CN100549116C - Autoxidisable architectural coating compositions - Google Patents
Autoxidisable architectural coating compositions Download PDFInfo
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- CN100549116C CN100549116C CNB2004800283950A CN200480028395A CN100549116C CN 100549116 C CN100549116 C CN 100549116C CN B2004800283950 A CNB2004800283950 A CN B2004800283950A CN 200480028395 A CN200480028395 A CN 200480028395A CN 100549116 C CN100549116 C CN 100549116C
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- composition
- weight
- coating
- autoxidation
- binder polymer
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 238000006701 autoxidation reaction Methods 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 22
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 230000005855 radiation Effects 0.000 claims abstract description 12
- 230000001012 protector Effects 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 43
- 239000011230 binding agent Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 9
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 6
- MKKMLBHHIZRHGI-UHFFFAOYSA-N [benzoyl(phenyl)phosphanyl]-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)P(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 MKKMLBHHIZRHGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 19
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- 239000010941 cobalt Substances 0.000 abstract description 17
- 239000011572 manganese Substances 0.000 abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052748 manganese Inorganic materials 0.000 abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
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- 238000005259 measurement Methods 0.000 description 9
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
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- 238000009738 saturating Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- 239000004952 Polyamide Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002170 ethers Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BPYXFMVJXTUYRV-UHFFFAOYSA-J octanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O BPYXFMVJXTUYRV-UHFFFAOYSA-J 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 239000011135 tin Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HLATYIHHROGXAG-UHFFFAOYSA-N CC(C)C(C=CC1Sc2ccccc22)=CC1C2=O Chemical compound CC(C)C(C=CC1Sc2ccccc22)=CC1C2=O HLATYIHHROGXAG-UHFFFAOYSA-N 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N CN(C)c(cc1)cc2c1cc(ccc(N(C)C)c1)c1n2 Chemical compound CN(C)c(cc1)cc2c1cc(ccc(N(C)C)c1)c1n2 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 241001125877 Gobio gobio Species 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 230000008033 biological extinction Effects 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
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- 235000021388 linseed oil Nutrition 0.000 description 1
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- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
A kind of be applicable to the unskilled user by the protector that breathes no more reach at normal temperatures be applied in the natural daylight interior of building and around lip-deep autoxidisable architectural coating compositions, wherein the surperficial autooxidation of said composition is by the low-concentration metallic ion, especially the combination of manganese or vanadium and at least a light trigger promotes.Said composition avoids using more than trace cobalt ionic needs, and this cobalt ion reportedly is the carinogenicity material but can reaches sufficient fast autoxidation speed.Preferablely avoid using cobalt fully.Use other metal ion of lower concentration often fading of composition to be reduced to use known cobalt accelerator to reach below horizontal.It also improves glossiness.The present invention also discloses a kind of correction, wherein promotes surperficial autooxidation by light trigger and the combination of trace cobalt ionic when not existing other surperficial autooxidation to promote metal ion.At last, but that the present invention discloses is a kind of to standing the natural daylight or the similar method of these autoxidation coating of surface applied of low-energy radiation at normal temperatures.
Description
Technical field
The present invention relates to a kind of autoxidisable architectural coating compositions of under normal temperature (such as 5 to 40 ℃), in natural daylight, using by the unskilled user who does not have special respiratory protection equipment of being fit to, but said composition contains the autoxidation binder polymer and contains or do not contain the surface promoter system of surperficial autooxidation that is used to promote this binder polymer of cobalt hardly.
Background technology
The autooxidation of architectural coating compositions betide under the normal temperature and natural daylight in and therefore take place very slowly, unless be subjected to the simultaneous acceleration of surface promoter system and complete accelerator systems.These promotor often are called " siccative ", obscure mutually with dry notion more generally avoiding but be referred to as " promotor " in this explanation, and this drying notion relates to the loss of solvent in the coating composition after it is applied on the surface.
Can be at normal temperatures in natural daylight architectural coating compositions such as autoxidizable coating, lacquer and varnish generally be used for on-the-spot coating interior of building or the surface around it.Therefore, usually said composition being called " autoxidisable architectural coating compositions " and they need be suitable for by breathe no more protector and use the unskilled user of simple application instruments such as brush, cylinder or liner to use at normal temperatures in natural daylight.In case be applied on the surface, this coating is incorporated into this surperficial solid-state adhesion dry coating by the promoted autooxidation of each metal ion species to form with regard to dry (just by the meaning of vaporization losses solvent with regard to) and experience.
But but autoxidisable architectural coating compositions can comprise the autoxidation binder polymer in the organic solvents such as being dissolved in petroleum solvent or the aqueous dispersions of autoxidation binder polymer.Generally speaking, said composition also will contain non-film forming component, for example particulate is inorganic and/or pigment dyestuff or opalizer (for example fine particulate titanium dioxide, especially rutile or contain the polymer organic particle in space) or extender (for example chalk, rhombspar, clay or talcum) and other optional member, as matting agent (for example silica), structural agent (for example titanium or zirconium chelate or laponite or wilkinite), defoamer and biocide.Pigment grade rutile particles is coated with so that the photodegradation of this coating minimizes with other oxide compounds such as silicas.
The base stock that this autoxidisable film-forming binder polymkeric substance is a kind of autoxidisable architectural coating compositions, partly form the bonding coat that is incorporated into its surface of using because of its autoxidation, and partly because it is bonded together any non-film forming component that is present in the said composition (as above-mentioned composition).During autoxidation, but thereby it is believed that the autoxidation part crosslinked weight-average molecular weight of this binder polymer that causes of formation between adjacent polymer chains in this binder polymer enlarges markedly.
The autoxidisable architectural coating compositions of knowing most contains the autoxidisable binder polymer of Synolac class.Synolac be described in that W M Morgans shows and by Griffin ofLondon in the 211st to 218 and 228 and 229 page of the 2nd edition the 1st volume of " coating technology outline " (" Outlines of PaintTechnology ") of publishing in 1988.The content that Morgans writes on these pages is classified this paper reference as.Morgans illustrates the condenses that Synolac is dicarboxylic acid and polyvalent alcohol substantially, contains the undersaturated long-chain part of autoxidation ethylene linkage but adhere on this polyvalent alcohol.These long-chain parts are usually available from vegetables oil.The Synolac that contains 60 to 85 these parts of weight % often is called " long oil " Synolac, is called " middle oil " Synolac and contains 25 to 45 weight % persons and be called " short oil " Synolac and contain 45 to 60 weight % persons.Synolac can be passed in time and be easy to yellowing, thereby they should avoid making the cycloolefin existence partly of yellowing problem worse.Synolac also should be avoided oxidable parts such as allyl ether group, and the allyl ether group can be degraded into propenal, and propenal is that a kind of meeting makes the user of the protector that breathes no more cause pain and may cause dangerous strong and poisonous lacrymator.But the example of suitable autoxidation part comprise from linseed oil, soybean oil, Thistle oil, Oleum Gossypii semen, dehydrogenated castor oil, Yatall MA (tall oil) and tung oil deutero-those.
The suitable dicarboxylic acid example that is used to make Synolac comprises: phthalic acid, m-phthalic acid, terephthalic acid, maleic acid, FUMARIC ACID TECH GRADE, hexanodioic acid and sebacic acid, or its acid anhydride.Suitable polyvalent alcohol comprises: ethylene glycol, glycerol, tetramethylolmethane, 1,2 propylene glycol, TriMethylolPropane(TMP) and neopentyl glycol.
As mentioned above, to such an extent as to but not promoted autoxidation binder polymer such as Synolac at normal temperatures in natural daylight autoxidation get too slowly very impracticable in building coating, because this coating is used at the scene and is not used in factory, can be in factory by using high-energy radiation (for example actinic radiation) or quickening autooxidation easily by oven dry under the temperature around being much higher than.Clearly, it is not to gear to actual circumstances very much that high-energy radiation or drying plant are provided at the scene, especially true for unskilled user's use, so architectural coating compositions need contain accelerator systems to quicken its autooxidation.Typical case's accelerator systems describe (using another title " siccative ") in GPA Turner show, Chapman and Hall of London is in the 3rd edition the 159th and 160 page of " coatings chemistry and know-why introduction " (" Introduction to PaintChemistry and Principles of Technology ") of publication in 1988.Content on the 159th and 160 page is classified this paper reference as.
As indicated earlier, general two kinds of accelerator systems, i.e. " surface promoter " and/or " promotor fully " of adopting in the building coating.Surface promoter absorbs by catalytic oxygen probably and peroxide breakdown causes autooxidation in the coating surface layer that crosslinked free radical quickens to be used with generation.In contrast, complete promotor is quickened the increase of the weight-average molecular weight of binder polymer in the deep layer coating.Known surface promoter comprise cobalt, manganese, vanadium, iron, chromium, copper, tin and cerium carboxylate salt, be preferably octylate, 2-ethylhexoate or naphthenate.Known complete promotor comprises above-mentioned carboxylate salt and zirconium, calcium, barium, strontium, lithium, sodium, potassium, zinc, neodymium, bismuth, lead, one or more carboxylate salt that reaches aluminium and the compound of aluminium-alcohol salt.
For reaching enough surperficial fast autooxidation, usually use a certain amount of known surface promoter, but feasible weight with all autoxidation binder polymers in the said composition is its transition metal ion concentration of benchmark extremely can be up to 0.1 weight % at least 0.001 weight %, and preferred range is 0.04 to 0.07 weight %.For reaching enough default fast autooxidation in the deep layer coating, usually use a certain amount of known complete promotor, make to be at least 0.3 weight % and generally can be up to 2 weight % with the concentration that is its all metal ions of benchmark of autoxidisable binder polymer weight in the said composition, preferred range is 0.5 to 1.5 weight %.
Several transition metal ions, especially copper, iron, chromium or mn ion can make coating composition fade, unless said composition is painted through severe.Armpit look effect owing to cobalt ion is much smaller, so the carboxylic acid cobalt has been asserted the surface promoter that can generally be used for building coating, because its use means easier manufacturing popular white cold.The hearsay cobalt ion may be for carinogenicity yet have at present, but thereby they only should to be used in concentration of cobalt ions be in the system of benchmark less than 0.01 weight % with the autoxidation binder polymer.Preferable this accelerator systems should not contain cobalt ion, and meaning is that it should be non-cobalt accelerator system.
Light trigger often uses the crosslinked of the coating used with acceleration with high-energy radiation (often being called " photochemical " radiation) under factory condition.Any the technical grade coating composition contain in light trigger and unsaturated polyester or unsaturated vinylformic acid (the comprising methacrylic ester) polymkeric substance is described in the 222nd and 223 page on same the book of Turner.Turner statement can be carried under the high power ultraviolet lamp of the artificial ultraviolet radiation coating object with high energy with the flat article of said composition coating, and the artificial UV-light of this high energy is decomposed light trigger and produced this coating of sclerosis and generate the free radical of bonding dry coating.Similarly, the combination of US Patent specification US 4 387 190 (being disclosed in nineteen eighty-three) a kind of light trigger of announcement and actinic radiation can be used for substituting autooxidation and making the coating polymerization that contains methacrylic acid two cyclopentenes esters or methacrylic acid alkoxy ester.Actinic radiation is the high-energy radiation that can obtain easily under factory condition, yet the scene obtains the illumination of daylight or low energy only realistically in buildings.This coating that means the US 4 387 190 that contains light trigger is not architectural coating compositions.
European patent specification EP 0 234 641A (being disclosed in 1986) disclose and contain the allyl ethers group to allow to use the autoxidisable coating composition of the littler solvent of volatility.As mentioned above, allyl ethers is partly degraded and is produced strong lacrymator propenal, so this coating composition is not suitable for use in architectural coating compositions, because architectural coating compositions must be used by the personnel of unequipped smoke mask.
Summary of the invention
A purpose of the present invention is applied to lip-deep autoxidisable architectural coating compositions for providing a kind of suitable unskilled user by the protector that breathes no more to reach at normal temperatures in the natural daylight, but said composition contains the autoxidation binder polymer and be used to promote containing of this binder polymer autooxidation to be low to moderate the accelerator systems of zero-dose cobalt ion.
Therefore; the invention provides a kind of suitable unskilled user and reach the autoxidisable architectural coating compositions that is applied to the surface in the natural daylight at normal temperatures by the protector that breathes no more; but but said composition contain the autoxidation binder polymer and be used to promote the accelerator systems of the surperficial autooxidation of this autoxidation binder polymer, wherein this system contains:
A) but the weight with autoxidation binder polymer in this coating composition is the cobalt ion of benchmark less than 0.01 weight % (being preferably 0 weight %),
B) metal ion of 0.001 to 0.04 weight % (but be benchmark with the weight of autoxidation binder polymer in this coating composition) except that cobalt ion can promote the metal ion of surperficial autooxidation,
C) at least a can be by natural daylight activated light trigger, but the weight that its amount is preferably with autoxidation binder polymer in the said composition is that benchmark 0.3 to 2 weight %, the best are 0.5 to 1.5 weight %.
Gained coating does not suffer from the aggravation yellowing that is partly caused by two ring-pentenyls.This coating also has smell and its propenal that not produced by allyl ethers group degraded littler than known autoxidisable architectural coating to pollute.But should also can contain known components such as other non-film forming component mentioned above by the autoxidation coating composition.In detail, may hinder light to arrive light trigger although expect pigment, said composition can contain rutile pigment/opalizers such as (especially pigment grade rutile).
Remove the cobalt external enwergy and promote the metal ion of surperficial autooxidation to be preferably manganese and/or vanadium, because they are faster than the promoted autooxidation speed of other non-cobalt ion.In this two, manganese is very fast person.Metal ion also can be or additionally is selected from (for example) nickel, iron, chromium, copper, tin and cerium.Surperficial autooxidation promotes that but the preferable total concn of metal ion is benchmark 0.004 to 0.03 weight % for the weight with autoxidation binder polymer in this coating composition in this coating composition.
Have now found that and use the non-cobalt autooxidation of lower concentration to promote the metal ion and the combination of at least a light trigger to reach and the similar acceptably autoxidation speed of speed that can reach with known cobalt accelerator system.Extremely the tangible required short period of time shows surperficial fast autooxidation by the coating exsiccation.This section period is called " touching time of drying (touch dry time) " and its process of measurement will be described hereinafter.Similarly, show fast default autooxidation in deep layer coating by saturating required short period of time of thorn of this coating opposing weight metering pin.This section period is called " complete drying time " and its process of measurement also is described in hereinafter.
Have now found that successful implementation of the present invention only need lower concentration manganese or vanadium ion and therefore the level of fading of the dry coating of this coating be at least permissible and even can be lower than the level that produces by known cobalt system.Whiteness percentage in decolourization and this dry coating color is inversely proportional to and can measures the whiteness percentage easily by known spectrophotometry.Therefore the whiteness percentage is contrary the measuring of convenience of decolourization.
Manganese/light trigger surface promoter system often has further advantage in being used in gloss paint the time, because the dry coating of gloss paint has usually than the higher mirror surface luster of corresponding coating that contains a known cobalt surface promoter system.According to nineteen ninety-five British Standard 3900 D5 partly use the arbitrary input angle in 60 ° or 20 ° to measure mirror surface luster, but be that this illustrative purposes uses 60 °.
This light trigger should activate by the natural daylight that comprises the light in 350 to 600nm (or even 650nm) wavelength region or from the similar low energy illumination that is installed on the light source (for example 40 to 250 watts of tungstenfilament lamps or fluorescent tubes) in the buildings.Some such light triggers are followed together with being shown in of its absorption spectrum among Fig. 1 and 2 of accompanying drawing of this specification sheets.Some light trigger only has absorptivity in this wavelength region part, therefore preferablely be used in combination at the systemic light trigger of these wavelength region other parts itself and those.A kind of good especially combination comprises oxidation dibenzoyl Phenylphosphine and camphorquinone.Other is fit to list among US Patent specification US 6 548 565B that issued in 2003 (referring to hurdling 6 and 7 paragraph with light trigger that daylight uses, its content is classified this paper reference as) or in disclosed European patent specification EP 1 048 706 in 2000 (referring to paragraph 21 and 22, its content is classified this paper reference as).Best light trigger has remarkable absorptivity to the non-absorbent wavelength of rutile.
Preferably, this metal/light trigger surface promoter system should be used in combination with at least a known complete promotor.Especially be preferably the complete accelerator systems of the combination of any two or all three kinds that comprise zirconium, calcium and lithium carboxylate salt.
The present invention also provides a kind of method that is used for the dry coating of architectural coating compositions is applied to the surface, wherein the coating with said composition is applied to this surface at normal temperatures and this coating composition is applied to this surface under light (especially the being natural daylight) illumination of 350 to 650nm wavelength regions, wherein but but said composition contains the system that autoxidation binder polymer and is used to promote the surperficial autooxidation of this autoxidation binder polymer, and wherein this system contains:
But a) with the weight of autoxidation binder polymer in this coating composition be benchmark less than 0.01 weight % (being preferably 0 weight %) cobalt ion,
B) 0.001 to 0.04 weight % (but be benchmark with the weight of autoxidation binder polymer in this coating composition) removes the metal ion that the cobalt ion external enwergy promotes surperficial autooxidation, and
C) at least a can be by natural daylight activated light trigger, but its amount is that benchmark is preferably 0.3 to 2 weight %, the best is 0.5 to 1.5 weight % with autoxidation binder polymer weight in the said composition.
This method can be used with the surface of coating interior of building or its periphery at the scene and not require and use high-energy radiation and be more suitable for careful control condition in the method for implementing in factory.
Description of drawings
Fig. 1 and 2 display light initiators are graphic together with its absorption spectrum.
Fig. 3 shows the perspective figure statement of the device that is used for " complete drying time measurement " program of a magnification ratio.
Fig. 4 with sectional view more vast scale show details among Fig. 3.
Embodiment
The present invention is further specified by the following example, wherein embodiment A to G be comparative example.In this example, normal temperature is about 18 ℃ and use follow procedure to measure to touch time of drying and complete drying time:
Touch and measure time of drying:
Measuring the fresh coating of using with following husky deposition program became dry to the tangible required time:
Remove the greasy dirt on a flat glass surface with acetone.Under 20 ℃ and 50% relative humidity, use the coating of its time of drying to be measured of 50 to 60 micron thickness by block coating machine.Dry under make that this coating kept in whole process of measurement 20 ℃ and 50% relative humidity.
To there be the funnel of a little outlet to fill with after the slowly effusive sand of this outlet in the bottom.This dry coating slowly leaks thereon through the while sand below this hopper outlet with 25.4 millimeters/hour speed.Initial sand sticks at still wet coating but this coating drying and autoxidation and sand occurs and stop sticking time point thereon as time passes.To reach the required time of this time point is considered as " touch time of drying ".Thereby the hangover that loose sand is blown on the coating of complete drying off the adhesion sand that stays certain-length easily detects this point, and this length is just obtained touching time of drying divided by this coating through the speed below this outlet.
Complete drying time measurement: Bake Ke Leer (Beck Koller) method:
Bake Ke Leerfa makes become thorn to a weight metering pin of a coating of newly using have the resistivity required time thoroughly and measure the white drying time by measurement.This method adopts among Fig. 3 with amplification ratio Bake Ke Leer device among graphics demonstration and Fig. 4.This Bake Ke Leer device can be available from Mickle Laboratory Engineering company of Gomsall in Surrey, England.
Fig. 3 shows that this horizon bar is installed between the parallel vertical forwarder 4 through gudgeon by the pin 1 that is attached to 2 carryings of arm on the horizon bar 3.Pin 1 thrusts the coating 5 that is applied to the coating composition on the sheet glass 6 downwards, and this sheet glass 6 then lies against on the can 7.The part of box 7 is analysed and observe, to expose hole 9 and screw 10.The low side of forwarder 4 is connected by the rod 8 that contains threaded hole 9, and rotatable screw drive screw 10 passes this threaded hole 9.
Thereby screw 10 is suitably rotating driving forwarder 4 and pin 1 on the arrow A direction on the direction.When coating 5 is newly used, still be viscous liquid thereby when pin 1 at point 11 the time (referring to Fig. 4), it can sting antireflective coating layer 5 and arrive on the sheet glass 6 and produce a cut 13.Along with pin 1 continues to move on the A direction, the drying of coating 5 and autooxidation are proceeded and it increases the saturating resistivity of the thorn of pin 1, and cut 13 becomes more shallow until point 12, and resistivity becomes fully and that thorn no longer takes place is saturating.Measure and use point 11 to the distance of point 12 together with known to the speed of pin 1 calculate the point of arrival 12 required times.This time is considered as " complete drying time ".
Except that using 100 micron thickness with touch program time of drying on the same surface that coating 5 is applied to sheet glass 6.Pin 1 is for the cylindrical of 40 millimeters of 1 millimeter of diameter and length and apply the power of 4 gram weight to this coating.Pin 1 is advanced with 12.25 millimeters/hour speed.Run through this program and keep 20 ℃ temperature and 50% relative humidity once more.
Embodiment 1
Prepare a kind of test coating, but omit the surface promoter system:
At first make wilkinite prepared group compound and red metal and stone prepared group compound.But, 10 weight % wilkinites, 35 weight % autoxidation long oil alkyds and 55 weight % aliphatic hydrocarbon solvents come together to make bentonite composition by being stirred in.But, 68 weight % pigment grade rutile, 21.5 weight % autoxidation long oil alkyds and 10.5 weight % aliphatic hydrocarbon solvents come together to make the rutile composition by being stirred in.
This prepared group compound is added into one successively together with other shown in the table 1 component to be had in 5 liters of cylindrical mixing vessels of stirring arm.Starch and stir by during adding this component, rotating this, and this stirring is proceeded 10 minutes with 400 rev/mins speed with 400 rev/mins speed.Generated a kind of homogeneous test coating that can add various surface promoter system subsequently therein.
Embodiment 2 and 3
Get the test coating of making among the embodiment 1 of three part of 300 gram quantity, in each part, be stirred into one of shown surface promoter system in the table 2.Each composition quantity of the accelerator systems of using also is shown in the table 2, and autoxidation Synolac binder polymer gross weight is the weight percent of benchmark in the quantity but this quantitaes is for restraining with 300.
Table 1
Be applicable to the test formulation for coating material that adds surface promoter subsequently
| Component | Used weight % |
| *But but autoxidation long oil alkyd autoxidation short-oil alkyd wilkinite prepared group compound aliphatic hydrocarbon solvent rutile prepared group compound **But the sad lithium complete drying of polyamide modified autoxidation Synolac thixotrope biocide zirconium caprylate complete drying promotor calcium octoate complete drying promotor promotor dimethyl silicone oil: flow promotor aliphatic hydrocarbon solvent | 34.0 2.9 2.0 2.0 34.25 16.0 0.4 1.4 1.69 0.9 0.15 4.31 |
*Long oil alkyd from tetramethylolmethane, Tetra hydro Phthalic anhydride and ready denier oil acid
*Medium oil alkyd resin
The coating that contains every umber amount of surface promoter system now stands surface drying time and measures, this measures under from the arbitrary light condition in known 60 watts of family expenses fluorescent tube bulb light or the dark and carries out under arbitrary temperature of normal temperature shown in the table 3 or 8 ℃, and table 3 also shows the surface drying time that is reached.Also under arbitrary temperature of normal temperature shown in the table 3 or 8 ℃, this coating is carried out the complete drying time measurement once more.The result of gained provides in table 3.
Table 2
Employed surface promoter
| Embodiment | Metal ion weight % | " Irgacure " 819 weight % | Camphorquinone weight % |
| 2 3 | 0.019 weight % *Manganese 0.019 weight % *Manganese | 0.53 1.06 | 0.53 0.27 |
| A | 0.064 weight % cobalt | - | - |
" Irgacure " 819 is oxidation dibenzoyl Phenylphosphine, by CIBA Geigy ofBasle, and the Switzerland supply
*From Elementis Plc of Staines, " Dappro " 5005 of England supply
To touch time of drying program the same with this, and also the coating with 100 micron thickness of this coating respectively is applied on the face glass, and make this coating under 20 ℃ and 50% relative humidity dry 24 hours.Use nineteen ninety-five British Standard 3900:D5 part and 60 ° of angles to come the then mirror surface luster of fixed every kind of coating.It the results are shown in the table 3.
The final dry coating of measuring this coating of being used as above-mentioned glossiness carries out the whiteness measurement after this coating is used 1 hour and after 24 hours.Measure and the results are shown in the table 3 of gained by known spectrophotometry.
Table 3 shows that the surface and the complete drying time of the accelerator systems that contains mn ion and light trigger are permissible, and the glossiness factor that is obtained is better slightly and whiteness that obtained is significantly higher than the glossiness factor of using known cobalt ion accelerator systems to be obtained, this means this manganese/photoinitiator system can cause less fade, especially less yellowing.
Table 3
Test result
Comparative example B to F
The importance of manganese or light trigger:
For showing the importance of mn ion and light trigger, compare routine B and D to F, wherein except that by omitting the program that repeats embodiment 3 mn ion or the light trigger shown in the table 4 successively.In comparative example C, light trigger is omitted in the triplication of employed manganese amount simultaneously.Also in table 4, provide time of drying as the touch of in embodiment 3, reaching by the drying of at normal temperatures light and operation in the dark.
Table 4
The importance of manganese and light trigger
*Use 0.056 weight % mn ion
Embodiment F shows that camphorquinone does not improve and touches time of drying, so it adds for helping the complete drying time.
Prepare a kind of alternative test coating that also omits surface promoter:
At first, as in the example 1, make rutile prepared group compound, then it is added in 5 liters of mixing vessels of used type in the example 1 with other shown in the table 5 component successively.
As example 1, stir, generate a kind of alternative homogeneous test coating that can add various surperficial autooxidation promotor subsequently.
Comparative example G
Get among the embodiment 5 of four part of 300 gram quantity manufacturing test coating and in each part, be stirred into vanadium shown in the table 6 or one of cobalt surface promoter system.
Table 5
Be applicable to the alternative test formulation for coating material that adds surface promoter subsequently
| Component | Employed weight % |
| *But autoxidation long oil alkyd aliphatic hydrocarbon solvent rutile prepared group compound **But polyamide modified autoxidation Synolac thixotrope biocide zirconium caprylate complete drying promotor calcium octoate complete drying promotor dimethyl silicone oil: flow promotor high boiling point aliphatic hydrocarbon solvent | 40.3 3.0 343 12.2 0.4 1.2 1.7 0.1 6.7 100.0 |
*Long oil alkyd from tetramethylolmethane, Tetra hydro Phthalic anhydride and ready denier oil acid
*Medium oil alkyd resin
Each of used accelerator systems becomes deal also to be shown in the table 6, but and the gross weights that are expressed as with autoxidation Synolac binder polymer in 300 gram quantity be the weight percent of benchmark.The quantitative coating of each part that contains the surface promoter system now carries out surface and the complete drying time measurement implemented in example 2 and 3 at normal temperatures.Gained is the result provide in table 7.
What will see is that example 7 and 8 relates to the accelerator systems that only contains the inapparent trace of carcinogenic risk (between 0.001 and 0.007 weight %) cobalt.
Table 6
Employed surface promoter
| Embodiment | Metal ion weight % | " Irgacure " 819 weight % | |
| 6 | 0.006 weight % vanadium | 0.5 | 0.25 |
| 7 8 | 0.006 weight % cobalt 0.003 weight % cobalt | 0.5 0.5 | 0.25 0.25 |
| G | 0.06 weight % cobalt | - | - |
Table 7
Test result
In more general application of the present invention, especially when fading very significantly with dead color and/or high chroma coating, this light trigger can use with the mn ion of greater concn so, but is that benchmark may be up to 0.1 weight % with autoxidation Synolac binder polymer weight in the said composition for example.This makes even also has good autoxidation speed and also can reach good gloss level in strong extinction look coating.Usually according to NCS or be identified as the Svensk Standard color diagram of Svensk Standard 01 91 02, dead color and/or high chroma coating have and surpass brightness/darkness factor of 60 and surpass 70 colourity factor.
It is desirable to very much now, if will use cobalt ion as promotor, but is that the trace concentration that benchmark is lower than 0.01 weight % uses it with the weight of autoxidation binder polymer in the said composition then.This causes promoting the significant delays of autooxidation certainly, but table 7 shows by cobalt ion and light trigger are used in combination and can offset this delay at least in part.Preferable this concentration of cobalt ions should be at least 0.001 weight %.Therefore in modification of the present invention, this surface promoter system comprises the cobalt ion of 0.001 to 0.01 weight % and does not have other metal ion.
Claims (16)
1. a suitable unskilled user by the protector that breathes no more reaches at normal temperatures and is applied to lip-deep autoxidisable architectural coating compositions in the natural daylight; but but said composition contain the autoxidation binder polymer and be used to promote the accelerator systems of this autoxidation binder polymer autooxidation, wherein this system contains:
But a) with autoxidation binder polymer weight in this coating composition be benchmark less than 0.01 weight % cobalt ion,
B) but be that benchmark 0.001 to 0.04 weight % removes the metal ion that the cobalt ion external enwergy promotes surperficial autooxidation with autoxidation binder polymer weight in this coating composition,
C) at least a can be by natural daylight activated light trigger.
2. the coating compound of claim 1, but wherein said at least a can be that benchmark is 0.3 to 2.0 weight % with autoxidation binder polymer weight in the said composition by the amount of natural daylight activated light trigger.
3. the coating composition of claim 1, wherein said composition does not also contain cobalt ion.
4. claim 1,2 or 3 coating composition, wherein said composition contains complete promotor, but is enough to that autoxidation binder polymer weight is benchmark 0.5 to 2 weight % metal ion in this coating composition provides with said composition.
5. wherein there are the combination of two or more light trigger in claim 1,2 or 3 coating composition in the said composition.
6. claim 1,2 or 3 coating composition, wherein said composition contains oxidation dibenzoyl Phenylphosphine as light trigger.
7. claim 1,2 or 3 coating composition, wherein said composition contains camphorquinone as light trigger.
8. the dry coating with architectural coating compositions is applied to lip-deep method, wherein the coating of said composition is to be applied at normal temperatures that this is lip-deep, wherein but but said composition contains the autoxidation binder polymer and is used to promote this autoxidation binder polymer to carry out the surperficial accelerating system of surperficial autooxidation, and wherein this accelerating system contains:
But a) with autoxidation binder polymer weight in this coating composition be benchmark less than 0.01 weight % cobalt ion,
B) but be that benchmark 0.001 to 0.04 weight % removes the metal ion that the cobalt ion external enwergy promotes surperficial autooxidation with autoxidation binder polymer weight in this coating composition,
C) at least a can be by natural daylight activated light trigger,
And this coating composition is to be applied under the low-energy radiation of the light of 350 to 650nm wavelength regions that this is lip-deep.
9. the method for claim 8, but wherein said at least a can be that benchmark is 0.3 to 2.0 weight % with autoxidation binder polymer weight in the said composition by the amount of natural daylight activated light trigger.
10. the method for claim 8, wherein said composition does not also contain cobalt ion.
11. claim 8,9 or 10 method, wherein said composition contains complete promotor, but is enough to that autoxidation binder polymer weight is benchmark 0.5 to 2 weight % metal ion in this coating composition provides with said composition.
12. wherein there are the combination of two or more light trigger in claim 8,9 or 10 method in the said composition.
13. claim 8,9 or 10 method, wherein said composition contains oxidation dibenzoyl Phenylphosphine as light trigger.
14. claim 8,9 or 10 method, wherein said composition contains camphorquinone as light trigger.
15. the method for claim 8, wherein this light is natural daylight.
16. the method for claim 8, wherein this light is from 40 to 250 watts light source.
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|---|---|---|---|
| GB0318641.8 | 2003-08-08 | ||
| GB0318641A GB0318641D0 (en) | 2003-08-08 | 2003-08-08 | An autoxidisable coating composition containing a manganese promoter system |
| GB0321140.6 | 2003-09-10 |
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| CN110234671A (en) * | 2017-01-31 | 2019-09-13 | 巴斯夫欧洲公司 | Silicon oxide particle dispersion in polyalcohol |
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| RU2669824C1 (en) * | 2015-11-19 | 2018-10-16 | Акцо Нобель Коатингс Интернэшнл Б.В. | Coating composition containing autoxidizable alkyd resin and composition of drier |
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| US4387190A (en) * | 1981-08-03 | 1983-06-07 | Rohm & Haas Company | Autoxidizable compositions containing low molecular weight polymers of dicyclopentenyl methacrylate or dicyclopentenyloxyalkyl methacrylate |
| EP0234641A1 (en) * | 1986-02-14 | 1987-09-02 | Akzo N.V. | Coating composition having a high solids content and containing an organic solvent with a high flash point |
| EP1048706A1 (en) * | 1999-04-29 | 2000-11-02 | Akzo Nobel N.V. | Coating composition comprising an oxidatively drying polyunsaturated condensation product, a polythiol, and a photoinitiator |
| WO2001046294A1 (en) * | 1999-12-22 | 2001-06-28 | Akzo Nobel N.V. | Coating composition comprising an oxidatively drying polyunsaturated condensation product, a polythiol, and a siccative |
| US6548565B1 (en) * | 1998-03-13 | 2003-04-15 | Akzo Nobel Nv | Non-aqueous coating composition based on an oxidatively drying alkyd resin and a photo-initiator |
| CN1415679A (en) * | 2001-11-02 | 2003-05-07 | 北京英力科技发展有限公司 | Visible light solidified compsn. |
-
2003
- 2003-08-08 GB GB0318641A patent/GB0318641D0/en not_active Ceased
-
2004
- 2004-07-21 CN CNB2004800283950A patent/CN100549116C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4387190A (en) * | 1981-08-03 | 1983-06-07 | Rohm & Haas Company | Autoxidizable compositions containing low molecular weight polymers of dicyclopentenyl methacrylate or dicyclopentenyloxyalkyl methacrylate |
| EP0234641A1 (en) * | 1986-02-14 | 1987-09-02 | Akzo N.V. | Coating composition having a high solids content and containing an organic solvent with a high flash point |
| US6548565B1 (en) * | 1998-03-13 | 2003-04-15 | Akzo Nobel Nv | Non-aqueous coating composition based on an oxidatively drying alkyd resin and a photo-initiator |
| EP1062288B1 (en) * | 1998-03-13 | 2003-05-02 | Akzo Nobel N.V. | Non-aqueous coating composition based on an oxidatively drying alkyd resin and a photo-initiator |
| EP1048706A1 (en) * | 1999-04-29 | 2000-11-02 | Akzo Nobel N.V. | Coating composition comprising an oxidatively drying polyunsaturated condensation product, a polythiol, and a photoinitiator |
| WO2001046294A1 (en) * | 1999-12-22 | 2001-06-28 | Akzo Nobel N.V. | Coating composition comprising an oxidatively drying polyunsaturated condensation product, a polythiol, and a siccative |
| CN1415679A (en) * | 2001-11-02 | 2003-05-07 | 北京英力科技发展有限公司 | Visible light solidified compsn. |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110234671A (en) * | 2017-01-31 | 2019-09-13 | 巴斯夫欧洲公司 | Silicon oxide particle dispersion in polyalcohol |
| CN110234671B (en) * | 2017-01-31 | 2022-05-31 | 巴斯夫欧洲公司 | Silicon oxide particle dispersion in polyol |
| US11479635B2 (en) | 2017-01-31 | 2022-10-25 | Basf Se | Oxidic silicon particle dispersion in polyol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1860194A (en) | 2006-11-08 |
| GB0318641D0 (en) | 2003-09-10 |
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Address after: London, England, England Patentee after: Imperial Chemical Industries PLC Address before: London, England, England Patentee before: Imperial Chemical Industries PLC |
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