A (en) * | 2017-06-02 | 2019-06-14 | 株式会社Lg化学 | Two-component adhesive composition |
| CN110607126A (en) * | 2019-08-15 | 2019-12-24 | 湖南梵鑫科技有限公司 | Electronic coating adhesive for protecting electronic circuit board and preparation method thereof |
| WO2021258720A1 (en) * | 2020-06-24 | 2021-12-30 | 广西七色珠光材料股份有限公司 | Pearlescent pigment for water-based paint, preparation method therefor, and sieving and impurity removal device |
| CN114525050A (en) * | 2022-03-31 | 2022-05-24 | 金发科技股份有限公司 | Hydrophobic antifogging coating, preparation method thereof and antifogging product |
| CN117244202A (en) * | 2022-06-09 | 2023-12-19 | 南京理工大学 | Preparation method of degradable hydrophobic oleophobic dry powder extinguishing agent |
| CN118791962A (en) * | 2024-08-09 | 2024-10-18 | 南京盛凯新材料有限公司 | EB-cured scratch-resistant and stain-resistant decorative film and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017487B (en) * | 2014-06-18 | 2017-01-04 | 湖南松井新材料有限公司 | Ultraviolet light cured burnished paint |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509893C (en) * | 2007-03-02 | 2009-07-08 | 中山大学 | Fluorine-containing nano inorganic particle toughening polymer and preparing method thereof |
| CN101161916A (en) * | 2007-10-09 | 2008-04-16 | 北京首创纳米科技有限公司 | Nano protective liquid for weaving and preparation method thereof |
-
2009
- 2009-03-06 CN CN2009100965348A patent/CN101497749B/en not_active Expired - Fee Related
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875710A (en) * | 2010-06-30 | 2010-11-03 | 长兴化学材料(珠海)有限公司 | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof |
| CN101875710B (en) * | 2010-06-30 | 2012-05-23 | 长兴化学材料(珠海)有限公司 | Siloxane-group light-initiated polyacrylic ester/silicon dioxide nanometer material and preparation method thereof |
| CN102086333B (en) * | 2010-11-29 | 2013-04-03 | 江苏足迹涂料有限公司 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
| CN102086333A (en) * | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
| CN102408757B (en) * | 2011-09-15 | 2014-03-05 | 中国科学院金属研究所 | A kind of solvent-type nano silicon dioxide concentrated slurry and preparation method thereof |
| CN102408757A (en) * | 2011-09-15 | 2012-04-11 | 中国科学院金属研究所 | A kind of solvent-type nano silicon dioxide concentrated slurry and preparation method thereof |
| CN103395790A (en) * | 2013-08-01 | 2013-11-20 | 广州大学 | Preparation method of esterified nano-SiO2 hydroxyl acrylate organic dispersion |
| CN103395790B (en) * | 2013-08-01 | 2015-10-28 | 广州大学 | Esterification Nano-meter SiO_2 2the preparation method of hydroxy acrylate organic dispersions |
| CN103709800A (en) * | 2013-11-19 | 2014-04-09 | 北京化工大学常州先进材料研究院 | High glass adhesion UV (ultraviolet) resin |
| CN104341799A (en) * | 2014-09-23 | 2015-02-11 | 中国石油大学(华东) | Fluorine-containing acrylic ester polymer-modified nano silicon dioxide scrubbing oil system, and preparation method and application thereof |
| CN104341799B (en) * | 2014-09-23 | 2016-01-13 | 中国石油大学(华东) | Fluorine-containing acrylate polymer modified nano-silica washing oil system and its preparation method and application |
| CN104312285A (en) * | 2014-09-26 | 2015-01-28 | 力嘉包装(深圳)有限公司 | Water-based ink and preparation method thereof |
| CN104761939A (en) * | 2015-04-28 | 2015-07-08 | 重庆卡勒斯通科技有限公司 | Stone surface protection nano coating and preparing process thereof |
| JPWO2018047686A1 (en) * | 2016-09-08 | 2018-12-13 | ダイキン工業株式会社 | Composition comprising a perfluoro (poly) ether modified amidosilane compound |
| WO2018047686A1 (en) * | 2016-09-08 | 2018-03-15 | ダイキン工業株式会社 | Composition containing perfluoro(poly)ether-modified amide silane compound |
| CN109072049A (en) * | 2016-09-08 | 2018-12-21 | 大金工业株式会社 | Composition containing the modified amide silane compounds of perfluor (poly-) ether |
| CN109890920B (en) * | 2017-06-02 | 2021-09-28 | 株式会社Lg化学 | Two-component adhesive composition |
| CN109890920A (en) * | 2017-06-02 | 2019-06-14 | 株式会社Lg化学 | Two-component adhesive composition |
| US10988640B2 (en) | 2017-06-02 | 2021-04-27 | Lg Chem, Ltd. | Two-component adhesive composition |
| CN109233423A (en) * | 2018-09-26 | 2019-01-18 | 广州市嵩达新材料科技有限公司 | A kind of modified Nano particle and preparation method thereof and super-hydrophobic selfreparing photocureable coating prepared therefrom |
| CN109233423B (en) * | 2018-09-26 | 2022-03-25 | 广州市嵩达新材料科技有限公司 | Modified nano particle, preparation method thereof and super-hydrophobic self-repairing photocureable coating prepared from modified nano particle |
| CN110607126A (en) * | 2019-08-15 | 2019-12-24 | 湖南梵鑫科技有限公司 | Electronic coating adhesive for protecting electronic circuit board and preparation method thereof |
| WO2021258720A1 (en) * | 2020-06-24 | 2021-12-30 | 广西七色珠光材料股份有限公司 | Pearlescent pigment for water-based paint, preparation method therefor, and sieving and impurity removal device |
| CN114525050A (en) * | 2022-03-31 | 2022-05-24 | 金发科技股份有限公司 | Hydrophobic antifogging coating, preparation method thereof and antifogging product |
| CN114525050B (en) * | 2022-03-31 | 2023-03-14 | 金发科技股份有限公司 | Hydrophobic antifogging coating, preparation method thereof and antifogging product |
| CN117244202A (en) * | 2022-06-09 | 2023-12-19 | 南京理工大学 | Preparation method of degradable hydrophobic oleophobic dry powder extinguishing agent |
| CN118791962A (en) * | 2024-08-09 | 2024-10-18 | 南京盛凯新材料有限公司 | EB-cured scratch-resistant and stain-resistant decorative film and preparation method thereof |
| CN118791962B (en) * | 2024-08-09 | 2025-02-25 | 南京盛凯新材料有限公司 | EB-cured scratch-resistant and stain-resistant decorative film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497749B (en) | 2012-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497749B (en) | Surface modified nano silicon dioxide and acrylic resin coating containing the same | |
| CN1284982A (en) | Liquid curable resin composition, coating, and cured coating therefrom | |
| CN1240787C (en) | Radiation-curable metal particles and curable resin compositions comprising these prrticles | |
| EP0408047B1 (en) | Radiation curable acryloxyfunctional silicone coating composition | |
| JP5387534B2 (en) | Coating composition | |
| CN102712730B (en) | Active energy ray-curable composition, and coated article | |
| KR20110016872A (en) | Process for producing curable composition and organosilicon compound | |
| CN113825636B (en) | Radiation-curable organopolysiloxane composition, cured product, and release sheet | |
| JP5051383B2 (en) | (Meth) acrylic modified siloxane compound and curable composition containing the same | |
| JP5353843B2 (en) | Plastic substrate for glazing | |
| CN1437632A (en) | Reactive particles, curable composition comprising the same and cured products | |
| CN1289613C (en) | curable liquid resin composition | |
| CN110003441B (en) | A kind of preparation method of UV-curable water-based isocyanate-grafted fluorosiloxane-modified epoxy acrylic resin | |
| CN102585667B (en) | A kind of hydrophilic ultraviolet light curing coating and preparation method thereof | |
| CN106750318B (en) | Polysiloxane acrylate containing tertiary amine structure and preparation method and application thereof | |
| CN115558111B (en) | UV/moisture dual-curing organic silicon resin and synthetic method and application thereof | |
| JP5063915B2 (en) | UV-curable coating composition and resin-coated article formed by coating the composition | |
| Karataş et al. | Synthesis and characterization of UV‐curable phosphorus containing hybrid materials prepared by sol–gel technique | |
| WO2014112470A1 (en) | Shape-memory sheet and manufacturing method therefor | |
| EP0424645B1 (en) | Radiation curable transparent coating compositions containing basic colloidal silica | |
| CN1950464A (en) | Curable liquid composition, cured film, and antistatic laminate | |
| KR20150135243A (en) | Active-energy-ray-curable coating composition | |
| JP2020530520A (en) | A coating film containing a coating resin composition and a cured product thereof as a coating layer. | |
| JP2004244428A (en) | Alkoxysilane derivative, curable composition and its cured product | |
| JP7276183B2 (en) | Active energy ray-curable composition, coating agent, and coated article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHEJIANG CHIHE TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: ZHEJIANG CHIHE CHEMICAL INDUSTRY CO., LTD. Effective date: 20120411 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20120411 Address after: Two, 323300 street block, Dongcheng Industrial Park, Lishui, Zhejiang, Suichang Patentee after: Zhejiang Chihe Technology Co., Ltd. Address before: 323300 Zhejiang County of Suichang province Miao Gao Zhen Mei Xi Road No. 90 Patentee before: Zhejiang Chihe Chemical Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120215 Termination date: 20170306 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |