CN102725359B - Coating composition - Google Patents
Coating composition Download PDFInfo
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- CN102725359B CN102725359B CN201080059071.9A CN201080059071A CN102725359B CN 102725359 B CN102725359 B CN 102725359B CN 201080059071 A CN201080059071 A CN 201080059071A CN 102725359 B CN102725359 B CN 102725359B
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- 239000008199 coating composition Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 73
- 238000000576 coating method Methods 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 39
- 239000004575 stone Substances 0.000 claims abstract description 33
- 239000011368 organic material Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000005755 formation reaction Methods 0.000 claims abstract description 4
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001338 self-assembly Methods 0.000 claims description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- -1 triazine heterocyclic Compound Chemical class 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- 235000019738 Limestone Nutrition 0.000 claims description 10
- 239000006028 limestone Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- 229910052904 quartz Inorganic materials 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052580 B4C Inorganic materials 0.000 claims description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N Boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052582 BN Inorganic materials 0.000 claims description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N N#B Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 8
- 229910001884 aluminium oxide Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002121 nanofiber Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 230000003993 interaction Effects 0.000 claims description 6
- 150000002894 organic compounds Chemical group 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 229910008051 Si-OH Inorganic materials 0.000 claims description 5
- 229910006358 Si—OH Inorganic materials 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 238000007306 functionalization reaction Methods 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N Dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002969 artificial stone Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001261 hydroxy acids Chemical group 0.000 claims description 3
- 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 claims description 2
- 210000004884 grey matter Anatomy 0.000 claims description 2
- 239000003049 inorganic solvent Substances 0.000 claims description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000001476 alcoholic Effects 0.000 claims 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-Triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims 1
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical group NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical group CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000005411 Van der Waals force Methods 0.000 abstract description 4
- TWXTWZIUMCFMSG-UHFFFAOYSA-N nitride(3-) Chemical compound [N-3] TWXTWZIUMCFMSG-UHFFFAOYSA-N 0.000 abstract description 3
- QXUAMGWCVYZOLV-UHFFFAOYSA-N boride(3-) Chemical compound [B-3] QXUAMGWCVYZOLV-UHFFFAOYSA-N 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 238000004026 adhesive bonding Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 11
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 10
- 239000004579 marble Substances 0.000 description 9
- 239000002928 artificial marble Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 229910021431 alpha silicon carbide Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000002269 spontaneous Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229960003563 Calcium Carbonate Drugs 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 210000002381 Plasma Anatomy 0.000 description 2
- 229920001225 Polyester resin Polymers 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000002045 lasting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical compound C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K Aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H Aluminium sulfate Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-L CHEBI:8154 Chemical group [O-]P([O-])=O ABLZXFCXXLZCGV-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N Tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001409 amidines Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000001473 noxious Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- NJRWNWYFPOFDFN-UHFFFAOYSA-L phosphonate(2-) Chemical group [O-][P]([O-])=O NJRWNWYFPOFDFN-UHFFFAOYSA-L 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching Effects 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910001929 titanium oxide Inorganic materials 0.000 description 1
- 238000004642 transportation engineering Methods 0.000 description 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
The method of the present invention is included in stone material substrate formation coating to improve its hardness, chemical resistance, wearability and scratch resistance, is included in substrate to use and includes organic material and include the Coating base of filler of inorganic nano-particle and/or micron particle；By adhesive bonding methods such as self-assembling method and/or covalent bond combination, electrostatical binding, Van der Waals force combination or hydrogen bonded, chemically bond described base material to substrate；Finally it is dried described base material.Described organic material is selected from organosilan, organic phosphate, polycarboxylate compound, compound based on triazine heterocyclic, and described nanoparticle is metal or semimetallic oxide, carbide, boride, the nanoparticle of nitride.
Description
Technical field
The present invention relates to a kind of method for coating stone material substrate in first aspect, described stone material substrate should be understood natural marble in this specification or includes that Calcareous material and/or white clouds fossil lime stone (dolomitic limestone) become the stone aggregate (stone aggregate) of agglomerate by binding agent, the method provides a kind of coating, it can improve the hardness of described stone material substrate, improve chemical resistance, wearability and scratch resistance.The coating of the present invention improves the stability of surface opposing chemical etches and decreases contamination.
While the technique of the present invention allows to improve the life-span using stone material substrate such as artificial marble plate in the best condition, it is significantly expanded the range of this series products (repellence to many factors in view of going out shown by exposed surface), and reduces the blocks in process, transport and installation process or the quantity of defect block.
The method of first aspect of the present invention provides a kind of coating based on self-assembling technique, and self-assembling technique allows to connect nano structural material.
A second aspect of the present invention relates to a kind of by the fuel plate made by the stone material comprising the coating formed according to proposed method.
A third aspect of the present invention provides a kind of compositions, and it is for coating by the fuel plate made by stone material, and said composition includes the first organosilan material and inorganic nano-particle and/or micron particle being attached in base material by self-assembling method.
Background technology
In the existing technique for obtaining artificial marble plate, using the mixture of the marble aggregate with excellent controlled particle size, it represents the material compositions more than 90%.Prior catalyst and accelerator reach the thermosetting resin Binder Composition generally as filler of required situation.Due to petrography character and the inherent character of polyester resin of mineral used, artificial marble paving material has low chemical resistance, can reduce the service life of substrate when friction occurring and scratching.Scratch resistance and wearability are relevant with the hardness of material or repellence, and a kind of material is scratched, by another, the repellence presented and is defined as Mohs scratch resistance and the mar proof of material.This situation is to include one of natural major defect of marble type stone material substrate with artificial marble (agglomerate marble).
Conventional transparent coatings based on siloxanes or other polymer have the good repellence impacted interval or attack, but they are to standing lasting pressure, such as during passage area, having low repellence, this is owing to the low wear-resistant and scratch resistance of product based on siloxanes and plastics.
There is different technology to solve drawbacks described above.Filler based on siloxanes (wollastonite, nanoclay) smoothing preparation or additive use the most in batch.These technology only effective to the application having low wearability to require.When the higher wearability of needs, the coating technology containing inorganic filler and the resin of laminated material is used.But this solution creates the surface of a kind of plastics vision not being expected in high-end decorative product market.
Using coating is one of state-of-the-art technology.Coating applies in general to protection, improves or decorate different products.But, between coating and polymeric material, there is low cohesive force due to the low polarity of the latter.The method improving cohesive force generally comprises the surface energy being improved plastics by different methods: be exposed to high energy source such as flame, corona, plasma and UV radiation treatment.In general, being allowed the surface with high surface energy become " moist " by coating is easily, the most also will be easier to improve the cohesive force between spraying substrate and phase.But, the most still some shortcoming, mainly due to environment reason, the fact that they are slow and are not the most homogeneous technique, be additionally present of these limit due to these material heat stability is bad the fact.
Special coating processes such as physical vapour deposition (PVD) (PVD), chemical vapors deposition (CVD), and wet method deposition (or sol-gel), be all that known technology is for by inorganic coating (SiO2, carbide, nitride, metal-oxide ...) be deposited in different substrates (including plastics).But, on plastic material, the technology of this type has certain restriction such as high cost, low deposition speed, high energy and especially produce poison.
Patent US5751018 discloses a kind of method including applying coated semiconductor in inorganic substrates by SAM technique.Particularly, it advocates the surface by first functional group's covalent bond link bridge structure to inorganic substrates, and is also that covalent bond is attached to semiconductor nanocrystal by its other functional groups.This technology of this patent is not suitable for the coating of stone material substrate, because all not accounting for the character of described substrate and the requirement of coating.
Application WO2004094303A2 proposes to connect two kinds of article by nanofiber, and wherein for an embodiment, one of article are made of stones.In its description, describe SAM technique combine to be configured to the nanofiber of above-mentioned connection with micro-spraying coating process that contacts.
Application EP1802455A2 proposes application aluminum phosphate coatings to substrate.In its description, it describes such coating, especially, it is provided that higher hardness.It also illustrates a kind of additional coatings, " protective coating ", it is possible to be applied to described coating by self-assembled monolayer or SAM technique.This additional coatings can include organic molecule or polymer, and coating is based on silane, the same with the aluminum sulfate material itself proposed.It also illustrates provided coating can include organic or inorganic additive, such as metal ion such as silicon, ferrum, zinc and magnesium or its mixture, and nanocrystal zinc, titanium oxide or their mixture.
In view of about the deficiencies in the prior art mentioned by protection stone material substrate; a kind of new coating has been achieved for development; it is formed with the chemical bonds such as the covalent bond of high-resistance, electrostatic, Van der Waals force between stone material substrate and clear coat; stone material substrate is to include Calcareous material and/or the aggregate of white clouds fossil lime stone, with the repellence that the quartz plate that reaches to have stone material vision is similar.
Summary of the invention
The present invention provides a kind of method for coating stone material substrate, and the method is by being formed on coating to improve the hardness of described substrate, wearability and resistance to marring.The coating provided also makes surface more etch resistant and resistant.
Mentioned stone material substrate be based on, in a preferred version, including Calcareous material and/or white clouds fossil lime stone stone aggregate mixture, become agglomerate by binding agent.
The method comprises the steps:
Use the Coating base (coating matrix) of the filler including at least one organic material and include inorganic nano-particle and/or micron particle on the substrate；
By described base material by implementing self-assembly process and/or being chemically bound in substrate by covalent bond combination, electrostatical binding, Van der Waals force combination or the associated methods of hydrogen bonded；With
Use suitable method in general by providing heat energy to be dried described base material,
Especially, quantity is at least one organic material and/or nanoparticle and/or micron particle has containing Si-OH, SiOR (R=organic compound), or Si-Cl, aldehydes or ketones or COOH, NH2, phosphate radical, phosphonate radical, sulfonate radical, the molecule of at least one group in sulfate radical, or combinations thereof.
The most in itself, the method of the present invention includes that the organic and inorganic precursor allowing to form three-dimensional network forms the coating of nanostructured by self-assembly process, it is securely joined with in substrate by chemical bond, encapsulate different nanoparticles and/or micron particle, and the coating obtained has high abrasion resistance and scratch resistance.
About organic material, according to an embodiment, it is selected from organosilan, organophosphorus ester, polycarboxylate compound, compound based on triazine heterocyclic, and described nanoparticle are described nanoparticle and/or the metal of micron particle composition functionalization or semimetallic oxide, carbide, boride, the nanoparticle of nitride, selected from aluminium oxide, boron carbide, boron nitride, silicate, glass microsphere, carborundum, silicon dioxide, quartz, copper oxide, micrometer fibers and nanofiber, core-shell particles, n-Na2SiO3Or a combination thereof.
Coating base farther includes organic or inorganic binding agent and organic or inorganic solvent.
Described binding agent particularly thermosetting aqueous-based polymers, and described solvent is aqueous or alcohol medium, and described thermosetting polymer is compound based on triazine heterocycle, the tripolycyanamide of such as methoxylation.
About the method using Coating base, preferably carried out by the codeposition of organic material and nanoparticle and/or micron particle.
In order to accelerate the dehydration of free functional groups during being dried described base material and improve the purpose of its cross-linking properties, described method farther includes the controlled heating steps of the substrate for coating.
A second aspect of the present invention is about having the fuel plate of the coating that the method provided by a first aspect of the present invention is formed, and it includes natural stone grey matter substrate or containing Calcareous material and/or the artificial stone of white clouds fossil lime stone.
According to an embodiment, the artificial stone by the substrate of the plate made by stone material material that a second aspect of the present invention is provided includes the calcium carbonate of powder and/or white clouds fossil lime stone and resin glue.
In another embodiment, described coating contain be absorbed in described base material selected from aluminium oxide, boron carbide, boron nitride, silicate, glass microsphere, carborundum, silicon dioxide, quartz, copper oxide, micron-and nanofiber, core-shell particles, n-Na2SiO3Or the inorganic micron-of the high rigidity of at least one material and/or nanoparticle in combinations thereof.
According to the third aspect, the present invention also relates to the compositions of fuel plate for the most just described stone material of coating, including the first organosilan material and inorganic nano-particle and/or micron particle, it has selected from Si-OH, SiOR (R=organic compound), or Si-Cl, aldehydes or ketones CO or COOH, phosphate radical, phosphonate radical, sulfonate radical, the molecule of at least one in sulfate groups, wherein said nanoparticle and organosilan material are bonded in base material by carrying out self-assembly process and/or other chemical bond or electrostatic or chemical interaction method.
In one embodiment, the compositions proposed according to the third aspect also includes water base organic binder bond, aqueous, alcohol, water alcohol solvent and reaction promoter.
In a preferred version, the first described organosilan material is the silane of functional organic, it is selected from following material: TEOS (tetraethyl orthosilicate), γ-methacryloxypropyl trimethoxy silane, BTSE (1, 2-bis-(triethoxysilyl) ethane), hexadecyl trimethoxy silane, 3-glycidyloxypropyl trimethoxy silane, dichloro base silane, dichlorodimethylsilane, organic phospho acid esters, polycarboxylate compound, compound based on triazine heterocycle, or have selected from 1, 3, the triazine group of 5-triazine or there is free amino group group, the organic material of the diaminourea-PEG selected from this group.It addition, described nanoparticle and micron particle are selected from aluminium oxide, boron carbide, boron nitride, silicate, glass microsphere, carborundum, Silicon stone, quartz, copper oxide, micron-and nanofiber, core-shell particles, n-Na2SiO3Or the material in combinations thereof.
According to a preferred version, the compositions imagination that third aspect present invention is proposed, form its nanometer-and micron particle, jointly or optionally, by phosphonate radical, amino, aldehyde, sulfonate radical, sulfate radical salt, hydroxy-acid group or organosilan functionalization.
About organic binder bond, the thermosetting polymer with reactive functional groups is used.
Aforesaid advantage and other advantage and feature will be more fully understood that by the detailed description and the accompanying drawings of following several embodiments, and this must be treated as non restrictive description.
Accompanying drawing explanation
In the accompanying drawings:
Fig. 1 illustrates suprabasil self assembling process, and this layer is formed by water alcohol organosilane solution.Due to SiOH ... the crosslinking that the dehydration of HOSi unit causes with generating Si-O-Si key occurs after Low Temperature Heat Treatment；
Fig. 2 shows nanoparticle, and the exterior portion that its structure is made up of 2 unit, a kind of core of forming, difference is formed；The nanoparticle of Bulbus Allii Cepae type；
Fig. 3 shows the thin Iy self-assembled layer on substrate surface, which show eight core Si4O4Unit；
Fig. 4 shows surface-functionalized other embodiments, based on using amino and the self assembly of aldehyde functional group；
Fig. 5 shows and wherein uses the molecule containing aldehyde functional group and triazine for the example of self assembling process.The triazine comprised allows to produce three-dimensional network；
Fig. 6 illustrates at suprabasil self assembling process, and it is according to the principle of the present invention: the mild oxidation on surface, the self assembly of nano composite material and deposition.This process can occur in 3 steps, in 2 steps, even occurs in a step.
Fig. 7 shows the combination of the silanol in the base material caused because of spontaneous self assembly.There occurs the formation of dehydration and key in this process；
Fig. 8 shows the coating structure only having micron particle according to the present invention at its top, and describes the structure of the combination of micron particle and nanoparticle in bottom.
Detailed description of the invention
The invention provides a kind of high hardness spray coating, it is based on Nano filling and/or micron filler and TEOS, silane adhesion base material etc..
The hard coat formulation that the present invention provides allows the case hardness of stone material substrate to increase above the Mohs' hardness of 2 or 3 points, and this hard conating is the dispersion in alcohol or water alcohol aqueous solvent based on described Nano filling and/or micron filler.
This progress is made up of the base material of multifunctional molecule, wherein one of functional group is self assembly or covalent bond to combine, therefore molecule at least includes the one of following radicals: Si-O (R=organic compound) or Si-Cl, aldehydes or ketones, CO or COOH, phosphate radical, sulfate radical, or the combination of these functional groups such as mercaptan phosphonate radical, it will produce three-dimensional network due to spontaneous self assembly.Some molecules used are: thio-alcohol, alkoxyl silicone alkanes, carboxylic acids, metal alkoxides salt (alkoxymetallates) and phosphonic acid based.
Second functional group be under controlled mode can trigger monomer polymerization group.
Some functional molecules used are: tetraethyl orthosilicate, two-1,2 (triethoxysilyl) ethane, 3-glycidoxypropyltrimewasxysilane, gamma-amino propyl silane, dichlorodimethylsilane, two-dichloromethyl phenyl silane, hexadecyl trimethoxy silane.
In order to promote the bonding of substrate and filler, aqueous/water alcohol medium can be by adding acetic acid, hydrochloric acid, tartaric acid, and ethylenediaminetetraacetic acid etc. is acidified, and this type of acid promotes self assembly by producing silanol, carboxyl or phosphonate groups.
The final micron particle selected and nanoparticle are stable in aqueous medium and/or colloid solution, and can add during the oligomerization forming molecule, thus Nano filling has the percentage ratio of control very well in additive.
The selection of filler used is based on compositions, structure, size and cost etc..Some fillers considered are:
Aluminium oxide (Al2O3)
Boron carbide (B4C)
Boron nitride (BN)
Silicate
Glass microsphere
Carborundum (SiC)
Silicon dioxide (SiO2)
Quartz
Copper oxide (CuO)
Micron and nanofiber
In order to promote the molecule bridging property between stone material substrate surface and multifunctional nano-structured coating, use self assembly (self-assembly, SAM) technology, it can produce the strong bond polarity without consideration surface to be combined, and can maintain the outward appearance of original sheet.
Self-assembling technique is based on the fact that, the surface of some material can be modified by surface active, and surface active can include described mild oxidation, and/or uses the chemical functionalization method of the molecule with self assembly ability.
This new technique provides at material surface and includes being effectively combined between micron and the coating of nanoparticle, and this is owing to the probability forming molecule crosslinking while keeping the outward appearance of original sheet from the teeth outwards.
Molecule anchor knot method includes 3 steps: activation, self assembly and micron and the codeposition of nanoparticle.When responsible activation and being responsible for forms the molecule of three-dimensional network and micron on the surface of the substrate and Nano filling is in same compositions, this 3 step of codeposition of activation, self assembly and micron and nanoparticle can complete in a step as described in Figure 6.
The first step is directed to make the activation under optimum conditions of the surface-functionalized purpose of pending substrate, produces the optimal functionalizing group of the self assembly for organic molecule on the surface, thus improves described surface and the probability of self-assembling reaction occurs.
The carboxyl formed in activation process (first step) and hydroxyl provide activation point, and therefore molecule and suitable functional group carry out self assembly (second step).In described second step, the self-assembling technique of formation based on the Van der Waals force between covalent bond and other weak interaction such as electrostatic or the functional group on activated base surface and di-or higher functional organic molecule is employed.Therefore, being incorporated into parts surface must be spontaneous generation stable molecular chemistry.
At the 3rd step, the inorganic micron of high rigidity and nanoparticle (SiC, BN, SiO2, TiO2, ZrO2, quartz, aluminium oxide, B4C etc.) codeposition occur at substrate surface to obtain high-quality coating.Micron and/or nanoparticle are absorbed in the network that can be formed by described molecule, maximize the interaction of base material-particle.The molecule of self assembly is attached to surface by chemisorption method (adsorbed material is attached to the surface of solids by the power that its energy level is close with those chemical bonds), it is provided that in substrate and intermolecular effective combination.
This three step can be reduced to a step, in order to the hard micron particle in three steps and nanoparticle must be used in same formula by that result, it will activate and pass through self assembly and produce the molecule codeposition of three-dimensional network in coating with making substrate surface.
Obtaining hard transparent coating by chemical or the interaction of electrostatic or key combination, it has high abrasion resistance, maintains mechanical performance simultaneously.
Use this technology, make organic and inorganic precursor that is different from micron and/or nanoparticle and that have the ability to be formed three-dimensional network packed.
Fig. 7 show owing to spontaneous self assembly combination of multifunctional molecule in base material creates three-dimensional network (situation of such as silanol), multifunctional molecule has selected from least following a kind of group: Si-O or Si-Cl, CO or COOH, amine, carbonyl, free aldehyde group, carboxylic acid, the combination of phosphate radical, sulfate radical, or these functional groups such as mercaptan phosphonate radical.
About the figure in accompanying drawing, it is emphasized that, when marble surface the compound such as organosilan, phosphonate ester being mainly made up of the metal carbonate (mainly calcium carbonate) of crystalline texture, mercaptan, there is the compound treatment of amino, aldehyde or hydroxy-acid group time, the deposition of shallow layer occurs in that XCO3Unit, generates-O-X-O-Si type bonds, such as organosilan.
For the material of this type, silicon compound forms Si-O-Si-O type bonds, thus is formed and have the excellent three dimensional structure combined with marble substrate.
If solution based on the water alcohol heat treatment at low temperatures of organosilan, it causes the dehydration of silanol units, and it will become Si-O-Si type bonds (being with or without organic chain) from Si-OH so that cross-link (Fig. 1) at interlayer.
According to silane molecule (BTSE used；TEOS, GLYMO, etc..), by eight nuclear unit (SiO)4(Fig. 3), Bulbus Allii Cepae type (Fig. 2), etc.. form nano particle structure.These silicon oxide (SiO) nanoparticles produced in original place are deposited on the surface of substrate, and are chemically bonded to surface by self-assembling method.
The functionalization on surface and another example of self assembly are the reactions between the surface of two senses or multifunctional aldehyde and amido chemical modification.In this case, self-assembling reaction will occur (Fig. 4) between amidine functional group and aldehyde group.When the molecule with aldehyde functional group is used for causing self-assembling reaction, it is possible to use different types of reagent, it can produce three-dimensional network by the reaction with free aldehyde radical or hydroxyl.These molecules must have at least 3 free amino group group such as tripolycyanamide, triamine or tetramine, etc..(Fig. 5).
Micron particle and/or the nanoparticle with high rigidity will be added in formula improve hardness and the wearability of coating more.The repellence of the coating of some nanostructureds is than the big approximation of the repellence of commonly used coating three times with persistently more than 40%.Adopting in this way, nanoparticle may be directly applied to coating surface, and ultimate cost can substantially reduce.And, it is thus achieved that the probability of the customizable thickness from nanometer layer to micron layer contributes to the minimizing of cost.
The product formed includes the new coating that thickness is 100nm-500 μm, it is formed by codeposition by the self assembly of the micron particle and nanoparticle with high rigidity, for this purpose, use the organic or organic metal base material with the ability causing self-assembling reaction between the surface and recipe ingredient of substrate, it is allowed to form three-dimensional network.
Detect the change in chemical composition of different types of functional molecules, solvent and filler, the structure of compositions and particle diameter, until obtaining the optimum formula of coating.
The parameter (coating layer thickness, baking temperature ...) of application, processing mode (dip-coating, roller coat ...), etc.. also affect quality results and the final performance of coating.
All of these factors taken together affects the hydrophobicity of coating, the surface tension of generation, intermolecular correct crosslinking, transparent appearance more or less, the generation of bubble, the surface of loss viscosity the most thereafter of caking property, cracking etc..
Therefore, correct binding agent, the activation of suitable solvent medium, the combination of optimal filler, also include application process and some concrete application parameter, ultimately result in and obtain effectively and the most stable coating.
Realization below by non-limiting detailed description several embodiments of the present invention.
Embodiment 1
1ml hydrochloric acid joins ethanol/water (80ml ethanol under magnetic stirring；20ml water) in water-alcohol solution, add the GLYMO (3-glycidyloxypropyl trimethoxy silane) of the TEOS (tetraethyl orthosilicate) and 23ml of 55ml.Continuously stirred 10 minutes of solution, adds the alpha-silicon carbide 5.4g that particle diameter is 80nm.Mixture, by continuously stirred 5 minutes, is applied to the surface of artificial marble plate afterwards.
The baking oven of 120 DEG C is dried 25 minutes.
Embodiment 2
1ml hydrochloric acid joins ethanol/water (80ml ethanol under magnetic stirring；20ml water) in water-alcohol solution, add the TEOS (tetraethyl orthosilicate) and 40ml GLYMO (3-glycidyloxypropyl trimethoxy silane) of 40ml.Continuously stirred 10 minutes of solution, adds the alpha-silicon carbide 5.4g that particle diameter is 1 μm.Mixture, by continuously stirred 5 minutes, is applied to the surface of artificial marble plate afterwards.
The baking oven of 85 DEG C is dried 45 minutes.
Embodiment 3
Artificial marble plate (substrate) processes 40 seconds in the HCl/water solution of 3.5 volume % at 25 DEG C.Substrate, through 3 washings, is dried afterwards.
1ml hydrochloric acid joins ethanol/water (80ml ethanol under magnetic stirring；20ml water) in water-alcohol solution, add the TEOS (tetraethyl orthosilicate) and 55ml GLYMO (3-glycidyloxypropyl trimethoxy silane) of 25ml.Continuously stirred 10 minutes of solution, adds the alpha-silicon carbide 4.4g that particle diameter is 1 μm and the alpha-silicon carbide 1g that particle diameter is 80nm.Mixture was by continuously stirred 5 minutes, and was applied to substrate.
The baking oven of 85 DEG C is dried 45 minutes.
Embodiment 4
Artificial marble plate (substrate) processes 40 seconds in the HCl/water solution of 3.5 volume % at 25 DEG C.Substrate is through 3 washings, afterwards through being dried.
1ml hydrochloric acid joins ethanol/water (80ml ethanol under magnetic stirring；20ml water) in water-alcohol solution, add the TEOS (tetraethyl orthosilicate) and 25ml GLYMO (3-glycidyloxypropyl trimethoxy silane) of 55ml.Continuously stirred 10 minutes of solution, adds the silicon dioxide 25g that particle diameter is 6 μm.Mixture, by continuously stirred 5 minutes, is applied to substrate afterwards.
The baking oven of 85 DEG C is dried 45 minutes.
By based on micron-and/or the combination of this combination technology of Nano filling and the new hard conating of described silane (or phosphonate) bonding base material and use substrate:
-in substrate, obtain stable coating.
The raising of-substrate hardness is achieved.
-the scratch resistance that improves substrate is achieved.
-owing to creating chemical bond between coating and polyester resin, therefore improve the associativity between coating and substrate.
Chemical resistance and the resistance to cleaning agent of-test sample are improved.
-constructing at low temperatures is achieved.
-because solvent used is aqueous or water alcohol medium, it is achieved that construct in hypotoxicity medium, therefore prevent the discharge of noxious volatile gas and there is no zest or other health risks for processing the people of solution.
Embodiment 5: etching test
Some marble blocks are polished to be completed etching the most thereon and stains test, and compares with the most polished block.Result is that the block of polishing is without coating and being easy to by hcl corrosion.
Observe these regions the most cated to keep not to change.Like this, with not processed for compared with 3, the hardness obtained has reached Mohs' hardness 6.Find that certain separating still is not observed and scratch the generation also not having spillage of material.
When hydrochloric acid and alkali liquor are poured into, there is no bubble and until within several hours, pass by the most not react generation.On the contrary, not processed block is directly etched and is depleted immediately with marble.
The method of the present invention can reach ensuing objectives:
-in the case of not changing substrate original appearance, improve abrasion resistance properties.
-it does not affect final products other performances (bending, resistance to impact, processing characteristics, physical characteristic, mechanical performance etc..)
-use this new processing method, define lasting stable coatings, be mainly due to obtain the high associativity with substrate by forming the firm interaction such as electrostatic, covalent bond type between coating and substrate.
-it acts on the stone material substrate of the mixture based on the stone aggregate being become agglomerate by organic binder bond of wide scope.Binding agent can be thermosetting and thermoplastic as the adhesion component of stone material.The character of mineral changes according to the petrography origin of selected natural stone (marble, limestone, quartz, granite etc..).
-it prevents the agglomeration problems when using in batch.
-which reduce the generation of waste product after Product processing: decrease the garbage of blocks.
The extra cost of-final products is minimum.
-because they are processing methods based on non-volatile solvent, so there is no environmental risk or health risk.
-at low temperatures operation can either with or without the block significantly degenerated, unlike ought be harsher sedimentary system such as plasma or corona these occurred.
Claims (20)
1., for the method coating stone-type substrate, described substrate becomes agglomerate based on by the first binding agent
Calcareous material and/or the stone aggregate mixture of white clouds fossil lime stone, described method is included in described
In substrate, formation coating is to improve its hardness, chemical resistance, wearability and scratch resistance, described method
It is characterised by that it comprises the following steps:
Use the Coating base comprising at least one organic material and filler on the substrate, described in have
Machine material is selected from organosilan, Organophosphonate, polycarboxylate compound, change based on triazine heterocyclic
Compound, described filler comprises inorganic nano-particle and/or micron particle；
By described base material by implementing self-assembly process and/or by covalent bond combination, electrostatical binding, model
De Huali combine or the associated methods of hydrogen bonded and be chemically bound to described substrate；With
Dry described base material is to form three-dimensional network, and it is securely joined with in described substrate by chemical bond,
Encapsulate different inorganic nano-particles and/or micron particle,
Wherein said Coating base farther includes organic solvent and/or inorganic solvent and is optionally present
Organic binder bond and/or inorganic binder；
At least one wherein said organic material and/or inorganic nano-particle and/or micron particle contain
Selected from Si-OH, SiOR wherein R=organic compound or Si-Cl, aldehyde radical or carbonyl or COOH,
NH2, phosphate radical, phosphonate radical, sulfonate radical, functional group in sulfate radical,
Wherein said inorganic nano-particle and/or micron particle selected from aluminium oxide, boron carbide, boron nitride,
Silicate, glass microsphere, carborundum, silicon dioxide, copper oxide, micrometer fibers and nanofiber,
Core-shell particles or a combination thereof.
Method the most according to claim 1, it is characterised in that described Coating base farther includes instead
Mixing of answering property accelerator, water base organic binder bond, and aqueous solvent, alcoholic solvent, aqueous solvent and alcoholic solvent
Compound thrin.
3. according to the method for claim 1 or 2, it is characterised in that use described Coating base to base
It is to be completed by the codeposition of organic material and nanoparticle and/or micron particle at the end.
4. according to the method for claim 1 or 2, it is characterised in that dry the including of described base material applies
Heat to coating substrate on accelerate free functional groups dehydration and improve its bridging property step.
Method the most according to claim 1, wherein said silicate is n-Na2SiO3。
Method the most according to claim 1, wherein said silicon dioxide is quartz.
7. the plate being made up of stone material, including natural stone grey matter substrate or limy material and/or white clouds
The artificial stone of limestone, and there is the coating that the method according to one of claim 1-6 is formed.
Plate the most according to claim 7, it is characterised in that the thickness of described coating is
100nm-500μm。
9. according to the plate of claim 7 or 8, it is characterised in that described coating includes having selected from oxygen
Change aluminum, boron carbide, boron nitride, silicate, glass microsphere, carborundum, silicon dioxide, copper oxide,
Micron and the high-hardness inorganic micron grain of at least one material in nanofiber, core-shell particles or a combination thereof
Son and/or nanoparticle.
Plate the most according to claim 9, wherein said silicate is n-Na2SiO3。
11. plates according to claim 9, wherein said silicon dioxide is quartz.
The compositions of 12. fuel plates being made up of stone-type substrate for coating, described substrate is based on logical
Cross the first binding agent and become Calcareous material and/or the stone aggregate mixture of white clouds fossil lime stone of agglomerate, its
The compositions being characterised by described comprise at least one organic material and include inorganic nano-particle and/or
The filler of micron particle, described organic material selects free organosilan, Organophosphonate, Polycarboxylated
Compound, compound based on triazine heterocyclic and have free amino group group organic material composition group；
Wherein said organic material or described inorganic nano-particle and micron particle are had
Si-OH, SiOR wherein R=organic compound or Si-Cl, aldehyde radical or carbonyl or COOH, NH2、
The functionalized molecule of at least one group in phosphate radical, phosphonate radical, sulfonate radical, sulfate radical, it leads to
Cross self-assembly process and/or other chemical bond or electrostatic or chemical interaction method and be incorporated into
Described substrate, and wherein said nanoparticle and micron particle are selected from aluminium oxide, boron carbide, nitrogen
Change boron, silicate, glass microsphere, carborundum, silicon dioxide, copper oxide, micrometer fibers and nanometer
Fiber, core-shell particles or a combination thereof.
13. compositionss according to claim 12, including water base organic binder bond, aqueous solvent, alcohol are molten
The mixture thrin of agent, aqueous solvent and alcoholic solvent and reaction promoter.
14. according to the compositions of claim 12 or 13, it is characterised in that described organosilan is selected from
Following material: tetraethyl orthosilicate, γ-methacryloxypropyl trimethoxy silane, 1,2-double (three
Triethoxysilyl) ethane, hexadecyl trimethoxy silane, 3-glycidoxypropyl three
Methoxy silane, dichloro (diphenyl) silane, the organic material of dichlorodimethylsilane.
15. according to the compositions of claim 12 or 13, it is characterised in that described inorganic nano-particle
With micron particle by phosphonate radical, NH2, aldehyde radical, sulfonate radical, sulfate radical, hydroxy-acid group or SiOR
Wherein any one functionalization in R=organic compound.
16. compositionss according to claim 12, wherein compound based on triazine heterocyclic is to have
The organic material of triazine group.
17. compositionss according to claim 16, in the wherein said organic material with triazine group
Triazine group selected from 1,3,5-triazine.
18. compositionss according to claim 12, the organic material wherein with free amino group group is
There is the organic material of diamino-PEG group.
19. compositionss according to claim 12, wherein said silicate is n-Na2SiO3。
20. compositionss according to claim 12, wherein said silicon dioxide is quartz.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09380197 | 2009-12-23 | ||
| EP09380197.5A EP2338940B1 (en) | 2009-12-23 | 2009-12-23 | Composition for coating |
| PCT/IB2010/003246 WO2011077211A1 (en) | 2009-12-23 | 2010-12-15 | Composition for coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102725359A CN102725359A (en) | 2012-10-10 |
| CN102725359B true CN102725359B (en) | 2016-11-30 |
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| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
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