NO143666B - COATING AGENT, SPECIFICALLY IN POWDER FORM, CONTAINING A POLYMER WITH REACTIVE GROUPS AND A CROSS-BONDING AGENT WITH BLOCKED ISOCYANATE GROUPS - Google Patents
COATING AGENT, SPECIFICALLY IN POWDER FORM, CONTAINING A POLYMER WITH REACTIVE GROUPS AND A CROSS-BONDING AGENT WITH BLOCKED ISOCYANATE GROUPS Download PDFInfo
- Publication number
- NO143666B NO143666B NO752199A NO752199A NO143666B NO 143666 B NO143666 B NO 143666B NO 752199 A NO752199 A NO 752199A NO 752199 A NO752199 A NO 752199A NO 143666 B NO143666 B NO 143666B
- Authority
- NO
- Norway
- Prior art keywords
- cross
- groups
- isocyanate
- agent
- carbon atoms
- Prior art date
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- 239000011248 coating agent Substances 0.000 title claims description 21
- 239000000843 powder Substances 0.000 title description 32
- 229920000642 polymer Polymers 0.000 title description 5
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 title description 2
- 239000007767 bonding agent Substances 0.000 title 1
- 239000003431 cross linking reagent Substances 0.000 claims description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 239000002981 blocking agent Substances 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 30
- -1 ethylhexyl Chemical group 0.000 description 25
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 238000001723 curing Methods 0.000 description 18
- 239000004014 plasticizer Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229940091173 hydantoin Drugs 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000001469 hydantoins Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 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
- ZKALVNREMFLWAN-VOTSOKGWSA-N (ne)-n-(4-methylpentan-2-ylidene)hydroxylamine Chemical compound CC(C)C\C(C)=N\O ZKALVNREMFLWAN-VOTSOKGWSA-N 0.000 description 1
- LMMTVYUCEFJZLC-UHFFFAOYSA-N 1,3,5-pentanetriol Chemical compound OCCC(O)CCO LMMTVYUCEFJZLC-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- PGTWZHXOSWQKCY-UHFFFAOYSA-N 1,8-Octanedithiol Chemical compound SCCCCCCCCS PGTWZHXOSWQKCY-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- QTCNKIZNNWURDV-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO.OCC(C)(C)CO QTCNKIZNNWURDV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101150081532 KLK8 gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 1
- NVUDVUDVVXAWGV-UHFFFAOYSA-N dodecane-1,12-dithiol Chemical compound SCCCCCCCCCCCCS NVUDVUDVVXAWGV-UHFFFAOYSA-N 0.000 description 1
- KXWYGEKTVZDTBV-UHFFFAOYSA-N dodecane-1,8-diamine Chemical compound CCCCC(N)CCCCCCCN KXWYGEKTVZDTBV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WJSATVJYSKVUGV-UHFFFAOYSA-N hexane-1,3,5-triol Chemical compound CC(O)CC(O)CCO WJSATVJYSKVUGV-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- UCFRVQXGPJMWPG-UHFFFAOYSA-N n-(2,6-dimethylheptan-4-ylidene)hydroxylamine Chemical compound CC(C)CC(=NO)CC(C)C UCFRVQXGPJMWPG-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- GDUWKVCUIFEAGC-UHFFFAOYSA-N octane-1,6-diol Chemical compound CCC(O)CCCCCO GDUWKVCUIFEAGC-UHFFFAOYSA-N 0.000 description 1
- QUADBKCRXGFGAX-UHFFFAOYSA-N octane-1,7-diol Chemical compound CC(O)CCCCCCO QUADBKCRXGFGAX-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YBTBNHOVLJXIRW-UHFFFAOYSA-N pentane-1,4-dithiol Chemical compound CC(S)CCCS YBTBNHOVLJXIRW-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Denne oppfinnelse vedrører et belegningsmiddel, spesielt et pulver-belegningsmiddel, som består av en polymer, fortrinnsvis en akryl-harpiks, og et tverrbindingsmiddel som har isocyanat-reaktivitet. This invention relates to a coating agent, in particular a powder coating agent, which consists of a polymer, preferably an acrylic resin, and a cross-linking agent which has isocyanate reactivity.
De kjente belegningsmidler, spesielt de i pulverform, The known coating agents, especially those in powder form,
, har liten evne til å flyte sammen og utjevnes under herdingen. Filmdannelsen krever høye temperaturer, og tverrbindingen enda høyere, omkring 190-260°C. Videre har de kjente pulvere tilbøye-lighet til å klumpe seg sammen ved lagring selv ved temperaturer på 21-27°C,,og de oppnådde belegg er sprø og har dårlig glans og klebeevne. , have little ability to flow together and level out during curing. The film formation requires high temperatures, and the cross-linking even higher, around 190-260°C. Furthermore, the known powders have a tendency to clump together during storage even at temperatures of 21-27°C, and the resulting coatings are brittle and have poor gloss and adhesiveness.
Løsningen på disse problemer ville være å bruke et tverrbindingsmiddel som er så rent som mulig, og som er forlikelig med den reaktive harpiks. Tverrbindingsmidlet bør kunne tilveiebrin-ge flyteevne ved en forholdsvis lav temperatur, og virke som et mykningsmiddel for harpiksen, og likevel være stabilt under lagring. Det bør også kunne tverrbinde harpiksen ved så lav temperatur som praktisk mulig og etter tverrbindingen inngå i beleggfil-men som et internt mykningsmiddel.'The solution to these problems would be to use a cross-linking agent which is as pure as possible and which is compatible with the reactive resin. The cross-linking agent should be able to provide flowability at a relatively low temperature, and act as a plasticizer for the resin, and still be stable during storage. It should also be able to cross-link the resin at as low a temperature as practically possible and, after cross-linking, enter the coating film as an internal plasticizer.'
US-patent 3 317 463 omhandler benyttelse av blokkerte isocyanat-blandinger (blokkert med hindrede fenoler) ved fremstilling av uretaner. Ifølge eksempel III B fremstilles et belegg som herdes i 60 minutter ved 160°C. US patent 3,317,463 deals with the use of blocked isocyanate mixtures (blocked with hindered phenols) in the production of urethanes. According to example III B, a coating is produced which is cured for 60 minutes at 160°C.
US-patent 3 583 943 omhandler blokkering av en isocyanatgruppe med et ketoksim. US patent 3,583,943 deals with the blocking of an isocyanate group with a ketoxime.
US-patent 3 621 000 omhandler et isocyanat som er blokkert med en bifunksjonell polyeter. US Patent 3,621,000 relates to an isocyanate which is blocked with a bifunctional polyether.
Det er en vanskelighet ved alle kjente pulverblandinger at belegget ikke hurtig kan herdes uten å opphetes til høy temperatur . It is a difficulty with all known powder mixtures that the coating cannot be quickly hardened without being heated to a high temperature.
Belegningsmidlet, spesielt pulver-belegningsmidlet, i henhold til foreliggende oppfinnelse kan imidlertid herdes ved relativt lav temperatur. Det har vært et behov for å oppnå slik However, the coating agent, especially the powder coating agent, according to the present invention can be cured at a relatively low temperature. There has been a need to achieve such
"lavtemperatur-herding", og likevel unngå sammenklumping av pulveret. Pulveret bør ha evnen til å flyte sammen til en film før herdingen. Blant annet ut fra energisparingshensyn er det foretrukket at pulverblandingen har en så lav herde- eller tverr-bindingstemperatur som mulig. Derfor må området for myknings- "low-temperature curing", and yet avoid agglomeration of the powder. The powder should have the ability to flow together into a film before curing. For reasons of energy saving, among other things, it is preferred that the powder mixture has as low a curing or cross-linking temperature as possible. Therefore, the area for softening
temperaturen være relativt snevert. Videre er det ved anvendelse av et blokkert isocyanat som tverrbindingsmiddel foretrukket at når blokkeringsmidlet avspaltes, skal det være lite eller ingen gassdannelse. temperature be relatively narrow. Furthermore, when using a blocked isocyanate as a cross-linking agent, it is preferred that when the blocking agent is split off, there should be little or no gas formation.
Gjenstanden for den foreliggende oppfinnelse er således et belegningsmiddel for fremstilling av løsningsmiddelresistente belegg, som for det første omfatter en polymer med isocyanatreaktive grupper, og for det annet et tverrbindingsmiddel som inneholder minst to blokkerte isocyanatgrupper pr. molekyl, og som er fremstilt av isoforon-diisocyanat, et blokkeringsmiddel og en forbindelse med minst to isocyanatreaktive grupper, idet den sist-nevnte forbindelse virker myknende på belegningsmidlet både under og etter herdningen. Belegningsmidlet er karakterisert ved at tverrbindingsmidlet er fremstilt ved at først isoforondiisocyanatet omsettes med blokkeringsmidlet slik at den mest reaktive av de to isocyanatgrupper blir blokkert, og deretter omsettes med den myknende forbindelse. The object of the present invention is thus a coating agent for the production of solvent-resistant coatings, which firstly comprises a polymer with isocyanate-reactive groups, and secondly a cross-linking agent that contains at least two blocked isocyanate groups per molecule, and which is made from isophorone diisocyanate, a blocking agent and a compound with at least two isocyanate-reactive groups, the last-mentioned compound having a softening effect on the coating agent both during and after curing. The coating agent is characterized in that the cross-linking agent is prepared by first reacting the isophorone diisocyanate with the blocking agent so that the most reactive of the two isocyanate groups is blocked, and then reacting with the softening compound.
Fra US-patent 3 867 347 er det riktignok kjent et beleg-ningspulver på basis av en hydroksylholdig akrylharpiks og et blokkert diisocyanat som tverrbindingsmiddel. Flere eksempler viser et tverrbindingsmiddel som er reaksjonsproduktet ("adduk-tet") av isoforon-diisocyanat (IPDI) og heksandiol, blokkert med kaprolaktam. Det finnes imidlertid ingen antydning om at blokke-ringen skal utføres før adduktdannelsen, og det ferdige, blokkerte tverrbindingsmiddel tilsettes allerede til den monomersats som skal gi akrylharpiksen. Fra NO-patent 137 553, som omhandler en lignende teknikk, er det imidlertid kjent å smelte det blokkerte ("maskerte") isoforon-diisocyanat sammen med den hydroksylholdige harpiks, hvorpå den stivnede masse pulveriseres i en slag-mølle. Også her kan IPDI være "forlenget" med polyoler. Som harpiks anvendes en hydroksylholdig polyester. Fordelen med den foreliggende oppfinnelse er at blokkeringsmidlet avspaltes fra den mest reaktive av isocyanatgruppene, hvorved herdningen skjer hurtigere. I henhold til de to ovennevnte patentskrifter omsettes isocyanatgruppene først med polyolen (det interne mykningsmiddel) , og derved blir de mest reaktive.isocyanatgrupper bundet til denne. Herdningen blir da ikke så hurtig. From US patent 3,867,347 it is true that a coating powder based on a hydroxyl-containing acrylic resin and a blocked diisocyanate as cross-linking agent is known. Several examples show a cross-linking agent which is the reaction product ("adduct") of isophorone diisocyanate (IPDI) and hexanediol, blocked with caprolactam. However, there is no indication that the blocking should be carried out before the adduct formation, and the finished, blocked cross-linking agent is already added to the monomer batch which is to give the acrylic resin. However, from NO patent 137 553, which deals with a similar technique, it is known to melt the blocked ("masked") isophorone diisocyanate together with the hydroxyl-containing resin, after which the solidified mass is pulverized in an impact mill. Here too, IPDI can be "extended" with polyols. A hydroxyl-containing polyester is used as resin. The advantage of the present invention is that the blocking agent is split off from the most reactive of the isocyanate groups, whereby curing occurs more quickly. According to the two above-mentioned patents, the isocyanate groups are first reacted with the polyol (the internal plasticizer), and thereby the most reactive isocyanate groups are bound to this. Hardening will then not be as fast.
Belegningsmidlet er som sagt fortrinnsvis en pulverblanding, vanligvis med et område for partikkelstørrelser fra omkring 0,1 til omkring 250 ym, fortrinnsvis 1-150 pm og enda mer foretrukket fra omkring 10 til 100 pm (gjennomsnittlig mindre enn 35 pm). As stated, the coating agent is preferably a powder mixture, usually with a range of particle sizes from about 0.1 to about 250 µm, preferably 1-150 µm and even more preferably from about 10 to 100 µm (average less than 35 µm).
Det substrat hvorpå belegget blir påført, kan være ikke-grunnet metall, plast, glass og lignende. Det skal forstås at på ikke-ledende overflater kan det før påføringen anbringes en ledende avsetning, så som karbon eller metall. Dette er spesielt til-fellet dersom pulverne skal avsettes elektrostatisk. Dersom man ikke ønsker å påføre et slikt ledende sjikt, vil det ofte være mulig å varme opp substratet slik at partiklene kan klebes til det. Det metalliske substrat kan vftsre renset på vanlig måte, og pulveret kan påføres direkte på substratet, men i noen tilfeller er det funnet ønskelig, for å oppnå langvarig korrosjonsresistens, å påføre en korrosjonsbeskyttende primer. The substrate on which the coating is applied can be non-primed metal, plastic, glass and the like. It should be understood that on non-conductive surfaces a conductive deposit, such as carbon or metal, can be placed before application. This is especially the case if the powders are to be deposited electrostatically. If one does not wish to apply such a conductive layer, it will often be possible to heat the substrate so that the particles can stick to it. The metallic substrate can be cleaned in the usual way, and the powder can be applied directly to the substrate, but in some cases it has been found desirable, in order to achieve long-term corrosion resistance, to apply a corrosion-protective primer.
En komponent av belegningsmidlet er altså en polymer (harpiks) som har isocyanat-reaktiv funksjonalitet. Harpiksen er med andre ord allerede polymerisert, men har utstikkende grupper som kan reagere med isocyanatgruppene fra tverrbindingsmidlet. Tverrbindingen vil foregå under herdingen (normalt ved oppvarming) av pulveret. A component of the coating agent is thus a polymer (resin) which has isocyanate-reactive functionality. In other words, the resin is already polymerised, but has protruding groups which can react with the isocyanate groups from the cross-linking agent. The cross-linking will take place during the curing (normally by heating) of the powder.
Som harpikser ved isocyanatreaktive grupper kan man anvende både termoherdnende og termoplastiske harpikser. Fortrinnsvis skal de utstikkende grupper inneholde utskiftbare hydrogenatomer, f.eks. de hydrogenatomer som er til stede i en hydroksylgrup-pe, en aminogruppe (primær eller sekundær), en merkaptogruppe eller en amidogruppe. Den polymeriserte harpiks er fortrinnsvis en line-ær polymer. Harpiksen kan være et polymerisat av en etylenisk umettet monomer, f.eks. av akryl-, metakryl- eller vinyl-typen. Both thermosetting and thermoplastic resins can be used as resins for isocyanate-reactive groups. Preferably, the protruding groups should contain replaceable hydrogen atoms, e.g. the hydrogen atoms present in a hydroxyl group, an amino group (primary or secondary), a mercapto group or an amido group. The polymerized resin is preferably a linear polymer. The resin may be a polymer of an ethylenically unsaturated monomer, e.g. of the acrylic, methacrylic or vinyl type.
En foretrukket harpiks er en hvor monomeren har formelen 4_[R1-0-(0)C]-A[C(0)0-R] hvor n og t er 0 eller 1 og n + t er t n ■ 3 A preferred resin is one where the monomer has the formula 4_[R1-0-(0)C]-A[C(0)0-R] where n and t are 0 or 1 and n + t is t n ■ 3
1-2, hvor A er alkenyl eller alkenylen med fra 2 til 8 karbonatomer eller en substituent derav hvor substituenten kan være klor, karboksyl eller cyano, og det skal forstås at A kan være forgre-net eller rettkjedet, og R og R<1> kan være like eller forskjellige og kan være hydrogen, alkyl med fra 1 til 20 karbonatomer, fortrinnsvis 2-8 karbonatomer, hydroksyl-substituert alkyl med fra 1 til 20 karbonatomer, fortrinnsvis 2-8 karbonatomer, og enda mer foretrukket 2-5 karbonatomer, en primær eller sekundær amino-substituert alkyl med fra 1 til 20 karbonatomer, fortrinnsvis 2-8 karbonatomer, hvor substituenten på aminogruppen er en alkylgruppe eller en hydroksyalkylgruppe med fra 1 til 6 karbonatomer, 1-2, where A is alkenyl or alkenylene with from 2 to 8 carbon atoms or a substituent thereof where the substituent can be chlorine, carboxyl or cyano, and it is to be understood that A can be branched or straight-chain, and R and R<1 > can be the same or different and can be hydrogen, alkyl with from 1 to 20 carbon atoms, preferably 2-8 carbon atoms, hydroxyl-substituted alkyl with from 1 to 20 carbon atoms, preferably 2-8 carbon atoms, and even more preferably 2-5 carbon atoms , a primary or secondary amino-substituted alkyl with from 1 to 20 carbon atoms, preferably 2-8 carbon atoms, where the substituent on the amino group is an alkyl group or a hydroxyalkyl group with from 1 to 6 carbon atoms,
merkapto-substituert alkylgruppe med fra 1 til 6 karbonatomer, merkapto-substituert alkyl med fra 1 til 20 karbonatomer, fortrinnsvis 2-8 karbonatomer, alkyltio-alkylen med opp til 20 karbonatomer, fortrinnsvis opp til 8 karbonatomer og en gruppe på mercapto-substituted alkyl group with from 1 to 6 carbon atoms, mercapto-substituted alkyl with from 1 to 20 carbon atoms, preferably 2-8 carbon atoms, alkylthio-alkylene with up to 20 carbon atoms, preferably up to 8 carbon atoms and a group of
opp til 8 karbonatomer inneholdende en oksiranring, og mest foretrukket 3 karbonatomer, f.eks. glycidyl. up to 8 carbon atoms containing an oxirane ring, and most preferably 3 carbon atoms, e.g. glycidyl.
Av de ovennevnte monomerer er de mest foretrukne slik hvor n + t = 1, spesielt akryl, metakryl og lignende. Of the above-mentioned monomers, those where n + t = 1 are most preferred, especially acrylic, methacrylic and the like.
Av ovennevnte monomerer er egnede eksempler på syrer akrylsyre, metakrylsyre, itakonsyre, etakrylsyre, maleinsyre, fumarsyre og lignende, egnede eksempler på alkylestere er slike hvor alkylgruppen er metyl, etyl, propyl, isopropyl, butyl, tert.-butyl, pentyl, heksyl, etyiheksyl, oktyl, decyl, dodecyl og lignende, egnede eksempler på hydroksy-substituert alkyl er hydroksy-etyl, hydroksypropyl, hydroksybutyl, hydroksypentyl, hydroksy-heksyl, hydroksyoktyl, hydroksydecyl, hydroksydodecyl og lignende, egnede eksempler på aminoalkyl er aminometyl, aminoetyl, amino-propyl, aminobutyl, aminopentyl, aminoheksyl, aminooktyl, amino-decyl, aminododecyl hvor aminogruppen er en primær aminogruppe eller en sekundær aminogruppe og substituenten på aminogruppen er en alkylgruppe med fra 1 til 6 karbonatomer, fortrinnsvis 1-4 karbonatomer, egnede eksempler på merkaptoalkyl er metylmerkapto, etylmerkapto, propylmerkapto, butylmerkapto, pentylmerkapto, heksyl-merkapto, oktylmerkapto, decylmerkapto og dodecylmerkapto, og på lignende måte kan alkoksyalkyl- og alkyltioalkylgruppene være metoksymetyl, etoksymetyl, etoksyetyl, metyltiometyl, etyltio- Of the above-mentioned monomers, suitable examples of acids are acrylic acid, methacrylic acid, itaconic acid, ethacrylic acid, maleic acid, fumaric acid and the like, suitable examples of alkyl esters are those where the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, ethylhexyl, octyl, decyl, dodecyl and the like, suitable examples of hydroxy-substituted alkyl are hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyoctyl, hydroxydecyl, hydroxydodecyl and the like, suitable examples of aminoalkyl are aminomethyl, aminoethyl, amino -propyl, aminobutyl, aminopentyl, aminohexyl, aminooctyl, amino-decyl, aminododecyl where the amino group is a primary amino group or a secondary amino group and the substituent on the amino group is an alkyl group with from 1 to 6 carbon atoms, preferably 1-4 carbon atoms, suitable examples of mercaptoalkyl are methyl mercapto, ethyl mercapto, propyl mercapto, butyl mercapto, pentyl mercapto, hexyl mercapto, octyl mercapto, decyl mercapto and dod ecylmercapto, and in a similar way the alkoxyalkyl and alkylthioalkyl groups can be methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthio-
etyl og lignende. ethyl and the like.
Det skal forstås at selv om den polymeriserte harpiks It should be understood that although the polymerized resin
kan være en homopolymer, så bør man helst anvende en blanding av monomerer for å oppnå beleggfilmer med ønskelige egenskaper som f.eks. forbedret avflakingsmotstand, krittingsmotstand, klebeevne, glans, fleksibilitet, holdbarhet, hårdhet, jevnhet og løsnings-middelmotstand. can be a homopolymer, then one should preferably use a mixture of monomers to obtain coating films with desirable properties such as e.g. improved flaking resistance, chalking resistance, adhesion, gloss, flexibility, durability, hardness, smoothness and solvent resistance.
En foretrukket monomerblanding er en som har en hoved-mengde med ester (R eller R i ovennevnte formel er alkyl eller substituert alkyl hvor substituenten er ikke-funksjonell eller ikke-reaktiv) (omkring 50-90 %), en liten mengde (omkring 0,1-5%) av en syre (R eller R<1> er hydrogen) og en betydelig mengde (omkring 5-25 %) av en funksjonelt substituert alkyl (R eller R<1>A preferred monomer mixture is one having a major amount of ester (R or R in the above formula is alkyl or substituted alkyl where the substituent is non-functional or non-reactive) (about 50-90%), a small amount (about 0 .1-5%) of an acid (R or R<1> is hydrogen) and a significant amount (about 5-25%) of a functionally substituted alkyl (R or R<1>
er en alkylgruppe som har en substituent som har isocyanat- is an alkyl group having a substituent having isocyanate-
reaktiv funksjonalitet). reactive functionality).
I tillegg kan det inngå andre kopolymeriserbare monomerer som har en etylenisk umettet gruppe, i mindre mengder (fra omkring 0,1 til 10 %), f.eks. alifatiske eller aromatiske vinyl-forbindelser (som vinylklorid, vinyltoluen og styren). In addition, other copolymerizable monomers having an ethylenically unsaturated group may be included, in smaller amounts (from about 0.1 to 10%), e.g. aliphatic or aromatic vinyl compounds (such as vinyl chloride, vinyl toluene and styrene).
Alt som kreves av den polymeriserte harpiks er at den har utstikkende isocyanat-reaktive grupper. All that is required of the polymerized resin is that it has protruding isocyanate-reactive groups.
Ved polymeriseringsreaksjonen av de forannevnte monomerer anvendes vanlig polymeriseringsteknikk, fortrinnsvis løsnings-polymerisering i et organisk løsningsmiddel. In the polymerization reaction of the aforementioned monomers, ordinary polymerization techniques are used, preferably solution polymerization in an organic solvent.
Siden blandingen fortrinnsvis skal benyttes som et pul-verbelegningsmiddel, bør temperaturen ved herdingen være så lav som mulig. Det er derfor foretrukket at molekylvekten til den polymeriserte harpiks skal være relativt lav, f.eks. fra 10 000 til 75 000, med så lite avvik fra det gjennomsnittlige tall som mulig. Med andre ord bør molekylvektområdet være så snevert som mulig, innen ovennevnte område. Since the mixture is preferably to be used as a pulverizing agent, the temperature during curing should be as low as possible. It is therefore preferred that the molecular weight of the polymerized resin should be relatively low, e.g. from 10,000 to 75,000, with as little deviation from the average figure as possible. In other words, the molecular weight range should be as narrow as possible, within the above range.
Ved å anvende en lavmolekylær harpiks oppnår man ønsket flyteevne, mindre tendens til "appelsin-skall"-utseende og lignende. En snever molekylvektsfordeling gir høy sammenklumpningstem-peratur (for pulver), bedre sammenflytning, bedre glans og bedre forlikelighet med de andre komponenter i blandingen. By using a low molecular weight resin, the desired fluidity, less tendency to an "orange peel" appearance and the like is achieved. A narrow molecular weight distribution gives a high agglomeration temperature (for powder), better flowability, better gloss and better compatibility with the other components in the mixture.
Det tverrbindingsmiddel som blir anvendt som en komponent i pulver-belegningsblandingen, er som sagt isoforondiisocyanat hvor den mest reaktive isocyanatgruppe er blokkert, og den andre er blitt omsatt med en forbindelse som etter herdingen blir et internt mykningsmiddel for harpiksen, men som før herdingen er et eksternt mykningsmiddel for harpiksen. Med "internt mykningsmiddel" menes et materiale som gir en myknende effekt til harpiksen og er kjemisk bundet til denne. Med "eksternt mykningsmiddel" menes et tilsvarende materiale som ikke er kjemisk bundet. Den mest reaktive isocyanatgruppe er den som er bundet til seksringen over en metylengruppe. Under herdingen vil denne gruppe bli av-blokkert og reagerer med de funksjonelle grupper i den polymeriserte harpiksen. The cross-linking agent that is used as a component of the powder coating mixture is, as mentioned, isophorone diisocyanate where the most reactive isocyanate group is blocked, and the other has been reacted with a compound which after curing becomes an internal plasticizer for the resin, but which before curing is a external plasticizer for the resin. By "internal softener" is meant a material which gives a softening effect to the resin and is chemically bound to it. By "external plasticizer" is meant a corresponding material that is not chemically bound. The most reactive isocyanate group is the one attached to the six ring over a methylene group. During curing, this group will be unblocked and react with the functional groups in the polymerized resin.
Med "blokkert isocyanat" menes en isocyanatgruppe som er blitt omsatt med et blokkeringsmiddel slik at reaksjonsproduktet er stabilt ved opptil 50°C i lange tidsperioder. Under herdingen blir det blokkerte isocyanat av-blokkert under oppvarming . By "blocked isocyanate" is meant an isocyanate group that has been reacted with a blocking agent so that the reaction product is stable at up to 50°C for long periods of time. During curing, the blocked isocyanate is de-blocked during heating.
Som isocyanat-reaktiv, myknende forbindelse kan man anvende mettede alifatiske glykoler eller polyhydroksy-alkaner eller cykloalkaner f. eks. fcutylenglykol, 1, 6-dih'ydroksyoktan, 1,7-dihydroksyoktan, 1,10-dihydroksydekan, 1,12-dihydroksydodekan, 2,2,2-trimetylolpentan, pentaerytritol, 1,3,5-trihydroksypentan, 2,4,6-trihydroksyheksan, neopentylglykol (2,2-dimetyl-l,3-dihydrok-sypropan), 2,2,4-trimetyl-l,3-pentandiol og 1,4-cykloheksandimeta-nol, polyoksyalkylenglykol hvor alkylen har fra 2 til 4 karbonatomer f.eks. polyoksyetylenglykol, polyoksypropylenglykol og poly-oksybutylenglykol, med molekylvekt opptil 500, hydroksylholdige materialer som har det repeterende ledd -[CH2~CH(CH20H)]n hvor n er fra 1 til 10, polyaminoforbindelser så som 1,4-diaminobutan, 1,6-diamino-heksan og 1,8-diamino-dodekan, det skal forstås at aminoforbindelsen bør være et primært eller sekundært amin med minst ett reaktivt hydrogenatom, en substituent kan være festet til nitrogenatomet, substituenten kan være an alkylgruppe eller hydroksyalkylgruppe med fra 1 til 6 karbonatomer. Saturated aliphatic glycols or polyhydroxyalkanes or cycloalkanes can be used as an isocyanate-reactive, softening compound, e.g. fcutylene glycol, 1, 6-dihydroxyoctane, 1,7-dihydroxyoctane, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 2,2,2-trimethylolpentane, pentaerythritol, 1,3,5-trihydroxypentane, 2,4, 6-trihydroxyhexane, neopentyl glycol (2,2-dimethyl-1,3-dihydroxypropane), 2,2,4-trimethyl-1,3-pentanediol and 1,4-cyclohexanedimethanol, polyoxyalkylene glycol where the alkyl has from 2 to 4 carbon atoms e.g. polyoxyethylene glycol, polyoxypropylene glycol and polyoxybutylene glycol, with molecular weight up to 500, hydroxyl-containing materials having the repeating unit -[CH2~CH(CH20H)]n where n is from 1 to 10, polyamino compounds such as 1,4-diaminobutane, 1,6 -diamino-hexane and 1,8-diamino-dodecane, it should be understood that the amino compound should be a primary or secondary amine with at least one reactive hydrogen atom, a substituent may be attached to the nitrogen atom, the substituent may be an alkyl group or hydroxyalkyl group with from 1 to 6 carbon atoms.
Egnede eksempler på merkaptoforbindelser er: 1,4-dimer-kaptopentan, 1,6-dimerkaptoheksan, 1,8-dimerkaptooktan, 1,10-di-merkaptodekan og 1,12-dimerkaptododekan. Suitable examples of mercapto compounds are: 1,4-dimercaptopentane, 1,6-dimercaptohexane, 1,8-dimercaptooctane, 1,10-dimercaptodecane and 1,12-dimercaptododecane.
De følgende er egnede eksempler på amidoforbindelser som kan anvendes: 1,4-diamidobutan, 1,6-diamidoheksan, 1,8-di-amidooktan, 1,10-diamidodekan og 1,12-diamidododekan. Det skal forstås at et hydrogenatom festet til amidogruppen kan utskiftes med en alkyl- eller hydroksyalkylgruppe og derved ha minst ett utskiftbart hydrogenatom som kan omsettes fra amidogruppen. The following are suitable examples of amido compounds which can be used: 1,4-diamidobutane, 1,6-diamidohexane, 1,8-diamidooctane, 1,10-diamidodecane and 1,12-diamidododecane. It should be understood that a hydrogen atom attached to the amido group can be replaced by an alkyl or hydroxyalkyl group and thereby have at least one replaceable hydrogen atom that can be converted from the amido group.
Den mest reaktive isocyanatgruppe skal som sagt blokke-res. De vanligste blokkeringsmidler er fenoler, alkoholer, kaprolaktam, aldoksimer eller ketoksimer. Fortrinnsvis anvendes et ketoksim. Egnede ketoksimer er omtalt i US-patent 3 583 943. De som er foretrukket, er dialkylketoksimer f.eks. dimetylketok-sim, metyletylketoksim, metylisobutylketoksim og diiso butylketoksim. Fremstilling av tverrbindingsmiddel a) Isoforondiisocyanat (IPDI) + blokkeringsmiddel i X As said, the most reactive isocyanate group must be blocked. The most common blocking agents are phenols, alcohols, caprolactam, aldoximes or ketoximes. Preferably, a ketoxime is used. Suitable ketoximes are described in US patent 3,583,943. Those that are preferred are dialkyl ketoximes, e.g. dimethylketoxime, methylethylketoxime, methylisobutylketoxime and diisobutylketoxime. Preparation of cross-linking agent a) Isophorone diisocyanate (IPDI) + blocking agent in X
b) X + polyfunksjonelt mykningsmiddel y Y b) X + polyfunctional plasticizer y Y
hvor X inneholder én blokkert, og én fri isocyanatgruppe, og Y inneholder den blokkerte isocyanatgruppe og en gruppe som stammer fra omsetningen med mykningsmidlet. where X contains one blocked and one free isocyanate group, and Y contains the blocked isocyanate group and a group originating from the reaction with the plasticizer.
Det skal forstås at ethvert mykningsmiddel som har minst to utskiftbare hydrogenatomer fra funksjonelle grupper, kan anvendes. Det kan eventuelt ha tre funksjonelle grupper, som kan reagere med diisocyanatet. Det foretrukne mykningsmiddel inneholder minst 4 karbonatomer og har funksjonelle grupper som er atskilt ved minst 1 karbonatom. Mykningsmidlet har fortrinnsvis fra 6 It should be understood that any plasticizer having at least two replaceable hydrogen atoms from functional groups can be used. It may possibly have three functional groups, which may react with the diisocyanate. The preferred plasticizer contains at least 4 carbon atoms and has functional groups separated by at least 1 carbon atom. The softener preferably has from 6
til ca. 20 karbonatomer. to approx. 20 carbon atoms.
Mykningsmidlet kan selv være et reaksjonsprodukt, f.eks. en ester som stammer fra omsetningen av et polyhydroksyl-materiale og en syre, dens anhydrid eller en dibasisk syre. Egnede polyhydroksy-forbindelser er beskrevet ovenfor. Egnede syrer, diba-siske syrer og deres anhydrider kan ha opptil 12 karbonatomer, f. eks. oksalsyre, malonsyre, glutarsyre, adipinsyre, pimelinsyre, suberinsyre, azelainsyre og sebacinsyre. En foretrukken ester er en som stammer fra omsetning av neopentylglykol og 2,2-dimetyl, 3-hydroksy-propionsyre, med strukturen The plasticizer can itself be a reaction product, e.g. an ester resulting from the reaction of a polyhydroxyl material and an acid, its anhydride or a dibasic acid. Suitable polyhydroxy compounds are described above. Suitable acids, dibasic acids and their anhydrides may have up to 12 carbon atoms, e.g. oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. A preferred ester is one derived from the reaction of neopentyl glycol and 2,2-dimethyl, 3-hydroxy-propionic acid, having the structure
HO-CH2-C(CH3)2-CH2-0-C(O)-C(CH3)2-CH2"OH. HO-CH2-C(CH3)2-CH2-O-C(O)-C(CH3)2-CH2"OH.
Andre egnede polyhydroksy-forbindelser som kan omsettes med et polyisocyanat, er polyhydroksy-hydantoinforbindelser som apTiprpl 1- har sl-rnkt.nrpn Other suitable polyhydroxy compounds which can be reacted with a polyisocyanate are polyhydroxy hydantoin compounds such as apTiprpl 1- har sl-rnkt.nrpn
hvor R og R kan være like eller forskjellige og kan være hydrogen, alkyl med 1-6 karbonatomer, hydroksyalkyl med 1-6 karbonatomer, fenyl og lignende. where R and R can be the same or different and can be hydrogen, alkyl with 1-6 carbon atoms, hydroxyalkyl with 1-6 carbon atoms, phenyl and the like.
R 3 og R 4 kan være like eller forskjellige og kan være hydrogen, alkyl med fra 1 til 6 karbonatomer, hydroksyalkyl med fra 1 til 6 karbonatomer, polyoksyalkylen med fra 2 til 4 karbonatomer pr. alkylengruppe med en hydroksy-endegruppe, repeterende enheter av R 3 and R 4 can be the same or different and can be hydrogen, alkyl with from 1 to 6 carbon atoms, hydroxyalkyl with from 1 to 6 carbon atoms, the polyoxyalkylene with from 2 to 4 carbon atoms per alkylene group with a hydroxy end group, repeating units of
-[0CH2-CH(CH20H)]-n -[OCH2-CH(CH2OH)]-n
hvor n er fra 1 til 10, og lignende. Det skal også forstås at hydantoin-materialene må inneholde minst to hydroksylgrupper. Vanligvis blir disse forbindelser fremstilt ved å omsette dimetyl-hydantoin (R5 og R<6> er metyl og R3 og R<4> er hydrogen) med en passende hydroksyl-innførende forbindelse, f.eks. epiklorhydrin, where n is from 1 to 10, and the like. It should also be understood that the hydantoin materials must contain at least two hydroxyl groups. Typically these compounds are prepared by reacting dimethyl hydantoin (R5 and R<6> are methyl and R3 and R<4> are hydrogen) with a suitable hydroxyl introducing compound, e.g. epichlorohydrin,
etylenoksyd,.propylenoksyd eller butylenoksyd. For reaksjonsproduktet av epiklorhydrin kan det være behov for hydrolyse for å fjerne klorgruppene. Vanligvis kan "polyhydroksy-hydantoin"sies å inneholde den grunnleggende 5-leddede ringstruktur anført ovenfor. ethylene oxide, propylene oxide or butylene oxide. For the reaction product of epichlorohydrin, hydrolysis may be required to remove the chlorine groups. Generally, "polyhydroxy-hydantoin" can be said to contain the basic 5-membered ring structure listed above.
Det er også blitt påvist at det også kan anvendes et bis-hydantoin-derivat, dvs. et passende hydroksy-derivat av mety-len-bis-(substituert hydantoin). It has also been demonstrated that a bis-hydantoin derivative can also be used, i.e. a suitable hydroxy derivative of methylene-bis-(substituted hydantoin).
Det foretrukne hydantoin er et hvor R~* og R begge er metyl og R 3 og R 4begge er - 02^ 2^ 2 ' Et annet foretrukket hydantoin er et hvor R^ og R^ begge er metyl, og R3 og R4 begge er The preferred hydantoin is one in which R~* and R are both methyl and R 3 and R 4 are both - 02^ 2^ 2 ' Another preferred hydantoin is one in which R^ and R^ are both methyl, and R 3 and R 4 are both
-CH2OH. -CH 2 OH.
På grunn av at den endelige pulverblanding bør herde hurtig, vil'blokkeringsmidlet bli frigitt ved en passende temperatur som fortrinnsvis er over 121°C. Siden den først omsatte -NCO-gruppe er den mest reaktive og nå avblokkert (121°C), kan den hurtig tverrbindes med de reaktive grupper som stikker ut fra den polymeriserte harpiks. Because the final powder mixture should cure rapidly, the blocking agent will be released at a suitable temperature which is preferably above 121°C. Since the first reacted -NCO group is the most reactive and is now unblocked (121°C), it can be quickly cross-linked with the reactive groups protruding from the polymerized resin.
Tverrbindingsmidlet og harpiksen kan anvendes som basis for en maling etter passende fortynning med et organisk løsnings-middel. Dertil kan de anvendes ved fremstilling av pulvermaling som beskrevet i US-patentskrift 3 737 401. The cross-linking agent and the resin can be used as a basis for a paint after suitable dilution with an organic solvent. In addition, they can be used in the production of powder paint as described in US patent 3 737 401.
Den foretrukne fremgangsmåte for fremstilling av pulverpartikler i henhold til foreliggende oppfinnelse er å fremstille partiklene ved utfellingsprosessen i US-patent 3 737 401. Ved denne fremgangsmåte blir det dannet findelte dråper av filmdanner pluss organisk løsningsmiddel for filmdanneren. Når den flytende maling blir brakt i kontakt med et annet løsningsmiddel som er et ikke-løsningsmiddel for filmdanneren, men er et gjensidig løsnings-middel (partielt blandbart) med det første løsningsmiddel, blir dråpene dannet. Pulverpartiklene blir utfelt når det første løs-ningsmiddel blir fjernet fra dråpene ved fortynning derifra under kontakt med et løsningsmiddel i hvilket det første løsningsmiddel er blandbart. Et foretrukket par løsningsmidler er et' keton (for film-danneren) og vann. Med hensyn til ytterligere omtale av fremstilling av pulverpartikler vises det til US-patent 4 112 214. The preferred method for producing powder particles according to the present invention is to produce the particles by the precipitation process in US patent 3 737 401. In this method, finely divided drops of film former plus organic solvent for the film former are formed. When the liquid paint is brought into contact with another solvent which is a non-solvent for the film former, but is a mutual solvent (partially miscible) with the first solvent, the droplets are formed. The powder particles are precipitated when the first solvent is removed from the droplets by dilution therefrom in contact with a solvent in which the first solvent is miscible. A preferred pair of solvents is a ketone (for the film former) and water. With regard to further discussion of the production of powder particles, reference is made to US patent 4,112,214.
Det kan tilsettes andre komponenter før fremstillingen av pulveret, f.eks. pigmenter, fyllstoffer, organiske farvestoffer og farvelakker, mykningsmidler og flyt-reguleringsmidler, kataly-satorer for å akselerere herdingen og antistatiske midler. Et ytterligere, foretrukket mykningsmiddel som kan tilblandes med tverrbindingsmidlene, er en ester som stammer fra omsetningen av en mettet alifatisk triol med opptil 12 karbonatomer (ca. 2 vektdeler) med en langkjedet monobasisk fettsyre (med minst 5 karbonatomer - ca. 2 vektdeler), hvilket reaksjonsprodukt så blir omsatt med en aromatisk eller mettet alifatisk dibasisk syre eller anhydrid (ca. 1 del), og dette resulterer i en blanding som har overskudd, fortrinnsvis 50 % overskudd, av hydroksylgrupper. Dette mykningsmiddels hydroksylgrupper kan omsettes med de av-blokkerte isocyanatgrupper i tverrbindingsmidlet under herdingen av pulveret. Other components can be added before the production of the powder, e.g. pigments, fillers, organic dyes and varnishes, plasticizers and flow control agents, catalysts to accelerate curing and antistatic agents. A further, preferred plasticizer that can be mixed with the cross-linking agents is an ester derived from the reaction of a saturated aliphatic triol of up to 12 carbon atoms (about 2 parts by weight) with a long-chain monobasic fatty acid (with at least 5 carbon atoms - about 2 parts by weight), which reaction product is then reacted with an aromatic or saturated aliphatic dibasic acid or anhydride (about 1 part), and this results in a mixture having an excess, preferably a 50% excess, of hydroxyl groups. The hydroxyl groups of this plasticizer can react with the unblocked isocyanate groups in the cross-linking agent during the curing of the powder.
Det kan også tilsettes andre mykningsmidler som kan reagere med overskytende, av-blokkerte isocyanatgrupper. Other softeners can also be added which can react with excess, unblocked isocyanate groups.
Hvilke som helst av de ovenfor oppregnede mykningsmidler kan anvendes. Foretrukne materialer er polyhydroksy-forbindelser, f.eks. cellulosederivater (celluloseacetat, celluloseacetatbuty-r.at) , alkanpolyoler, hydroksylholdige laktoner og laktamer med ringer på 5 til 7 ledd og hydroksylholdige hydantoin-materialer. Any of the softeners listed above can be used. Preferred materials are polyhydroxy compounds, e.g. cellulose derivatives (cellulose acetate, cellulose acetate butyrate), alkane polyols, hydroxyl-containing lactones and lactams with rings of 5 to 7 members and hydroxyl-containing hydantoin materials.
Basert på filmdannende bestanddeler, til sammen 100 vekt%, kan pulverblandinger i henhold til foreliggende oppfinnelse beskrives på følgende måte: Based on film-forming components, a total of 100% by weight, powder mixtures according to the present invention can be described as follows:
Ytterligere (eksternt) Additional (External)
mykningsmiddel 0-10 %, fortrinnsvis minst 1 %. plasticizer 0-10%, preferably at least 1%.
Pulverblandingen kan også beskrives ved angivelse av forholdet mellom de forskjellige reaktive grupper. The powder mixture can also be described by specifying the ratio between the different reactive groups.
Den totale mengde av B + C bør ha overskudd av NCO-grupper for å kunne reagere med harpiksen A. The total amount of B + C should have an excess of NCO groups to be able to react with the resin A.
Oppfinnelsen er nå beskrevet i store trekk, og neden-for er det gitt eksempler på utførelsen av oppfinnelsen. Alle prosenter er vektprosenter dersom ikke annet blir angitt. The invention is now described in broad terms, and examples of the implementation of the invention are given below. All percentages are percentages by weight unless otherwise stated.
En akryl-harpiks ble fremstilt ved til et organisk keton-løsningsmiddel å sette 1 del akrylsyre, 1 del etylheksyl-akrylat, 6 deler etylheksylmetakrylat, 20 deler etylmetakrylat og 5 deler hydroksypropylmetakrylat, og oppløsningen ble polymerisert med en azo-katalysator ved ca. 80°C. An acrylic resin was prepared by adding 1 part acrylic acid, 1 part ethylhexyl acrylate, 6 parts ethylhexyl methacrylate, 20 parts ethyl methacrylate and 5 parts hydroxypropyl methacrylate to an organic ketone solvent, and the solution was polymerized with an azo catalyst at approx. 80°C.
Tverrbindingsmidlet ble fremstilt ved i et organisk keton-løsningsmiddel å omsette 1 moldel isoforon-diisocyanat med 1 moldel metyletyloksim inntil omsetningen var fullstendig. Så ble en halv moldel av 1,6-heksandiol tilsatt. Dibutyltinn-oksyd ble tilsatt for å fullføre omsetningen. The cross-linking agent was prepared by reacting 1 mole part of isophorone diisocyanate with 1 mole part of methyl ethyl oxime in an organic ketone solvent until the reaction was complete. Then half a mole part of 1,6-hexanediol was added. Dibutyltin oxide was added to complete the reaction.
Det ble så fremstilt en løsning av akrylharpiks og tverrbindingsmiddel i vektforholdet 2:1. Kjønrøk ble tilsatt med et forhold på 1 del pr. 25 deler akrylharpiks, og det ble fremstilt et pulver i overensstemmelse med US-patent 3 737 401 ved tilsetning av den under røring til en blanding av vann og ketonet, ved hvilket tidspunkt dråpene begynte å dannes. Så ble løsnin-gen satt til ytterligere mengder vann for å bevirke utfelning av pulver ved uttynning av ketonet fra dråpene. Pulveret ble så separert fra væsken ved filtrering, vasking og tørking. A solution of acrylic resin and cross-linking agent was then prepared in a weight ratio of 2:1. Carbon black was added at a ratio of 1 part per 25 parts acrylic resin, and a powder was prepared in accordance with US Patent 3,737,401 by adding it with stirring to a mixture of water and the ketone, at which point droplets began to form. Then the solution was added to additional amounts of water to cause precipitation of powder by diluting the ketone from the droplets. The powder was then separated from the liquid by filtration, washing and drying.
Partiklene hadde diametere i området mellom 5 og 50um. The particles had diameters in the range between 5 and 50 µm.
En renset stålplate ble anvendt som substrat hvorpå partiklene ble elektrostatisk påsprøytet. Filmen ble herdet til et hårdt, fastsittende, høyglansbelegg ved oppvarming av platen til ca. 163°C. Herdetiden var 30 minutter. A cleaned steel plate was used as a substrate onto which the particles were electrostatically sprayed. The film was cured to a hard, adherent, high-gloss coating by heating the plate to approx. 163°C. The curing time was 30 minutes.
Eksempel 2 Example 2
Fremgangsmåten fra eksempel 1 ble fulgt, og det ble anvendt overskudd av isocyanat (50 % overskudd) ved fremstilling av tverrbindingsmidlet. Før utfellingen fra det agiterte medi-um ble det tilsatt ytterligere mykningsmiddel (0,1 del pr. del akrylharpiks). Det annet mykningsmiddel er reaksjonsproduktet av trimetylolpropan (2 moldeler), pelargonsyre (2 moldeler) og ftalsyreanhydrid (1 moldel). Pulveret ble dannet på samme måte som i eksempel 1. Pulverpartiklene ble sprøytet elektrostatisk på en stålplate og så herdet ved å utsette platen for ca. 163°C The procedure from example 1 was followed, and an excess of isocyanate (50% excess) was used in the preparation of the cross-linking agent. Before the precipitation from the agitated medium, further plasticizer was added (0.1 part per part acrylic resin). The other plasticizer is the reaction product of trimethylolpropane (2 mole parts), pelargonic acid (2 mole parts) and phthalic anhydride (1 mole part). The powder was formed in the same way as in example 1. The powder particles were sprayed electrostatically onto a steel plate and then hardened by exposing the plate to approx. 163°C
i 30 minutter. Filmen var hård og fastsittende, og den hadde høy glans. for 30 minutes. The film was hard and sticky, and it had a high gloss.
Eksempel 3 Example 3
Fremgangsmåten fra eksempel 2 ble fulgt bortsett fra at det ble tilsatt kapryl-laktondiol (1 del pr. 10 deler akryl-harpiks) før utfellingen. Det ble oppnådd like gode filmer. The procedure from Example 2 was followed except that caprylactonediol (1 part per 10 parts acrylic resin) was added before the precipitation. Equally good films were obtained.
Eksempel 4 Example 4
Fremgangsmåten fra eksempel 1 ble anvendt ved fremstillingen av harpiksen og pulveret, bortsett fra at følgende sammensetning ble anvendt for å fremstille tverrbindingsmidlet. The procedure from Example 1 was used in the preparation of the resin and powder, except that the following composition was used to prepare the cross-linking agent.
Herdetemperaturen var 163°Cf og herdetiden var 30 minutter. The curing temperature was 163°Cf and the curing time was 30 minutes.
Filmene fremstilt i henhold til dette eksempel er ve-sentlig ekvivalente med dem fra eksempel 1. The films prepared according to this example are substantially equivalent to those of example 1.
Eksempel 5 Example 5
Fremgangsmåten fra eksempel 1 ble anvendt ved fremstillingen av harpiksen og pulveret, bortsett fra at den føl-gende sammensetning ble anvendt for å fremstille tverrbindingsmidlet. The method from example 1 was used in the preparation of the resin and the powder, except that the following composition was used to prepare the cross-linking agent.
Herdetemperaturen var 163°C, og herdetiden var 30 minutter. The curing temperature was 163°C, and the curing time was 30 minutes.
Filmene fremstilt i henhold til dette eksempel er om-trent som dem som ble fremstilt i henhold til eksempel 1. The films produced according to this example are approximately the same as those produced according to example 1.
Claims (1)
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US48188474A | 1974-06-21 | 1974-06-21 | |
US49606674A | 1974-08-09 | 1974-08-09 |
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NO752199L NO752199L (en) | 1975-12-23 |
NO143666B true NO143666B (en) | 1980-12-15 |
NO143666C NO143666C (en) | 1981-03-25 |
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NO752199A NO143666C (en) | 1974-06-21 | 1975-06-20 | COATING AGENT, SPECIFICALLY IN POWDER FORM, CONTAINING A POLYMER WITH REACTIVE GROUPS AND A CROSS-BONDING AGENT WITH BLOCKED ISOCYANATE GROUPS |
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JP (1) | JPS5118741A (en) |
BR (1) | BR7503856A (en) |
CA (1) | CA1044400A (en) |
DE (1) | DE2527430A1 (en) |
DK (1) | DK280575A (en) |
ES (1) | ES438739A1 (en) |
FI (1) | FI62677C (en) |
FR (2) | FR2288771A1 (en) |
GB (1) | GB1505136A (en) |
IT (1) | IT1039162B (en) |
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DE2712931A1 (en) * | 1977-03-24 | 1978-09-28 | Veba Chemie Ag | ISOCYANURATE GROUPS - AND FINALLY BLOCKED ISOCYANATE GROUPS - CONTAINING COMPOUNDS |
DE2732662A1 (en) * | 1977-07-20 | 1979-02-01 | Veba Chemie Ag | ISOCYANURATE GROUPS AND TERMINALLY BLOCKED ISOCYANATE GROUP COMPOUNDS |
JPS6115998Y2 (en) * | 1977-11-30 | 1986-05-17 | ||
DE4130336A1 (en) * | 1991-09-12 | 1993-03-18 | Bayer Ag | METHOD FOR THE PRODUCTION OF POWDER VARNISHES AND THEIR USE |
CN116836367B (en) * | 2023-08-09 | 2023-12-08 | 东莞市宏成新材料有限公司 | Isocyanate composition and preparation method thereof |
-
1975
- 1975-05-30 FI FI751609A patent/FI62677C/en not_active IP Right Cessation
- 1975-06-04 SE SE7506407A patent/SE408306B/en unknown
- 1975-06-18 GB GB25966/75A patent/GB1505136A/en not_active Expired
- 1975-06-19 BR BR4960/75D patent/BR7503856A/en unknown
- 1975-06-19 CA CA229,729A patent/CA1044400A/en not_active Expired
- 1975-06-20 NL NL7507432A patent/NL7507432A/en not_active Application Discontinuation
- 1975-06-20 NO NO752199A patent/NO143666C/en unknown
- 1975-06-20 DE DE19752527430 patent/DE2527430A1/en not_active Ceased
- 1975-06-20 ES ES438739A patent/ES438739A1/en not_active Expired
- 1975-06-20 IT IT24593/75A patent/IT1039162B/en active
- 1975-06-20 DK DK280575A patent/DK280575A/en not_active Application Discontinuation
- 1975-06-20 FR FR7519485A patent/FR2288771A1/en active Granted
- 1975-06-20 JP JP50074563A patent/JPS5118741A/ja active Pending
- 1975-12-11 FR FR7537966A patent/FR2299354A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
FI62677C (en) | 1983-02-10 |
SE408306B (en) | 1979-06-05 |
FI62677B (en) | 1982-10-29 |
FR2288771B1 (en) | 1980-11-07 |
AU8158275A (en) | 1976-12-02 |
DE2527430A1 (en) | 1976-01-08 |
NO143666C (en) | 1981-03-25 |
GB1505136A (en) | 1978-03-22 |
NL7507432A (en) | 1975-12-23 |
CA1044400A (en) | 1978-12-12 |
DK280575A (en) | 1975-12-22 |
ES438739A1 (en) | 1977-05-16 |
BR7503856A (en) | 1976-07-06 |
FI751609A (en) | 1975-12-22 |
FR2299354B1 (en) | 1981-04-17 |
SE7506407L (en) | 1975-12-22 |
FR2288771A1 (en) | 1976-05-21 |
FR2299354A1 (en) | 1976-08-27 |
NO752199L (en) | 1975-12-23 |
IT1039162B (en) | 1979-12-10 |
JPS5118741A (en) | 1976-02-14 |
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